P2 Ref Man

SimSci-Esscor®
®
PRO/II 9.2
5HIHUHQFH0DQXDO
March 2013
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© 2013 by Invensys Systems, Inc. All rights reserved.
Invensys Systems, Inc.

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Contents
Components and Thermodynamics 1
Chapter 1: Component Data

Defined Components . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-2
Component Libraries. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-2
Fixed Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-4
Temperature-dependent Properties . . . . . . . . . . . . . . . . . . . . .1-4
Properties From Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-6
Petroleum Components . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-6
General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-6
Property Generation– SIMSCI Method . . . . . . . . . . . . . . . . .1-7
Property Generation– CAVETT Method. . . . . . . . . . . . . . . .1-13
Property Generation– Lee-Kesler Method . . . . . . . . . . . . . .1-17
Property Generation – Heavy Method10 . . . . . . . . . . . . . . .1-19
Assay Processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-22
General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-22
Cutpoint Sets (Blends) . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-23
Inter-conversion of Distillation Curves. . . . . . . . . . . . . . . . .1-26
Cutting TBP Curves . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-34
Gravity Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-37
Molecular Weight Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-39
Lightends Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-40
Generating Pseudocomponent Properties . . . . . . . . . . . . . . .1-41
Vapor Pressure Calculations . . . . . . . . . . . . . . . . . . . . . . . . .1-42
Flash Point Calculations . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-46
Chapter 2: Thermodynamic Methods

Basic Principles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-50
Phase Equilibria . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-51
Enthalpy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-55
Entropy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-58
Density . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-59
Application Guidelines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-60
Refinery and Gas Processes . . . . . . . . . . . . . . . . . . . . . . . . .2-61
Natural Gas Processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-63
Chemical Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-70
Generalized Correlations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-73
PRO/II Reference Manual 3

General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-73
Ideal (IDEAL). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-74
Chao-Seader (CS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-76
Grayson-Streed (GS). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-77
Erbar Modification to Chao-Seader (CSE) and Grayson-Streed
(GSE) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-78
Improved Grayson-Streed (IGS). . . . . . . . . . . . . . . . . . . . . . 2-78
Curl-Pitzer (CP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-79
Braun K10 (BK10) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-80
Johnson-Grayson (JG) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-81
Lee-Kesler (LK) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-81
API . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-82
Rackett . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-83
COSTALD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-84
SRK-Peneloux Density Method . . . . . . . . . . . . . . . . . . . . . . 2-86
PR-Peneloux Density Method . . . . . . . . . . . . . . . . . . . . . . . 2-87
Equations of State . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-89
General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-89
General Cubic Equation of State. . . . . . . . . . . . . . . . . . . . . . 2-90
Alpha Formulations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-92
Mixing Rules (for Equations of State) . . . . . . . . . . . . . . . . . 2-96
Soave-Redlich Kwong (SRK). . . . . . . . . . . . . . . . . . . . . . . . 2-97
Peng-Robinson (PR) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-97
SRK Kabadi-Danner (SRKKD) . . . . . . . . . . . . . . . . . . . . . . 2-98
SRK Panagiotopoulos-Reid (SRKP) and PR Panagiotopoulos-
Reid (PRP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-99
SRK Modified (SRKM) and PR Modified (PRM) . . . . . . . 2-100
SRK SimSci (SRKS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-101
SRK Huron-Vidal (SRKH) and PR Huron-Vidal (PRH) . . 2-102
Hexamer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-105
UNIWAALS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-108
Benedict-Webb-Rubin-Starling . . . . . . . . . . . . . . . . . . . . . 2-110
Lee-Kesler-Plöcker (LKP) . . . . . . . . . . . . . . . . . . . . . . 2-111
Twu-Bluck-Coon(TBC) . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-114
Predictive Peng-Robinson 78 . . . . . . . . . . . . . . . . . . . . . . . 2-116
Predictive Soave-Redlich-Kwong (PSRK) . . . . . . . . . . . . . 2-120
Fill Options (for Binary Interaction Coefficients) . . . . . . . 2-121
Fill Options for Use With Cubic Equations of State. . . . . . 2-121
Free Water Decant. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-124
Vapor Phase Fugacities . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-127
Liquid Activity-Based Methods . . . . . . . . . . . . . . . . . . . . . . . . 2-131
General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-132
Margules Equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-136
4
van Laar Equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-137
Regular Solution Theory . . . . . . . . . . . . . . . . . . . . . . . . . . .2-138
Flory-Huggins Theory. . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-139
Wilson Equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-140
NRTL Equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-141
UNIQUAC Equation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-142
UNIFAC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-145
Modifications to UNIFAC. . . . . . . . . . . . . . . . . . . . . . . . . .2-148
Fill Options . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-151
Henry's Law . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-155
Heat of Mixing Calculations . . . . . . . . . . . . . . . . . . . . . . . .2-157
Special Packages . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-159
General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-159
Alcohol Package (ALCOHOL). . . . . . . . . . . . . . . . . . . . . .2-159
Glycol Package (GLYCOL) . . . . . . . . . . . . . . . . . . . . . . . .2-164
Sour Package (SOUR). . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-166
GPA Sour Water Package (GPSWATER) . . . . . . . . . . . . . .2-169
Amine Package (AMINE). . . . . . . . . . . . . . . . . . . . . . . . . .2-172
Electrolyte Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-175
Electrolyte Mathematical Model. . . . . . . . . . . . . . . . . . . . .2-175
Electrolyte Thermodynamic Equations. . . . . . . . . . . . . . . .2-181
Thermodynamic Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-199
Solid-Liquid Solubility . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-199
Transport Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-202
Index
Unit Operations 240
Chapter 3: Flash Calculations

Basic Principles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-241
MESH Equations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-242
Two-phase Isothermal Flash Calculations. . . . . . . . . . . . . .1-243
Flash Tolerances . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-247
Bubble Point Flash Calculations . . . . . . . . . . . . . . . . . . . . .1-248
Dew Point Flash Calculations . . . . . . . . . . . . . . . . . . . . . . .1-249
Two-phase Adiabatic Flash Calculations . . . . . . . . . . . . . .1-250
Water Decant . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-250
Three-phase Flash Calculations . . . . . . . . . . . . . . . . . . . . .1-252
Equilibrium Unit Operations . . . . . . . . . . . . . . . . . . . . . . . . . . .1-253
Flash Drum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-253
Valve . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-255
Mixer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-255

Splitter. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-256
Chapter 2: Isentropic Calculations

General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-257
Compressor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-258
Basic Calculations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-258
ASME Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-262
GPSA Method. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-264
Expander . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-266
Chapter 3: Pressure Calculations

Pipes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-271
Pressure Drop Correlations . . . . . . . . . . . . . . . . . . . . . . . . . 3-274
Pumps . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-284
Chapter 4: Distillation and Liquid-Liquid Extraction

Columns
Rigorous Distillation Algorithms . . . . . . . . . . . . . . . . . . . . . . . 4-287
General Column Model . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-289
Mathematical Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-292
Inside Out Algorithm . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-293
Chemdist Algorithm . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-301
Reactive Distillation Algorithm . . . . . . . . . . . . . . . . . . . . . 4-306
Initial Estimates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-312
ELDIST Algorithm . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-316
Basic Algorithm . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-316
Rate-based Segment Modeling using RATEFRAC® . . . . . . . . 4-320
Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-321
Segments and Packed Towers. . . . . . . . . . . . . . . . . . . . . . . 4-321
Rate-based Tray or Segment Diagram . . . . . . . . . . . . . . . . 4-321
Variables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-322
Equations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-323
Equilibrium Relationships . . . . . . . . . . . . . . . . . . . . . . . . . 4-329
Interface Energy Balance Equation: (1 Equation) . . . . . . . 4-331
Calculations for Mass Transfer Rate. . . . . . . . . . . . . . . . . . 4-332
6
Column Hydraulics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-346
Tray Rating and Sizing . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-347
Random Packed Columns . . . . . . . . . . . . . . . . . . . . . . . . . .4-351
Structured Packed Columns . . . . . . . . . . . . . . . . . . . . . . . .4-356
Shortcut Distillation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-362
Fenske Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-363
Underwood Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-364
Kirkbride Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-368
Gilliland Correlation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-368
Distillation Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-369
Simple Columns . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-371
Complex Columns. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-372
Refinery Heavy Ends Columns. . . . . . . . . . . . . . . . . . . . . .4-374
Troubleshooting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-378
Liquid-Liquid Extractor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-382
Basic Algorithm . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-382
Column Tray Efficiency Calculations . . . . . . . . . . . . . . . . . . . .4-385
Murphree Efficiency . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-386
Vaporization Efficiency. . . . . . . . . . . . . . . . . . . . . . . . . . . .4-387
Equilibrium Efficiency . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-387
Equilibrium and Vaporization Efficiencies Together . . . . .4-387
Chapter 5: Heat Exchangers

Simple Heat Exchangers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5-389
Calculation Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5-390
Zones Analysis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5-393
Example. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5-395
Rigorous Heat Exchanger . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5-397
Heat Transfer Correlations . . . . . . . . . . . . . . . . . . . . . . . . .5-399
Pressure Drop Correlations . . . . . . . . . . . . . . . . . . . . . . . . .5-403
Calculation of Bundle weight, Shell weight (dry) and Shell
weight (with water) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5-409
Fouling Factors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5-412
LNG Heat Exchanger. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5-413

Zones Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5-415
Air Cooled Heat Exchanger. . . . . . . . . . . . . . . . . . . . . . . . . . . . 5-415
Air Side Pressure Drop Correlations . . . . . . . . . . . . . . . . . 5-415
Air Side Film Coefficient Correlations. . . . . . . . . . . . . . . . 5-431
Furnace Model. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5-438
Major Specifications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5-439
Initial Estimates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5-441
Equations in the Furnace Model . . . . . . . . . . . . . . . . . . . . . 5-441
Chapter 6: Reactors
Reactor Heat Balances. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-447
Heat of Reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-449
Conversion Reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-449
Shift Reactor Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-451
Methanation Reactor Model . . . . . . . . . . . . . . . . . . . . . . . . 6-451
Equilibrium Reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-451
Shift Reactor Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-454
Methanation Reactor Model . . . . . . . . . . . . . . . . . . . . . . . . 6-455
Calculation Procedure for Equilibrium. . . . . . . . . . . . . . . . 6-456
Gibbs Reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-456
Mathematics of Free Energy Minimization . . . . . . . . . . . . 6-457
Continuous Stirred Tank Reactor (CSTR). . . . . . . . . . . . . . . . . 6-463
Plug Flow Reactor (PFR) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-468
Chapter 7: Solids Handling Unit Operations

Dryer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7-475
Calculation Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7-476
Rotary Drum Filter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7-476
Filtering Centrifuge . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7-481
Countercurrent Decanter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7-486
Calculation Scheme . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7-490
Dissolver . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7-492
8
Particle Size Distribution . . . . . . . . . . . . . . . . . . . . . . . . . .7-496
Material and Heat Balances . . . . . . . . . . . . . . . . . . . . . . . .7-497
Phase Equilibria . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7-499
Residence Time . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7-499
Concentration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7-499
Solution Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7-499
Crystallizer. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7-500
Crystallization Kinetics and Population Balance Equations . .7-
502
Material and Heat Balances . . . . . . . . . . . . . . . . . . . . . . . .7-506
Phase Equilibria . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7-507
Solution Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7-508
Melter/Freezer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7-510
Chapter 8: Utilities
Phase Envelope . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8-513
Heating / Cooling Curves . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8-515
Calculation Options. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8-516
Critical Point and Retrograde Region Calculations . . . . . .8-516
VLE, VLLE, and Decant Considerations . . . . . . . . . . . . . .8-517
Water and Dry Basis Properties . . . . . . . . . . . . . . . . . . . . .8-518
GAMMA and KPRINT Options . . . . . . . . . . . . . . . . . . . . .8-518
Availability of Results. . . . . . . . . . . . . . . . . . . . . . . . . . . . .8-519
Binary VLE/VLLE Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8-522
Input Considerations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8-523
Output Considerations. . . . . . . . . . . . . . . . . . . . . . . . . . . . .8-523
Hydrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8-525
Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8-525
Check Solids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8-532
Input Considerations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8-532
Calculation Considerations . . . . . . . . . . . . . . . . . . . . . . . . .8-533
Report Considerations. . . . . . . . . . . . . . . . . . . . . . . . . . . . .8-534
Exergy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8-537

Interpreting Exergy Reports . . . . . . . . . . . . . . . . . . . . . . . . 8-537
Chapter 9: Stream Calculator

Feed Blending Considerations . . . . . . . . . . . . . . . . . . . . . . 9-541
Stream Splitting Considerations . . . . . . . . . . . . . . . . . . . . . 9-543
Stream Synthesis Considerations . . . . . . . . . . . . . . . . . . . . 9-544
Chapter 10: Flowsheet Solution Algorithms

Sequential Modular Solution Technique . . . . . . . . . . . . . . . . . 10-545
General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10-545
Methodology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10-545
Process Unit Grouping . . . . . . . . . . . . . . . . . . . . . . . . . . . 10-547
Calculation Sequence and Convergence . . . . . . . . . . . . . . . . . 10-549
Tearing Algorithms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10-549
Convergence Criteria . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10-551
Acceleration Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10-552
Wegstein Acceleration . . . . . . . . . . . . . . . . . . . . . . . . . . . 10-552
Broyden Acceleration . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10-554
Flowsheet Control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10-556
Feedback Controller . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10-556
Recommendations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10-558
Multi-variable Feedback Controller . . . . . . . . . . . . . . . . . . . . 10-561
The Algorithm. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10-563
Flowsheet Optimization. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10-564
Solution Algorithm . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10-570
Chapter 11: Depressuring

General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11-577
Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11-577
Calculating the Vessel Volume . . . . . . . . . . . . . . . . . . . . . . . . 11-579
Valve Rate Equations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11-580
Orifice Rate Equations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11-583
Heat Input Equations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11-584
Isentropic Efficiency Considerations. . . . . . . . . . . . . . . . . . . . 11-589
10
Chapter 12: Batch Distillation Modeling Using
BATCHFRAC®
Model Column Schematic . . . . . . . . . . . . . . . . . . . . . . . . . . . .12-591
Total Mass Balance Equations . . . . . . . . . . . . . . . . . . . . . . . . .12-592
Component Mass Balance Equations. . . . . . . . . . . . . . . . . . . .12-593
Enthalpy Balance Equations . . . . . . . . . . . . . . . . . . . . . . . . . .12-595
Other Equations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .12-596
Product Accumulator Equations . . . . . . . . . . . . . . . . . . . . . . .12-597
Appendix A: HXRIG Heat Transfer Correlations

Shell side . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .13-599
Modified Chen Vaporization Method . . . . . . . . . . . . . . . .13-599
HEX5 Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .13-605
Tubeside . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .13-611
Modified Chen Vaporization Method . . . . . . . . . . . . . . . .13-611
HEX5 Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .13-622
Index

12
Volume1: Components and Thermody-
namics
General Information
The PRO/II Reference Manual provides details on the basic equations and calculation techniques used in
the PRO/II simulation program and the PROVISION Graphical User interface. It is intended as a reference
source for the background behind the various PRO/II calculation methods.
What is in This Manual?

This volume of the PRO/II Reference Manual contains the correlations and methods used for the various
unit operations, such as the Inside/Out and Chemdist column solution algorithms.
For each method described, the basic equations are presented, and appropriate references provided for
details on their derivation. General application guidelines are provided, and, for many of the methods, hints
to aid solution are supplied.
Who Should Use This Manual?

For novice, average, and expert users of PRO/II, this manual provides a good overview of the calculation
modules used to simulate a single unit operation or a complete chemical process or plant. Expert users can
find additional details on the theory presented in the numerous references cited for each topic. For the nov-
ice to average user, general references are also provided on the topics discussed, e.g., to standard text-
books.
Specific details concerning the data entry steps required by the program can be found in the main PRO/II
Help. Detailed sample problems are provided in the PRO/II Application Briefs Manual, in the
\USER\APPLIB\ directory, and in the PRO/II Casebooks.
Finding What you Need

A Table of Contents in the electronic version of this manual includes hypertext links to the appropriate
chapters and sections. This provides quick access to information that may assist in preparing and entering
the required input data.
Chapter 1: Component Data
PRO/II allows the user to specify pure-component physical prop-

erty data for a given simulation. Pure component data are usually
associated with either a predefined component in a data library, a
user-defined (non-library) component, or a petroleum pseudocom-
ponent.
Properties for defined components can be accessed in a variety of
ways. They can be retrieved from an on-line databank or “library",
estimated from structural or other data, or input by the user as
‘‘non-library’’ components. User input can be used to override
properties retrieved from the libraries.
Properties for ‘‘pseudo’’ or petroleum components are derived from
generalized correlations based on minimal data, usually the normal
boiling point, molecular weight, and standard density. Hydrocarbon
streams defined in terms of assay data (including distillation data)
can be converted to discrete pseudo components by a number of
assay processing methods.
Defined Components
Petroleum Components
Assay Processing
Defined Components
Component Libraries
Fixed Properties
Temperature-dependent Properties
Properties From Structure
Component Libraries
Table 1-1 lists the property data available in the built-in component
libraries for predefined components. These libraries include the
PROCESS library (the physical property library used as the default
in PROCESS, PIPEPHASE, HEXTRAN, and early versions of
PRO/II), the SIMSCI library (a fully documented physical property
PRO/II Comp & Thermo Reference Manual 1-2

bank), the DIPPR (Design Institute for Physical Property Research)
library from the American Institute of Chemical Engineers, and the
OLILIB library of electrolyte species, which contains a subset of
the library component properties listed in the following sections.
Most of the fixed properties used in a simulation can be found in the
input reprint of the simulation. The coefficients of the correlations
used for the temperature-dependent properties stored in the libraries
are not shown because they are usually covered by contractual
agreements which disallow their display in a simulation.
Table 1-1: PRO/II Library Component Properties
Fixed Properties and Constants
Acentric Factor Heat of Formation
Carbon Number Hydrogen Deficiency Number
Chemical Abstract Number Liquid Molar Volume
Chemical Formula Lower Heating Value
Critical Compressibility Factor Molecular Weight
Critical Pressure Normal Boiling Point
Critical Temperature Rackett Parameter
Critical Volume Radius of Gyration
Dipole Moment Solubility Parameter
Enthalpy of Combustion Specific Gravity
Enthalpy of Fusion Triple Point Temperature
Flash Point Triple Point Pressure
Free Energy of Formation UNIFAC Structure
Freezing Point (normal melting van der Waals Area and Volume
point)
Gross Heating Value
Temperature-dependent-Properties
Enthalpy of Vaporization Solid Heat Capacity
Ideal Vapor Enthalpy Solid Vapor Pressure
Liquid Density Surface Tension
Liquid Thermal Conductivity Vapor Pressure
Liquid Viscosity Vapor Thermal Conductivity
Saturated Liquid Enthalpy Vapor Viscosity
Solid Density
Component Data 1-3

Reference
1 PPDS, Physical Property Data Service, jointly sponsored

by the National Physical Laboratory, National Engineering
Laboratory, and the Institution of Chemical Engineers in
the UK.
2 DIPPR, Design Institute for Physical Property Data, spon-
sored by the American Institute of Chemical Engineers.
Fixed Properties
 Specific gravities of permanent gases are often expressed as
relative to air, without any annotations in the output.
 Liquid molar volumes may be extrapolated from a condition
very different from 77F (25 C), if the component doesn't natu-
rally exist as a liquid at 77 F.
Also See:
Defined Components
The temperature-dependent correlations available for use in PRO/II
are listed in Table 8-6 in volume I of the PRO/II Component and
Thermodynamic Input Data Manual. The equations that are typi-
cally used to represent a property are listed in Table 1-2. While tem-
perature-dependent library properties are fitted and are usually very
accurate at saturated, sub-critical conditions, caution must be used
in the superheated or super-critical regions.Because of the form of
some of the allowable temperature-dependent equations, extrapola-
tion beyond the minimum and maximum temperatures is not done
using the actual correlation. PRO/II has adopted the rules shown in
Table 1-2, based on the property, for extrapolation of the tempera-
ture-dependent correlations
Table 1-2: PRO/II Temperature-dependent Property Equations and Extrapolation
Conventions
Temperature- Recommended Extrapolation
dependent Equations Method
Property
Vapor Pressure 14, 20, 21, 22 ln(Prop.) vs. 1/T
Liquid Density 1, 4, 16, 32 Prop. vs. T

Table 1-2: PRO/II Temperature-dependent Property Equations and Extrapolation
Conventions
Ideal Vapor Enthalpy 1, 17, 41 Prop. vs. T
Enthalpy of 4, 15, 36, 43 Prop. vs. T
Vaporization
Saturated Liquid 1, 42, 35 Prop. vs. T
Enthalpy
Liquid Viscosity 13, 20, 21 ln(Prop.) vs. 1/T
Vapor Viscosity 1, 19, 26, 27 Prop. vs. T
Liquid Thermal 1, 4, 34 Prop. vs. T
Conductivity
Vapor Thermal 1, 19, 33 Prop. vs. T
Conductivity
Surface Tension 1, 15, 30 Prop. vs. T
Solid Thermal 1 Prop. vs. T
Conductivity
Solid Density 1 Prop. vs. T
Solid Cp or Enthalpy 1 Prop. vs. T
Solid Vapor Pressure 20 ln(Prop.) vs. 1/T
Another note of caution concerns the use of equations 20 and 21 in

modeling component vapor pressures. These equations are actually
combinations of two or more traditionally used vapor pressure
equations (e.g., Antoine). It is intended that the user apply only sub-
sets of the available coefficients with these equations corresponding
to the more traditional equations. Table 1-3 gives some examples of
this mapping.
Table 1-3: PRO/II Vapor Pressure Equations
Common Equation 20 / 21 Coefficients
Vapor
Pressure
Equations C1 C2 C3 C4 C5 C6 C7
(#)
Clapeyron x x
(20 or 21)
Antoine (21) x x x
Riedel (20) x x x x
Frost- x x x x
Kalkwarf (21)
Component Data 1-5

Table 1-3: PRO/II Vapor Pressure Equations
Reidel-Plank- x x x x
Miller (20)
Also See:
Defined Components
Properties From Structure

Properties for defined components, either library or non-library,
may be estimated if the user supplies a component structure and
invokes the FILL option in the component data category of input.
This procedure primarily uses the methods of Joback. It is good for
components having molecular weights below 400 and components
with less than 20 unique structural groups. More accurate results are
obtained for components containing just one type of functional
group. For example, amine properties would be more accurate than
those predicted for an ethanol amine, which would contain func-
tional groups for both an alcohol and an alcohol amine. This feature
is available in PRO/II software for all versions subsequent to v3.3.
Also See:
Defined Components
General Information
Property Generation– SIMSCI Method
Property Generation– CAVETT Method
Property Generation– Lee-Kesler Method
Property Generation – Heavy Method10
General Information
Petroleum components (often called pseudo-components) are either
defined on a one-by-one basis on PETROLEUM statements or gen-
erated from one or more streams given in terms of assay data. The
processing of assays is described in Assay Processing section. Each
individual pseudo-component is typically a narrow-boiling cut or

fraction. Component properties are generated based on any two of
the following three properties:
Molecular weight.
 Normal boiling point (NBP).
 Standard liquid density.
When only two are supplied, the third is computed using the
(default) SIMSCI method (or another method if requested with the
MW keyword). These methods are described in the sections below.
From those three basic properties, the program estimates all other
properties needed for the calculation of thermophysical properties.
Assay Characterization
Assay Characterization
Several different sets of characterization methods are provided.
These are known as the SIMSCI (or TWU), CAVETT (API 1963),
Lee-Kesler, CAV8 (API 1980) EXTAPI, and (starting with PRO/II
version 8.2) the HEAVY methods. The Cavett methods developed
in the early 1960’s were the default in all versions of PRO/II up to
and including the 3.5 series. The SIMSCI methods use a combina-
tion of published (Black and Twu, 1983; Twu, 1984) and proprie-
tary methods developed by SimSci. These are the default for all
PRO/II versions subsequent to the 3.5 series. The LK option
accesses methods developed by Lee and Kesler in 1975 and
1976.The EXTAPI method is an extension of the method from the
1980 API technical data book with an adjustment for components
that boil below 300F. The most recently added HEAVY method is
an extension of the original Twu correlations. Also know as the
constant Watson K extension, it extrapolates to estimate critical
properties and molecular weight well beyond 1000 Kelvin.
Also See:
Property Generation– SIMSCI Method

Critical Properties and Acentric Factor
The SIMSCI characterization method was developed by Twu in
1984. It expresses the critical properties (and molecular weight) of
hydrocarbon components as a function of NBP and specific gravity.
The correlation is expressed as a perturbation about a reference sys-
Component Data 1-7

tem of normal alkanes. The critical temperature (in degrees Ran-
kine) is given by:
Equation (1-1):
Tc  Tco [(1  2 fT ) / (1  2 fT )]2

Equation (1-2):
fT  SGT 0.362456 / Tb1/2   0.0398285  0.948125 / Tb1/2  SGT 
Equation (1-3):
SGT  exp 5  SG o  SG    1

Equation (1-4):
SG o  0.843593  0.128624  3.36159 3  13749.5 12

Equation (1-5):
where:
SG =specific gravity
Tb = normal boiling point, degrees Rankine
 = 1 - Tb / Tc
SG = specific gravity correction
f = correction factor
subscript T refers to the temperature
subscript c refers to the critical conditions
superscript ° refers to the reference system
The critical volume (in cubic feet per pound mole) and the critical
pressure (in psia) are given by similar expressions:
Equation (1-6):
Vc  Vco 1  2 fV  / 1  2 fV  
2

Equation (1-7):

2

SGV  exp  4 SG o  SG 2   1
 
Equation (1-8):
fV  SGV 0.466590 / Tb1/2   0.182421  3.01721/ Tb1/2  SGV 
Equation (1-9):
Equation (1-10):
Pc  Pco Tc / Tco Vco / Vc  1  2 f P  / 1  2 f P  

2
Equation (1-11):
 2.53262  46.1955 / Tb1/2  0.00127885Tb  

f P  SGP  
  11.4277  252.140 / Tb1/2  0.00230535Tb  SGP 
 
Equation (1-12):
SGP  exp 0.5  SG o  SG    1

Equation (1-13):
where:
V = molar volume, ft3/lb-mole

P = pressure, psia
subscripts V and P refer to the volume and pressure
The acentric factor for the SIMSCI method is estimated with the use
of a generalized Frost-Kalkwarf vapor equation developed at Sim-
Sci. The equation is given by:
Equation (1-14):
A7 PR
ln PR   A1   A4    A2   A5  / TR   A3   A6  ln TR 
TR2
where:
Component Data 1-9

A1 to A7 = constants given in Table 1-4
PR = reduced pressure (P/Pc)
TR = reduced temperature (T/Tc),
 = a parameter evaluated at the NBP and given by:

Equation (1-15):

 ln P R ,b  A7 PR ,b / TR2,b   f o (TR ,b )
f ' (TR ,b )
where:
subscripts R,b indicate reduced properties evaluated at the nor-
mal boiling point
Functions f o and f’ are given by:
Equation (1-16):
f o TR   A1  A2 / TR  A3 ln TR
Equation (1-17):
f ' (TR )  A4  A5 / TR  A6 ln TR
The values of the seven constants in these equations are shown in

Table 1-4.
Table 1-4: Values of
Constants for Equations (1-14)-(1-17)
A1 10.2005
A2 -10.6317
A3 -5.58058
A4 2.09167
A5 -2.09167
A6 -1.70214
A7 0.4312
To compute the acentric factor, the parameter  is determined using

equation (1-15) and the known (or already estimated) values for the
critical temperature and pressure and the normal boiling point
(NBP). This is then used in equation (1-14) to compute the reduced

vapor pressure at a reduced temperature of 0.7, which is then used
in the definition of the acentric factor.
Equation (1-18):
   log10  PR ,TR  0.7

 1
Other Fixed Properties
The heat of formation is computed from a proprietary correlation
developed by SimSci. The solubility parameter is estimated from
the following equation:
Equation (1-19):
1/2
 H  RT 
  V 
 VL 
The molar latent heat of vaporization, HV, is computed from the
Kistiakowsky-Watson method described later on in this section,
while VL is the liquid molar volume at 25 C.
The ideal-gas enthalpy (needed for equation-of-state calculations) is
calculated from the method of Black and Twu developed in 1983.
The method was an extension of work done by Lee and Kesler and
involved fitting a wide variety of ideal-gas heat capacity data for
hydrocarbons from the API 44 project and other sources. The equa-
tion (which produces enthalpies in Btu/lb and uses temperatures in
degrees Rankine) is as follows:
Equation (1-20):
A3 2 A4 3
H o  A1  A2T  T  T
2 3
Equation (1-21):
A2  C1  C7 C4
Equation (1-22):
A3  C2  C7 C5
Equation (1-23):
A4  C3  C7C6
Component Data 1-11

Equation (1-24):
C1  0.33886  0.02827 K
Equation (1-25):
C2    0.9291  1.1543K  0.0368K 2  *104

Equation (1-26):
C3  1.6658*107
Equation (1-27):
C4    0.26105  0.59332 K 
Equation (1-28):
C5  4.92*104
Equation (1-29):
C6    0.536  0.6828K  *107

Equation (1-30):
C7  12.8  K 10  K  /10 K 

2
The Watson characterization factor, K, is defined as:

Equation (1-31):
NBP1/3
K
SG
where:
NBP = normal boiling point in degrees Rankine
SG = specific gravity (typically at 60F/60F)
The constant A1 in equation (1-20) is determined so as to give an
enthalpy of zero at the arbitrarily chosen zero for enthalpy, which is
the saturated liquid at 0 C. The latent heat of vaporization as
described below (to get from saturated liquid to saturated vapor)
and the SRK equation of state (to get from saturated vapor to ideal
gas) are used to compute the enthalpy departure between this refer-
ence point and the ideal-gas state.
The vapor pressure is calculated from the reduced vapor-pressure
equation (1-14) used above in the calculation of the acentric factor.

The latent heat of vaporization also is calculated from equation (1-
14), and then is related to the vapor pressure using the Clausius-
Clapyron equation. Saturated liquid enthalpy is calculated by com-
puting the departure from the ideal-gas enthalpy, as a sum of the
latent heat and the enthalpy departure (computed with the SRK
equation of state) for the saturated vapor. Saturated liquid density is
computed by applying the Rackett equation (see Section - General-
ized Correlation Methods) to saturated temperature and pressure
conditions as predicted by vapor-pressure equation (1-14).
Also See:
Property Generation– CAVETT Method

Optionally, the user may choose to compute critical properties from
the methods developed in 1962 by Cavett. This option is called the
CAVETT method. The equations are:
Equation (1-32):
Tc  768.07121  1.7133693Tb  0.0010834003Tb2

0.0089212579( API )Tb  0.38890584*106 Tb3
0.5309492( API )Tb2  0.327116*107 ( API ) 2Tb2
Equation (1-33):
where:
Tc = critical temperature in degrees Fahrenheit
Pc = critical pressure in psia
Tb = normal boiling point in degrees Fahrenheit
API = API gravity
Component Data 1-13

When the CAVETT characterization options are chosen, the acen-
tric factor is computed by a method due to Edmister (1958):
Equation (1-34):
3  log10 Pc 
    1
7  Tc / Tb   1 
In equation (1-34), Pc is in atmospheres. Finally, the critical volume

is estimated from the following equation:
Equation (1-35):
PV
Zc  c c
 0.291  0.08
RTc
Other Fixed Properties

When the CAVETT characterization option is chosen, the heat of
formation and solubility parameter are calculated exactly as in the
SIMSCI method above.
Ideal-gas enthalpies (in Btu/lb-mole) are computed with the follow-
ing equations:
Equation (1-36):
H o  A  BT  CT 2  DT 3
Equation (1-37):
A  a5 MW  a4  a0
Equation (1-38):
B  459.67(1379.01a1  2a2 )  a3
Equation (1-39):
C  a2  1379.01a1
Equation (1-40):
D  a1  (9.175*1011 API  5.633*108 ) MW

Equation (1-41):
a2  (3.107 *104  5.832*108 API ) MW

Equation (1-42):
1.7025*106 1.489*106 API  API  2.857*105  API 

  
a3   M
  4.293*10  3.084*10 K  K  0.088 K  0.819
3 4

Equation (1-43):
a4  459.67  459.67  459.67 a1  a2   a3 

Equation (1-44):
a5   0.351K  8.953 K  43.402 K  188.25

  3.535*104 API  0.053 API  5.956*103 K  3.544 API
where:
T=temperature in degrees Rankine
MW=molecular weight
API =API gravity
K=Watson K-factor defined by equation (1-31).
The constant 0 in equation (1-37) is determined so as to be consis-
tent with the arbitrary zero of enthalpy, which is the saturated liquid
at 0 C.
Vapor pressures (in psia) are computed from a generalized Antoine
equation:
Equation (1-45):
B
ln P  A 
T  80.0
Equation (1-46):
B
A  ln(14.696) 
Tb  80.0
Equation (1-47):
ln Pc  ln(14.696)
B
1 1

Tc  80.0 Tb  80.0
Component Data 1-15

Temperatures (including the critical temperature Tc and normal
boiling point Tb) are in degrees Rankine.
The saturated liquid density (in lb/ft3) is computed as follows:
Equation (1-48):
 L  A  BT  CT 2
Equation (1-49):
A  1.328  L ,60
Equation (1-50):
0.3076  L ,60
B
Tc
Equation (1-51):
0.3989  L ,60
C
Tc2
where:
 L ,60 = liquid density at 60 F, calculated from the specific

gravity and the density of water.
Temperatures are in degrees Rankine.
The latent heat of vaporization (in Btu/lb-mole) is calculated from a
combination of the Watson equation (Watson, 1943, Thek and Stiel,
1966), for the temperature variation of the heat of vaporization, and
the expression of Kistiakowsky (1923), for the heat of vaporization
at the normal boiling point:
Equation (1-52):
0.38
 T T 
H vap  H0  c 
 Tc  Tb 
Equation (1-53):
H 0  Tb (7.58  4.571ln Tb )
The critical temperature Tc, normal boiling point Tb, and tempera-
ture T are all in degrees Rankine.

The saturated liquid enthalpy is estimated with the correlation of
Johnson and Grayson. This method is discussed in Section: Gener-
alized Correlation Methods. A constant is added so that the satu-
rated liquid enthalpy is zero at 0 C.
Also See:
Property Generation– Lee-Kesler Method

Kesler and Lee used the following equations in 1976 to correlate
critical temperatures and critical pressures of hydrocarbons:
Equation (1-54):
Tc  341.7  811SG   0.4244  0.1174SG  Tb

  0.4669  3.2623SG  *105 / Tb
Equation (1-55):
ln Pc  8.3634  0.0566 / SG 
 0.24244  2.2898 / SG  0.11857 / SG  *10 T 2 3
b
 1.4685  3.648 / SG  0.47227 / SG  *10 T 2 7

b
2
  0.42019  1.6977 / SG  *10 T

2 10
b
3
where:
Tc,Tb = critical and normal boiling temperatures (both in
degrees Rankine)
Pc = critical pressure in psia
SG = specific gravity
The acentric factor is estimated from an equation in an earlier work
by Lee and Kesler (1975):
Component Data 1-17

Equation (1-56):
ln PR,b  5.92714  6.09648 / TR,b  1.28862ln TR,b  0.169347T


15.2518  15.6875 / TR,b  13.4721ln TR,b  0.43577TR6,b
where:
subscripts R, b indicate reduced properties evaluated at the nor-
mal boiling point.
The critical volume then is estimated from the equation:
Equation (1-57):
PV
Zc  c c
 0.2905  0.085
RTc
Molecular Weight and Other Fixed Properties Using Lee Kesler

Starting with version 8.3, PRO/II supports the Lee-Kesler method(4)
of predicting molecular weights of pseudo-components:
Equation (1-58):
When the Lee-Kesler characterization option is chosen, the heat of

formation and the solubility parameter are calculated exactly as in
the SIMSCI method described previously.
Temperature-dependent Properties Using Lee-Kesler

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

Equation (1-59):
The factor CF is given by:

Equation (1-60):
where:
K = Watson K-factor defined by equation (1-31).
T = temperature in degrees Rankine.
 = acentric factor as calculated by equation (1-56).
The constant of integration is determined so as to give an enthalpy
of zero at the arbitrarily chosen basis for enthalpy, which is the sat-
urated liquid at 0 C.
When the Lee-Kesler characterization option is chosen, the vapor
pressure, saturated liquid density, saturated liquid enthalpy, and
latent heat of vaporization are all calculated by the methods used for
CAVETT characterization, as described in the previous section.
Also See:
Property Generation – Heavy Method10

All the characterization methods discussed above apply predomi-
nantly to paraffinic fluids having API gravities greater than 20 and
Watson K factors in the 12.5 to 13.5 range. They have been shown
to be progressively less accurate as the API gravity drops to 10 or
less, and as the Watson K factor approaches 9 or 10.
The HEAVY characterization option provides a better estimation of
pseudo components or petro fractions generated from an assay
curve of heavy oil or bitumen. This extension of the SIMSCI
method exhibits better extrapolation qualities for heavier, more
naphthenic and aromatic materials typically present in heavy oils
Component Data 1-19

and bitumens. The method applies particularly well to the following
ranges:
Table 1-5:
Normal Boiling Point 111.111 to 1366.48 Kevin
Specific Gravity 0.49 to 1.2
Molecular Weight 16.00 to 2500.0
PRO/II issues warnings when data used with this option are outside
these ranges.
NBP Temperature, Specific Gravity, Molecular Weight

Equations (1-1) through (1-13) for the SIMSCI method serve as the
starting correlations. This method extrapolates those equations
using the following algorithm (demonstrated for molecular weight.
1 Compute the watson K from the NBP and the Specific
Gravity of the pseudo-component using equation (1-31).
2 Hold the Watson K constant and calculate Specific Gravity
at the upper temperature limit of 1000 K (NBP1800 R):
Equation (1-61):
13
 1800.0  -
SG 1800R = ----------------------------
K Watson
3 Compute molecular weight at NBP1800 R and SG1800 R:
Equation (1-62):
2
 1  2 fM 
ln( MW )  ln( MW )  o

 1  2 fM 
4 Compute a small change in Specific Gravity, NBP, and

MW:
Equation (1-63):
 SG  SG1800 R * 0.001
SG   SG   K W atson   SG   SG  
N B P1800 R   N B P   K W atson  SG 1800 R   SG  

3

5 Compute slope at NBP1800 R:
MW
Slope 
SG
6 Use the slope to extrapolate linearly to the given NBP and

SG
Equation (1-64):
MWtar  MW1800 R  Slope *  SGtar  SG1800 R 
Reference
1 Black, C., and Twu, C.H., 1983, Correlation and Prediction

of Thermodynamic Properties for Heavy Petroleum, Shale
Oils, Tar Sands and Coal Liquids, paper presented at
AIChE Spring Meeting, Houston, March 1983.
2 Cavett, R.H., 1962, Physical Data for Distillation Calcula-
tions - Vapor-Liquid Equilibria, 27th Mid-year Meeting of
the API Division of Refining, 42[III], 351-357.
3 Edmister, W.C., 1958, Applied Hydrocarbon Thermody-
namics, Part 4: Compressibility Factors and Equations of
State, Petroleum Refiner, 37(4), 173.
4 Kesler, M.G., and Lee, B.I., 1976, Improve prediction of
enthalpy of fractions, Hydrocarbon Proc., 53(3), 153-158.
5 Kistiakowsky, W., 1923, Z. Phys. Chem., 107, 65.
6 Lee, B.I., and Kesler, M.G., 1975, A Generalized Thermo-
dynamic Correlation Based on Three-Parameter Corre-
sponding States, AIChE J., 21, 510-527.
7 Thek, R.E., and Stiel, L.I., 1966, A New Reduced Vapor
Pressure Equation, AIChE J., 12, 599-602.
8 Twu, C.H., 1984, An Internally Consistent Correlation for
Predicting the Critical Properties and Molecular Weights of
Petroleum and Coal-tar Liquids, Fluid Phase Equil., 16,
137-150.
9 Watson, K.M., 1943, Ind. Eng. Chem., 35, 398.
Component Data 1-21

10 Spencer, Calvin; Nagvekar, Manoj; Watanasiri, Suphat;
Twu, Chorng H.; Petroleum Fraction Characterization - A
Viable Approach for Heavier, Highly Aromatic Fractions;
Paper presented at AIChe Spring Meeting, New Orleans,
LA, 2005
Also See:
Assay Processing
General Information
Cutpoint Sets (Blends)
Inter-conversion of Distillation Curves
Cutting TBP Curves
Gravity Data
Molecular Weight Data
Lightends Data
Generating Pseudocomponent Properties
Vapor Pressure Calculations
Flash Point Calculations
General Information
Hydrocarbon streams may be defined in terms of laboratory assay
data. Typically, such an assay would consist of distillation data
(TBP, ASTM D86, ASTM D1160, or ASTM D2887), gravity data
(an average gravity and possibly a gravity curve), and perhaps data
for molecular weight, light-ends components, and special refining
properties such as pour point and sulfur content. This information is
used by PRO/II to produce one or more sets of discrete pseudo-
components which are then used to represent the composition of
each assay stream.The process by which assay data are converted to
pseudo-components can be analyzed in terms of several distinct
steps. Before each of these is examined in detail, it will be useful to
list briefly each step of the process in order:
 The user defines one or more sets of TBP cut points (or accepts
the default set of cut points that PRO/II provides). These cut-

points define the (atmospheric) boiling ranges that will ulti-
mately correspond to each pseudo-component. Multiple cut
point sets (also known as blends) may also be defined to better
model different sections of a process.
 Each set of user-supplied distillation data is converted to a TBP
(True Boiling Point) basis at one atmosphere (760 mm Hg)
pressure.
 The resulting TBP data are fitted to a continuous curve and
then the program "cuts" each curve to determine what percent-
age of each assay goes into each pseudo-component as defined
by the appropriate cut-point set. Gravity and molecular weight
data are similarly processed so that each cut has a normal boil-
ing point, specific gravity, and molecular weight. During this
step, the lowest-boiling cuts may be eliminated or modified to
account for any lightends components input by the user.
 Within each cut-point set, all assay streams using that set
(unless they are explicitly excluded from the blending - this is
described later) are combined to get an average normal boiling
point, gravity, and molecular weight for each of the pseudo-
components generated from that cutpoint set. These properties
are then used to generate all other properties (critical proper-
ties, enthalpy data, etc.) for that pseudocomponent.
Note: Special refinery properties such as cloud point and sulfur

content may also be defined within assays. The distribution of these
properties into pseudo-components and their subsequent processing
by the simulator is outside the scope of this chapter but will be cov-
ered in a later document.
Cutpoint Sets (Blends)

Defining Cutpoints
In any simulation, there is always a "primary" cutpoint set, which
defaults as shown in Table 1-6.
Table 1-6: Primary TBP Cutpoint Set
 Number of Width per cut, F
TBP Range, F Components
100-800 28 25
800-1200 8 50
Component Data 1-23

Table 1-6: Primary TBP Cutpoint Set
1200-1600 4 100
The primary cutpoints shown in Table 1-6 may be overridden by

supplying a new set for which no name is assigned. In addition,
"secondary" sets of cutpoints may be supplied by supplying a set
and giving it a name. The blend with no name (primary cutpoint set)
always exists (even if only named blends are specifically given);
there is no limit to the number of named blends (secondary cutpoint
sets) that may be defined. The user may designate one cutpoint set
as the "default"; if no default is explicitly specified, the primary cut-
point set will be the default. Each cutpoint set (if it is actually used
by one or more streams) will produce its own set of pseudo compo-
nents for use in the flowsheet.
Association of Streams With Blends

Each assay stream is associated with a particular blend. By default,
an assay stream is assigned to the default cutpoint set. A stream
may be associated with a specific secondary cutpoint set by explic-
itly specifying the name of that cutpoint set (blend) in association
with the stream. If the assay stream is associated with a blend name
not given for any cutpoint set previously defined, a new blend with
that name is created using the same cutpoints as the primary cut-
point set. The user may also specify that a stream use a certain set of
cutpoints but not contribute to the blended properties of the pseudo-
components generated from that set (this might be appropriate if an
estimate were being supplied for a recycle stream, for example).
Use the XBLEND option to exclude the stream in question from
blending. Default behavior includes each stream in a blend to gen-
erate pseudo-component properties. This is called the BLEND
option. It is not allowed to use the XBLEND option on all streams,
since at least one stream must be blended in to define the pseudo-
component properties. Blending logic is best illustrated by exam-
ple:
Suppose two secondary cutpoint sets A1 and A2 are defined, with
A1 designated as the default. This means that three sets actually
exist, since the primary cutpoint set supplied by PRO/II still exists
(though it no longer is the set to which streams will be associated by
default). Now, suppose the following streams are declared (extrane-
ous information such as the initial conditions is not shown):
Table 1-7: Blending Example
Stream Blend Option Blend Name

Table 1-7: Blending Example
S1 none (default = BLEND) none (default = A1)
S2 XBLEND none (default = A1)
S3 XBLEND A1
S4 BLEND A2
S5 BLEND B1
S6 XBLEND B1
S7 BLEND B2
Streams S1 and S2 use the pseudo-components defined by second-
ary cutpoint set A1, which is the default. S3 also uses A1's pseudo-
components since it is specified directly. The pseudo-components
in blend A1 have properties determined only by the cuts from
stream S1, since the XBLEND option is used for S2 and S3. Stream
S4 uses the pseudo components defined by cutpoint set A2. Streams
S5 and S6 go into new blend B1 (that uses the cutpoints of the pri-
mary cutpoint set). Since XBLEND is used for stream S6, only
stream S5's cuts will be used to determine the properties of the
pseudo components in blend B1. Finally, stream S7 uses another
new blend, B2, also with cutpoints from the primary cutpoint set.
Since it is a different blend, however, the pseudo-components in
blend B2 are completely distinct (even though they have the same
cutpoint ranges) from those of blend B1.
Application Considerations
The selection of cutpoints is an important consideration in the simu-
lation of hydrocarbon processing systems. Too few cuts can result
in poor representation of yields and stream properties when distilla-
tion operations are simulated; moreover, desired separations may
not be possible because of component distributions. On the other
hand, the indiscriminate use of cuts not needed for a simulation
serves only to increase the CPU time unnecessarily. It is wise to
examine the cut definition for each problem in light of simulation
goals and requirements. The default primary cutpoint set in PRO/II
represents, in our experience, a good selection for a wide range of
refinery applications.
In some circumstances, it may be desirable to use more than one
cutpoint set in a given problem. This "multiple blends" functional-
ity is useful when different portions of a flow sheet are best repre-
sented by different TBP cuts; for example, one part of the process
may have streams that are much heavier than another and for which
more cutpoints at higher temperatures would be desirable. It is also
Component Data 1-25

useful when hydrocarbon feeds to a flow sheet differ in character;
for example, different blends might be used to represent an aromatic
stream (producing pseudo-components with properties characteris-
tic of aromatics) and a paraffinic stream feeding into the same flow-
sheet. The extra detail and accuracy possible with this feature must
be balanced against the increase in CPU time caused by the
increased number of pseudocomponents.
Also See:
Assay Processing
Inter-conversion of Distillation Curves

Types of Distillation Curves
Assays of hydrocarbon streams are represented by distillation
curves. A distillation curve represents the amount of a fluid sample
that is vaporized as the temperature of the sample is raised. The
temperature where the first vaporization takes place is referred to as
the initial point (IP), and the temperature at which the last liquid
vaporizes is called the end point (EP). Each data point represents a
cumulative portion (usually represented as volume percent) of the
sample vaporized when a certain temperature is reached.Estimation
of thermophysical properties for the pseudo components requires
(among other things) a distillation curve that represents the true
boiling point (TBP) of each cut in the distillation. However, rigor-
ous TBP distillations are difficult and not well standardized so it is
common to perform some other well-defined distillation procedure;
standard methods are defined by the American Society for Testing
and Materials (ASTM). The ASTM procedures most commonly
used for hydrocarbons are D86, D1160, and D2887.
ASTM D86 distillation is typically used for light and medium
petroleum products and is carried out at atmospheric pressure.
D1160 distillation is used for heavier petroleum products and is
often carried out under vacuum, sometimes at absolute pressures as
low as 1 mm Hg. The D2887 method uses gas chromatography to
produce a simulated distillation curve; it is applicable to a wide
range of petroleum systems. D2887 results are always reported by
weight percent; other distillations are almost always reported on a
volume percent basis. More details on these distillation procedures
may be found in the API Technical Data Book; complete specifica-
tions are given in volume 5 (Petroleum Products and Lubricants) of
the Annual Book of ASTM Standards.

Conversion of D1160 Curves
PRO/II converts D1160 curves to TBP curves at 760 mm Hg using
the three-step procedure recommended in the API Technical Data
Book:
 Convert to D1160 at 10 mm Hg using API procedure 3A4.1
(which in turn references procedure 5A1.13).
 This procedure is expressed as a way to estimate a vapor pres-
sure at any temperature given the normal boiling point, but the
same equations may be solved to yield a normal boiling tem-
perature given the boiling temperature at another pressure. The
equations used are as follows:
Equation (1-65):
3000.538 X  6.76156
log10 P  for X  0.0022 ( P  2mmHg )
43 X  0.987672
Equation (1-66):
2663.129 X  5.994296
log10 P  
95.76 X  0.972546
for 0.0013  X  0.0022 (2  P   760 mmHg )
Equation (1-67):
2770.085X  6.412631
log10 P  for X  0.0013 (P  760 mmHg)
36 X  0.989679
where:
P* = vapor pressure in mmHg at temperature T (in degrees
Rankine)
The parameter X is defined by:
Equation (1-68):
Tb
 0.0002867Tb
X T
748.1  0.2145Tb
where:
Tb = boiling point (in degrees Rankine) at a pressure of 760
mmHg
Component Data 1-27

For conversions where neither pressure is 760 mm Hg, the conver-
sion may be made by applying the above equations twice in succes-
sion, using 760 mm Hg as an intermediate point:
 Convert to TBP at 10 mm Hg using API Figure 3A2.1 (which
has been converted to equation form by SimSci).
 Convert to TBP at 760 mm Hg using API procedure 3A4.1.
Conversion of D2887 Curves to TBP 760 mmHg Curves

Starting with PRO/II version 8.1, the default method for converting
D2887 curves to atmospheric TBP curves (at 760 mmHg) was
changed to procedure 3A3.1 of the 1994 API Technical Data Book.
In PRO/II version 8.0 and earlier, the default was procedure 3A3.1
from the 1987 API Technical Data Book. There are significant
differences in the implementation of these two methods
Conversion of D2887 Curves Using the 1994 API Method
Starting with PRO/II version 8.1, the default option for converting
D2887 simulated distillation data to TBP curves at 760 mm Hg is
procedure 3A3.1 in the 1994 API Technical Data Book. The proce-
dure converts D2887 data directly to an atmospheric TBP curve in
three steps:
 Step 1: Calculate TBP at the 50% distilled point.
Equation (1-69):
TBP(50)  SD(50)
where:
TBP(50) true boiling point temperature at 50 volume percent
distilled, Fahrenheit.
SD(50) Simulated distillation temperature at 50 weight percent
 Step 2: Calculate necessary temperature differences between
adjacent cut points.
Equation (1-70):
Wi  CVi D
where:

Wi = True boiling point temperature difference between adjacent cut
points, Fahrenheit
Vi = Simulated distillation temperature difference between adjacent

cut points, Fahrenheit
C, D = constants that vary for cut point ranges, as shown in

Table 1-8
Table 1-8: Values of Constant C and D in Equation (1-70)

i Cut Point C D Approximate Maxi-
Range mum Allowable Vi,
(F)
1 100% - 95%* 0.02172 1.9733 30
2 95% - 90% 0.97476 0.8723 40
3 90% - 70% 0.31531 1.2938 75
4 70% - 50% 0.19861 1.3975 75
5 50% - 30% 0.05342 1.6988 75
6 30% - 10% 0.011903 2.0253 75
7 10% - 5% 0.15779 1.4296 40
*approximate --- use with care

 Step 3: Use equations 1 to calculate desired TBP tempera-
tures.
Table 1-9: Equations 1

TBP(5) = TBP(50) - W5 -W6 - W7
TBP(10) = TBP(50) - W5 -W6
TBP(30) = TBP(50) - W5
TBP(70) = TBP(50) + W4
TBP(90) = TBP(50) + W4 + W3
TBP(95) = TBP(50) + W4 + W3 + W2
TBP(100) = TBP(50) + W4 + W3 + W2 + W1
Component Data 1-29

Conversion of D2887 Curves - 1987 API Method
PRO/II can convert D2887 simulated distillation data to TBP curves
at 760 mm Hg using the two-step procedure recommended in the
1987 API Technical Data Book. This method was the default in
PRO/II version 8.0 and earlier. It no longer is the default starting
with the release of PRO/II version 8.1.
 Convert to D86 at 760 mm Hg using API procedure 3A3.1 in
the 1987 version of the API Technical Data Book (not the same
as procedure 3A3.1 in the 1994 API Technical Data Book).
This procedure converts D2887 Simulated Distillation (SD)
points (in weight percent) to D86 points (in volume percent)
using the following equation:
Equation (1-71):
D86  a ( SD)b F c
where:
D86 is the ASTM D86 temperature, and SD is the ASTM
D2887 temperature, both in degrees Rankine at each volume
percent (for D86) and the corresponding weight percent (for
SD). Constants a, b, and c vary with percent distilled according
toTable 1-10.
Table 1-10: Values of Constants a, b, c
Percent   
Distilled a b c
0 6.0154 0.7445 0.2879
10 4.2262 0.7944 0.2671
30 4.8882 0.7719 0.3450
50 24.1357 0.5425 0.7132
70 1.0835 0.9867 0.0486
90 1.0956 0.9834 0.0354
95 1.9073 0.9007 0.0625
The parameter F in equation (1-71) is calculated by the follow-

ing equation:
Equation (1-72):
F  0.00952( SD 10%)0.05434 ( SD 50%)0.6147

where:

SD10% and SD50% = D2887 temperatures in degrees Rankine
at the 10% and 50% points, respectively
 Convert to TBP at 760 mm Hg using the 1994 API procedure
3A1.1, or the 1987 API procedure. See b) Convert D86 Curves
Using the 1987 API Method.
D86 Curve Conversion Methods

PRO/II has several options for the conversion of D86 curves to TBP
curves at 760 mm Hg. These include:
 API94 This is API procedure 3A1.1 as described in volume 1
of the 1994 API Technical Data Book. Starting with PRO/II
8.3, this is the default. Invensys Simsci-Esscor do not publish
details of this proprietary method. Please refer to the API Tech-
nical Data Book.
 API87 Also known as the CAV87 method, this was the default
prior to PRO/II version 8.3.
 API63 Also known as the CAVETT method, this is the oldest
method still available in PRO/II to perform this conversion. It
is the version of the Edmister correlation that was recom-
mended prior to 1987.
 EDOK Another older correlation (prior to 1987). It is the
Edmister-Okimoto variation of the basic Edmister correlation.
Deprecated Cracking Option for D86 Curves

An optional correction for cracking may be applied to D86 data.
This correction was recommended by the API for use with their
older (1963) conversion procedure, but is not recommended for use
with the newer(1987and 1994) methods. PRO/II does not prevent
users from applying the correction improperly.
 If a cracking correction is desired, correct the temperatures above 475
F as follows:
Equation (1-73):
where: Torr, Tobs = the corrected and observed temperatures,

respectively, in degrees Fahrenheit.
Component Data 1-31

 If necessary, convert the D86 curve at pressure P to D86 at 760
mmHg with the standard ASTM correction factor:
Equation (1-74):
T760  TP  0.00012(760  P)(460  TP )
where:
TP = D86 temperature in Fahrenheit at pressure P
T760 = D86 temperature in Fahrenheit at 760 mm Hg.
 Convert from D86 at 760 mm Hg to TBP at 760 mm Hg using

one of themethods below.
a) Convert D86 Curves Using the 1994 API Method

Starting with PRO/II version 8.1, the default option for converting
ASTM D86 distillation data to TBP curves at 760 mm Hg is proce-
dure 3A1.1 in the 1994 API Technical Data Book. The procedure
consists of three steps:
 Step 1: Calculate TBP at the 50% distilled point.
Equation (1-75):
TBP(50)  0.87180( D86(50))1.0258
where:
TBP(50) = true boiling point temperature at 50 volume percent
D86(50) = Observed ASTM D86 distillation temperature at 50
weight percent distilled, Fahrenheit.
 Step 2: Calculate necessary temperature differences between
adjacent cut points.
Equation (1-76):
Yi  AX iB
where:
Yi = True boiling point temperature difference between two cut
points, Fahrenheit

Xi = Observed temperature difference between two ASTM D86
distillation cut points, Fahrenheit
A, B = constants that vary for cut point ranges, as shown in
Table 1-11
Table 1-11: Values of Constants A and B in Equation (1-76)

Maximum
Cut Point
i A B Allowable
Range
Xi, (F)
1 100% - 90% 0.11798 1.6606 ---
2 90% - 70% 3.0419 0.75497 100
3 70% - 50% 2.5282 0.82002 150
4 50% - 30% 3.0305 0.80076 250
5 30% - 10% 4.9004 0.71644 250
6 10% - 0 7.4012 0.60244 100
 Step 3: Use equations 14 to calculate desired TBP distillation

temperatures.
Table 1-12: Equation (2-75)

TBP(0) = TBP(50) - Y4 - Y5 - Y6
TBP(10) = TBP(50) - Y4 - Y5
TBP(30) = TBP(50) - Y4
TBP(70) = TBP(50) + Y3
TBP(90) = TBP(50) + Y3 + Y2
TBP(100) = TBP(50) + Y3 + Y2 + Y1
b) Convert D86 Curves Using the 1987 API Method

This option selects procedure 3A1.1 (developed by Riazi and Daubert in
1986) from the 1987 edition of the API Technical data Book. (It is not the
same as procedure 3A1.1 in the 1994 API Technical Data Book.) Use this
API87 option in PRO/II version 8.1 (and newer) to match the default D86
conversions of older PRO/II versions. The equation for this procedure is as
follows:
Component Data 1-33

Equation (1-77):
TBP  a ( D86)b
where a and b are constants varying with percent of liquid sample
distilled as given in Table 1-13.
Table 1-13: Values of Constants a, b
Percent Distilled a b
0 0.9167 1.0019
10 0.5277 1.0900
30 0.7429 1.0425
50 0.8920 1.0176
70 0.8705 1.0226
90 0.9490 1.0110
95 0.8008 1.0355
c) Conversion of D86 Curves with Old (1963) API Method

This method, while no longer the default, is still available for users
whose flow sheets may be tuned to the results using the old method.
This method was recommended (and shown in graphical form) in
older editions of the API Technical Data Book. The graphical corre-
lation has been converted to equation form by SimSci.
d) Conversion of D86 Curves with Edmister-Okamoto Method

Edmister and Okamoto (1969) developed a method which is still
widely used for converting ASTM D86 curves to TBP curves. If the
Edmister-Okamoto method is specified as the conversion method,
their procedure (converted from the original graphical form to equa-
tions by SimSci) is used for conversion of D86 to TBP curves.
Also See:
Assay Processing
Cutting TBP Curves

Fitting Distillation Curves
Before a curve is cut into pseudo-components, the distillation data
must be fitted to a continuous curve. This is necessary because the
supplied data points will not in general correspond to the desired
cutpoints. PRO/II offers three methods for fitting distillation curves.

SPLINE optionsStarting in PRO/II 8.3, the default curve fitting
method is the ALTERNATE cubic spline option. Previously, the
default was the original cubic SPLINE option).
All the cubic spline options fit all given volume percents between
the first and last points. Beyond those bounds, points 1 and 2 and
points N and N-1 are used by a normal distribution function to
extrapolate to the 0.01% and 99.99% points, respectively. If only
two points are supplied, the entire curve is defined by the distribu-
tion function fit. This extrapolation feature is particularly valuable
when extrapolating heavy ends distillations which often terminate
well below 50 volume percent. This method in general results in an
excellent curve fit.
The only exception is when the distillation data contain a significant
step function. Such a step often is an artifact of erroneously obtain-
ing or reporting the data. In these situations, the step creates an
instability that tends to propagate throughout the entire length of the
curve. This occurs because the original SPLINE option often
selects an integration interval that is inappropriately large. The
ALTERNATE spline method now is used as the default because it
almost always avoids this situation.
QUADRATIC optionThe quadratic fit method provides successive
quadratic approximations to the shape of the input assay curve. In
rare cases, this method is more stable than the original cubic spline
fit. Use of the ALTERNATE option makes this less necessary.
PDF option The Probability Density Function (PDF) method is dif-
ferent in that it does not necessarily pass through all the points input
by the user. Instead, it fits a probability density function to all points
supplied. The resulting curve maintains the probability-curve shape
characteristic of petroleum distillations, while minimizing the sum
of the squares of the differences between the curve and the input
data. If desired, the curve may be constrained to pass through either
or both of the initial point and end point. The PDF method is recom-
mended whenever it is suspected that the distillation data are
"noisy," containing significant random errors.
It is worth noting that the choice of curve-fitting procedure also has
a slight impact on the distillation inter-conversions described in the
previous section. That is because most of the conversion procedures
work by doing the conversion at a fixed set of volume percents,
which must be obtained by interpolation and sometimes extrapola-
tion, using some curve-fitting procedure.
Component Data 1-35

Division into Pseudo-components
Once a smooth distillation curve is obtained, the volume percent
distilled at each cutpoint is determined. The differences between
values at adjacent cutpoints define the percent of the stream's vol-
ume that is assigned to the pseudocomponent defined by the inter-
val between two adjacent cutpoints. For example, using the default
set of cutpoints shown in Table 1-6, the first pseudocomponent
would contain all material boiling between 100 F and 125 F, the
second would contain the material boiling between 125 F and 150 F,
and so forth. Material boiling above the last cutpoint (1600 F)
would be combined with the last (1500-1600) cut, while (with the
exception of lightends as discussed below) material boiling below
100 F would be combined with the first cut. If the distillation data
do not extend into all of the cut ranges (in this example, if the initial
point were higher than 125 F or if the end point were lower than
1500 F), the unused cuts are omitted from the simulation.
The normal boiling point (NBP) of each cut is determined as a vol-
ume-fraction average (or, in rare cases where TBP, D86, or D1160
distillations are entered on a weight basis, as a weight-fraction aver-
age) by integrating across the cut range. For small cut ranges, this
will closely approach other types of average boiling points. These
average boiling points are used (possibly after blending with cuts
from other assay streams in the flow sheet) as correlating parame-
ters when calculating other thermophysical properties for each
pseudocomponent.
These procedures are demonstrated in Figure 2.1 for a fictitious
assay with an IP of 90 F being cut according to the default cutpoint
set (Table 1-6); for simplicity only the first ten percent of the curve
is shown. In addition to its range, the first cut picks up the portion
boiling below 100 F, and its average boiling point (about 110 F in
this case) is determined by integrating the curve from the IP to the
125 F point. The second cut is assigned the material boiling from
125 F to 150 F, which is integrated to get a NBP of approximately
138 F. The third and subsequent cuts are generated in a similar man-
ner.
Figure 3: Cutting TBP Curves

Also See:
Assay Processing

Gravity Data
PRO/II requires the user to enter an average gravity (either as a Spe-
cific Gravity, API Gravity, or Watson K-factor) for each assay. If a
Watson K is given, it is converted to a gravity using the TBP data
for the curve. Entry of a gravity curve is recommended but not
required.
If a user-supplied gravity curve does not extend to the 95% point,
quadratic extrapolation is used to generate an estimate for the grav-
ity at the 100% point. A gravity for each cut is determined at its
mid-point, and an average gravity for the stream is computed. If this
average does not agree with the specified average, the program will
either normalize the gravity curve (if data are given up to 95%) or
adjust the estimated 100% point gravity value to force agreement.
Since the latter could in some cases result in unreasonable gravity
values for the last few cuts, the user should consider providing an
estimate of the 100% point gravity value and letting the program
normalize the curve, particularly when gravity data are available to
80% or beyond.
If no gravity curve is given, the program will generate one from the
specified average gravity. The default method for doing this is
Component Data 1-37

referred to as the WATSONK method. For a pure component, the
Watson K-factor is defined by the following equation:
Equation (1-76):
NBP1/3
K
SG
where:
NBP = normal boiling point in degrees Rankine
SG = specific gravity at 60 F relative to H2O at 60 F
For a mixture (such as a petroleum cut), the NBP is traditionally

replaced by a more complicated quantity called the mean average
boiling point (MeABP). For this purpose, however, it is sufficient to
simply use the volume-averaged boiling point computed from the
distillation curve. The gravity curve is generated by assuming a
constant value of the Watson K, applying equation (1-76) to each
cut to get a gravity, averaging these values, and then adjusting the
assumed value of the Watson K until the resulting average gravity
agrees with the average gravity input by the user.
Another method (known as the PRE301 option) is available primar-
ily for compatibility with older versions. It is similar to the pre-
ferred method described above, except that the average Watson K is
estimated from the 10, 30, 50, 70, and 90 percent points on a D86
curve (which can be obtained from the TBP curve by reversing one
of the procedures in the previous section) and then applied to the
NBP of each TBP cut to generate a gravity curve. This curve is then
normalized to produce the specified average gravity.
The preferred method (constant Watson K applied to TBP curve) is
justified by the observation that, for many petroleum crude streams,
the Watson K of various petroleum cuts above light naphtha tends
to remain fairly constant. For other types of petroleum streams,
however, this assumption is often incorrect. Hence, for truly accu-
rate simulation work, the user is advised to supply gravity curves
whenever possible.
Also See:
Assay Processing

Molecular Weight Data
In addition to the NBP and specific gravity, simulation with assays
requires the molecular weight of each cut. These may be omitted
completely by the user, in which case they are estimated by the pro-
gram.
The user may supply a molecular weight curve, which is quadrati-
cally interpolated and extrapolated to cover the entire range of pseu-
docomponents. Optionally, the user may also supply an average
molecular weight. In that case, the molecular weight value for the
last cut is adjusted so that the curve matches the given average, or if
the 100% value is provided, the entire molecular weight curve is
normalized to match the given average.
If no molecular-weight data are supplied, the molecular weights are
estimated. Several correlations are available.
Simsci (Twu) The default method is a proprietary modification
(known as the SIMSCI method) of the method developed by Twu
(1984). This method is a perturbation expansion using the normal
alkanes as a reference fluid.
Twu's method was originally developed to be an improvement over
Figure 2B2.1 in older editions of the API Technical Data Book.
That figure relates molecular weight to NBP and API gravity for
NBP’s greater than 300 F. The SIMSCI method matches that data
between normal boiling points of 300 F and 800 F, and better
extrapolates outside that temperature range.
Heavy Oil
Developed around 2006, this is the SIMSCI method modified to
better represent components having NBP’s above 1000 K. Below
1000 K, molecular weight calculations essentially are identical to
the SIMSCI method.
API63
The unaltered old API method is (API63) is also available.
API80
A newer 1980 API method, called CAV80, is available. This is API
procedure 2B2.1, an extension of the earlier API method that better
matches known pure-component data below 300 F. It has been cor-
related up to 1960 F.
Component Data 1-39

API94
Yet another newer version of this API procedure that is described in
the 1994 API Technical Data book.
Lee-Kesler
This correlation is based upon Normal Boiling Point (NBP, in Ran-
kine) and specificic gravity versus molecular weight. The complete
method is described in :
Kesler-Lee, Hydrocarbon Processing, March 1976, page 157.
The molecular weight method developed by Lee-Kesler also is
available. See equation (1-58).
EXTAPI
PRO/II additionally supports a composite method (known as
EXTAPI). This option uses the older API63 method for average
boiling temperatures of 300 F and lower. Above this temperature,
EXTAPI uses the CAV80 correlation.
Also See:
Assay Processing
Lightends Data
Hydrocarbon streams often contain significant amounts of light
hydrocarbons (while there is no universal definition of "light," C6 is
a common upper limit). Simulation of such systems is more accu-
rate if these components are considered explicitly rather than being
lumped into pseudocomponents. If the distillation curve is reported
on a lightends-free basis, the light components can be fed to the
flow sheet in a separate stream and handled in a straightforward
manner. Typically, however, the lightends make up the initial part of
the reported distillation curve, and adjustment of the cut-up curves
is required to avoid double-counting the lightends components.
By default, the program "matches" user-supplied lightends data to
the TBP curve. The user-specified rates for all lightends compo-
nents are adjusted up or down, all in the same proportion, until the
NBP of the highest-boiling lightends component exactly intersects
the TBP curve. All of the cuts from the TBP curve falling into the
region covered by the lightends are then discarded and the lightends
components are used in subsequent calculations. This procedure is
illustrated in Figure 2.2 where light end component flows are

adjusted until the highest-boiling light end (nC5 in this example)
has a mid-volume percent (point "a") that exactly coincides with the
point on the TBP curve where the temperature is equal to the NBP
of nC5. The cumulative volume percent of lightends is represented
by point "b," and the cuts below point b (and the low-boiling por-
tion of the cut encompassing that point) are discarded.
Figure 3-4: Matching Lightends to TBP Curve

Alternatively, the lightends may be specified as a fraction or percent
(on a weight or liquid-volume basis) of the total assay or as a fixed
lightends flowrate. In these cases, the input numbers for the light-
ends components can be normalized to determine the individual
component flow rates. A final alternative is to specify the flow rate
of each lightends component individually.
Also See:
Assay Processing
Generating Pseudocomponent Properties

Once each curve is cut, the program processes each blend to pro-
duce average properties for the pseudo-components from each cut-
point interval in that blend. All the streams in a given blend (except
Component Data 1-41

for those for which the XBLEND option was used) are totaled to get
the weights, volumes, and moles for each cutpoint interval. Using
the above totals, the average molecular weight and gravity are cal-
culated for each cut range. Finally, the normal boiling point for each
pseudocomponent is calculated by weight averaging the individual
values from the contributing streams.Once the normal boiling point,
gravity, and molecular weight are known for each pseudocompo-
nent, all other properties (critical properties, enthalpies, etc.) are
determined according to the characterization method selected by the
user (or defaulted by the program). These methods are described in
Also See:
Assay Processing
Vapor Pressure Calculations

While not a part of the program's actual processing of assay
streams, many problems involving hydrocarbon systems will
involve a specification on some vapor pressure measurement. The
two most common of these are the True Vapor Pressure (TVP)
and the Reid Vapor Pressure (RVP). PRO/II allows specification
of these quantities from several unit operations, and they may be
reported in output in the Heating/Cooling Curve (HCURVE) utility
or as part of a user-defined stream report.True Vapor Pressure
(TVP) Calculations.
True Vapor Pressure

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

The RVP laboratory procedure provides an inexpensive and repro-
ducible measurement correlating to the vapor pressure of a fluid.
The measured RVP is usually within 1 psi of the TVP of a stream. It
is always reported as "psi," although the ASTM test procedures
(except for D5191 which, as mentioned below, uses an evacuated
sample bomb) actually read gauge pressure. Since the air in the
bomb accounts for approximately 1 atm, the measured gauge pres-

sure is a rough measure of the true vapor pressure. Six different cal-
culation methods are available. Within each calculation method, the
answer will depend somewhat on the thermodynamic system used.
As with the TVP, the thermodynamic system for RVP calculations
may be specified explicitly or, by default, the thermodynamic sys-
tem used to generate the stream will be used.
The APINAPHTHA method calculates the RVP from Figure 5B1.1
in the API Technical Data Book, which represents the RVP as a
function of the TVP and the slope of the D86 curve at the 10%
point. The graphical data have been converted to equation form by
Simsci. This method is the default for PRO/II's RVP calculations. It
is useful for many gasolines and other finished petroleum products,
but it should not be used for oxygenated gasoline blends.
The APICRUDE method calculates the RVP from Figure 5B1.2 in
the API Technical Data Book, which represents the RVP as a func-
tion of the TVP and the slope of the D86 curve at the 10% point.
The graphical data have been converted to equation form by Sim-
Sci. It is primarily intended for crude oils.
The ASTM D323-82 method (known as the D323 method) simu-
lates a standard ASTM procedure for RVP measurement. The liquid
hydrocarbon portion of the sample is saturated with air at 33 F and 1
atm pressure. This liquid is then mixed at 100 F with air in a 4:1
volume ratio. Since the test chamber is not dried in this procedure, a
small amount of water is also added to simulate this mixture. The
mixture is flashed at 100 F at a constant volume (corresponding to
the experiment in a sealed bomb), and the gauge pressure of the
resulting vapor-liquid mixture is reported as the RVP. Both air and
water should be in the component list for proper use of this method.
The obsolete ASTM D323-73 method (known as the P323 method)
is available for compatibility with earlier versions of the program.
The ASTM D4953-91 method (known as the D4953 method) was
developed by the ASTM primarily for oxygenated gasolines. The
experimental method is identical to the D323 method, except that
the system is kept completely free of water. The algorithm for simu-
lating this method is identical to that for D323, except that no water
is added to the mixture. Air should be in the component list for
proper use of this method.
The ASTM D5191-91 method (known as the D5191 method) was
developed as an alternative to the D4953 method for gasolines and
gasoline-oxygenate blends. In this method, the air-saturated sample
Component Data 1-43

is placed in an evacuated bomb with five times the volume of the
sample, and then the total pressure of the sample is measured. In the
simulator, this is accomplished by flashing, at constant volume, a
mixture of 1 part sample (at 33 F and 1 atm) and 4 parts air (at the
near-vacuum conditions of 0.01 psia and 100 F). The resulting total
pressure is then converted to a dry vapor pressure equivalent
(DVPE) using the following equation:
Equation (1-77):
DVPE  0.965 X  A
where:
X = the measured total pressure
A = 0.548 psi (3.78 kPa)
This number is then reported as the RVP. Air should be in the com-
ponent list for proper use of this method.
Comments on RVP and TVP Methods

Because of the sensitivity of the RVP (and the TVP) to the light
components of the mixture, these components should be modeled as
exactly as possible if precise values of RVP or TVP are important.
This might mean treating more light hydrocarbons as defined com-
ponents rather than as pseudo-components; oxygenated compounds
blended into gasolines should also be represented as defined com-
ponents rather than as part of an assay. It is also important to apply a
thermodynamic method that is appropriate for the stream in ques-
tion (see section - Application Guidelines). The thermodynamics
becomes particularly important for oxygenated systems, which are
not well-modeled by traditional hydrocarbon methods such as
Grayson-Streed. These systems are probably best modeled by an
equation of state such as SRK with the SimSci alpha formulation
and one of the advanced mixing rules (see section - Equations of
State). It is important to have binary interaction parameters between
the oxygenates and the hydrocarbon components of the system.
PRO/II's databanks contain many such parameters, but others may
have to be regressed to experimental data or estimated.
One should not be too surprised if calculated values for RVP differ
from an experimental measurement by as much as one psi. Part of
this is due to the uncertainty in the experimental procedure, and part
is due to the fact that the lightends composition inside the simula-
tion may not be identical to that of the experimental sample.

One of the less appreciated effects in experimental measurements is
the presence of water, not only in the sample vessel, but also in the
air in the form of humidity. The difference between the D323 (a
"wet" method) RVP and the D4953 (a "dry" method) RVP will be
approximately the vapor pressure of water at 100 F (about 0.9 psi),
with the D323 RVP being higher. Both of these calculations assume
that dry air is used in the procedure. The presence of humidity in the
air mixed with the sample can alter the D323 results, lowering the
measured RVP because of the decreased driving force for vaporiza-
tion of the liquid water. In the extreme case of 100% humidity, the
D323 results will be nearly identical with the D4953 results. There-
fore, a "wet" test performed with air that was not dry would be
expected to give results intermediate between PRO/II's D323 and
D4953 calculations. The results from the D5191 method (both in
terms of the experimental and calculated numbers) should in gen-
eral be very close to D4953 results.
The primary application guideline for which RVP calculation model
to use is, of course, to choose the one that corresponds to the exper-
imental procedure applied to that stream. Secondary considerations
include limitations of the individual methods. The APINAPHTHA
and APICRUDE methods are good only for hydrocarbon naphtha
and crude streams, respectively. The D323 method (and its obsolete
predecessor, P323) is intended for hydrocarbon streams; the pres-
ence of water makes it less well-suited for use with streams contain-
ing oxygenated compounds. The D4953 and D5191 methods are
both better suited for oxygenated systems, and calculations with
these methods should give similar results.
Reference
1 American Petroleum Institute, 1988, Technical Data Book -

Petroleum Refining, 5th edition (also previous editions),
American Petroleum Institute, Washington, DC.
2 American Society for Testing of Materials, Annual Book of
ASTM Standards, section 5 (Petroleum Products, Lubri-
cants, and Fossil Fuels), ASTM, Philadelphia, PA (issued
annually).
3 Edmister, W.C., and Okamoto, K.K., 1959, Applied Hydro-
carbon Thermodynamics, Part 12: Equilibrium Flash
Vaporization Calculations for Petroleum Fractions, Petro-
leum Refiner, 38(8), 117.
Component Data 1-45

4 Twu, C.H., 1984, An Internally Consistent Correlation for
Predicting the Critical Properties and Molecular Weights of
Petroleum and Coal-tar Liquids, Fluid Phase Equil., 16,
137-150.
Also See:
Assay Processing
Flash Point Calculations

Flash point is the lowest temperature at which a liquid can form an
ignitable mixture with oxygen in air near the surface of the liquid
under specific test conditions. Typically, the temperature is cor-
rected to 14.7 psia (1 atmosphere) at which application of a test
flame causes the vapor to ignite.
At this temperature the vapor may cease to burn when the source of
ignition is removed. A slightly higher temperature, the fire point, is
defined at which the vapor continues to burn after being ignited.
Neither of these parameters is related to the temperatures of the
ignition source or of the burning liquid, which are much higher.
There are two basic types of flash point measurement - open cup
and closed cup.
In open cup devices, the sample is contained in an open cup that
allows free mixing with ambient air. The sample is heated, and at
intervals a flame is brought over the surface. The measured flash
point will actually vary with the height of the flame above the liquid
surface, and at sufficient height the measured flash point tempera-
ture will coincide with the fire point.
Closed cup testers are sealed with a lid through which the ignition
source can be introduced periodically. The vapor above the liquid is
assumed to be in reasonable equilibrium with the liquid. Closed cup
testers give lower values for the flash point (typically 5-10 K) and
are a better approximation to the temperature at which the vapor
pressure reaches the Lower Flammable Limit (LFL). See reference
(1) at the end of this section.
Index and User Mixing methods

PRO/II supports methods for calculating the flash point from user-
supplied average values or sets of values at cut-point temperatures.
The data may be obtained from experiments using flash point test
equipment, or from any other sources available to the user. In PRO/

II, these are basically mixing methods that are not further discussed
here. Since the data itself determines the type of flash point, the
open cup and closed cup options serve only to properly the label the
values when they appear in reports. Refer to the topic “Special
Property Data” in the chapter Streams with Assay Data of the PRO/
II keyword Input Manual. Also see the chapter Transport and Spe-
cial Properties in volume 2 of the Component and Thermodynamic
Data Input Manual.
Correlated Methods
Empirical methods are derived equations based on the lower end
boiling temperatures of distillation curves. Generally, continuous-
component streams are characterized into discrete "cut-points"
using the ASTM D86 method. Depending upon the correlation, the
boiling temperatures ranging between the zero percent and the 10
percent cut points are used and combined using various weighting
strategies to obtain a representative temperature. This temperature
then is incorporated as a variable in an empirical equation that com-
putes the flash point directly.
The two non-proprietary methods available in PRO/II are the SIM-
SCI (or Nelson) method and a modified version of the API meth-
ods. These forms have not been updated since their first appearance
in PRO/II version 3.3. In these forms, both closed cup and open cup
calculations use identical equations.
API Correlation
The equation in PRO/II is an older API method that Simsci-Esscor
has recast from the original Fahrenheit to Rankine temperatures to
eliminate zero from the division and LOG terms. It has been super-
seded by procedure 2B7.1 of the API technical Data book (2). The
form used in PRO/II is shown in equation (1-78).
Equation (1-78):
where:
TFP = Flash point temperature, Rankine
TBP10% = Boiling temperature of the ASTM D86 10% cut
point, Rankine
Component Data 1-47

Range over which the equation was evaluated
Table 1-14:
Flash point, F 0-450
ASTM D86 TBP, F 150-850
API makes the following statements about the equation:

The equation may be extrapolated to a limited extent. The flash
point could be more accurately correlated to the ASTM D86
5% point, but a lack of data prevented development of a corre-
lation. (3)
SIMSCI Correlation
This implements the method of Nelson (4), which is similar to the
API method and is based on ASTM D86 distillation curve data. It
calculates a weighted average of the 0%, 5%, and 10% cut point
boiling temperatures to compute a representative boiling tempera-
ture. These values then are used in the equation to compute the flash
point temperature directly as shown in equation (1-79).
Equation (1-79):
TFP  TBPinit  2.0* TBP5%  TBP10%  / 4.0  *0.64  100.0
where:
TFP = Calculated flash point temperature, Fahrenheit
TBPinit = Boiling temperature of the initial cut point, typically

the ASTM D86 0% point, Fahrenheit
TBP5% = Boiling temperature of the ASTM D86 5% cut point,
Fahrenheit
TBP10% = Boiling temperature of the ASTM D86 10% cut
point, Fahrenheit
Reference
1 51758, ASTM 93, Determination of flash point - Closed

cup equilibrium method (ISO 1523:2002).
2 API Technical Data Book, vol. 1, 6 ed., 1997, pp 2-30
3 API Technical Data Book, vol. 1, 6 ed., 1997, pp 2-31

4 Petroleum Refinery Engineering, 3rd ed., pg 125, 127; Nel-
son, W. L; McGraw-Hill, Inc., New York, 1949
Also See: Assay Processing
Component Data 1-49

Chapter 2: Thermodynamic Methods
PRO/II offers numerous methods for calculating thermodynamic

properties such as K-values, enthalpies, entropies, densities, gas and
solid solubilities in liquids, and vapor fugacities. These methods
include:
 Generalized correlations, such as the Chao-Seader K-value
method, and the API liquid density method,
 Equations of state, such as the Soave-Redlich-Kwong method
for calculating K-values, enthalpies, entropies, and densities,
 Liquid activity coefficient methods, such as the Non-Random
Two-Liquid (NRTL) method for calculating K-values,
 Vapor fugacity methods, such as the Hayden-O'Connell
Method for dimerizing species,
 Special methods for calculating the properties of specific sys-
tems of components such as alcohols, amines, glycols, and sour
water systems.
Basic Principles
Application Guidelines
Basic Principles
General Information
Phase Equilibria
Enthalpy
Entropy
Density
General Information
When modeling a single chemical process, or entire chemical plant,
the use of appropriate thermodynamic methods and precise data is
essential in obtaining a good design. PRO/II contains numerous

proven thermodynamic methods for the calculation of the following
thermophysical properties:
 Distribution of components between phases in equilibrium
(K-values).
 Liquid and vapor phase enthalpies.
 Liquid and vapor phase entropies.
 Liquid and vapor phase densities.
Phase Equilibria
When two or more phases are brought into contact, material is
transferred from one to another until the phases reach equilibrium,
and the compositions in each phase become constant. At equilib-
rium for a multi-component system, the temperature, pressure, and
chemical potential of component i is the same in every phase, i.e.:
Equation (2-80):
T   T   ...  T 
Equation (2-81):
P  P   ...  P
Equation (2-82):
      ...   
where:
T = system temperature
P = system pressure
 = the chemical potential
,,...,  represent the phases
The fugacity of a substance is then defined as:
Equation (2-83):
i  i0  RT ln  fi / f i 0 
where:
fi
= fugacity of component i
Thermodynamic Methods 2-51

fi o = standard state fugacity of component i at T, P
io = standard state chemical potential of component i at T, P
It follows from (3) and (4) that the fugacities in each phase must
also be equal:
Equation (2-84):
fi  f i   ...  fi  , i  1, 2, ... n
The fugacity of a substance can be visualized as a “corrected partial

pressure” such that the fugacity of a component in an ideal-gas mix-
ture is equal to the component partial pressure.
For vapor-liquid equilibrium calculations, the ratio of the mole frac-
tion of a component in the vapor phase to that in the liquid phase is
defined as the K-value:
Equation (2-85):
K i  yi / xi
where:
Ki = K-value, or equilibrium ratio
yi = mole fraction in the vapor phase
xi = mole fraction in the liquid phase
For liquid-liquid equilibria, a corresponding equilibrium ratio or

distribution coefficient is defined:
Equation (2-86):
K Di  xiI / xiII
where:
KDi = liquid-liquid distribution coefficient
I, II represent the two liquid phases

The vapor-phase fugacity coefficient of a component,  j is defined
V
as the ratio of its fugacity to its partial pressure, i.e.:

Equation (2-87):
iV  fiV / yi P
where:
 Vj = vapor-phase fugacity coefficient of component i
If a liquid activity coefficient method is used in the liquid phase cal-

culation, then the activity coefficient of the liquid phase can be
related to the liquid fugacity by the following relationship:
Equation (2-88):
fi L   iL xi fi 0 L
where:
 iL = liquid-phase activity coefficient
fi 0 L = standard state fugacity of pure liquid i
With this definition of liquid fugacity,  i  1 as xi  1. The stan-

L
dard state fugacity is as follows:

Equation (2-89):
fi OL  Pi satisat exp  P
Pi sat
viL / RTdP 
where:
Pi sat = saturated vapor pressure of component i at T
R = gas constant
viL = liquid molar volume of component i at T and P

isat = fugacity coefficient of pure component i at T and P sat
i
Equation (2-89) provides two correction factors for the pure liquid
fugacity. The fugacity coefficient, isat,corrects for deviations of the
saturated vapor from ideal-gas behavior. The exponential correction
factor, known as the Poynting correction factor, corrects for the

effect of pressure on the liquid fugacity. The Poynting correction
factor is usually negligible for low and moderate pressures.
Combining equations (2-85), (2-87), and (2-88) yields:
Equation (2-90):
K i   iL fi OL / PiV
Combining equations (2-86) and (2-88) yields:

Equation (2-91):
K Di   iLI /  iLII
If an equation of state is applied to both vapor and liquid phases, the

vapor-liquid K-values can be written as:
Equation (2-92):
K i  iL / iV
The liquid-liquid equilibria can be written as:

Equation (2-93):
iLII
K Di 
iL I
Equations (2-90), (2-91), (2-92), and (2-93) are used to calculate the
distribution of components between phases.
For vapor-liquid equilibria, equation-of-state methods may be used
to calculate the fugacity coefficients for both liquid and vapor
phases using equation (2-92). One important limitation of equation-
of-state methods is that they have to be applicable over a wide range
of densities, from near-zero density for gases to high liquid densi-
ties, using constants obtained from pure-component data. Equations
of state are not very accurate for non-ideal systems unless combined
with component mixing rules and alpha formulations appropriate
for those components. See “Mixing Rules (for Equations of State)”
Equation (2-90) may be solved by using equation-of-state methods
to calculate vapor fugacities combined with liquid activity methods
to compute liquid activity coefficients. See Liquid Activity-Based
Methods. Liquid activity methods are most often used to describe
the behavior of strongly non-ideal mixtures.

Reference
1 Prausnitz, J. M., Lichtenthaler, R. N., and Gomes de Aze-

vedo, E., 1986, Molecular Thermodynamics of Fluid-Phase
Equilibria, 2nd Ed., Prentice-Hall, N.Y.
2 Sandler, S. I., 1989, Chemical and Engineering Thermody-
namics, 2nd ed., John Wiley & Sons, New York.
3 Smith, J. M. and Van Ness, H. C., 1987, Introduction to
Chemical Engineering Thermodynamics, 4th ed., McGraw-
Hill, New York.
4 Van Ness, H. C. and Abbott, M. M., 1982, Classical Ther-
modynamics of Non-electrical Solutions: With Applica-
tions to Phase Equilibria, McGraw-Hill, New York.
Also See:
Basic Principles
Enthalpy
The enthalpy of a system, H, is defined in terms of the energy of the
system, U as follows:
Equation (2-94):
H  U  PV
where:
H = enthalpy of the system of nT moles
U = internal energy of the system of nT moles
V = total volume of the system
At constant temperature and pressure, the internal energy of the sys-

tem is related to the volume by:
Equation (2-95):
dU  T  P / T V , n  P  dV
 T 
The enthalpy of the system is then given by:

Equation (2-96):

H    P  T  P / T V ,n  dV  RT  z  1  H 
V  T 
where:
H* = mixture ideal gas enthalpy = n h i i
0
hi0 = molar enthalpy of ideal gas i at temperature T
z = compressibility factor  PV/(nRT)
PRO/II provides two distinct approaches to the calculation of

enthalpy. For the majority of thermodynamic systems of methods,
enthalpy is calculated as a departure from the ideal-gas enthalpy of
the mixture. Enthalpy departure functions for both vapor and liquid
phases are calculated by an equation of state or corresponding states
model.
For liquid activity coefficient thermodynamic systems, however,
PRO/II, by default, invokes the LIBRARY thermodynamic method
for vapor and liquid enthalpy calculations.
The LIBRARY method consists of two correlations. The first corre-
lates saturated-liquid enthalpy as a function of temperature and the
second correlates latent heat of vaporization, also as a function of
temperature. At temperatures below the critical, vapor enthalpy is
calculated by adding the latent heat to the saturated liquid enthalpy
at the system temperature. In other words, the vapor enthalpy is the
saturated vapor enthalpy at the system temperature. For both
phases, the pressure is implicitly the saturated vapor pressure at the
system temperature. No other pressure correction term is applied.
For almost all library components, the correlations in use for liquid
enthalpy can be used safely up to a reduced temperature, T/Tc, of
approximately 0.9. Tc is the temperature at the critical point,
beyond which vapor and liquid become indistinguishable.
Note: The normal boiling point of a library component typically

occurs when Tr is approximately equal to 0.7.
In general, the use of liquid activity coefficient models is not rec-

ommended for system pressures above 1000 kPA. Below these con-
ditions, the use of LIBRARY enthalpy methods will not introduce
significant errors provided that the system temperature is below the

critical temperatures of all components present in significant quan-
tities. Quite often, however, we would like to use a liquid activity
coefficient model when permanent gases are present in the mixture.
As the system temperature is usually above the critical temperature
of these gases, there is no standard-state liquid fugacity at system
conditions, so we replace that term by the Henry's Law constant.
However, the problem of adding the super-critical components' con-
tribution to the liquid enthalpies remains. For the liquid phase con-
tribution, PRO/II extrapolates the component's saturated liquid
enthalpy curve linearly from the critical temperature.Above the crit-
ical this extrapolation uses the slope of the library enthalpy tangent
to the liquid saturation curve at the normal boiling point. At temper-
atures above the critical, there is no distinction between vapor and
liquid phases and the vapor enthalpy is set equal to the extrapolated
liquid enthalpy. The point at which the slope for linear extrapolation
is obtained is chosen quite arbitrarily; as mentioned, we use the nor-
mal boiling point temperature.
Note: At temperatures near Tc, the enthalpy of the saturated vapor

for a pure component exhibits a decrease with temperature. This
can lead to the computation of a negative value of the constant-pres-
sure heat capacity Cp when using the LIBRARY method for vapor
enthalpies. This is entirely an artifact of the fact that the saturation
curve is not a constant-pressure path. The printout of a negative
heat capacity is therefore a sign that the temperature is too high to
be using LIBRARY vapor enthalpies, and the user should switch to
another method.
For low pressure and temperatures well below the lowest critical,
LIBRARY enthalpies are often satisfactory. For high pressures or
temperatures above the critical of a component, it will usually be
better to use an equation of state for vapor and, possibly, liquid
enthalpies. Beware, however, if a liquid activity coefficient method
was selected for K-value; in such systems the traditional cubic
equation of state may not be capable of describing the liquid phase
non-ideality, and it is therefore unlikely that the equation of state
will predict the correct liquid phase enthalpy. In this situation, one
of the more advanced cubic equations using an alpha formulation
which correctly predicts pure component vapor pressures, is a better
choice. As the contribution to the liquid enthalpy of dissolved
super-critical components is usually small, the LIBRARY method
can usually safely be used for liquid enthalpies. Ideal-gas based
enthalpies and saturation enthalpies can be used in combination for
vapor and liquid, respectively, for defined components because the

ideal-gas enthalpy datum has been fixed relative to the saturated-
liquid enthalpy datum (HL = 0 at T = 273.15 K). For components
that are sub-critical at 273.15 K, the SRK vapor enthalpy departure
function, which applied to the ideal gas enthalpy, gives the equiva-
lent results as adding the latent heat to zero-liquid enthalpy. For
components that are super-critical at 273.15 K, using an alpha for-
mulation will give consistent results between departure-based and
library enthalpies.
Also See:
Basic Principles
Entropy
The entropy of a system, S, is defined in terms of the enthalpy, as
follows:
Equation (2-97):
S  S   R ln   R ln  P / Pref    H  H   / T
and
Equation (2-98):
S    ni si0  R  ni ln xi
i i
where:
 = fugacity coefficient of mixture
Pref = reference pressure of 1 atmosphere
S* = mixture ideal-gas entropy
s0i = molar entropy of ideal gas i
ni = moles of component i
xi = mole fraction of component i
The ideal molar entropy is related to the ideal molar enthalpy by:

Equation (2-99):
T  hi0 
T
s   c dT / T    
0
i

pi  * dT / T
Tref Tref
 T  Pconst
where:
Tref = reference temperature, 1 degree Rankine in PRO/II
c*pi = ideal-gas heat capacity of component i
Ideal-gas entropy at the reference temperature is set equal to zero.

As for enthalpy computations, liquid and vapor entropies are calcu-
lated in PRO/II using either an equation of state method such as
SRKM, or a generalized correlation method such as Curl-Pitzer.
Also See:
Basic Principles
Density
Cubic equation-of-state methods are generally not very accurate in
predicting liquid densities. More accurate predictive methods have
been developed especially for liquid mixtures. Such methods
include the API and Rackett correlation methods. These methods
are described in detail in Section, Generalized Correlation Methods.
Vapor densities are computed in PRO/II using the following formu-
lae:
Equation (2-100):
v  zRT / P
Equation (2-101):
v  MW / v
where:
v = vapor density
MW = molecular weight
v = molar vapor volume

z = compressibility factor
Vapor densities can be predicted quite accurately using equation of

state methods, in addition to generalized correlation methods. The
IDEAL vapor density method corresponds to z = 1.
General Information
Refinery and Gas Processes
Natural Gas Processing
Chemical Applications
General Information
Choosing an appropriate thermodynamic method for a specific
application is an important step in obtaining an accurate process
simulation. Normally, there may be any number of thermodynamic
methods suitable for a given application. The user is left to use his
or her best judgement, experience, and knowledge of the available
thermodynamic methods to choose the best method.
It is important to note that for most thermodynamic methods, the
PRO/II databanks contain adjustable binary parameters obtained
from fitting published experimental and/or plant data. The thermo-
dynamic method chosen should ideally be used only in the tempera-
ture and pressure ranges at which the parameters were regressed.
Ideally, for each simulation, actual experimental or plant data
should be regressed in order to obtain the best interaction parame-
ters for the application.
There are several places where the user can find information and
guidelines on using the thermodynamic methods available in PRO/
II. These are:
 PRO/II Case books
 PRO/II Application Briefs Manual
These show how PRO/II is used to simulate many refinery, chemi-
cal, and petrochemical processing applications using the thermody-
namic methods appropriate to each system.

Refinery and Gas Processes
These processes may be subdivided into the following:
 Low pressure crude systems (vacuum towers and atmospheric
stills)
 High pressure crude systems (including FCCU main fraction-
ators, and coker fractionators)
 Reformers and hydrofiners
 Lube oil and solvent de-asphalting units
Low Pressure Crude Units

Low pressure crude units generally contain less than 3 volume%
light ends. Moreover, the petroleum fractions present in the feed
exhibit nearly ideal behavior. For these units, the characterization of
the petroleum fractions is far more important than the thermody-
namic method used. The user should try different assay and charac-
terization methods first if the simulation results do not match the
plant data.
Since these units contain a small amount of light ends, the Braun
K10 (BK10) method should be used quickly as a first attempt, and
will likely give acceptable answers. The BK10 method does, how-
ever, provide only gross estimates for the K-values for H2, and is
not recommended for streams containing H2. For such systems, and
for other systems where the BK10 results are not satisfactory, the
Grayson-Streed (GS), Grayson-Streed Erbar (GSE), or Improved
Grayson-Streed (IGS) methods should be chosen. These methods
contain special coefficients for hydrogen and methane, and as such,
provide better predictions for streams containing small amounts of
H2 at low pressures. It is important to note that the pre-defined ther-
modynamic systems GS, GSE, and IGS use the Curl-Pitzer (CP)
method for calculating enthalpies. For systems containing heavy
ends such as vacuum towers, however, the saturated vapor is often
at reduced temperatures of less than 0.6. This is the lower limit of
the Curl-Pitzer enthalpy method. For these units, therefore, substi-
tuting the Lee-Kesler (LK) method for Curl-Pitzer enthalpies may
improve the results.
In addition, the top of many of these low pressure units often con-
tain significant amounts of light components such as methane.
Under these conditions, an equation of state method such as Soave-

Redlich-Kwong (SRK) or Peng-Robinson (PR) will provide better
answers than the BK10 or Grayson-Streed methods.
Table 2-15: Methods Recommended for Low Pressure

Crude Systems
BK10 Gives fast and acceptable answers.
GS/GSE/IGS Generally more accurate than BK10
especially for streams containing H2. Use
LK enthalpies instead of CP enthalpies for
vacuum towers.
SRK/PR Provides better results when light ends
dominate.
High Pressure Crude Units

High pressure crude units generally contain greater amounts of light
ends than low pressure units. Still, for these units, as for the low
pressure crude units, the characterization of the petroleum fractions
remains far more important than the thermodynamic method used.
The user should again try different assay and characterization meth-
ods first if the simulation results do not match the plant data. Since
these units contain larger amounts of light ends, the GS, GSE, IGS,
SRK or PR methods should be used, and will likely give acceptable
answers.
For FCCU main fractionators, the petroleum fractions are much
more hydrogen deficient than are crude fractions. Since most char-
acterization correlations are derived from crude petroleum data, it is
expected that the results will be less accurate than for crude frac-
tions.
Table 2-16: Methods Recommended for High Pressure

Crude Systems
GS/GSE/IGS Quicker but generally less accurate than SRK or
PR, especially for streams containing light ends.
Use LK enthalpies instead of CP enthalpies for
vacuum towers.
SRK/PR Provides better results when light ends dominate.
Reformers and Hydrofiners

These units contain streams with a high hydrogen content. The
Grayson-Streed method, which contains special liquid activity
curves for methane and hydrogen, may be used to provide adequate
answers. For the SRK and PR methods, the PRO/II databanks con-

tain extensive binary interaction parameter data for component
pairs involving hydrogen.
Table 2-17: Methods Recommended for Reformers and

Hydrofiners
GS/GSE/IGS Quicker but generally less accurate than SRK or PR,
especially for predicting the hydrogen content of the
liquid phase.
SRK/PR Provides better results than GS methods.
SRKM/PRM Provides better results than SRK/PR when predicting
the hydrogen content of the liquid phase.
These methods provide results comparable or better than the GS

methods. Moreover, these methods are more accurate than GS
methods in predicting the hydrogen solubility in the liquid phase. If
the user wishes to obtain the most accurate prediction of hydrogen
solubility in the hydrocarbon liquid phase, he/she should use the
SimSci modified SRK or PR methods, SRKM or PRM.
Lube Oil and Solvent De-asphalting Units

These units contain streams with non-ideal components such as
H2S and mercaptans. The SimSci modified SRK or PR methods,
SRKM or PRM, are recommended, but only if user-supplied binary
interaction data are available. If no binary interaction data specifi-
cally regressed for the system are available, then the data in the
PRO/II databanks can be used, and the SRK or PR methods are rec-
ommended.
Table 2-18: Methods Recommended for Lube Oil and

Solvent
De-asphalting Units
SRKM/ Recommended when user-supplied binary interac-
PRM tion data are available
SRK/PR Recommended when no user-supplied binary
interaction data are available
Also See:
Natural Gas Processing

Natural gas systems often contain inerts such as N2, acid or sour
gases such as CO2, H2S, or mercaptans, and water, along with the

usual light hydrocarbon components. Natural gas streams may be
treated by a number of methods, e.g., to sweeten using amines, or to
dehydrate using glycol.
For natural gas systems containing less than 5% N2, CO2, or H2S,
but no polar components, SRK, PR, or BWRS methods provide
excellent answers. The SRK and PR binary interaction parameters
between these lower molecular weight molecules and other compo-
nents are estimated by correlations based on the molecular weight
of the hydrogen molecule. For small amounts of these components,
this is satisfactory. The BWRS equation of state also contains many
binary interaction parameters for component pairs involving lower
weight components supplied in Dechema. Unlike cubic equations
of state such as SRK or PR, the BWRS equation of state does not
satisfy the critical constraints, and so does not extrapolate well into
the critical region.
For natural gas systems containing more than 5% N2, CO2, or H2S,
but no polar components, equation-of-state methods such as SRK or
PR are still recommended, although the binary parameters esti-
mated by molecular weight correlations may not produce the best
results. The user should provide binary interaction parameters for
component pairs involving these lower molecular weight compo-
nents if possible.
For natural gas systems containing water at low pressures, equa-
tion-of-state methods such as SRK or PR may be used, along with
the default water decant option, to predict the behavior of these sys-
tems.
Table 2-19: Methods Recommended for Natural Gas

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

as SRKM, PRM or SRKS, or the Kabadi-Danner modification to
SRK (SRKKD) should be used to predict the vapor-liquid-liquid
behavior of these systems. These methods provide the best answers
if all the relevant binary interaction parameters are available. For
the SRKKD method in particular, PRO/II contains binary interac-
tion parameters for component pairs involving N2, H2, CO2, CO,
and H2S. For SRKM, PRM, or SRKS methods, the user should
make sure that all relevant binary interaction data are entered.
For natural gas systems containing polar components such as meth-
anol, the SRKM, PRM, or SRKS methods are recommended to pre-
dict the vapor-liquid-liquid behavior of these systems.
The processes used to treat natural gas streams may be sub-divided
into the following:
 Glycol dehydration systems
 Sour water systems
 Amine systems.
Glycol Dehydration Systems

The predefined thermodynamic system GLYCOL has been spe-
cially created for these systems. This system uses the predefined
system SRKM but invokes the GLYCOL databank. This databank
contains binary interaction parameters for component pairs involv-
ing glycols tri-ethylene glycol (TEG) and, to a lesser extent, dieth-
ylene glycol (DEG) and ethylene glycol (EG). These data have been
regressed in the temperature and pressure range normally seen in
glycol dehydrators:
Temperature: 80-400 F
Pressure: up to 2000 psia
This method is described in more detail in “Electrolyte Methods”.
SourWater Systems
The standard version of PRO/II contains two methods, SOUR and
GPSWATER, for predicting the VLE behavior of sour water sys-
tems. These methods are described in more detail in Special Pack-

ages Section. The recommended temperature, pressure and
composition ranges for each method is given in Table 2-20 below.
Table 2-20: Methods Recommended for Sour Water

Systems
SOUR Recommended Ranges:
68 < T (F) < 300
P(psia) < 1500
wNH3 + wCO2 + wH2S < 0.30
GPSWATER Recommended Ranges:
68 < T(F) < 600
P(psia) < 2000
wNH3 < 0.40
PCO2 + PH2S < 1200 psia
Electrolyte Recommended when strong electrolytes such as caustic
Version of are used, or when pH control or accurate prediction of
PRO/II HCN or phenol phase distribution is important.
Recommended Ranges: 32 < T(°F) < 400
P(psia) < 3000 x dissolved gases < 0.30
Amine Systems
Amine systems used to sweeten natural gas streams may be mod-
eled in PRO/II using the AMINE special package (see Section, Spe-
cial Packages). Data is provided for amines MEA, DEA, DGA,
DIPA, and MDEA. Results obtained for MEA and DEA are accu-
rate enough for use in final design work. However, results for DIPA
systems are not suitable for final design work. For MDEA or DGA
systems, the results may be made to more closely fit plant data by
the use of a dimensionless residence time correction.
The recommended temperature, pressure, and loading ranges
(gram-moles sour gases per gram-moles amine) for each amine sys-
tem available in PRO/II is given in Table 2-21.
Table 2-21: Methods Recommended for Amine Systems

MEA Recommended Ranges:
25 < P(psig) < 500
T(F) < 275
wamine ~ 0.15 - 0.25
0.5-0.6 gmole gas/gmole amine

Table 2-21: Methods Recommended for Amine Systems
DEA Recommended Ranges:
100 < P(psig) < 1000
T(F) < 275
wamine ~ 0.25 - 0.35
0.45 gmole gas/gmole amine
DGA Recommended Ranges:
100 < P(psig) < 1000
T(F) < 275
wamine ~ 0.55 - 0.65
MDEA Recommended Ranges:
100 < P(psig) < 1000
T(F) < 275
wamine ~ 0.50
DIPA Recommended Ranges:
100 < P(psig) < 1000
T(F) < 275
wamine ~ 0.30
Also See:
Petrochemical Applications
Common examples of these processes are the following:
 Light hydrocarbon applications
 Aromatic systems
 Aromatic/non-aromatic systems
 Alcohol dehydration systems
Light Hydrocarbon Applications

Most light hydrocarbon mixtures at low pressures may be modeled
well by the SRK or PR equations of state. The BWRS equation of
state, which was developed for light hydrocarbon mixtures is also
recommended, but not near the critical region. At high pressures,
the SRKM or SRKS equation of state should be used to best predict
the water solubility in the hydrocarbon phase. The COSTALD liq-
uid density was developed expressly for light hydrocarbon mix-

tures. This method is over 99.8% accurate in predicting the liquid
densities of these mixtures, and should be requested by the user.
Table 2-22: Methods Recommended for Light

Hydrocarbons
SRK/PR/ Recommended for systems of similar light
BWRS hydrocarbons at low pressures
SRKM Recommended at higher pressures
/SRKS
COSTALD Recommended for liquid density
Aromatic Systems
Mixtures of pure aromatic components such as aniline, and nitro
benzene at low pressures less than 2 atmospheres exhibit close to
ideal behavior. Ideal methods can therefore be used to predict phase
behavior, and compute enthalpies, entropies, and densities. At pres-
sures above 2 atmospheres, the Grayson-Streed, or SRK, or PR
methods provide good results in the prediction of phase equilibria.
The SRK or PR equations of state should provide better results, but
with a small CPU penalty.
Table 2-23: Methods Recommended for Aromatics

IDEAL Recommended for systems at low pressures below 2
atm
GS/ SRK/ PR Recommended at pressures higher than 2 atm
IDEAL/ API/ Recommended for liquid density. The COSTALD
COSTALD method is best at high temperatures and if light
components such as CH4 are present.
Aromatic/Non-aromatic Systems
Systems of mixtures of aromatic and non-aromatic components are
highly non-ideal. Liquid activity methods such as NRTL or UNI-
QUAC, or equation-of-state methods with advanced mixing rules
such as SRKM or SRKS can be used to model these systems. Both
types of methods can be used to successfully model aromatic/non-
aromatic mixtures, provided that all the binary interaction data for
the components in the system are provided. The PRO/II databanks
contain an extensive variety of interaction data for the NRTL and
UNIQUAC, and SRKM methods. One advantage to using the liquid
activity methods NRTL or UNIQUAC however, is that the FILL
option may be used to fill in any missing interaction parameters
using UNIFAC. All library components in the PRO/II databanks
have UNIFAC structures already defined. PRO/II also will estimate

UNIFAC structures for petro components based on their Watson K
and molecular weight values, and the user may supply UNIFAC
structures for components not in the PROII databanks.
When gases such as H2, N2, or O2 are present in small quantities
(up to about 5 mole %), the Henry's Law option may be used to cal-
culate the gas solubilities. Once the Henry's Law option is selected
by the user, PRO/II arbitrarily defines all components with critical
temperatures less than 400 Kelvin as solute components, though the
user may override these selections.
For large amounts of super-critical gases, an equation-of-state
method with an advanced mixing rule should be used to predict the
phase behavior.
Table 2-24: Methods Recommended for Aromatic/Non-

aromatic Systems
SRKM/ Recommended at high pressures or when > 5 mole %
PRM super-critical gases are present
NRTL/  Recommended with the FILL option when binary
UNIQUAC interaction parameters are not available or with the
HENRY option when < 5 mole % super-critical gases
are present
Alcohol Dehydration Systems

The PRO/II special package ALCOHOL is recommended for sys-
tems containing alcohols with water. This package uses a special
databank of NRTL parameters containing interaction parameters
expressly regressed under temperature and pressure conditions
commonly found in dehydration systems. The NRTL method is
suggested if user-supplied interaction data are to be used.
Table 2-25: Methods Recommended for Alcohol Systems

ALCOHOL Recommended for all alcohol dehydration systems.
NRTL/ Recommended when user-supplied data are
UNIQUAC provided.
Also See:

Chemical Applications
Non-ionic Systems
These systems, which typically contain oxygen, nitrogen, or halo-
gen derivatives of hydrocarbons such as amides, esters, or ethers,
are also similar to non-hydrocarbon systems found in petrochemical
applications. For low pressure systems, a liquid activity coefficient
method is recommended. For single liquid phase systems, the WIL-
SON, NRTL, or UNIQUAC methods are equally good, provided all
interaction parameters are provided. PRO/II databanks contain
extensive parameters for NRTL and UNIQUAC, but the user must
supply interaction data for the WILSON method. The WILSON
method is the simplest, and requires the least CPU time.
For systems with two liquid phases, the NRTL or UNIQUAC meth-
ods should be used, provided that at least some interaction data is
available. The FILL option can be used to fill in any missing inter-
action data using the UNIFAC method. If no interaction data are
available, the UNIFAC method should be used since the PRO/II
databanks contain a large amount of group interaction data for both
VLE and LLE applications. For moderate pressure systems up to 10
atmospheres, a liquid activity method can still be used, provided
that the interaction parameters used are still valid in that pressure
range. For example, if the system pressure were much higher than
the pressure at which the interaction parameters were regressed, the
vapor phase fugacity may be taken into account in modeling the
phase behavior. If the PHI option is selected, the liquid-phase
Poynting correction factor is automatically selected also.
It is also important to note that all the interaction parameters in the
PRO/II databanks, except for dimerizing components such as car-
boxylic acids, were regressed without including any vapor-phase
nonideality. This means that the PHI option should be used for car-
boxylic acid systems at all pressures, but should only be used for
most components at high pressures. For systems containing compo-
nents such as carboxylic acids that dimerize in the vapor phase, the
Hayden-O'Connell fugacity method may be used to calculate all
vapor-phase properties such as fugacity, enthalpy, and density. For
components such as hydrogen fluoride which forms hexamers in the
vapor phase, PRO/II contains an equation of state specially created
for such systems, HEXAMER. This method is recommended for
processes such as HF alkylation or the manufacture of refrigerants
such as HFC-134a. For all other components, an equation-of-state

method such as SRK or PR may be used to calculate vapor-phase
fugacities.
When super-critical gases are present in small quantities (generally
less than 5 mole %), the Henry's Law option should be used to com-
pute gas solubilities. For high pressure systems, greater than 10
atmospheres, or for systems with large quantities of super-critical
gas, an equation-of-state method using an advanced mixing rule
such as SRKM or PRM should be used. The UNIWAALS equation-
of-state method uses UNIFAC structure information to predict
phase behavior. This method is useful when interaction data are not
available and, unlike a liquid activity method such as UNIFAC, is
able to handle super-critical gases.
Table 2-26: Methods Recommended for Non-ionic

Chemical Systems
WILSON Recommended for single liquid phase slightly non-
ideal mixtures. If all interaction data are not available
use the FILL=UNIFAC option.
NRTL/ Recommended for all non-ideal mixtures. Use with
UNIQUAC the FILL option when binary interaction parameters
are not available or with the HENRY option when <
5 mole % super-critical gases are present. For
moderate pressures use the PHI option for vapor
phase nonidealities.
SRKS/ Recommended for high pressure systems or when >
SRKM/ 5 mole % super-critical gases are present.
PRM/
UNIWAALS
HOCV Recommended for vapor fugacity and enthalpy and
density calculations in systems containing dimerizing
components such as carboxylic acids. Use with a
liquid activity method.
HEXAMER Recommended for systems containing hexamerizing
components such as HF.
Ionic Systems
A special version of PRO/II expressly made for aqueous electro-
lytes is recommended when modeling these systems. This version
combines the PRO/II flow-sheet simulator with rigorous electrolyte
thermodynamic algorithms developed by OLI Systems, Inc. Chemi-
cal systems which may be modeled by this special version include
amine, acid, mixed salts, sour water, caustic, and Ben-field systems.

See Sections, Electrolyte Mathematical Model, and 1.2.10, Electro-
lyte Thermodynamic Equations for further details.
Table 2-27: Methods Recommended for Ionic Chemical

Systems
PRO/II Electrolyte Version
Environmental Applications
These systems typically involve stripping dilute pollutants out of
water. By themselves, liquid activity methods such as NRTL do not
model these dilute systems with much accuracy. A better approach
is to use a liquid activity method in combination with Henry's Law
constants at the process temperature to model these dilute aqueous
systems. PRO/II contains Henry's Law constants for many compo-
nents such as HCl, SO2, and ethanediol in water. Some additional
Henry's Law constants for chlorofluorocarbons (CFC’s) and hydro-
fluorocarbons (HFC’s) in water are also available in the PRO/II
databanks. Other sources for Henry's Law data include the U.S.
Environmental Protection Agency.
Table 2-28: Methods Recommended for Environmental

Applications
Liquid Activity Method + Henry's Law Option
Solid Applications
Solid-liquid equilibria for most systems can be represented in PRO/
II by the van’t Hoff (ideal) solubility method or by using user-sup-
plied solubility data. In general, for those systems where the solute
and solvent components are chemically similar and form a near-
ideal solution, the van’t Hoff method is appropriate. For non-ideal
systems, solubility data should be supplied. For many organic crys-
tallization systems, which are very near ideal in behavior, the van’t
Hoff SLE method provides good results. The VLE behavior can
usually be adequately represented by IDEAL or any liquid activity
methods. Precipitation of solid salts and minerals from aqueous
solutions can be calculated more rigorously by using the electrolyte
version of PRO/II.
Table 2-29: Methods Recommended for Solid Applications

Ideal or Liquid Activity Recommended for most solid systems
Method(VLE) + VANT involving organics.
HOFF Method (SLE)

Table 2-29: Methods Recommended for Solid Applications
PRO/II Electrolyte Version Recommended for solid salt and
mineral precipitation from aqueous
solutions.
Also See:
Generalized Correlations
General Information
Ideal (IDEAL)
Chao-Seader (CS)
Grayson-Streed (GS)
Erbar Modification to Chao-Seader (CSE) and Grayson-Streed
(GSE)
Improved Grayson-Streed (IGS)
Curl-Pitzer (CP)
Braun K10 (BK10)
Johnson-Grayson (JG)
Lee-Kesler (LK)
API
Rackett
COSTALD
SRK-Peneloux Density Method
PR-Peneloux Density Method
General Information
Vapor-liquid equilibria can be predicted for hydrocarbon mixtures
using various general correlation methods. Examples of these are
those developed by Chao and Seader, or Grayson and Streed.
Vapor-liquid equilibria can also be predicted by convergence pres-
sure correlations such as the K10 charts developed by Cajander et

al. Densities, enthalpies, and entropies can also be calculated using
a number of correlation methods such as Lee-Kesler, and
COSTALD.
Ideal (IDEAL)
Ideal K-values are generally applicable to systems which exhibit
behavior close to ideality in the liquid phase. Mixtures of similar
fluids often exhibit nearly ideal behavior. In an ideal solution at
constant temperature and pressure, the fugacity of every component
is proportional to its mole fraction. For every component i, the fol-
lowing fundamental thermodynamic equilibrium relationship holds:
Equation (2-102):
f i L  f iV
where:
superscript L refers to the liquid phase
superscript V refers to the vapor phase
fi = fugacity of component i
In the vapor phase, the fugacity is assumed to be equal to the partial

pressure:
Equation (2-103):
fiV  yi P
where:
yi = vapor mole fraction
P = system pressure
In the liquid phase for an "ideal" liquid (ignoring correction factors
that are usually small):
Equation (2-104):
fi L  xi f pure
L
i  xi Pi
sat
where:
xi = liquid mole fraction
L
f pure i

= pure component i liquid fugacity
Pi sat = vapor pressure of component i at the system tempera-
ture
Raoult's law thus holds:

Equation (2-105):
yiP  xi Pi sat
The ideal K-value is therefore given by:

Equation (2-106):
K i  yi / xi  Pi sat / P
Note: The K-values have no compositional dependencies. They are

only a function of temperature (due to the dependence of Pisat on
temperature) and pressure.
Ideal vapor densities are obtained from the ideal gas law:
Equation (2-107):
  P / RT
where:
 = vapor density of mixture
Ideal-liquid densities are obtained from pure-component saturated-
liquid density correlations. Ideal liquid enthalpies are obtained from
pure-component liquid enthalpy correlations, and the corresponding
vapor enthalpies are obtained by adding in the effect of the known
latent heat of vaporization of the component. Ideal entropies are
calculated from the ideal enthalpy data using the following equation
Equation (2-108):
Si   c pi dT / T    H i / T  P dT / T
where:
Si = ideal entropy
cpi = ideal component heat capacity

Hi = ideal enthalpy
Tref = reference temperature (1 degree Rankine)
T = temperature of mixture
Also See:
Chao-Seader (CS)
Chao and Seader calculated liquid K-values for the components of
non-ideal mixtures using the relationship:
Equation (2-109):
 i  fi 0 L 
K i  yi / xi   
i  P 
where:
fi 0L = the standard-state fugacity of component i in the pure
liquid phase
i = the activity coefficient of component i in the equilib-
rium liquid mixture
i = the fugacity coefficient of component i in the equilib-
rium vapor mixture
It was shown that i could be calculated from molar liquid volumes
and solubility parameters, using the Scatchard-Hildebrand equation,
with regular liquid solution assumed. The Redlich-Kwong equation
of state was used to evaluate . (See “General Cubic Equation of
State” ) Chao and Seader presented a generalized correlation for
fi0L/P, the fugacity coefficient of pure liquid "I" in real and hypo-
thetical states.
In the development of their correlation for their vapor-liquid K-
value correlation, Chao and Seader used the framework of Pitzer's
modified form of the principle of corresponding states for the pure-
liquid fugacity coefficients, giving values of fi0L/P as a function of
reduced temperature, reduced pressure, and acentric factor for both
real and hypothetical liquids:

Equation (2-110):
ln  f i OL / P   ln  fi OL / P    ln  f i OL / P 
0 1
where:
 = acentric factor
The first term on the right hand side of equation (2-110) represents
the fugacity coefficient of simple fluids. The second term is a cor-
rection accounting for the departure of the properties of real fluids
from those of simple fluids.
Limitations of the Chao-Seader method are given below:
 For all hydrocarbons (except methane)
Pressure: up to 2000 psia, but not exceeding 0.8 of the critical
pressure of the system.
Temperature: -100 oF to 500 oF, and pseudo-reduced tempera-
ture, Tr, of the equilibrium liquid mixture less than
0.93. The pseudo-reduced temperature is based on the
molar average of the critical temperatures of the com-
ponents.
Concentration: up to 20 mole % of other dissolved gases in the
liquid.
 This method is not suitable for other non-hydrocarbon compo-
nents such as N2, H2S, CO2, etc.
Reference
1 Chao, K. C., and Seader, J. D., 1961, A Generalized Corre-

lation of Vapor-Liquid Equilibria in Hydrocarbon Mixtures,
AIChE J., 7(4), 598-605.
Also See:
Grayson-Streed (GS)
Grayson and Streed modified the Chao-Seader correlation in 1963
by fitting data over a wider range of conditions and hence deriving
different constants for the equations giving the fugacity coefficients
of the pure liquids. Special coefficients for hydrogen and methane
are supplied because typical application temperatures are far above

the critical points of these two components. Grayson and Streed's
modifications have extended the application range for hydrocarbon
systems up to 800 oF and 3000 psia. The lower limits imposed by
Chao and Seader still apply.
Reference
1 Grayson, H. G., and Streed, C. W., 1963, Vapor-Liquid

Equilibria for High Temperature, High Pressure Hydrocar-
bon-Hydrocarbon Systems, 6th World Congress, Frankfurt
am Main, June 19-26.
Also See:
Erbar Modification to Chao-Seader (CSE) and Grayson-

Streed (GSE)
In 1963, Erbar and Edmister developed a new set of constants for
the Chao-Seader liquid fugacity coefficient specifically for N2,
H2S, and CO2, in order to improve the prediction of the K-values of
these gases. At the same time, new solubility parameter and molar
volume values were found for these components.
A limitation of this modified method, however, is that the H2S cor-
relation cannot be used in any cases where an azeotrope may exist
(e.g., H2S / C3H8 mixtures), as the azeotrope will not be predicted.
Reference
1 Erbar, J. H., and Edmister, W. C., 1963, Vapor-Liquid Equi-

libria for High Temperature, High Pressure Hydrocarbon-
Hydrocarbon Systems, 6th World Congress, Frankfurt am
Main, June 19-26.
Also See:
Improved Grayson-Streed (IGS)

For hydrocarbon-water mixtures, the Grayson-Streed and Erbar-
modified Grayson-Streed methods accurately predict the phase
behavior of the hydrocarbon-rich phase, but does not do as well in
predicting the water-rich phase. A separate set of solubility parame-
ters was used in the water-rich phase, and a new set of liquid fugac-
ity coefficients developed for N2, H2O, H2S, CO, and O2. This

new method is known as the Improved Grayson-Streed. It was
found that the Grayson-Streed liquid fugacity coefficient for the
"simple" fluid decreases rapidly as Tr increases above 2.5, and can
in fact become negative. The liquid fugacity coefficient for the
"simple" fluid was therefore replaced by that for hydrogen at
reduced temperatures of 2.5 and above.
Also See:
Curl-Pitzer (CP)
This correlation may be used to predict both liquid and vapor
enthalpies and entropies. It computes the enthalpy deviation using
the principle of corresponding states, i.e. in terms of the reduced
temperature, reduced pressure, and acentric factor. The critical tem-
perature and pressure for the mixture is computed using the mixture
rules of Stewart, Burkhart, and Voo. The mixture acentric factor
used is the molar average value.
The Curl-Pitzer method is limited to nonpolar mixtures, and may be
used for Pr up to 10, and Tr from 0.35 to 4.0 for liquids, and Tr from
0.6 to 4.0 for vapors. For systems containing heavy ends, the satu-
rated vapor is sometimes at a reduced temperature of less than 0.6.
In this case, the CP correlation extrapolates reasonably, producing
satisfactory results.
The Curl-Pitzer method is generally useful for refinery hydrocar-
bons, and in oil absorption gas plants.
Reference
1 Stewart, Burkhart, and Voo, 1959, Prediction of Pseudo-

Critical Constants for Mixtures, Paper presented at AIChE
Meeting, Kansas City.
Petroleum Refining, 2nd Ed., Procedure 7B3.1, 7-29 - 7-
286.
Petroleum Refining, 2nd Ed., Procedure 7H2.1, 7-201 - 7-
202.
Also See:

Braun K10 (BK10)
The K-value of each component is a function of the system temper-
ature, pressure, and the composition of the vapor and liquid phases.
For natural gas systems, the convergence pressure can be used as
the parameter that represents the composition of the vapor and liq-
uid phases in equilibrium. The convergence pressure is, in general,
the critical pressure of a system at a given temperature at which the
K-values of all components converge to unity (when the system
pressure reaches the convergence pressure).
The Braun K10 charts developed by Cajander et al. in 1960 show
the low pressure equilibrium ratio, arbitrarily taken at 10 psia sys-
tem pressure and 5000 psi convergence pressure. For many hydro-
carbon systems, no experimental data are available. For these cases,
the equilibrium K-values may be predicted from vapor pressure:
Equation (2-111):
K10  P sat /10
where:
Psat = saturated vapor pressure in psia.

The relationship given in equation (2-111) only holds for K-values
less than 2.5. For H2, the K-value is assumed to be 10 times as large
as the methane value. For N2, O2, and CO, the K-values are
assumed to be identical to that of methane. The K-values for CO2
and H2S are assumed to be identical to that of propylene.
For petroleum fractions in which the form of the vapor pressure
curve is unknown, a rough K10 chart is developed from the normal
boiling point of the fraction. The following method is used:
 On the appropriate K10 chart, the point K10 = 14.7/10 = 1.27 is
plotted at the atmospheric boiling point.
 The whole K10 curve can then be sketched in by similitude to
the known K10 curves for homologous hydrocarbons.
The K10 charts apply to mixtures that behave ideally at low pres-
sures, e.g., for mixtures of one molecule type such as mixtures of
paraffins and olefins. For mixtures of naphthalenes mixed with ole-
fins and paraffins, the accuracy of BK10 is slightly poorer. Large
errors can be expected for mixtures of aromatics with paraffins, ole-

fins, or naphthalenes, which cause non-idealities and form azeo-
tropes.
Reference
1 Cajander, B. C., Hipkin, H. G., and Lenior, J. M., 1960, Pre-

diction of Equilibrium Ratios from Nomographs of
Improved Accuracy, J. Chem. Eng. Data, 5(3), 251-259.
Also See:
Johnson-Grayson (JG)
enthalpies. It is essentially an ideal-enthalpy correlation, using satu-
rated liquid at 0 C as the datum for the correlation (-200 F in ver-
sions 3.5 and earlier). Vapor phase corrections are calculated using
the Curl-Pitzer correlation. Pressure effects are not considered for
the liquid phase.
Johnson-Grayson is useful for systems containing heavy ends
between 0 F and 1200 F. However, it can be extrapolated to higher
temperatures. The correlation should not be used if the mixture is
C4-C5 or lighter.
Reference
1 Johnson, and Grayson, 1961, Enthalpy of Petroleum Frac-

tions, Petroleum Refiner, 40(2), 123-29.
Also See:
Lee-Kesler (LK)
enthalpies, entropies, and densities. This correlation uses the three-
parameter corresponding-states theory, which essentially states that
all fluids having the same acentric factor must have the same prop-
erties at the same reduced temperature and pressure. Special mixing
rules have been used to calculate the mixture reduced properties.
For most fluids, the Lee-Kesler method is 98% accurate in predict-
ing the gas phase compressibility factors. The method also gives
reasonable results for slightly polar mixtures. This method is not
recommended for highly polar mixtures, or those which form

strongly associative hydrogen bonds. However, the Lee-Kesler
method provides accurate results for polar fluids at low tempera-
tures near the saturated vapor region. The Lee-Kesler method is not
recommended for calculating liquid densities of hydrocarbons
heavier than C8.
Reference
1 American Petroleum Institute, 1975, Technical Data Book,

Petroleum Refining, 3rd Ed., 2-1 - 7-4.
2 Lee, B. I., and Kesler, M. G., 1975, A Generalized Thermo-
3 Kesler, M. G., and Lee, B. I., 1976, Improved Prediction of
Enthalpy of Fractions, Hydrocarbon Proc., 53, 153-158.
Also See:
API
This correlation may be used to predict liquid densities. An initial
density is calculated at 60 F using the weight average of the compo-
nents. The reduced temperature and pressure of the stream at 60 F
and 14.7 psia are computed using Kay's rule, i.e., the reduced tem-
perature and pressure are assumed to be a linear function of the liq-
uid mole fraction. A density factor C, is then read from Figure
6A2.21 in the API Technical Data Book. A second correction factor
is then determined corresponding to the reduced temperature and
pressure at the actual fluid conditions. The actual liquid density is
then calculated according to:
Equation (2-112):
 act
L
  60L  Cact / C60 
where:
Cact = actual correction factor
C60 = correction factor at 60 F

The API method works well for most hydrocarbon systems, pro-
vided that the reduced temperature is less than 1.0.
Reference

Petroleum Refining, 5th Ed., 6-45 - 6-46.
Also See:
Rackett
This correlation may be used to predict liquid densities. The satu-
rated liquid density is obtained from:
Equation (2-113):
RT ci 
V si =  ----------- Z rai
 P ci 
27
 i = 1 +  1 –  ri 
where:
Vsi = saturated liquid volume
Zrai = Rackett parameter for component i
Tci , Pci = critical temperature and pressure for component i
Tri = reduced temperature for component i
The PRO/II databanks contain Rackett parameters for many compo-

nents. However, if Rackett parameters are not available, PRO/II
will use the critical compressibility factor, zc. When the Rackett
parameter is missing for a petroleum or assay component, PRO/II
back-calculates the missing parameter to ensure the specific gravity
of the pseudocomponent is correct.
For mixtures, there are two ways to use the Rackett equation. The
most straightforward, known as the RACKETT method in PRO/II,
is to use equation (2-113) for the molar volume of each pure com-
ponent and then mix the volumes together linearly. A second
approach is the "One-Fluid" Rackett method (known as the RCK2
method), in which mixing rules are used to determine effective crit-
ical parameters for the mixture and then equation (2-113) is used to

determine the mixture density. For most mixtures, the difference
between these two methods will not be significant.
Note: Rackett liquid densities is only appropriate for low pressure

systems.
Reference
1 Rackett, H. G., 1970, Equation of State for Saturated Liq-

uids, J. Chem. Eng. Data, 15, 514.
2 Spencer, C. F., and Danner, R. P., 1972, Improved Equation
for Prediction of Saturated Liquid Density, J. Chem. Eng.
Data, 17, 236-241.
3 Spencer, C. F., and Adler, S. B., 1978, A Critical Review of
Equations for Predicting Saturated Liquid Density, J.
Chem. Eng. Data, 23, 82-89.
Also See:
COSTALD
The corresponding-states liquid density model for predicts the liq-
uid densities of “LNG-like” fluids. This accurate and reliable
method is over 99.8% accurate in predicting the densities of light
hydrocarbon mixtures. This model uses two characteristic parame-
ters for each pure component in the mixture - a characteristic vol-
ume, V*, and a “tuned” acentric factor, . The acentric factor is
chosen such that the SRK equation of state best matches the vapor
pressure data. Typically, this “tuned” acentric factor varies little in
value from the standard acentric factor. The saturated volume is
given by:
Equation (2-114):
Vs / V *  Vr(0) 1  SRKVr( ) 

Equation (2-115):
4
Vr(0)  1   Ak 1  Tr 
k /3
, 0.25  Tr  0.95
1

Equation (2-116):
 3 
V r
( )
   Bk Trk  / Tr  1.00001 , 0.25  Tr  1.0
 0 
where:
Vs = saturated molar volume
V* = characteristic volume
Vr = reduced volume
Ak,Bk = COSTALD parameters
SRK = SRK “tuned” acentric factor
For mixtures, the following mixing rules are used:

Equation (2-117):
 
Tcm    xi x j vij * Tcij  / Vm*
 i j 
Equation (2-118):
  2/3   1/3  
Vm*  1/ 4   xiVi *  3   xi Vi*     xi Vi*   
 i  i  i 
Equation (2-119):
Vij*Tcij  Vi *TciV j*Tcj 

1/ 2
Equation (2-120):
SRK   xiSRK i
i
where:
subscript m refers to mixture properties.
For compressed pure liquids and liquid mixtures, the original work
was extended by Thomson et al. in 1982, adding a pressure correc-
tion of the form:
Equation (2-121):

V  Vs 1  C ln  B  P  /  B  Psat   

where:
B, C are constants, dependent on composition
Psat = saturated vapor pressure, obtained from a generalized
vapor pressure relationship.
V = molar volume
The COSTALD method is valid for aromatics and light hydrocar-

bons up to reduced temperatures of 0.95. PRO/II databanks contain
COSTALD characteristic volume, V* for many components. How-
ever, if the characteristic volume is not available, PRO/II will use
the critical volume of the pure component, Vc. For petroleum and
assay components, however, PRO/II will back calculate a character-
istic volume, if missing, in order to provide a correct specific grav-
ity for the pseudocomponent.
Reference
1 Hankinson, R. W., and G. H. Thomson, 1979, A New Cor-

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

Use the following correlation to calculate the Peneloux Volume
Shift for Hydro Carbons.
Equation (2-122):
Where,

c1 = 2.9056e - 01, c2 = 8.775e - 02
c3 = 1.1537e - 01, c4 = 4.4064e - 01
Tci = Critical Temperature for component i, K
Pci = Critical Pressure for component i, Kpa
wi = Acentric Factor for component i
xi = Mole Fraction of component i
N = Total number of components
Vs = Peneloux Volume Shift, m3/Kmol
Shift for water.
Equation (2-123):
A1 = 3.73625
A2 = -2.70717
A3 = 0.642567
Calculate Peneloux Density by using the Peneloux Volume Shift,
and the Compressibility and Density values obtained from the SRK
method.
Equation (2-124):
Here, Z and Vmix are calculated using the SRK method.

T, P = Temperature and Pressure of the system.
R = Universal Gas Constant.
PR-Peneloux Density Method

Shift for Hydro Carbons.

Equation (2-125):
Where,
c1 = 2.9056e - 01, c2 = 8.775e - 02
c3 = 1.1537e - 01, c4 = 4.4064e - 01
Tci=Critical Temperature for component i, K
Pci=Critical Pressure for component i, Kpa
wi = Acentric Factor for component i
xi = Mole Fraction of component i
N = Total number of components
Vs = Peneloux Volume Shift, m3/Kmol
Shift for water.
Equation (2-126):
A1 = 3.73625
A2 = -2.70717
A3 = 0.642567
Calculate Peneloux Density by using the Peneloux Volume Shift,
and the Compressibility and Density values obtained from the PR
method.
Equation (2-127):
Here, Z and Vmix are calculated using the PR method.

T, P = Temperature and Pressure of the system.
R = Universal Gas Constant.

Equations of State
General Information
Soave-Redlich Kwong (SRK)
Peng-Robinson (PR)
SRK Kabadi-Danner (SRKKD)
SRK Panagiotopoulos-Reid (SRKP) and PR Panagiotopoulos-Reid
(PRP)
SRK Modified (SRKM) and PR Modified (PRM)
SRK SimSci (SRKS)
SRK Huron-Vidal (SRKH) and PR Huron-Vidal (PRH)
Hexamer
UNIWAALS
Benedict-Webb-Rubin-Starling
Lee-Kesler-Plöcker (LKP)
Twu-Bluck-Coon(TBC)
Predictive Peng-Robinson 78
Predictive Soave-Redlich-Kwong (PSRK)
Fill Options (for Binary Interaction Coefficients)
Free Water Decant
Vapor Phase Fugacities
General Information
Equations of state for phase-equilibrium calculations are applicable
to wide ranges of temperature and pressure conditions. They can
also be used to calculate all the related thermodynamic properties
such as enthalpy and entropy. The reference state for both the vapor
and liquid phase is the ideal gas, and deviations from the ideal-gas
state are determined by calculating fugacity coefficients for both
phases. For cubic equations of state in particular, critical and super-
critical conditions can be predicted quite accurately. By using an
appropriate temperature-dependent function to describe the attrac-
tive forces between molecules, volume function, and mixing rule,

cubic equations of state have been shown to be quite successful in
predicting vapor-liquid equilibria for highly non-ideal systems.
Alpha Formulations
Mixing Rules (for Equations of State)
General Cubic Equation of State
General Cubic Equation of State

A general two-parameter cubic equation of state can be expressed
by the equation:
Equation (2-128):
RT aT
P  2
v  b v  ubv  wb 2
where:
P = the pressure
T = the absolute temperature
v = the molar volume
u, w = constants, typically integers
The values of u and w determine the type of cubic equation of state.
Table 2-30 shows three of the best known of these. The van der
Waals equation developed in 1873 is obtained by setting u = w = 0.
By setting u = 1 and w = 0, the Redlich-Kwong equation (1949) is
obtained. Peng and Robinson developed their equation of state in
1976 by setting u = 2 and w = -1.
Table 2-30: Some Cubic Equations of State

u w Equation of state
0 0 van der Waals (vdW)
1 0 Redlich-Kwong (RK)
2 -1 Peng-Robinson (PR)
The parameters a and b at the critical temperature, (ac and bc) are
found by setting the first and second derivatives of pressure with
respect to volume equal to zero at the critical point. Application of
these constraints at the critical point to equation (2-128) yields:

Equation (2-129):
  u  12  u  13  3  2 1  2
u    Bc  u  w   2 c
B
 3 27   3  u  1 9  u  1 
1 1  1
   Bc  0
 3 9  u  1  27
Equation (2-130):
Ac  3Z c2  uBc   u  w  Bc2
Equation (2-131):
1  u  1 Bc
Zc  
3 3
where:
Ac  Pc ac / R 2Tc2
Bc  Pc bc / RTc
subscript c refers to the critical point

The critical constraints result in three expressions for three
unknowns, Ac, Bc, and Zc. These unknowns depend on the values of
u and w. Actually, Ac and Bc are the only true unknowns appearing
in these equations, because Pc, Tc, and Vc (and consequently Zc) are
properties of a substance, having numerical values independent of
any equation of state. In solving these three equations, Vc is in fact
treated as a third unknown. Table 2-31 lists these constants for the
van der Waals, Redlich-Kwong, and Peng-Robinson equations of
state.
Table 2-31: Constants for Two-Parameter Cubic

Equations of State
Ac Bc Zc Equation of state
0.42188 0.1250 0.3750 van der Waals (vdW)
0.42747 0.0866403 0.3333 Redlich-Kwong (RK)
0.45724 0.0778 0.3074 Peng-Robinson (PR)

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

19(3), 596-601.
2 van der Waals, J. D., 1873, Over de Constinuiteit van den
gas-en Vloeistoftoestand, Doctoral Dissertation, Leiden,
Holland.
3 Redlich, O., and Kwong, N. S., 1949, On the Thermody-
namics of Solutions. v: An Equation of State. Fugacities of
Gaseous Solutions, Chem. Rev., 44, 233.
4 Peng, D. Y., and Robinson, D. B., 1976, A New Two-con-
stant Equation of State for Fluids and Fluid Mixtures, Ind.
Eng. Chem. Fundam., 15, 58-64.
Also See:
General Information
Alpha Formulations
The temperature dependent parameter a(T) can be rewritten as:
Equation (2-132):
a T    T  a Tc 
In equation (2-132), (T) is a temperature-dependent function

which takes into account the attractive forces between molecules.
The accuracy of the equation of state for pure-component vapor
pressures (and therefore to a large extent for mixture phase equilib-
ria) depends on the form of the alpha formulation, (T), from equa-
tion (2-132). The real-gas behavior approaches that of the ideal gas
at high temperatures, and this requires that  goes to a finite number
as the temperature becomes infinite. Three basic requirements for
the temperature-dependent alpha function must therefore all be sat-
isfied:
 The  function must be finite and positive for all temperatures,
 The  function must equal unity at the critical point, and
 The  function must approach a finite value as the temperature
approaches infinity.
For the Redlich-Kwong equation of state, which works well for the
vapor phase at high temperatures, (T) is given by:

Equation (2-133):
 T   Tr1/2
PRO/II allows the user to utilize a choice of 11 different alpha for-

mulations for cubic equations of state (SRK, PR, modified SRK or
PR, or UNIWAALS). Table 2-3 shows the 11 available alpha for-
mulations for (T).
Table 2-32: Alpha Formulations

Form Equation Reference
01  Soave (1972)
 
2
  1  C1 1  Tr 
0.5
02 Peng-Robin-
 
2
  C1  C2 1  TrC3  son (1980)
03  Soave (1979)
 C 
  1  1  Tr   C1  2 
 Tr 
04 Boston-
  exp C1 1  TrC   2
Mathias
(1980)
05 Twu (1988)
  Tr2C 1 exp C1 1  Tr2C  
2 2
06 Twu-Bluck-
  TrC C 1 exp C1 1  TrC C  
3 2 2 3
Cunning-
ham-Coon
(1991) (Rec-
ommended
by SimSci)
07  Alternative
 2C 

  exp  1 1  TrC1 1/ 2 
1  C1 
 for form (04)

08 Alternative
  TrC exp C1 1  TrC  
3 2
for form (06)
09 Mathias-
Copeman
(1983)


10 Mathias
1  C1 1  Tr0.5 
2
 (1983)
   
 C2 1  Tr  0.7  Tr  

11 Melhem-
  exp C1 1  Tr   C2 1  Tr0.5  
2
Saini-Good-
  win (1989)
Some newer formulations(9) have been added for the temperature
dependent alpha term. These forms do not require the user to supply
values for constants (C1, C2, etc.) Instead, they perform transforms
on the acentric factors of the components of interest.
Note: These forms automatically are applied to PETRO compo-

nents whenever the SIMSCI alpha formulation method (equation 6
above) is in effect.

Form Equation Reference
15 Twu-Coon-Cun-

    0    1    0  ningham (1995)
where :

0.14159 1Tr2.29528 
  0  Tr0.201158e
and
 1  Tr0.660145e

0.500315 1Tr2.63165 

16 Twu-Coon-Cun-

    0    1    0  ningham (1995)
where :
  0  Tr0.171813e

0.125283 1Tr1.77634 
and
 1  Tr0.607352 e

0.51161 1Tr2.20517 
where:
C1 , C2 , C3 = constants
Tr = T / Tc = reduced temperature
Reference
1 Soave, G., 1972, Equilibrium Constants from a Modified

Redlich-Kwong Equation of State, Chem. Eng. Sci., 35,
1197.
2 Soave, G, 1979, Application of a Cubic Equation of State to
Vapor-Liquid Equilibria of Systems Containing Polar Com-
ponents, Inst. Chem. Eng. Symp. Ser., No. 56, 1
3 Boston, J. F., and Mathias, P. M., 1980, Phase Equilibria in
a Third Generation Process Simulation, Proc. of the 2nd
Inter. Conf. on Phase Equil. & Fluid Properties in the
Chemical Process Industries, Berlin (West), March 17-21.
4 Twu, C. H, 1988, A Modified Redlich-Kwong Equation of
State for Highly Polar, super-critical Systems, Inter. Symp.
on Thermodynamics in Chemical Engineering and Indus-
try, May 30-June 2.
5 Twu, C.H., Bluck, D., Cunningham, J.R., and Coon, J.E.,
1991, A Cubic Equation of State with a New Alpha Func-
tion and New Mixing Rule, Fluid Phase Equil., 69, 33-50.
6 Mathias, P. M., and Copeman, T. W., 1983, Extension of the
Peng-Robinson Equation of State to Complex Mixtures,
Fluid Phase Equil., 13, 91-108.

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

The accuracy of correlating vapor-liquid equilibrium data using a
cubic equation of state can be improved further by choosing an
appropriate mixing rule for calculating a and b in equation (2-128)
for mixtures. The original mixing rule was derived from the van der
Waals one-fluid approximation:
Equation (2-134):
a   xi xi aij
i j
Equation (2-135):
b   xi bi
i
where:
xi = mole fraction of component i.
The binary interaction parameter, kij, is introduced into the mixing

rule to correct the geometric mean rule of parameter a in the general
cubic equation of state (2-128):
Equation (2-136):
aij   ai a j  1  k 
1/2
ij
where:
Kij = Kji = binary interaction parameter.

The original mixing rule is capable of representing vapor-liquid
equilibria for nonpolar and/or slightly polar systems using only one
(possibly temperature-dependent) binary interaction parameter.
Also See:
General Information
Soave-Redlich Kwong (SRK)

In 1972, to improve the prediction of the vapor pressure of pure
components, and thus multi-component vapor-liquid equilibria,
Soave proposed the following form of (T):
Equation (2-137):
 T   1  M 1  Tr1/2  
2
Equation (2-138):
M  0.48  1.574  0.176 2

where:
Tr = reduced temperature, T / Tc
The constants in (2-138) were obtained from the reduction of vapor-
pressure data for a limited number of common hydrocarbons. This
limits the use of the SRK equation of state to non-polar compo-
nents. This equation of state does not accurately predict the behav-
ior of polar components or light gases such as hydrogen. However,
the simplicity of equations (2-137) and (2-138), and its accuracy for
calculating vapor pressures at temperatures higher than the normal
boiling point for hydrocarbons allowed it to gain widespread popu-
larity in industry. PRO/II contains correlations for the kijs of hydro-
carbons with N2, O2, H2, H2S, CO2, mercaptans, and other sulfur
compounds.
Also See:
General Information
Peng-Robinson (PR)
The form of (T) proposed by Peng and Robinson in 1976 is the
same as that proposed in 1972 by Soave. The numerical values for

the constants in equation (2-138) are different because the volume
function is different and because a somewhat different set of data
was used.
M  0.37464  1.54226  0.26992 2
Also See:
General Information
SRK Kabadi-Danner (SRKKD)

While the K-values between the hydrocarbon-rich liquid phase and
vapor phase can be accurately predicted by most cubic equations of
state, the K-values involving the water-rich liquid phase are not. To
apply cubic equations of state to water-hydrocarbon systems,
Kabadi and Danner in 1985 proposed a two-parameter mixing rule
for the SRK equation of state. This proposed mixing rule is compo-
sition dependent, and is designed expressly for water and well-
defined hydrocarbon systems:
Equation (2-140):
a   xi x j  ai a j  1  k    a
1/2 ' 2
ij x x
wi w i
i j iw
Equation (2-141):
'
awi  Gi 1  Trw0.8 

Gi   g j
j
where:
Trw = T/Tcw
gj = hydrocarbon group contribution from group j
Gi = sum of group contributions from the different structural

groups forming a hydrocarbon molecule i.

To estimate water/hydrocarbon equilibria when no data are avail-
able, Kabadi and Danner developed a procedure to estimate binary
interaction parameters kij and Gi. Within a homologous hydrocar-
bon series, they found kij’s to be approximately constant, and they
recommended values for seven hydrocarbon classes. A group con-
tribution method was proposed for estimating Gi.
One limitation of this method, however, is that the solubility of
hydrocarbon in the aqueous phase is predicted only within an order
of magnitude.
Reference
1 Kabadi, V. N., and Danner, R. P., 1985, A Modified Soave-

Redlich-Kwong Equation of State for Water-Hydrocarbon
Phase Equilibria, Ind. Eng. Chem. Proc. Des. Dev., 24(3),
537-541.
Also See:
General Information
SRK Panagiotopoulos-Reid (SRKP) and PR Panagioto-

poulos-Reid (PRP)
In 1986 Panagiotopoulos and Reid proposed an asymmetric mixing
rule containing two parameters for the SRK and PR equations of
state (denoted as SRKP and PRP). The interaction parameter they
proposed to be used in equation (2-134) is given by:
Equation (2-143):
aij   ai a j  1  kij    kij  k ji  xi 

1/2
The two adjustable interaction parameters are kij and kji. This
asymmetric definition of the binary interaction parameters signifi-
cantly improves the accuracy in correlating binary data for polar
and non-polar systems. This mixing rule has been used to test sev-
eral systems, including low pressure non-ideal systems, high pres-
sure systems, three-phase systems, and systems with super-critical
fluids. The results in all cases reported are in good agreement with
experimental data.
The Panagiotopoulos-Reid mixing rule, however, is fundamentally
inconsistent for multi-component systems. This inconsistency is
exhibited in two (related) flaws:

The dilution of the mixture with additional components (reducing
all the mole fractions xi) nullifies the effect of the second binary
parameter kij. In the limit of an infinite number of components so
that all the xi approach zero, the mixing rule reduces to the original
van der Waals mixing rule, equation(2-136).
The mixing rule is not invariant to dividing a component into a
number of identical pseudo-components. For example, if methane
in a mixture is divided arbitrarily into “alpha” and “beta” methane,
the calculated properties of the mixture will be slightly different.
Reference
1 Panagiotopoulos, A. Z., and Reid, R. C., 1986, A New Mix-

ing Rule for Cubic Equations of State for Highly Polar
Asymmetric Systems, ACS Symp. Ser. 300, American
Chemical Society, Washington, DC, 71-82.
Also See:
General Information
SRK Modified (SRKM) and PR Modified (PRM)

SimSci has modified equation (2-143) in a way that eliminates the
first of the two flaws noted above. This improvement provides bet-
ter predictions of properties for multi-component systems:
Equation (2-144):

aij   ai a j  1  kij    kij  k ji  xi /  xi  x j   
1/2 cij
 
Equation (2-144) is identical to equation (2-143) for binary systems
if c12 = 1. The expression for aji, which is similar to equation (2-
144), can be obtained by interchanging subscripts i and j. The four
adjustable interaction parameters are kij and kji, and cij and cji. For
binary nonpolar systems, where deviations from ideality are not
large, or are only weakly asymmetric, only two parameters, k12 and
k21 are sufficient to fit the data (i.e., c12 = c21 = 1). In this case,
equation (2-144) becomes identical to the mixing rule proposed
(also for the purpose of overcoming the first flaw noted above) by
Harvey and Prausnitz in 1989. For binary polar or polar-nonpolar
systems, where the non-ideality is large or strongly asymmetric, it
may be necessary to include the additional parameters c12 and c21.
In particular, for binary polar-nonpolar systems, which have the
greatest deviation from ideality, c12 is not set equal to c21. For

binary polar systems however, c12 can generally be set equal to
c21.
Reference
1 Harvey, A. H., and Prausnitz, J. M., 1989, Thermodynam-

ics of High-Pressure Aqueous Systems Containing Gases
and Salts, AIChE J., 35, 635-644.
Also See:
General Information
SRK SimSci (SRKS)

In 1991, Twu et al. proposed another modified mixing rule that
eliminated both of the inconsistencies of the Panagiotopoulos-Reid
mixing rule noted above. For a binary system, the mixing rule can
be expressed in the following form for a12:
Equation (2-145):
a12   a1a2  1  k12    H12G12 x22 / x1  G12 x2  

1/2
Equation (2-146):
H12  k21  k12

Equation (2-147):
G12  exp   12 H12 
The four adjustable parameters are; k12, k21, 12, and 21. As for the
SRKM equation of state, in binary non-polar systems where devia-
tions from ideality are not large, or are only weakly asymmetric,
only two parameters, k12 and k21 are sufficient to fit the data (i.e.,
12 =21 = 1). For binary polar or polar-nonpolar systems, where
the non-ideality is large or strongly asymmetric, it may be neces-
sary to include the additional parameters 12 and 21. In particular,
for binary polar-nonpolar systems, which have the greatest devia-
tion from ideality, 12 is not set equal to 21. For binary polar sys-
tems however, 12 can generally be set equal to 21.
Twu et al.(1) have derived the activity coefficients from the SRKS
equation of state, and have found that for a binary system, k12 or k21
are directly related to the infinite dilution activity coefficients 1 or
2 respectively. The values of k12 and k21 are therefore determined
when both values of the infinite dilution activity coefficients are

known for a binary system. The physical meaning of the binary
parameters k12 and k21 is that they are used to locate the infinite
dilution activity coefficients in a binary system containing compo-
nents 1 and 2.
After both end points of the liquid activity coefficients are found,
the parameters 12 and 21 are then required to describe the shapes
of the liquid activity coefficient curves for components 1 and 2 in
the finite range of concentration. In general, for real systems, kij is
not equal to kji, and ij and ji are not equal to zero. The conven-
tional mixing rule obtained by setting k12 = k21 and 12 = 21 = 0
for a binary system either results in a compromise of the phase equi-
librium representation, or fails to correlate highly asymmetric sys-
tems.
For a multi-component system, (17) can be generalized as:
Equation (2-148):
3
am  xi xj  aa
i j 1 kij   xi Hij1/3Gij1/3  aai j  xj  / Gij xj
1/2 1/6
i j i i  j
Equation (2-149):
H ij   kij  k ji 
Equation (2-150):
Gij  exp    ij H ij 
where subscript m refers to the multi-component system mixture.

Reference
1 Twu, C. H., Bluck, D., Cunningham, J. R., and Coon, J. E.,

1991, A Cubic Equation of State with a New Alpha Func-
tion and New Mixing Rule, Fluid Phase Equil., 69, 33-50.
Also See:
General Information
SRK Huron-Vidal (SRKH) and PR Huron-Vidal (PRH)

The previous SRK and PR mixing rule modifications include com-
position-dependence for applying these equations of state to com-
plex mixtures. A more complicated way to represent the phase
behavior of strongly non-ideal systems is to develop the relation-

ship between the mixing rule and excess Gibbs free energy such
that the infinite-pressure Gibbs free energy could be expressed by a
NRTL-like method (see Section, Liquid Activity Methods). This
approach was proposed by Huron and Vidal in 1979.(1) The general
equation relating excess Gibbs free energy to fugacity coefficients
is given by:
Equation (2-151):
 
g E  RT  ln    xi ln i 
 i 
where:
gE = excess Gibbs free energy per mole

 = fugacity coefficient of the mixture
i = fugacity coefficient of pure component i
At infinite pressure, the excess Gibbs free energy is calculated using

the Redlich-Kwong equation of state and linear mixing rules for the
parameter b from the general cubic equation of state. At infinite
pressure, equation (2-151) then becomes:
Equation (2-152):
 
g E    a / b    ai xi / bi   ln  2 
 i 
Where:
Equation (2-152) can be rewritten to produce a new mixing rule for

the cubic equation of state parameter a:
Equation (2-153):
 
a  b    ai xi / bi   g E / ln  2  
 i 
The excess Gibbs free energy can be calculated by any liquid activ-
ity method. Huron and Vidal chose to use the NRTL liquid activity
method to calculate

Equation (2-154):
cij  g ji  g ii
Equation (2-155):
G ji  b j exp   a ji c ji / RT 
Equation (2-156):
G ji  b j exp   a ji c ji / RT 
The only difference between the classical NRTL equation and equa-
tions (2-154)-(2-155) is the definition of the local composition as
corrected volume fractions, which leads to the introduction of the
volume parameter bj in the calculation of Gji. Substituting for the
excess Gibbs free energy in (25) yields:
Equation (2-157):
   
a  b xi  ai / bi   1/ ln  2    x j G ji c ji  /  xk Gki 
i   j  k 
By regressing experimental data to obtain the parameters in the
modified NRTL expression, excellent representation of vapor-liquid
equilibria can be made for several systems. The Huron-Vidal mix-
ing rules are highly empirical in nature. However, the prediction of
equilibria at low densities is reasonable, and the equation of state
can be expected to yield better results at higher pressures, because
the mixing rules have been derived at the infinite pressure limit of
the excess Gibbs free energy. One limitation of this model is that it
cannot directly utilize parameters for the NRTL method correlated
from low temperature data. This is because an excess Gibbs energy
model from an equation of state at infinite pressure cannot be
equated with an activity coefficient excess Gibbs energy model at
low pressure.
Reference
1 Huron, M. J., and Vidal, J., 1979, New Mixing Rules in

Simple Equations of State for Representing Vapor-Liquid
Equilibria of Strongly Non-ideal Mixtures, Fluid Phase
Equil., 3, 255-271.
Also See:
General Information

Hexamer
Hydrogen fluoride is an important chemical used in many vital pro-
cesses, including HF alkylation, and in the manufacture of refriger-
ants and other halogenated compounds. Unlike hydrocarbons,
however, hydrogen fluoride is polar and hydrogen bonded, and
therefore self-associates not only in the liquid phase, but also in the
vapor phase. Experimental evidence strongly suggests that the HF
vapor exists primarily as a monomer and a hexamer mixture. In
addition, evidence points to the hexamer existing in the form of a
cyclic benzene-like species. This behavior results in significant
departures from ideality, especially in calculating fugacity coeffi-
cients, vapor compressibility factors, heat of vaporization, and
enthalpies.
Twu et al.(1), developed a cubic equation of state with a built-in
chemical equilibrium model to account for HF association. The
cubic equation of state incorporating association is given by:
Equation (2-158):
RT a T 
P  nr  2
 v  b  v  ubv  wb2
Equation (2-159):
nT
nr 
n0
Equation (2-160):
V
v
n0
where:
a(T) = (T)a(Tc) = Redlich-Kwong equation of state parameter
which refers to the monomer
b = Redlich-Kwong equation of state parameter which refers to
the monomer
v = molar volume
V = total volume
nr = extent of association
nT = total number of moles of monomer and hexamers

n0 = the number of moles that would exist in the absence of
association
Note: Only 1 hexamerizing component (HF) may be present when

using the HEXAMER method.
The values of a(Tc) and b can be obtained from the critical constants
for the Redlich-Kwong equation of state (see Table 2-31), and the
critical temperature and pressure for HF. The alpha function, (T),
is obtained by matching the equation of state to HF vapor pressure
data. Comparing equation (2-158) to the general two-parameter
equation of state given by equation (2-128), it can be seen that the
only difference is the term nr, which accounts for the contribution
of association. The value of nr is 1.0 when there is no association,
and approaches 1/6 when there is complete hexamerization. As the
temperature increases, the extent of hexamerization should
decrease, i.e., the value of nr should increase.
The total number of moles of monomer and hexamer, nT, and the
total number of moles that would exist in the absence of associa-
tion, n0, are related by:
Equation (2-161):
n0
  izi , i  1, 6
nT i
where:
zi = the true mole fraction of species i
ni = number of moles of species i
The hexamerization equilibrium reaction is written as:

Equation (2-162):
6  HF    HF 6
The corresponding chemical equilibrium constant for this reaction,

which is a function of temperature only, is defined as:
Equation (2-163):
6 z6 1
K T  
16 z16 P 5

where:
K = equilibrium constant
1 = fugacity coefficient of the true monomer species
6 = fugacity coefficient of the true hexamer species
z1 = true mole fraction of the monomer species
z6 = true mole fraction of the hexamer species
P = total pressure
The fugacity coefficients in equation (2-163) are found from the

cubic equation of state using classical thermodynamics. Substitut-
ing equation (2-161) into equation (2-163), and using the overall
material balance, reduces this to:
Equation (2-164):
5
1  z1  , K  K 
RT 
K z   6  5 z1 
* 6 5 *
1 
 v b 
where K* is the reduced equilibrium constant.
Once the equilibrium constant K is known, equation (2-164) can be
solved to obtain a value for z1 and a corresponding value for z6.
The equilibrium constant for HF hexamerization can be calculated
from the following relationship:
Equation (2-165):
8910
log10 K  43.65 
T
where:
K = equilibrium constant, 1/mmHg2
T = temperature, K
Twu et al.(1) have shown that, at the critical point, the values of z1,
the true mole fraction of monomer, and nr, are given by:

Equation (2-166):
z1 Tc   0.7006
Equation (2-167):
nr Tc   0.4005
So, even at the critical point, there is still a considerable amount of

the hexamer species present.
Mixture properties may be computed by using the SRKS mixing
rule, equation (2-149) on page 102.
Reference
1 Twu, C. H., Coon, J. E., and Cunningham, J. R., 1993, An

Equation of State for Hydrogen Fluoride, Fluid Phase
Equil., 86, 47-62.
Also See:
General Information
UNIWAALS
In the UNIWAALS model proposed by Gupte et al.(1) in 1986, the
cubic equation of state is combined with the excess Gibbs free
energy model. By using this approach, the same parameters of the
excess Gibbs free energy model based on low pressure VLE data
can be extended to apply to high pressures by using the equation of
state. This is a valuable method because group interaction parame-
ters from group contribution methods such as UNIFAC (see Sec-
tion, Liquid Activity Methods) are readily available for numerous
groups.
The equations for the UNIWAALS method are developed by equat-
ing the gE derived from the van der Waals equation of state to the
gE derived from UNIFAC at the system temperature and pressure.
This equality produces the following mixing rule:
Equation (2-168):
a   
 f PvE / RT  ln  P  v  b / RT    xi ln  P  vi  bi  / RT   
RTb   i 
 f  xi ai /  fi RTbi   f g / RT
E

Equation (2-169):
f b/v
Equation (2-170):
fi  bi / vi
where:
vE = excess volume
The mixing rule for the a/b parameter contains the mixture (v) and
pure (vi) fluid volumes. The pure component volumes are obtained
for the liquid phase at the given temperature and pressure condi-
tions. Parameter b for the mixture is calculated using the original
mixing rule developed for the RK equation of state (equation (2-
135) on page 96), and UNIFAC is used to calculate gE/RT. Subse-
quently, the van der Waals equation of state and equation (2-170)
are solved simultaneously to obtain the mixture volume, v, and a/
RTb.
Several limitations to this method should be noted:
 For the calculation of the parameter a, the mixture and pure-
component liquid volumes (v and vi) are required, even if the
liquid phase does not actually exist at the given temperature
and pressure.
 The mixture parameter v is volume dependent, and thus pres-
sure and volume become related through a differential equa-
tion, rather than through a conventional algebraic equation.
 The critical constraints of the UNIWAALS equation of state are
no longer satisfied by the values of the parameters a and b at
the critical temperature. The resulting equation of state is no
longer a cubic equation of state, and analytical solution of the
equation of state is impossible.
 The fugacity coefficients are cumbersome to evaluate.
 The accuracy of the UNIWAALS model is not better than that
of the UNIFAC model at low temperatures, and the accuracy
deteriorates with increasing temperatures.

Reference
1 Gupte, P. A., Rasmussen, P., and Fredenslund, A., 1986, A

New Group-Contribution Equation of State for Vapor-Liq-
uid Equilibria, Ind. Eng. Chem. Fundam., 25, 636-645.
Also See:
General Information
Benedict-Webb-Rubin-Starling
The Benedict-Webb-Rubin equation(1) of state was first proposed in
1940 to predict liquid and vapor properties at high temperatures,
and to correlate vapor-liquid equilibria for light hydrocarbon mix-
tures. This original (BWR) equation of state however provided poor
results at low temperatures, and around the critical point. To
improve the accuracy of this equation in predicting thermodynamic
properties for light hydrocarbons in the cryogenic liquid, gas, and
dense fluid regions, and at high temperatures, the BWR equation
was modified by Starling(2) in 1973 to give the following form:
Equation (2-171):
 C D E 
P   RT   Bo RT  Ao  o2  3o  o4   2
 T T T 
 d  d
  bRT  a    3    a    6
 T  T
c 3
 2 1   2  exp   2 
T
The eleven parameters for pure components (B0 , A0 , etc.) are gen-
eralized as functions of component acentric factor, critical tempera-
ture, and critical density. The mixing rules for the eleven mixture
parameters are analogous to the mixing rules used for the BWR
equation. The single binary interaction parameter for the BWRS
equation of state is built into the mixing rules. The BWRS equation
of state can predict pure-component properties for light hydrocar-
bons very accurately when experimental data covering entire ranges
are available.
Limitations to the BWRS equation of state are given below:

 Because the equation is generalized in terms of critical temper-
atures, critical density, and acentric factor, it has difficulty pre-
dicting properties for heavy hydrocarbons and polar systems.
 The BWRS equation does not satisfy the critical constraints,
and therefore the equation is inferior to cubic equations of state
when applied to the critical and super-critical regions.
 The BWRS equation is less predictive than cubic equations of
state for mixture calculations.
 Unlike cubic equations of state, BWRS cannot be solved ana-
lytically, and normally requires more CPU time.
Reference
1 Benedict, M, Webb, G. R., and Rubin, L. C., 1940, An

Empirical Equation for Thermodynamic Properties of Light
Hydrocarbons and Their Mixtures. I. Methane, Ethane, Pro-
pane, and Butane, J. Chem. Phys., 8, 334-345.
2 Starling, K. E., 1973, Fluid Thermodynamic Properties for
Light Petroleum Systems, Gulf Publishing Company,
Houston, TX.
Also See:
General Information
Lee-Kesler-Plöcker (LKP)
The LKP equation(1) is based on the Benedict-Webb-Rubin equa-
tion of state and on Pitzer's(3) extended theory of corresponding
states. Thermodynamic data are correlated as a function of critical
temperature and pressure and the acentric factor as follows:
Equation (2-172):
 
z  z o     z r  zo 
 r 
where:
Z = compressibility factor

subscripts o, r denote Simple and Reference fluids, respec-
tively.
The work of Plöcker et al.(4) introduces new mixing rules which are
purported by the authors to better handle mixtures of asymmetric
molecules. This is accomplished by the introduction of an exponent,
 into the mixing rules.
The mixing rules proposed here are:
Equation (2-173):
Tc ,mix
Pc , mix  .2905  0.085mix  R
Vc ,mix
Equation (2-174):
Vc , mix   zi zkVcjk
i k
Equation (2-175):
mix   z j j
j
where:
Vc = the molar critical volume
Tc = the critical temperature
z = mole fraction in vapor or liquid phase

 = the acentric factor
The cross coefficients are given by:
Equation (2-176):
Tcjk  TcjTck 
1/ 2
K jk
Equation (2-177):
1 1/3
Vcj  Vck1/3 
3
Vcjk 
8
where:
Kjk is an adjustable binary parameter, characteristic of the j-k
binary, independent of temperature, density, and composition.

The pseudo-critical pressure is found by:
Equation (2-178):
Tc ,mix
Pc , mix   0.2905  0.085mix  R
Vc , mix
When  is zero, the mixing rules are similar to those of Prausnitz

and Gunn(5)(6); when  is 1.0, the mixing rules become the van der
Waals mixing rules, as used by Leland et al(2). For symmetric mix-
tures,  is zero; for strongly asymmetric mixtures,  is a positive
value less than unity. Based on an analysis of experimental data, the
authors suggest using a value of 0.25 when a specific determination
is not available. PRO/II uses a default  value of 0.25.
Adjustable binary parameters, Kij's are also used in the mixing
rules. Values reported by Plöcker et al. have been incorporated into
PRO/II. The LKP method is claimed by the authors to be superior to
Starling's BWRS equation for highly asymmetric systems. The
method is not accurate around the critical point because the mixture
critical constants are empirical, and do not represent the true critical
point. Therefore, the authors recommend that the method not be
used above a reduced temperature of 0.96.
Reference
1 Lee, B.I., and Kesler, M.G., 1975, A Generalized Thermo-

2 Leland, T.W., and Mueller, W.H., 1959, Applying the The-
ory of Corresponding States to multi-component Mix-
tures,Ind. Eng. Chem., 51, 597-600.
3 Pitzer, K.S., and Hultgren G.O., 1958, The Volumetric and
Thermodynamic Properties of Fluids, V. Two Component
Solutions, J. Am. Chem. Soc., 80, 4793-96.
4 Plöcker, U., Knapp, H., and Prausnitz, J.M., 1978, Calcula-
tion of High-Pressure Vapor-Liquid Equilibria from a Cor-
responding States Correlation with Emphasis on
Asymmetric Mixtures, Ind. Eng. Chem. Proc. Des. Dev.,
17, 324-332.
5 Prausnitz, J.M., and Gunn, R.D., 1958, Volumetric Proper-
ties of Nonpolar Gaseous Mixtures, AIChE J., 4, 430-35.

6 Prausnitz, J.M., and Gunn, R.D., 1958, Pseudo-critical
Constants from Volumetric Data for Gas Mixtures, AIChE
J., 4, 494.
Also See:
General Information
Twu-Bluck-Coon(TBC)
The previous SRK and PR mixing rule modifications included com-
position-dependence for applying these equations of state to com-
plex mixtures. A more rigorous way to represent the phase behavior
of strongly non-ideal systems is to develop the relationship between
the mixing rule and excess free energy model such that the zero-
pressure Gibbs free energy could be expressed by a NRTL-like
method (see Section, Liquid Activity Methods). Such approach had
been extended by Twu, Bluck and Coon(1) in 1998 with a newly
developed zero-pressure-based mixing rule which would accurately
reproduce the excess Gibbs model and allow the available activity
coefficient models at low pressures be used directly.
The general Helmholtz free-energy departure function is given by:
Equation (2-179):
AE  Avdw
E
 A  Avdw
At zero pressure, equation (2-179) may be derived as:
Equation (2-180):
A0E A0Evdw b   a a 
  ln  vdw   Cv0    vdw
 
RT RT  b  b bvdw 
where:
A0E = excess Helmholtz free energy at zero-pressure;

A0Evdw = excess Helmholtz free energy at zero-pressure
calculated by a CEOS, such as SRK;
C v0 = density function calculated from SRK;
Equation (2-180) can be written to obtain the new mixing rule:

Equation (2-181):
 a 1  A0E A0Evdw  b  
a   b   vdw

    ln  vdw   
 bvdw Cv0  RT RT  b   
and
Equation (2-182):
b   bvdw

At zero pressure, the value of the excess Helmholtz energy is identi-

cal to the excess Gibbs energy model. Therefore, any activity model
such as the NRTL equation can be used directly. For a solution of n
components, the NRTL equation is expressed as,
Equation (2-183):
n
GE n x j ji G ji
  xi
j
n
RT i
x Gk
k ki
where:
Equation (2-184):
Aji
 ji  and G ji  exp   ji ji 
T
By regressing experimental data to obtain the parameters in the
NRTL expression, excellent representation of vapor-liquid equilib-
ria can be made. The prediction of equilibria at low densities is rea-
sonable, and the equation of state can be expected to yield better
results at higher pressures, because the mixing rules have been
derived at the zero pressure limit of the excess Gibbs free energy.
The TBC equation of state overcomes the limitation of infinite-
pressure based models, such as Huron-Vidal (SRKH, PRH,…) that
it can directly utilize parameters for the NRTL method correlated
from low temperature data.
Reference
1 Twu, C. H.; Coon, J. E.; Bluck, D. “Comparison of the

Peng-Robinson and Soave-Redlich-Kwong Equations of
State UsingThe present implementation is limited to PPR78
model supported groups only. For unsupported components
the calculations for kij will be defaulted to PR EOS. a New

Zero-Pressure-Based Mixing Rule for the Prediction of
High-Pressure and High-Temperature Phase Equilibria”.
Ind. Eng. Chem. Res. 1998, 37, 1580-1585.
Also See:
General Information
Predictive Peng-Robinson 78
The Predictive Peng-Robinson equation of state (PPR78) method
can be used for the prediction of phase equilibria of binary mixtures
in both the subcritical and critical regions very accurately.
This model uses temperature-dependent binary interaction parame-
ter, kij , to predict the critical locus of the binary systems and the
phase behavior of asymmetric systems with high accuracy.
PPR78 uses a group contribution method to estimate the kij(T)
parameters.
Limitations
Functionality
Technical Information:
Limitations
The limitations of PPR78 Thermo is as follows :
 This method has been applied to mixtures containing alkenes,
aromatics, napthenes, carbon dioxide, hydrogen sulfide and
nitrogen.
 The present implementation is limited to “PPR78 model” - sup-
ported groups only. For unsupported components, the calcula-
tions for kij will be defaulted to PR EOS.
Functionality
The following functionality is provided for PPR78 Thermo:
 User will be able to select the PPR78 method for Equilibrium,
Enthalpy, Entropy, and Density.
 All properties relevant to PPR78 will be provided, e.g., fugac-
ity, fugacity coefficient, compressibility, molar volume, partial
molar properties, etc.

 All properties that represent derivatives will be calculated ana-
lytically. This is customary for other methods in Thermo.
Technical Information:
The technical information for PPR78 Thermo is given below :
 In 1976, Peng and Robinson proposed a two-constant equation
of state, the well-known PR EOS. In 1978, they proposed an
improved version of their equation of state for the heavy hydro-
carbons. This improved equation is called PPR78.
 For a pure component, the PPR78 EOS is given by:
Equation (2-185):
RT ai T 
P 
v  bi v  v  bi   bi  v  bi 
where
Equation (2-186):
R  83144721 J .mol 1.K 1

RTC,i
bi  0.0777960739
PC,i
2
R2TC2,i   T 
ai  0.457235529 1 mi 1 
PC,i   TC,i 
  
if i  0.491 mi  0.37464 1.54226i  0.2699i2
if i  0.491 mi  0.37464 1.48503i  0.164423i2  0.016666i3
In the above, P is the total pressure, R the ideal gas constant, T

the temperature, a and b are EOS parameters, υ the molar vol-
ume, TC the critical temperature, PC the critical pressure, and ω
the acentric factor.
An important feature of (2-186) is that the function mi that
enters the alpha function ai takes on two forms depending on
the value of the acentric factor. This is a key departure from the
1976 version of the PR model.
 For mixtures, the values of a and b are calculated using classic
mixing rules:

Equation (2-187):
N N
a   zi z j ai a j 1  kij T  
i 1 j 1
Equation (2-188):
N
b   zi bi
i 1
where zk represents the mole fraction of component k in a mix-

ture, and N the number of components in the mixture. kij(T) is
the binary interaction parameter characterizing molecular inter-
actions between molecules i and j.
Note: kij = 0 when i = j.
The common practice is to fit the kij(T) so as to represent the

vapor-liquid equilibrium data of the mixture under consider-
ation.
 For the PPR78 model, the binary interaction parameter calcu-
lated by group contribution method is given by
Equation (2-189):
 Bk ,l 
 1
1 Ng Ng  298.15  Ak ,l 
   i ,k   j ,k  i ,l   j ,l Ak ,l 


2 k 1 l 1  T 
ki , j  T  
ai T  a j T 
2
bi b j
2
 a T  a j T  
 i  
 bi bj 
 
ai T  a j T 
2
bi b j
In (2-189), T is the temperature, ai and bi are calculated in

equations (n) and (2-188) , is the number of different groups
defined by the method, ik is the fraction of molecule i occu-
pied by group k, and Akl , Bkl are constant parameters allowing
the calculation of the binary interaction parameters.

 PPR78 uses a group contribution method to estimate the kij(T)
parameters. At present this PPR78 model supports limited
groups which are documented.
Refer to Table 4-11, Chapter 4-Equations of State of “Thermody-
namic Keyword Manual” for PPR78 - supported groups.
Reference
1 Jean-Noel Jaubert; Fabrice Mutelet. VLE predictions with

the Peng-Robinson equation of state and temperature
dependent calculated through a group contribution method.
Fluid Phase Equilibria . 2004, 224, 285-304.
2 Jean-Noel Jaubert; Stephane Vitu; Fabrice Mutelet; Jean
Pierre Corriou. Extension of the PPR78 model (predictive
1978, Peng-Robinson ESO with temperature dependent
calculated through a group contribution method) to systems
containing aromatic compounds. Fluid Phase Equilibria .
2005, 237, 193-211.
3 Stephane Vitu; -Noel Jaubert; Fabrice Mutelet; Extension
of the PPR78 model (predictive 1978, Peng-Robinson ESO
with temperature dependent calculated through a group
contribution method) to systems containing naphthenic
compounds. Fluid Phase Equilibria . 2006, 243, 9-28.
4 Romain Privat; Jean Noel Jaubert; Fabrice Mutelet; Addi-
tion of the sulfhydryl group (-SH) to the PPR78 model (pre-
dictive 1978, Peng-Robinson EOS with temperature
dependent calculated through a group contribution method.
J.Chem.Thermodynamics, 2008, 40, 1331-1341.
5 Stephane Vitu; Romain Privat; Jean Noel Jaubert; Fabrice
Mutelet; Predicting the phase equilibria of CO2+hydrocar-
bon systems with the PPR78 model (PR EOS and calcu-
lated through a group contribution method. J. of
Supercritical Fluids, 2008, 45, 1-26.
6 Romain Privat; Jean Noel Jaubert; Fabrice Mutelet; Addi-
tion of the Nitrogen Group to the PPR78 Model (Predictive
1978, Peng-Robinson EOS with Temperature Dependent
Calculated through a Group Contribution method.
Ind.Eng.Chem.Res., 47, 2008, 2033-2048.

7 Romain Privat; Fabrice Mutelet;Jean Noel Jaubert; Addi-
tion of the Hydrogen Sulfide Group to the PPR78 model
(Predictive 1978, Peng-Robinson EOS with Temperature
Dependent calculated through a group contribution
method. Ind.Eng.Chem.Res.47, 2008, 10041-100
8 Ding-Yu Peng, Donald B.Robinson. A New Two-Constant
Equation of State. Ind.Eng.Chem., Fundam., 15, No.1,
1976, 59-64.
9 D.B. Robinson, D.Y. Peng, The characterization of the hep-
tanes and heavier fractions for the GPA Peng–Robinson
programs, Gas processors Association, Research Report
RR-28, 1978 (booklet only sold by the GPA, Gas Proces-
sors Association).
Also See:
General Information
Predictive Soave-Redlich-Kwong (PSRK)

PSRK is a group contribution equation of state based on a combina-
tion of the Soave-Redlich-Kwong equation of state and a mixing
rule whose parameters are determined by the UNIFAC method.
This model can be used for VLE-predictions over a large tempera-
ture and pressure range and is easily extended to mixtures contain-
ing supercritical compounds.
The PSRK mixing rule calculates the parameters 'a' and 'b' of the
equation of state by
Equation (2-190):
E
g0 a i RT b-
a = b -------- +  x i ---- + -------  x i ln ---
A1 bi A1 bi
Equation (2-191):
b =  xi bb
Where:
A1=-0.64663

ai and bi are parameters of the pure substances. Their mole fractions
are given by xi and the excess Gibbs energy (gE). The excess Gibbs
energy is calculated by a modified UNIFAC model.
Applications
 This model yields good results for vapor-liquid-equilibria
(VLE) of non-polar and polar mixtures.
 This model can be used for VLE predictions at high tempera-
tures and pressures.
 This model can predict phase equilibria of the mixtures con-
taining supercritical components.
Limitations
 The SRK EOS describes the vapor densities of pure compo-
nents and mixtures quite well, but predicts the liquid density
poorly.
 For the VLE predictions of mixtures with components that
have varying sizes, large systematic errors are found.
 Heats of mixing and activity coefficients at infinite dilution are
predicted poorly.
Reference
1 Holderbaum T., Gmehling J., PSRK: A Group Contribution

Equation of State Based on UNIFAC, Fluid Phase Equilib-
ria. 1991, 70, 251-265.
Fill Options (for Binary Interaction Coefficients)

The ability of equation-of state methods to accurately predict vapor-
liquid equilibria and/or vapor-liquid-liquid equilibria depends to a
great degree on whether or not binary interaction parameters are
available for that method. Refer to the Kij term of equation (2-136).
Fill Options for Use With Cubic Equations of State
Fill Options for Use With Cubic Equations of State

PRO/II implements a number of binary interaction prediction meth-
ods for hydrocarbon/hydrocarbon mixtures. These prediction meth-
ods automatically provide the optimal light/heavy kij’s for methane,
ethane and propane with other hydrocarbons. They were designed
specifically with an eye towards heavy petroleum fractions, to be

used in conjunction with SimSci's generalized alpha forms listed in
Table 2-3 on page 2-94.
GOR The GOR method was developed by Simsci to automati-

cally generate kij’s between methane and ethane and other
heavier hydrocarbons. It is based on correlating existing
deepwater US Gulf of Mexico experimental data.
GAO The modified Gao et al method, is a modification where

only interactions for methane, ethane and propane are used
with an extension to undefined fractions of the method
published in Fluid Phase Equilibria. The original work was
based upon the Peng-Robinson equation of state.
1 Gao, Guanghua; Daridon, Jean-Luc; Saint-
Guirons, Henri; Xans, Pierre; Montel, Francois; A
simple correlation to evaluate binary interaction
parameters of the Peng-Robinson equation of
state: binary light hydrocarbon systems; Fluid
Phase Equilibria; 74, (1992) 85-93.
CPHC The modified Chueh-Prausnitz method is an adaptation of

a method reported in the AIChE Journal, 13(6), (1967),
1099-1107. It predicts interactions between all hydrocar-
bons present in the problem.
2 Cheuh, P. L.; Prausnitz, J. M.; Vapor-Liquid Equi-
libria at High Pressures: Calculation of Partial
Molar Volumes in Nonpolar Liquid Mixtures;
AIChE Journal, Vol. 13, no. 6, pg 1099-1107
(1967).
The methods listed above were selected based on their applicability

and are ordered so each subsequent method in the list generates
more and more kij’s. In this respect, they provide a spectrum of
results that can be selected based on the goodness of fit to the spe-
cific data being modeled. Applying these changes to a PRO/II input
can improve the initial estimates for gas oil separations.
When a cubic equation-of-state method such as SRK or PR is
selected for phase equilibrium calculations, and a FILL option is
specified, PRO/II uses the following hierarchy to obtain the binary
interaction data the model needs. For VLE or LLE calculations:

 First, use any user-supplied binary interaction parameters, or
mutual solubility, infinite dilution, or azeotropic data.
 Second, search VLE and LLE databanks that contain binary
interaction parameters.
 Third, search the SimSci azeotropic databanks for appropriate
azeotropic data, which then are regressed to provide binary
interaction data.
 If some binary interaction parameters still are missing after
completing steps 1 through 3, then the specified FILL method
is employed.
 Finally, if binary interaction parameters are still missing after
completing steps 1-4, all remaining missing parameters are
assigned a value of zero.
Figure shows the mechanism used by PRO/II to backfill missing
binary parameters for VLE, or VLLE calculations.
For VLLE calculations, in order to avoid conflicts between VLE
and LLE binary interaction data, PRO/II follows a number of strict
rules when filling in these binary interaction data.
 If no VLE or LLE interaction data are supplied by the user,
PRO/II uses the following order in searching for interaction
data for both VLE and LLE calculations:
 The LLE databank
 The VLE databank
 When the user supplies VLE interaction data only, PRO/II uses
the following order in searching for binary parameters for both
VLE and LLE calculations:
 User-supplied values on the KVALUE(VLE) statements
 If the user supplies LLE interaction data only, or both VLE and
LLE interaction data, for LLE calculations, the databanks are
searched in the order:
 User-supplied data on KVALUE(LLE) statements

LLE interaction data, for VLE calculations, the databanks are
 User-supplied data on KVALUE(VLE) statements
Also See:
General Information
Free Water Decant

General Information
Calculation Methods
Water Solubility Calculation Methods
General Information
In many hydrocarbon-water mixtures, including those found in
refinery and gas processing plants, the water phase formed is nearly
immiscible with the liquid hydrocarbon phase. For such systems,
the water phase can be assumed to decant as a pure aqueous phase.
This reduces the number of computations involved with rigorous
VLLE methods. The water-decant method as implemented in PRO/
II follows these steps:
 Water vapor is assumed to form an ideal mixture with the
hydrocarbon vapor phase.
 The water partial pressure is calculated using one of two meth-
ods.
 The pressure of the system, P, is calculated on a water-free
basis, by subtracting the water partial pressure.
 A pure water liquid phase is formed when the partial pressure
of water reaches its saturation pressure at that temperature.
 The amount of water dissolved in the hydrocarbon-rich liquid
phase is computed using one of a number of water solubility
correlations.
Note: The free water decant option may only be used with the
Soave-Redlich-Kwong, Peng-Robinson, Grayson-Streed, Chao-

Seader, Improved Grayson-Streed, Erbar modifications to Grayson-
Streed and Chao-Seader, Braun K10, or Benedict-Webb-Rubin-
Starling methods. Water decant is automatically activated when
either one of these methods is selected.
Calculation Methods
The amount of water dissolved in the hydrocarbon-rich liquid phase
can be computed once the water K-values, , are known. These
are calculated using the following relationship:
Equation (2-192):
K w  Pw /  Pxw 
where:
Pw = water partial pressure at temperature T
xw = solubility of water in the hydrocarbon-rich liquid phase
P = system pressure
The water partial pressure is calculated using the ASME steam
tables, or Chart 20-4 in the 12th edition of GPSA Data Book or
WICHERT Method. The GPSA Data Book option is recommended
for natural gas mixtures above 2000 psia. The WICHERT method is
based on the article with the title “New charts provide accurate esti-
mations for water content of sour natural gas” by Gordon C.Wichert
and Edward Wichert from the Oil and Gas Journal dated Oct. 27,
2003. This method is recommended for low pressures. Three sets of
steam tables can be used:
 Water properties can be calculated assuming saturated vapor
and liquid conditions.
 Steam tables for superheated water vapor based on the Keenan
and Keyes equation of state.
 IF 97 Steam Tables - International Association for the Proper-
ties of Water and Steam - Industrial Formulation 1997 steam
tables are used for the property calculations.
Water Solubility Calculation Methods

The water solubility, xw , can be computed by one of several meth-
ods in PRO/II:

1 The default method developed by SimSci. In this method,
water solubility is calculated for individual hydrocarbons
and light gases given in Table 2-4. The SimSci method uses
a correlation based on the number of carbon and hydrogen
atoms present in the component. For pseudo-components,
the water solubility is calculated as a function of the Wat-
son (UOP) K-factor.
2 The second method is used to get the extrapolated values in
the temperature range of below 0 Deg C, because the first
method (SIMSCI) cannot be used for calculating "Solubil-
ity of water in hydrocarbon" due to a limitation in this
range. SIMSCI method defaults to one value.
Table 2-4: Components Available in the SIMSCI Water

Solubility Method
Paraffins Naphthenes
Unsaturated Hydrocarbons Aromatics
Methyl Mercaptan CS2
NH3 Argon
CO2 Helium
HCl H2S
N2 NO
O2 SO2
3 A third method uses Figure 9A1.2 in the API Technical

Data Book to compute water solubility in kerosene. PRO/II
will automatically invoke this option if the SIMSCI decant
option is chosen, and a component not included in Table 2-
4 is present in the system.
4 A fourth method employs the equation-of-state method that
is being used for calculating the K-values of the other com-
ponents present in the system to compute the water K-
value. Missing binary interaction parameters for the water-
hydrocarbon components pairs are estimated using the
Soave-Redlich-Kwong Kabadi-Danner equation of state.
This method is only valid for SRK or PR equations of state

5 The following methods are from the 1999 API Technical
Data Book, Procedure 9A1.3. They calculate the solubility
of water in various liquid hydrocarbon mixtures.
1999 API Technical Data Book Water Solubility Methods

LUBE lube oil Refer to the Component and
Thermodynamic Data Keyword Input
NAPH Naphtha
Manual, Volume II, Table 1-5, “Properties
APIKERO Kerosene of Water Solubility Fluids,” for a listing of
PARA Paraffin oil the basic properties of these fluids.
GASO Gasoline
JP3 JP-3 fuel
JP4 JP-4 fuel

General Information
Equations of State
Truncated Virial Equation of State
Hayden-O'Connell
General Information
In vapor-liquid equilibrium calculations, it becomes necessary to
calculate separately the fugacity of each component in the vapor
and liquid phases. Each of the two phases usually requires different
techniques. For example, liquid-phase non-idealities may be
described by activity coefficients, while deviations from ideal gas
behavior in the vapor phase are described by fugacity coefficients.
The vapor phase fugacity coefficients may be obtained through the
use of an equation of state. The fugacity coefficients are obtained
from classical thermodynamics as follows:
Equation (2-193):
1 
 P  RT 
ln i 
RT  V
  
 ni T ,V , n j V 
 dV  ln z
 
Equation (2-194):
i  f i / yPi
where:

i = fugacity coefficient of component i
fi = fugacity of component i
R = gas constant
P = system pressure
ni = number of moles of component i
yi = mole fraction of component i in the vapor phase
V = volume of system
z = compressibility factor of the mixture
In equation (2-193), the partial derivatives of P with respect to ni
must be evaluated using an appropriate equation of state. Therefore,
the problem of calculating fugacities of components in a gaseous
mixture is equivalent to the problem of establishing a reliable equa-
tion of state for such a mixture. Once such an equation is found, the
fugacities can be computed from equations (2-193) and (2-194).
Equations of State
Equations of state are powerful methods for calculating vapor-
phase fugacities at low and high densities. The analytical expres-
sion of the fugacity coefficient can be derived from a cubic equation
of state. The derivation of the fugacity coefficient from a cubic
equation of state is straightforward because the cubic equation of
state in pressure is volume-explicit. Cubic equations of state are
usually applied to systems comprising mixtures of nonpolar or
weakly polar components. The usefulness of a cubic equation of
state can be greatly enhanced by using an advanced alpha function,
and an advanced mixing rule. Modified cubic equations of state can
be suitable for systems containing polar components. See “General
Cubic Equation of State”
Additionally, a cubic equation of state (incorporated with a chemi-
cal theory of association) is suitable for systems containing polar
and hydrogen-bonding molecules. These include carboxylic acids
which form monomer-dimer pairs and hydrogen fluoride. Such
methods include the Associating Equation of State and the Hayden
O'Connell method. See “Hayden-O'Connell” .

The equation-of-state methods are generally more reliable for cal-
culating vapor phase fugacity coefficients than any other method,
except for dimerizing components where the Hayden-O'Connell
method should be used.
Truncated Virial Equation of State

Many equations of state have been proposed for calculating vapor
fugacities, as mentioned in the previous section, but almost all of
them are empirical in nature. The virial equation of state for gases
has a sound theoretical foundation, and is free of arbitrary assump-
tions. The virial equation gives the compressibility factor as a
power series in the reciprocal molar volume:
Equation (2-195):
Pv B C D
z  1   2  3  ...
RT v v v
where:
v = molar volume
B, C, D, .. = second, third, fourth etc. virial coefficients
The virial coefficients are a function of temperature and composi-
tion only. For low or moderate vapor densities, the virial equation
can be truncated after the second virial coefficient and converted to
a pressure-explicit form:
Equation (2-196):
z  1  BP / RT
The compositional dependence of B for a mixture containing N
components is given by:
Equation (2-197):
N N
B   yi y j Bi , j
i j
where:
Bii = second virial coefficient for pure component i
Bij = second virial cross coefficient

The cross coefficients characterize on interaction using between
one molecule of component i and one of component j. They may be
obtained from mixture data, though often they are estimated from
the pure component coefficients.
O'Connell and Prausnitz developed a correlation for the reduced
second virial coefficient (both pure component and cross coeffi-
cients) which consists of three generalized functions:
 One for nonpolar contributions to the second virial coefficient,
 One for polar interactions based on the dipole moment, and,
 An association function for substances which exhibit specific
forces such as hydrogen bonds.
Use of this correlation requires the critical temperature, critical
pressure, critical volume, acentric factor, dipole moment, and asso-
ciation constant for each component present. Missing dipole
moments and association constants are assumed to be zero. One
limitation of this method is that as the virial equation of state is an
expansion about the compressibility factor of an ideal gas, higher-
order terms cannot be neglected in high density regions. The virial
equation of state can provide reliable estimates of vapor-phase
fugacity coefficients at low pressures or high temperatures only.
Reference
1 O'Connell, J. P., and Prausnitz, J. M., 1967, Empirical Cor-

relation of Second Virial Coefficients for Vapor-Liquid
Equilibrium Calculations, Ind. Eng. Chem. Proc. Des. Dev.,
6(2), 245-250.
Hayden-O'Connell
The truncated virial equation of state described above is useful for
predicting deviations from ideality in those systems where moder-
ate attractive forces yield fugacity coefficients not far removed
from unity. However, in systems containing carboxylic acids, two
acid molecules tend to form a dimer, resulting in large negative
deviations from vapor ideality even at very low pressures.
To account for dimerization, Hayden and O'Connell(1) developed a
fugacity coefficient expression based on a chemical theory of vapor
imperfection. The “chemical theory” assumes dimerization equilib-
ria exist for a binary mixture of components A and B:

Equation (2-198):
K K

A1  A1 
A2
A2 
B1  B1 
B2
B2
Equation (2-199):

 AB
A1  B1 

K AB
where:
A1, B1 = monomers
A2, B2 = dimers
AB = cross dimer
Hayden and O'Connell related second virial coefficients to the
dimerization equilibrium constants, KA2, KB2, and KAB, and devel-
oped generalized second virial coefficients for simple and complex
systems. Properties required to use this correlation are; the critical
temperature, critical pressure, mean radius of gyration, dipole
moment, association parameter, and solvation parameter. Associa-
tion and solution parameters for common associating components
are available in PRO/II's databanks.
This method is a reliable generalized method for calculating vapor
phase fugacities up to moderate pressures, especially for systems
where no data are available.
Reference
1 Hayden, J. G., and, O'Connell, J. P., 1975, A Generalized

Method or Predicting Second Virial Coefficients, Ind. Eng.
Chem. Proc. Des. Dev., 14(3), 209-216.
Liquid Activity-Based Methods

General Information
Margules Equation
van Laar Equation
Regular Solution Theory
Flory-Huggins Theory
Wilson Equation
NRTL Equation

UNIQUAC Equation
UNIFAC
Modifications to UNIFAC
Fill Options
Henry's Law
Heat of Mixing Calculations
General Information
Liquid activity coefficient methods for phase equilibrium calcula-
tions differ at a fundamental level from equation of state (EOS)
methods. In EOS methods, fugacity coefficients (referring to an
ideal-gas state) are computed for both vapor and liquid phases. In
activity coefficient methods, the reference state for each component
in the liquid phase is the pure liquid at the temperature and pressure
of the mixture. It is often more convenient and accurate to use this
approach when the liquid phase is a mixture of components which
do not differ greatly in volatility; it is also often easier to describe
strongly non-ideal systems with a liquid activity coefficient model
than with an equation of state.
The thermodynamics of liquid mixtures within an activity coeffi-
cient framework is covered in standard textbooks, a few of which
are referenced at the end of this section. The activity coefficient is
introduced in the way the fugacity of component i in the liquid
phase is written:
Equation (2-200):
fi L   i xi f i oL
where:
fi L = fugacity of component i in liquid phase
fi oL = standard-state liquid fugacity of component i
xi = mole fraction of component i in liquid
i = liquid-phase activity coefficient of component i

The standard-state fugacity oL is defined as that of the pure liquid
fi
i at the temperature and pressure of the mixture. With this defini-
tion, gi approaches one in the limit xi  1. The standard-state
fugacity may be related to the vapor pressure of component i as fol-
lows:
Equation (2-201):
f i oL  Pi satisat exp   viL / RTdP 

P
 Pisat 
where:
P = system pressure
sat
Pi = vapor pressure of component i at system temperature
R = gas constant
L
 i = liquid molar volume of component i at T and P
 isat = fugacity coefficient of pure component i at temperature

sat
T and pressure Pi .
The exponential term in Equation (2-201) is the Poynting factor

which accounts for the effect of pressure on the liquid fugacity. If
the pressure does not exceed a few atmospheres, this correction can
generally be neglected. Since liquid volumes do not depend greatly
on pressure, Equation (2-201) can be simplified to:
Equation (2-202):
f i oL  Pi satisat exp  P  Pi sat  viL / RT 
When liquid activity coefficients are used, any method may be used
to compute the vapor-phase fugacity. An ideal gas is often assumed,
but in general vapor fugacities may be written as:
Equation (2-203):
f iV  iV yi P
where:
f i V = fugacity of component i in vapor phase

yi = mole fraction of component i in vapor
 iV = fugacity coefficient of component i in vapor

V
For an ideal gas, the fugacity coefficient  i is one, but it may also
be computed from an equation of state or other correlation.
Equations (2-200) and (2-203) are fundamentally different in the
way they describe liquid and vapor fugacities, respectively. The two
equations do not in general “match” at the vapor-liquid critical
point, where vapor and liquid phases become indistinguishable.
Phase equilibrium calculations near a vapor-liquid critical point
must be carried out with some other method such as an equation of
state.
The familiar vapor-liquid K-value is defined as the ratio of yi to xi,
and can be obtained by combining Equations (2-200) and (2-203):
Equation (2-204):
f i oL  Pi satisat exp  P  Pi sat  viL / RT 
At low and moderate pressures, the Poynting correction is often

ignored and Equation (2-204) becomes
Equation (2-205):
 iisat Pi sat
Ki 
iV P
Unless there is vapor-phase association (as is the case with carbox-
ylic acids, for example), the fugacity coefficients may also be
ignored at low and moderate pressures. Equation (2-204) then sim-
plifies to
Equation (2-206):
 i Pi sat
Ki 
P
For most low-pressure systems, the regression of experimental
vapor-liquid equilibrium data will produce essentially the same
parameters if equation (2-205) or (2-206) is used in place of the full
equation (2-204). This is not necessarily the case at higher pressures
and for systems where vapor-phase non-ideality is important. Sig-
nificant errors can be introduced when the regression and calcula-
tions using the regressed parameters employ differing sets of

simplifying assumptions. In general, calculations should be per-
formed using the same assumptions about vapor fugacities and the
Poynting factor as those employed in fitting the parameters. An
important exception to this rule is the case where parameters were
fitted at low pressure but the calculations are at a substantially
higher pressure; in such a case it is best to employ non-ideal vapor-
phase fugacities and the Poynting correction in the calculation even
if they were not used in the original fit.
Liquid activity coefficients are derived from expressions for the
excess Gibbs energy of a liquid mixture. The defining equation is:
Equation (2-207):
1  G E 
ln  i   
RT  ni T , P ,n
ji
where:
GE = excess Gibbs energy of liquid mixture

ni = moles of component i in liquid
The following sections describe the expressions available for

describing liquid-phase activity coefficients.
Reference
1 Prausnitz, J.M., Lichtenthaler, R.N. and Gomes de Aze-

vedo, E., 1986, Molecular Thermodynamics of Fluid Phase
Equilibria, 2nd ed., Prentice Hall, Englewood Cliffs, NJ.
2 Sandler, S.I., 1989, Chemical and Engineering Thermody-
namics, 2nd ed., John Wiley & Sons, New York.
3 Smith, J.M. and Van Ness, H.C., 1987, Introduction to
Chemical Engineering Thermodynamics, 4th ed., McGraw
Hill, New York.
4 Van Ness, H.C. and Abbott, M.M., 1982, Classical Thermo-
dynamics of Non-electrolyte Solutions: With Applications
to Phase Equilibria, McGraw Hill, New York.
5 Walas, S.M., 1985, Phase Equilibria in Chemical Engineer-
ing, Butterworth, Boston.

Margules Equation
Table 2-5: Margules Equation
Required Pure
Component Properties
Vapor pressure Temperature: Use at or near
temperatures where parameters were
fitted
The oldest empirical correlations for liquid activity coefficients,

such as the Margules equation (1895), are derived from simple
polynomial expansions. The most popular form of the Margules
equation was proposed by Redlich and Kister (1948). When that
expansion is truncated after the quadratic term, the resulting three-
parameter correlation is known as the four-suffix Margules equa-
tion. The resulting expression for the activity coefficient is:
Equation (2-208):
ln  i  1  xi   Ai  2  Bi  Ai  Di  xi  3Di xi2 
2
where:
N N
Ai   x j aij / 1  xi  Bi   x j a ji / 1  xi 
j 1 j 1
N
Di   x j dij / 1  xi  dij  d ji
j 1
Thus, for each ij binary pair in a multi-component system, the

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

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

van Laar Equation
Table 2-6: van Laar Equation
Required Pure
Component Properties Application Guidelines
Vapor pressure Components Use for chemically
similar components
Another old correlation which is still frequently used is the van Laar
equation. It may be obtained by discarding ternary and higher order
terms in an alternative expansion of the excess Gibbs energy
(known as Wohl's equation), though that is not how van Laar
derived it originally. The resulting expression for the activity coeffi-
cient is:
Equation (2-209):
N N
1 N N aij
ln  i   ail Z l   aij Z i Z j   a jk Z j Zk
l 1 j 1 2 j 1 k 1 a ji
j ,k l
where:
xl
Zl 
a 
j x j  ail 
 li 
Two parameters, aij and aji, are required for each binary. As with
the Margules equation, no method is included for making the
parameters temperature dependent. It should also be noted that the
van Laar equation, because of its functional form, is incapable of
representing maxima or minima in the relationship between activity
coefficient and mole fraction. In practice, however, such maxima
and minima are relatively rare.
Reference
1 van Laar, J. J., 1910, The Vapor Pressure of Binary Mix-

tures, Z. Phys. Chem., 72, 723-751.
2 Wohl, K., 1946, Thermodynamic Evaluation of Binary and
Ternary Liquid Systems, Trans. AIChE, 42, 215-249.
Also See:

Regular Solution Theory
Table 2-7: Regular Solution Theory
Required Pure
Vapor pressure Components: Not valid for polar
Liquid molar volume  components and solutions
Solubility parameter containing fluorocarbons
Hildebrand defined a regular solution as one in which the excess

entropy vanishes when the solution is mixed at constant tempera-
ture and constant volume. This is nearly the case for most solutions
of nonpolar compounds, provided the molecules do not differ
greatly in size. The excess Gibbs energy is then primarily deter-
mined by the attractive intermolecular forces. Scatchard and Hil-
debrand made a simple assumption relating mixture interactions to
those in pure fluids; the result is a simple theory in which the activ-
ity coefficients are a function of pure-component properties only.
The important property is the solubility parameter, which is related
to the energy required to vaporize a liquid component to an ideal
gas state. The activity coefficient expression is
Equation (2-210):
2
 
RT ln  i  Vi  i    j i 
L
 j 
L
xv
j  j j L
 xk vk
k
where:
Vi L = liquid molar volume of component i
i = solubility parameter of component i
There are no adjustable parameters in regular solution theory. It is

useful for mixtures of nonpolar components, but it should not be
used for highly non-ideal mixtures, especially if they contain polar
components. Solubility parameters have been tabulated for numer-
ous compounds, and these parameters are included for most compo-
nents in PRO/II's library.

Reference
1 Hildebrand, J.H., Prausnitz, J. M. and Scott, R. L., 1970,

Regular and Related Solutions, Van Nostrand Reinhold
Co., New York.
Flory-Huggins Theory
Table 2-8: Flory Huggins Theory
Required Pure
Vapor pressure Components Best for components that
Liquid molar volume  are chemically similar and differ
Solubility parameter only in size (e.g. polymer
solutions)
The Flory-Huggins model may be considered a correction to the

Regular Solution Theory for the entropic effects of mixing mole-
cules which differ greatly in size. It is therefore suitable for poly-
mer/solvent systems, especially if the molecules involved are
nonpolar. In this simplest implementation of the theory, there are no
binary parameters. The activity coefficient expression is:
Equation (2-211):
 vL  vL
ln  i  ln  ireg  ln  iL   1  iL
v  v
where:
 ireg = activity coefficient from regular solution theory
Vi L = liquid molar volume of component i
VL = liquid molar volume of solution
Reference
1 Flory, P. J., 1942, Thermodynamics of Higher Polymer

Solutions, J.Chem.Phys., 10, 51.
2 Huggins, M. L., 1942, Thermodynamic Properties of Solu-
tions of Long Chain Compounds, Ann. N.Y. Acad. Sci., 43,
9.

3 Misovich, M. J., Grulka, E. A., and Banks, R. F., 1985,
Generalized Correlation for Solvent Activities in Polymer
Solutions, Ind. Eng. Chem. Proc. Des. Dev., 24, 1036.
Also See:
Wilson Equation
Table 2-9: Wilson Equation
Required Pure
Vapor pressure Components: Useful for polar or associating
Liquid molar volume components in nonpolar solvents
and for completely miscible liquids
The Wilson equation was the first to incorporate the concept of

“local composition.” The basic idea is that, because of differences
in intermolecular forces, the composition in the neighborhood of a
specific molecule in solution will differ from that of the bulk liquid.
The two parameters per binary are, at least in principle, associated
with the degree to which each molecule can produce a change in the
composition of its local environment. The expression for the activ-
ity coefficient is:
Equation (2-212):
N N
xk Aki
ln  i  1  ln  x j Aij   N
j 1 k 1
x A
j 1
j kj
where:
viL  aij 
Aij  L
exp   (when unit of a ij is K)
vj T 
vL  a 
Aij  iL exp  ij  (when unit of a ij is KCal or KJ)
vj  RT 
Aij  aij (when unit of a ij is NODIME)
L
and v i is the liquid molar volume of component i.
aij represents a characteristic energy of interaction between species
i and j. While there is no explicit temperature dependence in the

Wilson equation's parameters, the derivation is such that the equa-
tion may be used with some confidence over a wider range of tem-
peratures than either the Margules or van Laar equations. It is also
much more successful in correlating mixtures containing polar
components. The Wilson equation cannot describe local maxima or
minima in the activity coefficient. Its single significant shortcom-
ing, however, is that it is mathematically unable to predict the split-
ting of a liquid into two partially miscible phases. It is therefore
completely unsuitable for problems involving liquid-liquid equilib-
ria.
Reference
1 Holmes, M. H. and van Winkle, M., 1970, Wilson Equa-

tion Used to Predict Vapor Compositions, Ind. Eng. Chem.,
62(1), 2231.
2 Orye, R. V. and Prausnitz, J. M., 1965, multi-component
Equilibria with the Wilson Equation, Ind. Eng.Chem.,
57(5), 1826.
3 Wilson, G. M., 1964, Vapor-Liquid Equilibrium XI. A New
Expression for the Excess Free Energy of Mixing, J. Amer.
Chem. Soc., 86, 127.
Also See:
NRTL Equation
Table 2-10: NRTL Equation
Required Pure
Vapor pressure Components: Useful for strongly non-
ideal mixtures and for partially
miscible systems.
The NRTL (non-random two-liquid) equation was developed by

Renon and Prausnitz to make use of the local composition concept,
while avoiding the Wilson equation's inability to predict liquid-liq-
uid phase separation. The resulting equation has been quite success-
ful in correlating a wide variety of systems. The expression for the
activity coefficient is:

Equation (2-213):
 j  ji G ji x j x j G ij  k x k  kj G kj
- +  -------------------   ij – -------------------------
In  i = ---------------------- -
 k G ki x k  k G kj x k   k G kj x k 
j
Equation (2-214):
When unit is K:
b c
 ij = a ij + -----ij + -----ij + d ij InT + e ij T + f ij TInT
T T2
When unit is KCAL or KJ:
b ij c ij
 ij = a ij + ------ - + d ij In  RT  + e ij RT + f ij RTIn  RT 
- + -----------
RT R 2 T 2
G ij = exp  –  ji  ij   ji = ' ji + ' ji T
Three parameters, ij, ji, and ij = ji are required for each binary.
These parameters may be made temperature dependent as described
above. If tij is to be represented with only one constant, it has been
found empirically that better results over a range of temperatures
are obtained if only bij is used and aij = cij = 0. The  parameter
does not vary greatly from binary to binary, and it is often satisfac-
tory to fix it at 0.3 for vapor-liquid systems and 0.2 for liquid-liquid
systems.
Reference
1 Renon, H. and Prausnitz, J. M., 1968, Local Composition

in Thermodynamic Excess Functions for Liquid Mixtures,
AIChE J., 14, 135144.
2 Harris, R. E., 1972, Chem. Eng. Prog., 68(10), 57.
Also See:
UNIQUAC Equation
Table 2-11: UNIQUAC Equation
Required Pure
Component Properties

Vapor pressure Components:Useful for non-electrolyte
van der Waals area mixtures containing polar or
van der Waals volume nonpolar components and for
partially miscible systems
The UNIQUAC (universal quasi-chemical) equation was developed

by Abrams and Prausnitz based on statistical-mechanical consider-
ations and the lattice-based quasi chemical model of Guggenheim.
As in the Wilson and NRTL equations, local compositions are used.
However, local surface-area fractions are the primary composition
variables instead of volume fractions. Each molecule i is character-
ized by a volume parameter ri and a surface-area parameter qi.
The excess Gibbs energy (and therefore the logarithm of the activity
coefficient) is divided into a combinatorial and a residual part. The
combinatorial part depends only on the sizes and shapes of the indi-
vidual molecules; it contains no binary parameters. The residual
part, which accounts for the energetic interactions, has two adjust-
able binary parameters. The UNIQUAC equation has, like the
NRTL equation, been quite successful in correlating a wide variety
of systems. The expression for the activity coefficient is:
Equation (2-215):
ln  i  ln  iC  ln  iR
Equation (2-216):
  z  i  i M
ln  iC  ln  i   qi ln    li  x l
 i
j j
 xi  2  xi j 1
Equation (2-217):
 
  M
 M   
ln  iR  qi 1  ln    j ji    M 
j ij
  k kj 

 j 1  j 1

k 1


where:
 U ij 
 ij  exp    (when the unit is K)
 T 
 U 
 ij  exp   ij  (when the unit is KCal or KJ)
 RT 
xr xq
i  M i i i  M i i
 x j rj
j 1
 x jq j
i 1
Vwi Awi
ri  qi 
15.17 2.5*109
U ij  aij  bijT z  10
z
li   ri  qi    rj  1
2
Awi = van der Waals area of molecule i
Vwi = van der Waals volume of molecule i
Two parameters, Uij and Uji, are required for each binary; they may
be made temperature dependent as described above. If no tempera-
ture dependence is used for Uij, better results over a range of tem-
peratures are normally obtained by using aij and setting bij = 0.
Reference
1 Abrams, D. S. and Prausnitz, J. M., 1975, Statistical Ther-

modynamics of Mixtures: A New Expression for the
Excess Gibbs Free Energy of Partly or Completely Misci-
ble Systems, AIChE J., 21, 116-128.
2 Anderson, T. F. and Prausnitz, J. M., 1978, Application of
the UNIQUAC Equation to Calculation of multi-compo-
nent Phase Equilibria. 1. Vapor-Liquid Equilibria, Ind. Eng.
Chem. Proc. Des. Dev., 17, 552-561.
3 Anderson, T. F. and Prausnitz, J. M., 1978, Application of
the UNIQUAC Equation to Calculation of multi-compo-
nent Phase Equilibria. 2. Liquid Liquid Equilibria, Ind.
Eng. Chem. Proc. Des. Dev., 17, 561-567.

4 Maurer, G. and Prausnitz, J. M., 1978, On the Derivation
and Extension of the UNIQUAC Equation, Fluid Phase
Equilibria, 2, 91-99.
Also See:
UNIFAC
Required Pure
Vapor Pressure Pressure up to 100 atmospheres
van der Waals area Temperature 32 300F
van der Waals volume
Components: All components well below
their critical points
The UNIFAC (universal functional activity coefficient) method was

developed in 1975 by Fredenslund, Jones, and Prausnitz. This
method estimates activity coefficients based on the group contribu-
tion concept following the Analytical Solution of Groups (ASOG)
model proposed by Derr and Deal in 1969. Interactions between
two molecules are assumed to be a function of group-group interac-
tions. Whereas there are thousands of chemical compounds of inter-
est in chemical processing, the number of functional groups is much
smaller. Group-group interaction data are obtained from reduction
of experimental data for binary component pairs.
The UNIFAC method is based on the UNIQUAC model which rep-
resents the excess Gibbs energy (and logarithm of the activity coef-
ficient) as a combination of two effects. Equation (2-215) on page
143 is therefore used:
ln  i  ln  iC  ln  iR
The combinational term,  iC , is computed directly from the UNI-

QUAC equation (2-216) on page 143 using the van der Waals area
and volume parameter calculated from the individual structural
groups:
  z  i  i M
ln  iC  ln  i   qi ln    li  x l
 i
j j
 xi  2  xi j 1

where:
xi ri xi qi
i  NOG
i  NOG
xr
j 1
j j xq
j 1
j j
z
li   ri  qi    rj  1
2
NOG NOG
ri   vki Rk
k 1
qi  v Q
k 1
i
k k
where:
NOC = number of components
NOG = number of different groups in the mixture
z = lattice coordination number = 10
 ki = number of functional groups of type k in molecule i
Rk = volume parameter of functional group k
Qk = area parameter of functional group k
xi = mole fraction of component i in the liquid phase
The group volume and area parameters are obtained from the
atomic and molecular structure.
Equation (2-218):
Vwk
Rk 
15.17
Equation (2-219):
Awk
Qk 
2.5*109
where:
Vwk = van der Waals volume of group k
Awk = van der Waals area of group k
The residual term, ln  i , is given by:

R

Equation (2-220):
NOG
ln  iR    ln 
k 1
k  ln ik 
where:
 k = residual activity coefficient of group k in the mixture
ik = residual activity coefficient of group k in a reference solu-
tion containing only molecules of group type i. This quantity is
required so that:
 iR  1 as xi  1
The residual activity coefficient is given by:
Equation (2-221):
 
    m 
ln  k  Qk 1  ln    m mk   
  m  m   n nm 
 n 
where: m, n = 1, 2, ... NOG

The parameter mk is given by
Equation (2-222):
 amk 
 mk  exp   
 RT 
where:
amk = binary interaction parameter for groups m and k
The binary energy interaction parameter amk is assumed to be a

constant and not a function of temperature. A large number of inter-
action parameters between structural groups, as well as group size
and shape parameters have been incorporated into PRO/II.
Reference
1 Derr, E.L., and Deal, C.H., 1969, Inst. Chem. Eng. Symp.
Ser., 32(3), 40.
2 Fredenslund, Aa., Jones, R.L., and Prausnitz, J.M., 1975,
Group Contribution Estimation of Activity Coefficients in
non-ideal Liquid Mixtures, AIChE J., 27, 1086-1099.

3 Skjold-Jørgensen, S., Kolbe, B., Groehling, J., and Rasmus-
sen, P., 1979, Vapor-Liquid Equilibria by UNIFAC Group
Contribution. Revision and Extension, Ind. Eng. Chem.
Proc. Des. Dev., 18(4), 714-722.
4 Gmehling, J., Rasmussen, P., and Fredenslund, Aa., 1983,
Vapor-Liquid Equilibria by UNIFAC Group Contribution.
Revision and Extension, Ind. Eng. Chem. Proc. Des. Dev.,
22(10), 676-678.
5 Hansen, H.K., Rasmussen, P., Fredenslund, Aa., Schiller,
M., and Gmehling, J., 1991, Vapor-Liquid Equilibria by
UNIFAC Group Contribution. 5. Revision and Extension,
Ind. Eng. Chem. Res., 30(10), 2352-2355.
Also See:
Modifications to UNIFAC
The UNIFAC method provides good order-of-magnitude estimates.
The accuracy of the method can be improved by incorporating a
temperature-dependent form for the binary group energy interaction
parameter.
UFT1 Lyngby modified UNIFAC

Researchers at Lyngby developed a three-parameter temperature
dependent form for the binary interaction parameter. The parameter
mk is now given by:
Equation (2-223):
 Amk 
 mk  exp   
 RT 
Equation (2-224):
 T 
Amk  amk  bmk T  To   cmk  T ln o  T  To 
 T 
where:
amk , bmk , cmk = binary interaction parameters
To = 298.15 K

The combinatorial part of the logarithm of the activity coefficient is
given by:
Equation (2-225):
wi w
ln  ic  ln 1 i
xi xi
Equation (2-226):
ri 2/3 xi
wi  NOG
r
i 1
i
2/3
xi
Reference
1 Larsen, B.L., Rasmussen, P., and Fredenslund, Aa., 1987, A

Modified UNIFAC Group Contribution Model for Predic-
tion of Phase Equilibria and Heats of Mixing, Ind. Eng.
Chem. Res., 26(11), 2274-2286.
UFT2 Dortmund modified UNIFAC

For this modified method, the temperature-dependent form of Amk
is given by:
Equation (2-227):
Amk  amk  bmk T  cmk T 2
The combinational part of the logarithm of the activity coefficient is

given by:
Equation (2-228):
wi w zq  ln i  
ln  ic  ln 1 i  i  1 i 
xi xi 2  i Qi 
Equation (2-229):
ri3/4 xi
wi  NOG
r
i 1
i
3/4
xi
where:
z = lattice coordination number = 10

xi ri xi qi
i  NOG
i  NOG
xr
j 1
j j xq
j 1
j j
Reference
1 Weidlich, V., and Gmehling, J., 1987, A Modified UNIFAC

Model. 1. Prediction of VLE, hE, and , Ind. Eng. Chem.
Res., 26, 1372-1381.
2 Gmehling, J., Li, J., and Schiller, M., 1993, "A Modified
UNIFAC Model. 2. Present Parameter Matrix and Results
for Different Thermodynamic Properties,” Ind. Eng. Chem
Res., 32(1) 178.
3 Gmehling, J., Lohmann, J., Jakob, A., Li, J., Joh, R., 1998,
“A Modified UNIFAC Model. 3. Revision and Extension,”
Ind. Eng. Chem Res., 37,4876.
UFT3
For this modified UNIFAC method, the temperature-dependent
form of Amk is given by:
Equation (2-230):
Amk  amk  bmk T  cmk T 2
The combinatorial and residual parts of the activity coefficient are

identical to those described previously for the UNIFAC method.
Reference
1 Torres-Marchal, C., and Cantalino, A.L., 1986, Industrial

Applications of UNIFAC, Fluid Phase Equil., 29, 69-76.
UNFV - Free volume modification to UNIFAC

This method was developed for modeling polymer systems. The
liquid activity coefficient is given by a combination of the same
combinatorial and residual terms as UNIFAC, plus a free volume
effect term:
ln  i  ln  iC  ln  iR  ln  iFV

Equation (2-232):
 V 1/3
i 1
  V   1 
ln  FV
 3Ci ln  1/3   Ci  i  1 / 1  1/3  
i
 
 V m 1   Vm   V i  
where:
Vwi 1 NOG i
Vi 
15.17bri
ri  vk Rk
Mi k1
i i Vj wj
Vw
Vm  b 1.28
15.17b rw
i i  rj wj 
where:
Vi = volume per gram of solvent i
Mi = molecular weight of solvent i
wi = weight fraction of component i
Ci = number of effective degrees of freedom per molecule of

solvent i = 3.3
Reference
1 Oishi, T., and Prausnitz, J.M., 1978, Estimation of Solvent

Activities in Polymer Solutions Using a Group Contribu-
tion Method, Ind. Eng. Chem. Proc. Des. Dev., 17(3), 333-
339.
Also See:
Fill Options
The ability of a liquid activity method to accurately predict vapor-
liquid equilibria and/or vapor-liquid-liquid equilibria depends to a
great degree on whether or not binary interaction parameters are
available for that method. PRO/II contains a proven mechanism for
filling in missing binary interaction parameters for liquid activity
methods. When a liquid activity method such as NRTL is selected
for phase equilibrium calculations, and the FILL option is selected,
PRO/II uses the following mechanism in order to obtain the binary
interaction data the model needs:

1 Any user-supplied binary interaction parameters, or mutual
solubility, infinite dilution, or azeotropic data are used in
preference to any other data.
2 The VLE and LLE databanks which contain binary interac-
tion parameters are then searched for data.
3 The SimSci azeotropic databank is searched for appropriate
azeotropic data, which are then regressed to provide binary
interaction data.
4 For VLE calculations, if steps 1 through 3 do not supply the
required parameters, then the group contribution methods
UNIFAC or its modification UFT1, or the regular solution
method, or the Flory-Huggins or CIUNIFAC method may
be used to provide estimates for the interaction parameters.
For LLE calculations, UNIFAC or CIUNIFAC or the modi-
fied UNIFAC method UFT1 is used to supply the parame-
ter estimates.
5 Finally, if binary interaction parameters are still missing
after steps 1-4 are followed, then all missing parameters are
set equal to zero.
Figure shows the mechanism used by PRO/II to backfill missing
binary parameters for VLE, or VLLE calculations.

Figure 2-1: Flowchart for FILL Methods

For VLLE calculations, in order to avoid conflicts between VLE
and LLE binary interaction data, PRO/II follows a number of strict
rules when filling in these binary interaction data.
 If no VLE or LLE interaction data are supplied by the user,
PRO/II uses the following order in searching for interaction
data for both VLE and LLE calculations:
 If the user supplies VLE interaction data only, then PRO/II uses
the following order in searching for binary parameters for both
VLE and LLE calculations:
 The user-supplied values given on the KVALUE(VLE)
statement
LLE interaction data, for LLE calculations, the databanks are
 The user-supplied data given on the KVALUE(LLE) state-
ment
LLE interaction data, for VLE calculations, the databanks are
 The user-supplied data given on the KVALUE(VLE) state-
ment
Also See:

Henry's Law
When liquid activity methods are used, the standard-state fugacity
for a component is the fugacity of the pure liquid. This standard
state is not convenient, however, for dissolved gases, especially if
the temperature is above the critical temperature of the solute in
question. For super-critical gases, and also for trace solutes such as
organic pollutants in water, it is more convenient to use a standard
state defined at infinite dilution. This standard-state fugacity is the
Henry's constant.
Thermodynamically, the Henry's constant of a solute i in a solvent j
is defined as the infinite-dilution limit of the ratio of the fugacity to
the mole fraction:
Equation (2-233):
fi
H ij  lim
xi  0 x
x 1 i
j
Unless the pressure is high or there is vapor-phase association, the

fugacity fi can be replaced by the partial pressure yiP. The K-value
can then be expressed as:
Equation (2-234):
H ij
Ki 
P
This relationship is strictly true only in the infinite-dilution limit,
but K-values from Henry's law generally remain accurate at solute
mole fractions up to approximately five percent.
PRO/II correlates Henry's constants to the following functional
form:
Equation (2-235):
C2
ln H ij  C1   C3 ln T  C4 P
T
The temperature dependence in equation (2-232) is that expected
from a thermodynamic analysis provided the solvent's critical point
is not approached too closely. Thermodynamics also predicts that
the effect of pressure on the effective Henry's constant at conditions
beyond infinite dilution is linear in pressure (with C4 proportional
to the solute's partial molar volume). The pressure correction is neg-

ligible at low and moderate pressures; if the pressure is sufficiently
high for that term to become important it is likely that better results
could be obtained by an equation of state with an advanced mixing
rule.
When the HENRY option is specified, components with critical
temperatures below 400 K are automatically designated as solute
components by PRO/II. The user may, however, override these des-
ignations as desired. PRO/II has an extensive databank of Henry's
constants for super-critical gases in various solvents and also for
many organic compounds in water. Henry's constants may also be
input by the user. If no Henry's constant is given for a solute, PRO/
II substitutes the solute's vapor pressure (extrapolated if necessary).
This substitution is good only for nearly ideal solutions. In particu-
lar if no Henry's constant is available for an organic solute in water
it is better to remove the organic from the list of solutes and allow
the liquid activity method (with interaction parameters filled in via
UNIFAC if necessary) to compute the K-value.
Note: The temperature dependence of Henry's constants is very

important. Especially for organic solutes in water, often only a sin-
gle value at 25 C is reported. Calculations using this input value at
significantly different temperatures (for example, steam stripping
near 100 C) are likely to produce unrealistic answers (for example,
drastically overestimating the amount of steam required). In such
cases, the user can obtain a better answer by assuming that the tem-
perature dependence of the solute's Henry's constant is the same as
for its vapor pressure. The slope of ln Psat versus 1/T becomes C2
in equation (2-233), and (with C3=C4=0) the 25 C point can then be
used to solve for C1.
The Henry's constant of a solute in a mixture of solvents is com-

puted from the following mixing rule:
Equation (2-236):
n
ln H i , mix   x j ln H ij
j 1
where the sum is taken over all solute species j, and the mole frac-
tions xj used in the sum are computed on a solute-free basis.

Reference
1 Prausnitz, J.M., Lichtenthaler, R.N., and Gomes de Aze-

vedo, E., 1986, Molecular Thermodynamics of Fluid Phase
Equilibria, 2nd edition, Prentice Hall, Englewood Cliffs,
NJ, Chapter 8.
Also See:

For many liquid mixtures, the enthalpy may be accurately approxi-
mately as a mole fraction sum of pure-component enthalpies (see
Ideal in Section, Generalized Correlations). For some systems,
however, the excess enthalpy, or heat of mixing, is not negligible
and should be accounted for if accurate prediction of the liquid
enthalpy is important. It should be noted that SimSci's equations of
state and generalized correlations produce a heat of mixing as a nat-
ural part of their calculations. Therefore, explicit calculation of the
heat of mixing is only used in conjunction with the IDEAL method
for liquid enthalpy, which is normally used with liquid activity
coefficient K-value methods.
Gamma Method
Thermodynamics allows the excess enthalpy to be computed
directly from the activity coefficients in a mixture and their temper-
ature dependence. This is known as the GAMMA option, and the
equation is:
Equation (2-237):
ex  – RT 2 In
------------i
H =  i
x
T 
i
where: 
Hex = excess heat of mixing
Despite the attractiveness of this direct thermodynamic computa-
tion, experience has shown that the activity-coefficient parameters
which correlate phase equilibria do not in general produce very
accurate values for excess enthalpies. GAMMA is a viable option
when no other method is available, but the resulting heats of mixing
may only be accurate to within a factor of two.
Also See:

Redlich-KisterExpansion
Experimental data for heats of mixing for binary systems are most
often represented by an expansion about an equi-molar mixture:

Equation (2-238):
H ex  a12  b12 X  c12 X 2  d12 X 3  e12 X 4  f12 X 5  g12 X 6  h12 X 7
where:
X = x1 - x2
In equation (2-238), known as the Redlich-Kister expansion, 12

represents the excess enthalpy of a 50-50 binary mixture. Higher-
order terms correlate asymmetry in the curve of excess enthalpy
versus composition.
SimSci's databanks contain regressed values of the coefficients in
equation (2-238) for approximately 2200 binary mixtures. In addi-
tion, these parameters may be regressed to heat-of-mixing data with
SimSci's REGRESS program (now available through the Thermo
Data Manager) and then entered through input by the user.
The empirical nature of the Redlich-Kister expansion means that
there is some degree of arbitrariness in the way it is extended to
mixtures. SimSci offers two options, known as RK1 and RK2. Both
have the same basic form:
Equation (2-239):
 aij  bij X  cij X 2  d ij X 3  eij X 4 

H ex
  xi x j  
 f X5  g X 6  h X 7 
i j
 ij ij ij 
where:
X  xi  x j (form RK1)
xi  x j
X (form RK2)
xi  x j
Note: Which mixture rule is better for a multi-component system

(they are equivalent for binaries) depends upon the system, and

there are no general guidelines. RK2 is, however, somewhat prefer-
able from the standpoint of theoretical consistency.
Also See:
Special Packages
General Information
Alcohol Package (ALCOHOL)
Glycol Package (GLYCOL)
Sour Package (SOUR)
GPA Sour Water Package (GPSWATER)
Amine Package (AMINE)
General Information
PRO/II contains a number of thermodynamic methods specifically
developed for special industrial applications. Data packages are
available for the following applications:
 Alcohol systems
 Glycol systems
 Sour water systems
 Amine systems
For many applications, databanks containing binary interactions
specifically regressed for components commonly found in the
application have been developed and incorporated into PRO/II. For
example, for alcohol systems, a special alcohol databank, in combi-
nation with the NRTL K-value method is used to calculate the K-
values. For other applications, such as the SOUR or GPSWAT
method for sour systems containing NH3, H2S, CO2, and H2O, a
K-value method has been specifically developed for phase equilib-
rium calculations.
Alcohol Package (ALCOHOL)

The alcohol data package uses the NRTL liquid activity method to
calculate phase equilibria (see Section, Liquid Activity Methods).
This system uses a special set of NRTL binary interaction data for

systems containing alcohols, water, and other polar components.
The binary parameters have been obtained by the regression of
experimental data for alcohol systems. The recommended tempera-
ture and pressure ranges for the ALCOHOL data package are as fol-
lows:
Temperature:
122-230 oF for H2O-alcohol systems
150-230 oF for all other systems
The vapor enthalpy and density and the vapor and liquid entropies
are calculated using the SRKM equation of state (see Section,
Equations of State), while the liquid enthalpy and density are calcu-
lated using ideal methods (see Section, Generalized Correlation
Methods).
Table 2-13 shows the components present in the ALCOHOL data-
bank for which there are binary interaction parameters available.
Figure 2-2 on page 2-162 shows the availability of binary interac-
tion data in the Alcohol data bank.
Table 2-13: Components Available for ALCOHOL

Package
Components Formula LIBID
Miscellaneous
Acetaldehyde C2H4O ACH
Sulfolane C4H8O2SH2S SULFLN
Light Gases
Hydrogen H2 H2
Nitrogen N2 N2
Oxygen O2 O2
Carbon Dioxide CO2 CO2
Hydrocarbons  
Isopentane C5H12 IC5

Table 2-13: Components Available for ALCOHOL
Package
N-pentane C5H12 NC5
Cyclopentane C5H10 CP
2 Methylpentane C6H14 2MP
1-Hexene C6H12 1HEXENE
N-Hexane C6H14 NC6
Methylcyclopentane C6H12 MCP
Benzene C6H6 C6H6
Cyclohexane C6H12 CH
2-4 Dimethylpentane C7H16 24DMP
3-Methylhexane C7H16 3MHX
1-Trans-2-Dimethyl-
cyclopentane C7H14 1T2MCP
n-heptane C7H16 NC7
Methylcyclohexane C7H14 MCH
Toluene C7H8 TOLU
2-4 Dimethylhexane C8H10 24DMHX
1-Trans-2-Cis-4-Tri-
methylcyclopentane C8H10 1T2C4MCP

Figure 2-2: Binary Interaction Data in the Alcohol Databank

Figure 2-3: Alcohol Binary Interaction Data (Continued)
Figure 2-4: Alcohol Binary Interaction Data (Continued)

The glycol data package uses the SRKM equation of state to calcu-
late phase equilibria for glycol dehydration applications (see Sec-
tion, Equations of State).
Table 2-14 shows the components present in the GLYCOL databank
for which there are binary interaction parameters available.
Table 2-14: Components Available for GLYCOL Package

Components Formula LIBID
Hydrogen H2 H2
Nitrogen N2 N2
Oxygen O2 O2
Carbon Dioxide CO2 CO2
Hydrogen Sulfide H2S H2S
Methane CH4 C1
Ethane C2H6 C2
Propane C3H8 C3
Isobutane C4H10 IC4
N-butane C4H10 NC4
Isopentane C5H12 IC5
Pentane C5H12 NC5
Hexane C6H14 NC6
Heptane C7H16 NC7
Cyclohexane C6H12 CH
Methylcyclohexane C7H14 MCH
Ethylcyclohexane C8H16 ECH
Benzene C6H6 BNZN
Toluene C7H8 TOLU
O-xylene C8H10 OXYL
M-xylene C8H10 MXYL
P-xylene C8H10 PXYL
Ethylbenzene C8H10 EBZN
Ethylene Glycol C2H6O2 EG
Diethylene Glycol C4H10O3 DEG
Triethylene Glycol C6H14O4 TEG
Water H2O H2O
This system uses a special set of SRKM binary interaction data and
alpha parameters for systems containing glycols, water, and other
components. The binary parameters and alpha parameters have
been obtained by the regression of experimental data for glycol sys-
tems.
Figure 2-5 shows the binary interaction parameters, denoted by
"x", present in the glycol databank.

Interaction parameters denoted by "o" are supplied from the SRK
databank. It should be noted that for all pairs not denoted by "x" or
"o", the missing binary interaction parameters are estimated using a
molecular weight correlation, or are set equal to 0.0.
Figure 2-5: Binary Interaction Data in the Glycol Databank
Other thermodynamic properties such as the vapor and liquid

enthalpy, entropy, and vapor density are calculated using the SRKM
equation of state, while the liquid density is calculated using the
API method (see Section, Generalized Correlation Methods).
The recommended temperature and pressure ranges for the GLY-
COL package are:

Temperature: 80-400 F
Also See:
Special Packages
Sour Package (SOUR)

This sour water package uses the SWEQ (Sour Water EQuilibrium)
method developed by Wilson for a joint API/EPA project. Phase
equilibria for sour water components NH3, H2S, CO2, and H2O are
modeled using a modified van Krevelen approach. The van Krev-
elen model assumes that H2S and CO2 only exist in solution as ion-
ized species. This is only true for solutions containing an excess of
NH3 or other basic gas. This limitation has been removed in the
SWEQ method by considering the chemical equilibrium between
ionic species of H2S or CO2 and their undissociated molecules in
the liquid phase.
In the SWEQ model, the partial pressure in the vapor phase for H2S
or CO2 is given by:
Equation (2-240):
pH 2 S  H H 2 S * CH 2 S
Equation (2-241):
pCO2  H CO2 * CCO2
where:
pi = partial pressure of component i
Hi = Henry's Law constant for component i in water
Ci = concentration of component i in the liquid phase, gmoles/

kg solution
The SWEQ model uses Henry's Law constants for each component
in solution as a function of temperature and composition of the
undissociated molecular species in the liquid phase. The Henry's
constants for H2S and CO2 were obtained from data published by
Kent and Eisenberg who developed a model for predicting H2S-
CO2-MEA-H2O and H2S-CO2-DEA-H2O systems. The Henry's
Law constants used in the SWEQ model for equations (2-240) and
(2-241) are:

Equation (2-242):
 
ln H CO2  18.33  2.48951*104 / T  2.23996*107 / T 2
 9.0918*109 / T 3  1.2601*1012 / T 4
Equation (2-243):
 
ln H H 2 S  100.684  2.46254*105 / T  2.3902*108 / T 2
 1.01898*1011 / T 3  1.5973*1013 / T4
 5.0*102 CNH3   0.965  486 / T  CCO2
where:
T = system temperature, degrees Rankine
The Henry's Law constant for water was obtained by correlating
H2O vapor pressure data from the A.S.M.E. steam tables over the
range 25 C to 150 C:
Equation (2-244):
 
ln H H 2O  14.466  6.9966*103 / T  77.67 
The Henry's Law constant for NH3 was taken from data published
by Edwards et al.:
Equation (2-245):
ln  NH 3   178.339  1.55179*104 / T  25.6767 ln T 

 1.966*102 T  131.4 / T  0.1682  CNH3

 6.0*102 2CCO2  CH 2 S 
The chemical equilibria of all the main reactions in the liquid phase
due to the dissociation of the sour gas molecules are considered in
the model. The reaction equilibrium constants, Ki, are correlated as
functions of temperature, composition of undissociated sour gas
molecules in the liquid phase, and ionic strength. 
ln K i  ln K io aCH 2 S  bCCO2  cI 0.4
where:
Ki = equilibrium constant of reaction i

= equilibrium constant at infinite dilution for all species
K io
a,b,c = constants
1
I = ionic strength =  C j Z 2j
2 j
Zj = ionic charge of species j
The reaction equilibrium constants at infinite dilution, K io, are given

in the form first proposed by Kent and Eisenberg:
Equation (2-246):
ln K io  A  B / T  C / T 2  D / T 3  E / T 4
where:
A, B, C, D, E = constants
The constants used in the SWEQ model for equations () and (2-
246), obtained by the regression of experimental data, are given in
the original EPA report. The original SWEQ method was developed
for pressures less than 50 psia where non-idealities in the vapor
phase are not important. Corrections for vapor-phase non-idealities
using SRKM have been incorporated PRO/II, thus extending the
applicable pressure range to 1500 psia.
The phase behavior of all other components present in the system is
modeled using the SRKM equation of state (see Section, Equations
of State). The following limits apply to the SOUR method as imple-
mented in PRO/II:
Composition: wNH 3  wCO2  wH 2 S  0.30
where: wi = weight fraction of component i
Note: NH3 and water must be present when using the SOUR
method.
Other thermodynamic properties such as the vapor enthalpy, vapor

and liquid entropy, and vapor density are calculated using the
SRKM equation of state, while the liquid enthalpy and density are
calculated using ideal methods (see Section, Generalized Correla-
tion Methods).

Reference
1 Wilson, G. M., 1980, A New Correlation for NH3, CO2,

H2S Volatility Data from Aqueous Sour Water Systems,
EPA Report EPA-600/2-80-067.
2 van Krevelen, D. W., Hoftijzer, P. J., and Huntjens, F. J.,
1949, Rec. Trav. Chim., 68, 191-216.
3 Black, C., 1958, Vapor Phase Imperfections in Vapor-Liq-
uid Equilibria, Ind. Eng. Chem., 50(3), 391-402.
4 Kent, R. L., and Eisenberg, B., 1976, Better Data for Amine
Treating, Hydrocarbon Processing, Feb., 87-90.
5 Handbook of Chemistry and Physics, 1971, 51st Edition,
The Chemical Rubber Co.
6 Edwards, T. J., Newman, J., and Prausnitz, J. M., 1975,
Thermodynamics of Aqueous Solutions Containing Vola-
tile Weak Electrolytes, AIChE J., 21, 248-259.
Also See:
Special Packages

This sour water package uses the method developed by the Gas Pro-
cessors Association in 1990 for sour water systems containing com-
ponents NH3, H2S, CO2, CO, CS2, MeSH, EtSH, and H2O. This
model uses the SWEQ model (see above) as a precursor, extending
the temperature range of applicability to 600 F. The total pressure
limit is increased to 2000 psia by allowing for vapor phase non-ide-
alities, and accounting for pressure effects in the liquid phase using
a Poynting correction factor.
As in the SWEQ model, the chemical equilibria for all the reactions
involving the NH3, H2S, CO2, CO, methyl mercaptan (MeSH), and
ethyl mercaptan (EtSH) in water are considered. The components
CO, methyl mercaptan (MeSH), and ethyl mercaptan (EtSH) are

treated as Henry's Law components (see Section, Liquid Activity
Methods) Reactions considered include:
Water:
Equation (2-247):
Ammonia:
Equation (2-248):
Hydrogen Sulfide:
Equation (2-249):
Bisulfide:
Equation (2-250):
Carbon Dioxide:
Equation (2-251):
Bicarbonate:
Equation (2-252):
Carbon Dioxide and Ammonia:

Equation (2-253):
Equation (2-254):

Equation (2-255):
The chemical equilibrium constants, Ki, are correlated as functions

of temperature and composition. In addition, the effect of inert
gases such as N2 and H2 on phase equilibria is also considered. In
the liquid phase, pressure effects are accounted for by the use of a
Poynting correction factor, and electrostatic effects are incorporated
into the calculated liquid activity coefficients.
Vapor-phase non-idealities are computed using a truncated virial
equation of state. The virial equation used is truncated after the
third virial coefficient as follows:
Equation (2-256):
z  1  B / v  C / v2
where:
B, C are the second and third virial coefficients
v = molar volume
z = compressibility factor
Phase equilibria for all other components present in the system are
modeled using the SRKM equation of state (see Section, Equations
of State).
The following limits apply to the GPSWATER method:
Composition: wNH3 < 0.40
PCO2  PH 2 S  1200 psia

where:
wi = weight fraction of component i
pi = partial pressure of component i in the vapor phase
Note: NH3, CO2, H2S, and water must be present when using the
GPSWATER method.

Other thermodynamic properties such as the vapor enthalpy, vapor
and liquid entropy, and vapor density are calculated using the
SRKM equation of state, while the liquid enthalpy and density are
calculated using ideal methods (see Section, Generalized Correla-
tion Methods).
Reference
1 Wilson, G. M., and Eng, W. W. Y., 1990, GPSWAT: GPA

Sour Water Equilibria Correlation and Computer Program,
GPA Research Report RR-118, Gas Processors Associa-
tion.
Also See:
Special Packages

The PRO/II simulation program contains a method to model the
removal of H2S and CO2 from natural gas feeds using alkanol-
amines. Alkanolamines are formed by ammonia reacting with an
alcohol. Amines are considered to be either primary, secondary, or
tertiary, depending on whether 1 or 2 or 3 of the hydrogen atoms
have been replaced on the ammonia molecule. PRO/II provides data
for the primary amines monoethanolamine (MEA), secondary
amines diethanolamine (DEA), diglycolamine (DGA), and diiso-
propanolamine (DIPA), and the tertiary amine methyldiethanol-
amine (MDEA). MEA and DEA are the most frequently used
amines in industry.
In aqueous solutions, H2S and CO2 react in an acid-base buffer
mechanism with alkanolamines. The acid-base equilibrium reac-
tions are written as chemical dissociations following the approach
taken by Kent and Eisenberg:
Water:
Equation (2-257):
Hydrogen Sulfide:
Equation (2-258):

Bisulfide:
Equation (2-259):
Carbon Dioxide:
Equation (2-260):
Bicarbonate:
Equation (2-261):
Alkanolamine:
Equation (2-262):
where:
Ki = equilibrium constant for reaction i
RR’NR” = alkanolamine
R represents an alkyl group, alkanol, or hydrogen
In addition to the acid-base reactions above, CO2 also reacts
directly with primary and secondary alkanolamines to form a stable
carbamate, which can revert to form bicarbonate ions.
Carbamate Reversion to Bicarbonate:
Equation (2-263):
Tertiary amines such as MDEA are not known to form stable carba-
mates. In an aqueous solution with MDEA, CO2 forms bicarbonate
ions by reaction (22) only.
Note: CO2, H2O, and H2S must be present when using the AMINE
method.

The chemical equilibrium constants, Ki, are represented by the fol-
lowing equation:
Equation (2-264):
ln K i  A  B / T  C / T 2  D / T 3
The equilibrium constant for the protonated amine dissociation

reaction given in reaction (24) is corrected to the pure amine refer-
ence state. This is done by relating the constant to the infinite-dilu-
tion activity coefficient of the amine in water estimated from
experimental data for the system amine-water.
The liquid enthalpy is calculated using ideal methods and adding a
correction for the heat of reaction as follows using either a modified
Clausius-Clapeyron equation or fits of data from the Gas Processors
Association:
Equation (2-265):
 
H r  ln KT1 / KT2 R / 1/ T1  1/ T2 
where:
Hr = heat of reaction
R = gas constant
KT1, KT2 = K-values at temperatures T1 and T2
The vapor phase enthalpy and density, and liquid and vapor phase
entropy are calculated using the SRKM equation of state (see Sec-
tion, Equations of State). Ideal methods are used to calculate the liq-
uid-phase density (see Section, Generalized Correlation Methods).
For MEA and DEA systems, data have been regressed from a large
number of sources, resulting in good prediction of phase equilibria
for these systems. For systems containing DIPA, a limited amount
of experimental data was available, and so the DIPA results are not
recommended for final design purposes. For MDEA and DGA sys-
tems, the user is allowed to input a residence time correction to
allow the simulation results to more closely match plant data. The
following application ranges are suggested for amine systems:
Table 2-15: Application Guidelines for Amine Systems

MEA DEA DGA MDEA DIPA

Table 2-15: Application Guidelines for Amine Systems
Pressure, 25-500 100-1000 100-1000 100- 100-
psig 1000 1000
Temperat <275 <275 <275 <275 <275
ure, F
Concentra ~15-25 ~25-35 ~55-65 ~50 ~30
tion, wt %
amine
Acid gas 0.5-0.6 0.45 0.50 0.4 0.4
loading,
gmole
gas/gmole
amine
Reference
1 Kent, R. L., and Eisenberg, B., 1976, Better Data for Amine
Treating, Hydrocarbon Processing, Feb., 87-90.
2 Maddox, R. N., Vaz, R. N., and Mains, G. J., 1981, Ethanol-
amine Process Simulated by Rigorous Calculation, Hydro-
carbon Processing, 60, 139-142.
Related Topics:
Sour Package (SOUR)
Also See:
Special Packages
Electrolyte Methods
Electrolyte Mathematical Model
Electrolyte Thermodynamic Equations
Electrolyte Mathematical Model

Discussion of Equations

Modeling Example
Discussion of Equations
The mathematical model employed in PRO/II Electrolytes is a
deterministic set of nonlinear algebraic equations. The equation set
always includes equilibrium expressions and an electroneutrality
equation. These are discussed below. It also may include additional
equations for liquid-liquid equilibria.
Equilibrium Expressions
For each vapor-liquid, liquid-liquid, solid-liquid, and liquid intra-
phase equilibrium, there is an equation of the form:
Equation (2-266):
    m  
niP niP
iP iP 
K iP
      
niR niR
 m
iR
 iR iR 
where:
K = thermodynamic equilibrium constant: a function of tem-
perature and pressure
 iP ,  iR =activity coefficient or, for vapors, fugacity coefficient
of the ith product and reactant, respectively; a function of tem-
perature, pressure, and composition
niP , niR =stoichiometric coefficient of the ith product and reac-
tant, respectively
miP , miR =molality or, for vapors, partial pressure of the ith
product and reactant, respectively.
Note: When H2O (the solvent) appears in the equilibrium expres-

sion, its contribution is expressed as aH2O, the activity of water.
All pure solid component activities are assumed to be one. The
fugacity coefficient, i is defined as fi/yiP or fi/Pi, where f denotes
fugacity, P represents total pressure, and Pi stands for partial pres-
sure. The adopted convention is that i approaches one as total pres-
sure approaches zero. The activity ai is given by imi, where i

approaches one as the molality of all solutes approaches zero.
Note: Equilibrium constants often are written entirely in terms of

fugacities, in which case thermodynamics requires that K is a func-
tion of temperature only. When activities are used instead of fugac-
ities , as in the present treatment, then K is affected by the choice
of standard state. Since the standard state for solutes is infinite dilu-
tion in H2O, a pressure dependence is introduced from the pressure
dependence of the water properties. This effect is negligible except
at conditions approaching water's critical point. Consequently, over
the temperature and pressure validity range for the electrolyte ther-
modynamic methods (0-200 C; 0-200 atm), K is treated only as a
function of temperature.
An electroneutrality equation
Equation (2-267):
NC NA
Z
i 1
i mi   Z i mi
i 1
where:
Zi = species charge
NC, NA = number of cations and anions, respectively
Equations For a Second Liquid Phase

(liquid-liquid equilibrium)
Equation (2-268):
aiA  aiO i  1, NM
where:
ai = activity of ith species.
A, O = represent aqueous and organic phases, respectively.

NM = number of molecular species distributing between
phases.
Note: The required number of material balances, i.e. NB, completes

the model and assures that the number of equations and the number
of unknowns are equal. Normally these balances include an overall,

a vapor phase, an organic phase, and several component balances.
Thus, assuming NK equilibrium equations, the model has NK + NB

+ NM + 1 equations. The customary unknowns are:
 The moles of H2O in the aqueous liquid phase plus all ionic
and molecular species molalities.
 The vapor phase: species mole fractions plus overall vapor
fraction.
 The organic liquid phase: species mole fractions plus overall
organic phase fraction (if second liquid phase is present).
 The solid phase composition: moles precipitated for all solid
species.
As noted above, the number of NB equations required is that num-
ber which assures that the number of equations equals the overall
number of unknowns. This is a natural consequence of the phase
rule.
Also See:
General Information
Modeling Example
To better understand this modeling concept, consider the aqueous
system represented by H2O-CO2-NACL. The reactions considered
will be:
Equation (2-269):
H 2Ovap  H 2O
Equation (2-270):
CO2 vap  CO2 aq

Equation (2-271):
H 2Oaq  H 1  OH 1
Equation (2-272):
CO2 aq  H 2Oaq  H 1  HCO31

Equation (2-273):
NaCl ppt  Na 1  Cl 1

Equation (2-274):
NaCl ppt  Na 1  Cl 1
Based upon the general model described earlier, this leads to:
Equilibrium Expressions
Equation (2-275):
H O
K H 2Ovap  2
H Ovap yH Ovap P
2 2
Equation (2-276):
 CO aq mCO aq
K CO2vap  2 2
H Ovap yH Ovap P
2 2
Equation (2-277):
 H mH  OH mOH
1 1 1 1
K H 2Oaq 
a H 2O
Equation (2-278):
 H mH  HCO mHCO
1 1 1 1
K CO2 aq  3 3
 CO aq mCO aq aH O
2 2 2
Equation (2-279):
 Na mNa  Cl mCl
1 1 1 1
K NaClppt 
aNaClppt
Electro-neutrality Equation
Equation (2-280):
mH 1  mNa 1  mHCO1  2mCO2  mOH 1  mCl 1

3
Liquid-liquid Equilibrium Equations

There are none in this example.

Material Balance Equations
 Overall material balance:
Equation (2-281):
3H 2Oin  3CO2in  2 NaClin  2 NaCl ppt  3H 2O

 H 2O / 55.51 
 
 
 3mCO2 aq  5mHCO1  4mCO2  mH 1  2mOH 1  mCl 1  mNa1
3 3
 


V 3 yH 2Ovap  3 yCO2vap 
where:
in = inflow or feed component in units of moles
V = overall vapor fraction on a mole basis
In equation (2-281), the products H2O and NACLppt are in units of
moles.
 Vapor balance
Equation (2-282):
yH 2Ovap  yCO2vap  1
where:
y = mole fraction for vapor species
 Sodium balance
Equation (2-283):
NaClin   H 2O / 55.51 mNa1  NaCl ppt
 Chlorine balance
Equation (2-284):
NaClin   H 2O / 55.51 mCl 1  NaCl ppt

 Carbon balance
Equation (2-285):
 
CO2in   H 2O / 55.51 mCO2  mHCO 1  mCO2 aq  VyCO2vap
3
Equations (2-275) – (2-285) are the required 12 equations. Assum-

ing that the temperature and pressure are known, and further assum-
ing that deterministic formulations are available for the equilibrium
constants, activity coefficients, fugacity coefficients, and the activ-
ity of water, then the corresponding 12 unknowns (calculated vari-
ables) are:
V , yH 2Ovap , yCO2vap , mH 1 , mOH 1 , mCO 2 ,
3
mHCO1 , mNa1 , mCl 1 , mCO2 aq , moles NaCl ppt and moles of water
3
Also See:
General Information

Thermodynamic Framework
Equilibrium Constants
Thermodynamic Framework in PRO/II
Aqueous Phase Activity Coefficients
Organic Phase Activities
Aqueous Liquid Phase
Molar Volume and Density

Thermodynamic Framework
The mathematical model described in the previous section utilizes
several thermodynamic quantities. Specifically these are:
 Equilibrium constants - normally strong functions of tempera-
ture and weaker functions of pressure.
 Aqueous-phase activity coefficients - normally strong functions
of temperature and composition and weaker functions of pres-
sure.
 Vapor-phase fugacity coefficients - normally significant func-
tions of temperature, pressure and composition, particularly at
elevated pressures.
 Organic liquid-phase activities - normally strong functions of
temperature and composition and weaker functions of pressure.
The formulations used by PRO/II Electrolytes for each of these
quantities are described below. In addition, the thermodynamic
framework includes formulations for the calculation of enthalpies
and densities for aqueous liquid, organic liquid, vapor, and solid
phases. These latter formulations are also presented below.
Also See:
Equilibrium Constants
By considering basic thermodynamic relationships and assuming a
constant heat capacity of reaction, the following general equation
can be derived:
Equation (2-286):
G o H o  1 1  CPo  Tr Tr 
ln K T         ln   1
RTr R  T Tr  R  T T 
where:
T = temperature in Kelvin
Tr = reference temperature, 298.15 K
G° = free energy of the reaction in the standard state at the

reference temperature (and pressure, 1 bar). This is derived
from the standard-state Gibbs free energies of formation, G°f,

by first, summing the product of the reaction coefficient times
G°f over all reactants and then, over all products. Next, the
sum for the reactants is subtracted from the sum for the prod-
ucts to obtain G°.
H° = corresponding standard state heat of reaction at the ref-
erence conditions. Obtained from the standard-state enthalpy of
formation, H°f, using the same general procedure as used for
G°.
Cp°= corresponding standard state heat capacity of reaction at
the reference conditions. Obtained from the standard state heat
capacity, Cp°, using the same general procedure as used in G°.
R = gas constant
The derivation of the relationship given in equation (2-286) can be
found in the Handbook of Aqueous Electrolyte Thermodynamics
(Ref. 1). Values of G°f, H°f, and Cp° for reaction species are usu-
ally available in the critically evaluated data compilations of the
National Bureau of Standards (Ref. 2) or the Russian Academy of
Sciences (Ref. 5).
The chosen standard states for the thermodynamic framework are as
follows:
 Aqueous solutes - hypothetical, infinitely dilute solution at
unit molality;
 Solvent - pure fluid;
 Gaseous species - hypothetical 1 bar ideal gas;
 Solid species - pure solid.
These are the same standard states as used by the NBS (Ref. 4).
The original implementation now is referred to as the "Old Frame-
work". For some reactions, where sufficient measurements are
available, it uses empirically fitted functions for K values as a func-
tion of temperature instead of equation (1). The "Old Framework"
is used for all models supplied by SIMSCI and by the PUBLIC
library.
A new framework was introduced in the PUBNEW library starting
with PRO/II 5.11. This new form uses an equation of state to predict
K values as a function of both temperature and pressure. Starting
with version 8.0, PRO/II no longer supports the old framework or

the obsolete Electrolyte Utility Package (EUP) used previously to
prepare electrolyte data.
With this version of PRO/II, OLI Systems, Inc. provides and sup-
ports the OLI Chemistry Wizard, a Windows wizard-style applica-
tion. That software program leads you through the process of
creating an OLI chemistry model file and associated model data-
base file for use with PRO/II (or any other OLI product or custom
solution that incorporates OLI Engine).
Refer to the OLI Chemistry Wizard 1.0 User Guide for guidance in
creating your first set of chemistry model files.
Also See:
Thermodynamic Framework in PRO/II

The original implementation in PRO/II now is referred to as the
“Old Framework”. For some reactions, where sufficient measure-
ments are available, it uses empirically fitted functions for K values
as a function of temperature instead of equation (2-286). The “Old
Framework” is used for all models supplied by SIMSCI and by the
PUBLIC library.
A new framework was introduced in the PUBNEW library starting
with PRO/II 5.11. This form uses an equation of state to predict K
values as a function of both temperature and pressure.
Version 7.0 of PRO/II replaced the Electrolyte Utility Package
(EUP) with the newer Chemistry Wizard from OLI Systems, Inc. A
newer version of the Chemistry Wizard became available starting
with PRO/II version 8.0. Contact your OLI Systems representative
for the most appropriate information.
Note: The older EUP no longer is supported by Invensys Simsci-

Esscor or OLI Systems, Inc. Documentation of the Chemistry Wiz-
ard is available separately from OLI Systems, Inc.
Also See:

The key to successful simulation of aqueous systems is to accu-
rately predict the reaction equilibria described in the previous sec-

tion. Greater precision is added by a good description of the
following correction factors:
 Activity coefficients of ions in solution.
 Activity coefficients of molecules in solution.
 Activity of water.
In PRO/II Electrolytes, these quantities can be represented in terms
of a number of alternative as well as complementary formulations.
The common element of all of these formulations is that they
involve the interaction of pairs of species in solution. Two general
assumptions are made:
 Interactions between like-charged ions are not significant.
 Higher-level interactions (involving more than two species) are
not significant.
Also See:
Ionic Species
For ions the formulation used is:
Equation (2-287):
ln  i  DH i  BZ i  Pi
DHi = Debye-Huckel term for long-range, ion-ion interactions,

defined as:

2
 A Z i I 1/2
DH i 
1  I 1/2
where:
A = Debye-Hückel constant, a known function of temperature
and solvent density (Ref. 1)
NI
1 2
ionic strength = I = ---  Z i m i
2
i=1
where: m = molality,

Zi = charge on ion i
The Debye-Hckel term predicts the long-range or electrostatic

effects. For dilute solutions of ionic strength less than 0.1, this is the
only term needed.
BZi = Bromley-Zemaitis (Ref. 6),(Ref. 7) term for short-range, ion-
ion interactions, defined as:
Equation (2-288):
2
NO  Zi  Z j 
BZ i      ij m j
j 1  2 
 
where:
Equation (2-289):
 ij 
 0.06  0.6B  Z Z ij i j
 Bij  Cij I  Dij I 2
1  1.5 / Z Z I 
2
i j
NO = number of ions with charge opposite to that of the ion

being represented.
Bij,Cij, Dij = three interaction coefficients for each cation-
anion interaction. These are each made 3-parameter functions
of temperature. Thus, for each cation-anion interaction, there
are 9 coefficients that must be established.
Pi = Pitzer (Ref. 8),(Ref. 9) term for short-range, ion-molecular
interactions, defined as:
NM
 Z2 
Pi    BPij  12 BPS j  m j
j 1  4I 
where:
Equation (2-291):

BPij   ij 0   ij 0 1  2 I 1/2  1  exp  2 I 1/ 2  / 2 I 
and

Equation (2-292):
NS
BPS j  0.86859 BPPjk mk
k 1
and
Equation (2-293):
BPPjk   jk1 1  1  2 I 1/2  2 I  exp  2 I 1/2  
where:
NM = number of molecular species in solution
NS = number of species in solution
 jk0=,  jk1 two interaction coefficients for each ion-molecule or
molecule-molecule interaction.
Note: Each of the ij interaction coefficients is a 3-parameter func-

tion of temperature. Thus, for each interaction, there are 6 coeffi-
cients that must be established.
Also See:
Molecules Other Than Water

For molecules other than water, the Setschenow equation is used.
Where ij(0) and ij(1) parameters are available, the preferred formula-
tion is from Pitzer (Ref. 8),(Ref. 9). The Setschenow and Pitzer rela-
tions are:
Equation (2-294):
NI
ln  i  bi I   b j m j
j 1
where:
bi = Setschenow coefficient for the neutral species
bj = "Salting-out" coefficient particular to each ion
NI = the number of ionic species in solution

and

Equation (2-295):
NS
ln  i  2 BPij mi
j 1
where
BPij is defined by equation (2-291) above.
Also See:
Water Activity
The water activity for multi-component systems is obtained from an
integrated form of the Gibbs-Duhem equation, together with a mix-
ing rule suggested by Meissner and Kusik (Ref. 10). The formula-
tion can be represented as:
Equation (2-296):
1 NC NA NM
 NS
ln aH2O  
AZ i 1 j 1
Zi Z j ij mi m j  0.01801 m j  2 BPWij mi
i 1  j 1
where:
 NC   NA 
AZ    Z i2 mi    Z i2 mi 
 i 1   i 1 
BPWij  ij   ij  exp  2 I 1/2 

0 1
NC = the number of cation species in solution

NA = the number of anion species in solution
The above formulations are, in cases where the necessary interac-
tion coefficients have been fit to cover the conditions being simu-
lated, quite adequate for predicting systems in which water is the
principal solvent.

Also See:

Four alternative methods are provided:
 Ideal, all fugacity coefficients are assumed to be 1.0.
 Nothnagel method, generally valid up to 20 atmospheres.
 Nakamura method, generally valid up to 200 atmospheres.
 Soave-Redlich-Kwong (SRK) method, valid over a wide range
of conditions and generally recommended when vapor-phase
non-ideality is important.
Also See:
Nothnagel Method
Nothnagel et al.(Ref. 11) developed a method for calculating fugac-
ity coefficients in mixtures at moderate pressures. The main feature
of the method is the inclusion of dimerization effects on the second
virial coefficient.
The equation of state is written as:
Equation (2-299):
nT RT
P
V  nT bm
where:
bm = size parameter for mixture, cm3 / mole
nT = number of moles of true species
P = pressure, atmospheres
R = gas constant, 82.056 cm3 atm / mole K

T = temperature, Kelvins
V = total volume, cm3

nT is obtained from the solution of the dimerization equilibria
described below. bm is given by a sum over all true species:

Equation (2-300):
nT bm   ni bi
i
where:
bi = size parameter for true species i, cm3 / mole
ni = number of moles of true species i
If i is a dimer formed by monomers A and B, bi is given by:

Equation (2-301):
1 1/3 1/3 3
bi 
8
 bA  bB 
Values of b for monomers are tabulated in the original reference.
For component j, the fugacity coefficient is given by:
Equation (2-302):
zj
j  exp  b j P / RT 
yj
where:
bj = size parameter for monomer j, cm3 / mole
yj = apparent mole fraction of component j
zj = true mole fraction of component j monomer
The true mole fractions zj are computed from the dimerization equi-
libria. Each dimerization is described by an equilibrium constant
Kij:
Equation (2-303):
zij  ij
K ij  P
zi z j  i  j
Equation (2-304):
 ij  exp  bi1/3  b1/3

j  P / 8 RT 

3
 
The dimerization equilibrium constants are related to the enthalpy
and entropy of dimerization:

Equation (2-305):
 ln  RTK ij   H ij / RT  Sij / R
where:
Hij = enthalpy of dimerization, cal/mole
Sij = entropy of dimerization, cal/mole
R = gas constant, 82.056 cm3 atm/mole K (left side of equation

(2-305)), 1.987 cal/mole K (right side of equation (2-305)).
The correlations for Hij and Sij , along with the necessary
parameters for 178 components, may be found in the original paper
(Ref. 11).
Also See:
Nakamura Method
Nakamura et al. (Ref. 12) proposed the following perturbed-hard-
sphere equation of state for gas mixtures:
Equation (2-306):
RT 1     2   3  a
P  
 1     v  v  c 
3
v
where:
P = pressure, atmospheres
R = gas constant, 0.082056 liter atm/mole K
T = temperature, Kelvins
v = molar volume, liter / mole
e = reduced density, b/4v
b = parameter signifying the hard-core size of the molecule,
liter / mole
a = parameter signifying the attractive force strength, atm/mole

In addition to equations for the reduced enthalpy difference and
entropy difference, the following equation was presented for calcu-
lating the fugacity coefficient of a species k in the gas mixture:
Equation (2-307):
 4  3 2  b  4  2 2 
ln k   2 
 k 3 
 1     bM  1    
  5  1  cM  
m m
2  n
   j kj  
y a     1
RTv  j 1   m 1 m  1  v  
aM ck  4  1  m  1  cM  1
m m
       ln z
RTv  m 1 m2  v  2 
With the P, R, T, v, and e terms defined earlier, the following defini-

tions and calculations apply:
n = number of species
Equation (2-308):
bk  exp  2.30259     T  
where:
g = pure-component parameter
d =pure-component parameter
Equation (2-309):
n
bM   yi bi
i 1
where:
yi = vapor mole fraction of i
ck = pure-component parameter
n
cM   yi ci
i 1

Equation (2-311):
Pv
z  compressibility factor 
RT
Equation (2-312):
n n
aM   yi y j aij
i 1 j 1
Equation (2-313):
ij
aij   ij 
T
where:
a = pure-component parameter
aij = interaction parameter
Equation (2-314):
 ij   ij0   ij1
Equation (2-315):
ij  ij0   ij1

Equation (2-316):
 ij1   i1 1j
Equation (2-317):
ij1  i1 1j
Equation (2-318):
1 0
 ij0 
2
  i   0j 
Equation (2-319):
 i1  i1  0.0 for non polar gas

where:
i = pure component parameter
ij = interaction parameter

Values for the pure-component and interaction parameters used in
equations (2-305) through (2-318) are given in the original paper by
Nakamura et al. for the following components: Ar, CH4, C2H4,
C2H6, C3H6, C3H8, CO, CO2, H2, H2O, H2S, N2, NH3, and SO2.
Also See:
SRK Method
Calculation of fugacity coefficients from the Soave-Redlich-Kwong
equation of state is described in Soave-Redlich Kwong (SRK).
Note: For both the Nothnagel and Nakamura options, if an electro-

lyte model contains a volatile species not covered in the original
paper by Nakamura et al. for the method (MEA and HCl are exam-
ples of such species) the fugacity coefficients all default to 1.0
(ideal gas). The SRK option does not suffer from this limitation.
Also See:
Organic Phase Activities

Activities of components in an organic liquid phase (if one exists)
are obtained from the Kabadi-Danner modification to the SRK
equation of state. This method is described in Equations of State.
Enthalpy
The pressure dependence of the enthalpy for vapor, liquid, and solid
phases is neglected in this thermodynamic framework. However,
this does not introduce significant uncertainties in enthalpy calcula-
tions over the stated model validity ranges for temperature (0 to 200
C) and pressure (up to 200 bars). Because enthalpy is treated as
pressure-independent, PRO/II Electrolytes users will receive a
warning about potential failure of the flash when pressure is varied
to meet a duty specification.
Also See:

Vapor and Solid Phases
The enthalpy of the vapor or solid phase at the temperature and
solution composition of interest is evaluated using:
Equation (2-320):
NC
H vap or H sol   yi H io
i 1
where:
Hio , yi = the standard state molar enthalpy and the mole frac-
tion, respectively, of the ith vapor or solid component
NC = the total number of components present in the vapor or
solid phase.
At the temperature of interest, Hio is evaluated using:
Equation (2-321):
T
H io  H ofi ,Tr   CPoi dT
Tr
where:
CPoi , H ofi ,Tr = the standard state, isobaric, molar heat capacity,
and the standard state molar enthalpy of formation for the ith
vapor or solid component.
Tr = the reference temperature of 298K.
Values of CPo for vapor and solid species are obtained from empiri-
i
cal functions of temperature, which are given by:
Equation (2-322):
CPoi  Ai  BiT  CiT 2 (for vapor)

Equation (2-323):
CPoi  Ai  BiT  Ci / T 2 (for solid)
where:
Ai, Bi, Ci = temperature-independent, but phase-dependent
constants of the ith vapor or solid component.
Also See:

Enthalpy

The enthalpy of the aqueous solution, Haq, at the temperature and
solution composition of interest is evaluated using:
Equation (2-324):
NM NI
H aq  X w H w   xi H i   xi H i
i 1 i 1
where:
Hw = the molar enthalpy of pure water at the temperature of
interest and at the vapor/liquid saturation pressure of H2O
xi = the mole fraction of the ith solute species
NM, NI = the total number of molecular and ionic solute spe-

cies, respectively
The enthalpy of pure water may be obtained from the equation of
state for H2O given by Haar, Gallagher, and Kell (Ref. 13). At the
temperature and solution composition of interest, Hi is evaluated
using:
Equation (2-325):
  ln  i 
H i  H io  RT 2  
 T 
where:
gi = the activity coefficient of the ith solute species
R = the gas constant

Values of gi and  ln  i / T are obtained from equations (2-287)
through (2-293) on page 2-187 for ionic species. Equations (2-294)
and (2-295) on page 188 are used for molecular solutes.
Values of Hi° are obtained from equation (2-321) on page 195,
 and HfiTr for aqueous species.
using values of C pi
Also used C o
are
Pi
the following relations to represent CPoi for ionic and
molecular solutes:

Equation (2-326):
CPoi  CPoi ,Tr (for ionic solutes)

Equation (2-327):
CPoi  Ai  BiT  CiT 2 (for molecular solutes)
where: Ai, Bi, and Ci = temperature-independent, but phase-

independent constants of the ith molecular solute.
Also See:
Molar Volume and Density
Vapor Phase
The density of the vapor phase is evaluated using the equation of
state which corresponds to the chosen vapor fugacity method.

The molar volume of the aqueous solution, vaq, at the temperature,
pressure, and solution composition of interest is evaluated using:
Equation (2-328):
NM NI
vaq  xwvw   xi vio,Tr   xi vio,Tr
i 1 i 1
where:
vw = the molar volume of pure water at the temperature and
pressure of interest, as given by the HGK(Ref. 13) equation of
state.
vio,Tr = the standard-state molar volume of the ith molecular or
ionic aqueous solute species, at the reference temperature.
Organic Liquid Phase

The density of an organic liquid phase is calculated using the Rack-
ett method for liquid density. This method is described in Section,
Generalized Correlations, of this manual.
Solid Phase
The molar volume of the solid phase, vsol, at the temperature of
interest is evaluated using:

Equation (2-329):
NC
vsol   xi vio,Tr
i 1
where:
vio,Tr = the standard state molar volume of the ith pure solid
component at the reference temperature.
Reference
1 Zemaitis, J.F. Jr., Clark, D.M., Rafal, M., and Scrivner, N.C., 1986,
Handbook of Aqueous Electrolyte Thermodynamics, AIChE.
2 Wagman, D.D., et al., 1968-1973, Selected Values of Chemical Ther-
modynamic Properties, NBS Tech Note, 270-3 to 8.
3 Chase, M.W. Jr., Davies, C.A., Downey, J.R. Jr., Frurip, D.J.,
McDonald, R.A., and Syverud, A.N., 1985, JANAF Thermodynamic
Tables, 3rd edn., J. Phys. Chem. Ref. Data, 14, Supplement no. 1,
1856 pp.
4 Wagman. D. D., et al., 1982, The NBS Tables of Chemical Thermo-
dynamic Properties, J. Phys. Chem. Ref. Data, 11, Supplement no. 2,
392 pp.
5 Glushko, V.P., editor, 1965-1981, Thermal Constants of Compounds,
Russian Academy of Sciences, Vols. I-X.
6 Zemaitis, J.F., Jr., 1980, Predicting Vapor-Liquid-Solid Equilibria in
multi-component Aqueous Solutions of Electrolytes, Thermodynam-
ics of Aqueous Systems with Industrial Applications, S.A. Newman,
ed., ACS Symposium Series, 133, 227-246.
7 Bromley, L.A., 1973, Thermodynamic Properties of Strong Electro-
lytes in Aqueous Solutions, AIChE J., 19, 313-320.
8 Pitzer, K.S., 1979, Theory: Ion Interaction Approach, Activity Coef-
ficients in Electrolyte Solutions, 1, 157-208, R.M. Pytkowicz, ed.,
CRC Press, Boca Raton, FL.
9 Pitzer, K.S., 1980, Thermodynamics of Aqueous Electrolytes at Vari-
ous Temperatures, Pressures and Compositions, Thermodynamics of
Aqueous Systems with Industrial Applications, S.A. Newman, ed.,
ACS Symposium Series, 133, 451-466.
10 Meissner, H.P., and Kusik, C.L., 1973, Aqueous Solutions of Two or
More Strong Electrolytes - Vapor Pressures and Solubilities, Ind.
Eng. Chem. Proc. Des. Dev., 12, 205-208.

11 Nothnagel, K.H., Abrams, D.S., and Prausnitz, J.M., 1973, General-
ized Correlation of Fugacity Coefficients in Mixtures at Moderate
Pressures, Ind. Eng. Chem. Proc. Des. Dev., 12, 25-35.
12 Nakamura, R., Breedveld, G.J.F., and Prausnitz, J.M., 1976, Thermo-
dynamic Properties of Gas Mixtures Containing Polar and Nonpolar
Components, Ind. Eng. Chem. Proc. Des. Dev., 15, 557-564.
13 Haar, L., Gallagher, J.S., and Kell, G.S., 1984, NBS/NRC Steam
Tables, Hemisphere Press, Washington D.C., 320 pp.
Also See: Electrolyte Thermodynamic Equations
Thermodynamic Properties
Solid-Liquid Solubility
Transport Properties
Solid-Liquid Solubility
General Information
van't Hoff Equation
Solubility Data
Fill Options for Solubility Data
General Information
The solubility of solids in liquids can be described by the van't Hoff
(ideal-solubility) equation. This is sufficient for many systems
where non-idealities are small. Alternatively, solubility data, corre-
lated as a function of temperature, may be entered directly. Precipi-
tation of solid salts and minerals from aqueous solutions may be
calculated rigorously using PRO/II Electrolytes. These capabilities
are described in separate sections of Electrolyte Methods.
van't Hoff Equation

The simplest description of the solubility of a solid in a liquid phase
is obtained by assuming that the activity coefficient of the solute in
the liquid phase is one. The solubility is then entirely determined by
the ratio of the pure solid's fugacity to its standard-state fugacity in
the liquid phase, which is that of a pure sub-college liquid. This
ratio is one at the solute's triple point where the solubility also
becomes one. At lower temperatures, it can be calculated with fair
accuracy using the heat of melting; a more accurate estimate results
if the heat capacity change of melting is known.

A full derivation of the ideal solubility equation (or van't Hoff, after
the Dutch chemist who first proposed it) is given by Prausnitz et
al.(Ref. 1) The result is:
Equation (2-330):
H m  T  CP  Tt  CP Tt
ln xi    1    1  ln
RT  Tt  R T  R T
where:
Hm = enthalpy change of melting
Cp = heat capacity change of melting
Tt = triple-point temperature
In practice, the more easily accessible melting temperature is usu-

ally used instead of the triple-point temperature. The difference is
almost always negligible. The ideal-solubility equation predicts the
same solubility for a given solute regardless of solvent composition.
It is therefore primarily useful for systems where the solute and sol-
vent are of a similar chemical nature and form a nearly ideal solu-
tion. For example, the solubility of aromatic hydrocarbons in
benzene is well described by equation (2-330).
Table 2-16: van't Hoff

Required pure component
properties Application Guidelines
Triple-point temperature (Tt) Components Solute and solvent

(melting temperature if Tt is should be of similar
not available) chemical nature
(e.g., form a near-
ideal solution).
Enthalpy of melting
Also See:
General Information
Solubility Data
For systems where sufficient data exist, solid solubilities may be
entered by the user in the form of a correlation of solubility versus
temperature. This correlation has the same functional form as the
van't Hoff equation:

Equation (2-331):
ln xij  Aij  Bij / T  Cij ln T 
where:
xij = the equilibrium solubility of solute i in solvent j at temper-
ature
For solubility of a solid solute i in a mixed solvent, theory dictates
that the mixing rule should have the following form:
Equation (2-332):
ln xi   Z j ln xij
j
In equation (2-332) the sum is over all solvent species, and Zj is the
mole fraction of solvent component j normalized to a solute-free
basis. If the “normal” liquid mole fractions are denoted by z, this is
written as:
Equation (2-333):
zj
Zj 
1  zi
Also See:
General Information
Fill Options for Solubility Data

In a multi-component mixture, data may be missing for one or more
of the i,j pairs appearing in the sum in equation (2-332). Three
options are provided for filling in missing values of xij. The default
option is to fill in missing values with xij as calculated by equation
(2-330), the van't Hoff equation.
Note: When the van't Hoff equation is used as a FILL option, the
Cp terms are ignored.
The FILL = ONE option uses values of one (complete miscibility) for
the solute's solubility in the missing solvents. The FILL = FREE
option causes the missing solvent or solvents to be ignored in the
solubility calculation. In other words, if a solvent k is missing solu-
bility data for the solute, the sum in equation (2-332) is only taken

over those solvents for which data exist, and the mole fractions in
that sum are re-normalized to a k-free (as well as solute-free) basis:
Equation (2-334):
zj
Zj 
1  zi   z k
k
In equation (2-334) the sum is over all solvents k for which there
are no solubility data. Note that equation (2-334) is meaningless if
no solvent in the mixture has solubility data. If FILL = FREE is spec-
ified in such a case, the calculations are defaulted to the van't Hoff
equation.
Reference
1 Prausnitz, J.M., Lichtenthaler, R.N., and Gomes de Aze-

vedo, E., 1986, Molecular Thermodynamics of Fluid-Phase
Equilibria, 2nd edition, Prentice-Hall, Englewood Cliffs,
NJ, Chapter 9.
Also See:
General Information
Thermodynamic Methods
General Information
PURE Methods
PETRO Methods
TRAPP Correlations
Special Methods for Liquid Viscosity
Liquid Diffusivity
Special Methods for Surface Tension
NIST Transport Properties

General Information
The transport properties listed in Table 2-17 are calculated and/or
used by PRO/II:
Table 2-17: Transport Properties

Liquids Vapors
Viscosity Viscosity
Thermal Conductivity Thermal Conductivity
Diffusivity
In addition, PRO/II may calculate the vapor-liquid surface tension

for a stream. Most library components include saturated vapor and
liquid values for viscosity, thermal conductivity, and surface ten-
sion as part of the stored physical property data. Several correla-
tions are included in PRO/II to predict these properties for
hydrocarbon mixtures. Liquid diffusivity is used by some of the
unit operations but is not stored in component libraries.
The methods for computing these transport properties are described
in the sections that follow. With the exception of the PURE and
TRAPP methods, there are no special provisions to characterize the
hydrocarbon type ( as paraffinic, olefinic, etc.). While these non-
characterizing methods may be applied to all hydrocarbon types or
petroleum fractions, expect the best accuracy for paraffins. There
will be a degradation in accuracy for olefins or aromatics. Non-
hydrocarbon transport properties are best represented by the proper-
ties from structure methods discussed in Component Data.
Also See:
PURE Methods
PRO/II provides options to compute transport properties as a
weighted average of pure-component values. These PURE methods
(also known as LIBRARY methods) require an available property
value for each component in a mixture. An exception to this
requirement is any petroleum pseudo-components. For a pseudo-
component, a missing property value (not supplied by the user) is
calculated using the PETRO method below. The pure-component
properties (at the temperature of interest) are combined to calculate
stream average properties according to the mixing rules listed in

Table 2-18: 
Table 2-18: Stream Average Properties
Stream Property Mixing Rule Additive Basis
Liquid Thermal Conductivity
wi = Weight fraction (1)
m2   wi 12 
i
Vapor Thermal Conductivity
 y   MW 
1/3
i i i
m  i
yi = Mole fraction (2)
 y  MW 
1/3
i i
i
Liquid Viscosity
3
 
m    xi i1/3  xi = Mole fraction (3)
 i 
Vapor Viscosity
 y   MW 
1/ 2
i i i
m  i
yi = Mole fraction (4)
 y  MW 
1/2
i i
i
Surface Tension
 m   xi i xi = Mole fraction (5)

i
Users also may provide individual component values as a function

of temperature in either tabular or equation form.
Also See:

PETRO Methods
Liquid Viscosity
The method selected for liquid viscosity is dependent on the
reduced temperature, which is in turn calculated by Kay's rule.
When the system is near the critical point (0.98<Tr<1.0), the
method developed by Letsou and Steil is used. For the range
0.76<Tr<0.98, equations relating viscosity to reduced temperature
and acentric factors developed by Letsou and Steil (as cited in sec-
tion 9-12 in Reid, Prausnitz and Poling, (Ref. 7)) are used. These
methods were developed from data on simple liquid hydrocarbons.
For low temperatures in which the temperature is below the normal
boiling point, a method based on the Arrhenius relation and the
Thomas equation was developed by SimSci. This method relates
liquid density at the normal boiling point, the critical temperature,
and the system temperature. The density at the normal boiling point
is estimated using the equation of Gunn and Yamada. (Ref. 2)
For intermediate ranges (Tb<T<0.76<Tc), the Andrade equation
(Ref. 1) is used to determine the viscosity, based on reference values
at the normal boiling point and a reduced temperature of 0.76. The
reference values are computed by the methods described above.
After the mixture viscosity has been estimated using one of the
above methods, it is corrected for the effects of pressure using the
method of Kouzel (also see the API Technical Data Book, pp. 11-
47, 2nd edition). Vapor pressure (needed for this method) is esti-
mated using the Reidel equation (Ref. 8).
When water decant is active, water viscosities are taken from the
component data library. A “wet” viscosity is then calculated for
water/hydrocarbon streams by combining the hydrocarbon and
water viscosities with the following mixing rule:
Equation (2-335):
3
wet xaqaq
1/ 3
xhchc
1/ 3
where:
 = viscosity
x = mole fraction

Subscripts aq and hc refer to the aqueous and hydrocarbon portions
of the stream.
Reference
1 Andrade, E. N., 1930, The Viscosity of Liquids, Nature,

125, 309-310.
2 Gunn, R. D., and Yamada, T., 1971, A Corresponding
States Correlation of Saturated Liquid Volume, AIChE J.,
17, 1341-1345.
3 Kendall, J., and Monroe, K. P., 1917, The Viscosity of Liq-
uids, II, The Viscosity - Composition Curve for Ideal Liq-
uid Mixtures, J. Amer. Chem. Soc., 39, 1787-1802.
4 Kouzel, 1965, Hydrocarbon Proc., 44, 120.
5 Letsou, A. and Stiel, L. I., 1973, Viscosity of Saturated
Nonpolar Liquids at Elevated Pressures, AIChE J., 19, 409-
411.
6 Partington, J. R., 1949, An Advanced Treatise in Physical
Chemistry, 2, Longmans, London.
7 Reid, R. C., Prausnitz, J. M., and Poling, B. E., 1987, The
Properties of Gases and Liquids, 4th edition, McGraw-Hill,
New York.
8 Reidel, L., 1954, Eine Neue Universelle Dampfdrukformel,
Chem. Ing. Tech., 26, 83.
9 Thomas, L. H., 1946, The Dependence of Viscosities of
Liquids on Reduced Temperature and a Relation Between
Viscosity, Density, and Chemical Constitution, J. Chem.
Soc., Part II, 573-579.
Liquid Thermal Conductivity

The method of Sato and Reidel (Ref. 2) is used to calculate liquid
thermal conductivities. Figure 12A4.1 in the API Technical Data
Book (Ref. 1) is used to correct thermal conductivities for pressure
effects.
When water decant is active, water thermal conductivities are taken
from the component data library. A “wet” thermal conductivity then
is calculated for water/hydrocarbon streams by combining hydro-

carbon and water viscosities with the mixing rule in equation (2-
336):
Equation (2-336):
1
wet 
w   whc hc2 
2 1/2
aq aq
where:
 = thermal conductivity
w = weight fraction in the liquid phase
Subscripts aq and hc refer to the aqueous (water) and hydrocarbon
portions of the stream.
Reference
1 American Petroleum Institute, 1978, Data Book, 5th edi-

tion.
2 Reidel, L., 1950, The Determination of the Thermal Con-
ductivity and the Specific Heat of Various Mineral Oils,
Chem. Ing. Tech., 21, 349.
Surface Tension
The surface tension for hydrocarbon liquids is estimated with pro-
cedure 10A3.1 in the API Technical Data Book (3rd edition). Sur-
face tension for water is extracted from the component data library.
“Wet” surface tension values for decant hydrocarbon systems are
computed with the formula:
Equation (2-337):
 wet  xaq aq  xhc hc
where:
= surface tension
x = mole fraction in the liquid phase
Subscripts aq and hc refer to the aqueous and hydrocarbon por-
tions of the stream.

Vapor Viscosity
Vapor viscosities at low pressures are computed by the method of
Thodos et al. They are then corrected for pressure effects using the
equation of Dean and Stiel. Water vapor viscosities are taken from
the component library. “Wet” vapor viscosities for decant systems
are calculated by the following combinatorial formula:
Equation (2-338):
yaq aq MWaq1/2  yhc hc MWhc1/2

 wet 
yaq MWaq1/ 2  yhc MWhc1/2
where:
 = mole fraction in the vapor phase
subscripts aq and hc refer to the aqueous and hydrocarbon por-
tions of the stream
Reference
1 Thodos, G., and Yoon, 1970, Viscosity of Nonpolar Gas-

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

The Roy-Thodos method (Ref. 2) is used to determine vapor ther-
mal conductivities. The function of temperature used is the one that
is presented by the authors for saturated hydrocarbons. This method
is corrected for pressure effects using the equations of Stiel and
Thodos (Ref. 3).
Data for water are retrieved from the component data library. “Wet”
conductivities are predicted for water/hydrocarbon systems as fol-
lows:

Equation (2-339):
yaq aq MWaq1/3  yhc hc MWhc1/3

wet 
yaq MWaq1/3  yhc MWhc1/3
where:
y = mole fraction in the vapor phase
Subscripts aq and hc refer to the aqueous and hydrocarbon por-
tions of the stream.
Reference
1 Perry, R.H., and Green, D., 1984, Perry's Chemical Engi-

neers Handbook, 6th edition, McGraw-Hill, New York.
2 Roy, D., and Thodos, G., 1979, Thermal Conductivity of
Gases, Ind. Eng.Chem.Fundam., 9, 71-79.
3 Stiel, L.I., and Thodos, G., 1964, The Thermal Conductivity
of Nonpolar Substances in the Dense Gaseous and Liquid
Regions., AIChE J., 10, 26.
Also See:
TRAPP Correlations
The TRAPP method predicts viscosities and thermal conductivities
for pure hydrocarbon components and mixtures of hydrocarbons
and light inorganics for both vapor and liquid phases.
Note: Since this method does not predict surface tension, this prop-
erty is computed from the PETRO correlation described earlier in
this section
A brief description of the method is presented here. For additional

details, see the Ely and Hanley reference paper (Ref. 2).
The TRAPP method uses a one-fluid conformal model coupled with
the extended corresponding-states approach developed by Leland
and his co-workers (Ref. Reference). Mathematically, the viscosity
of a fluid mixture or component is given by:

Equation (2-340):
 x   , T   o  o , To  F
and the thermal conductivity is represented by:

Equation (2-341):
   , T   o'  o , To  F"   , T 
where:
 = viscosity
 = thermal conductivity
F = a dimensional factor
= the fluid density
Subscripts x and o denote unknown and reference fluids.
Superscript ' refers to the potential or translational contribution.
Superscript " refers to the contribution due to internal degrees
of freedom.
This method is applicable to the full range of densities and tempera-
tures, from the dilute gas to the dense liquid. The required constants
for each component are the critical constants (Tc, Pc and Vc) and
the acentric factor.
Note: The method originally was developed for, and was restricted
to, the list of components given in Table 2-19.
Note: Complete parameters are available in the component libraries

for these components. However, in the current versions of PRO/II,
correlations have been added to generate any required parameters
that are not supplied by the user. Currently, the TRAPP method
applies to all library, petro, and non-library components. It may not
be suitable for use with electrolyte or polymer components.
Note: The authors of the TRAPP method recommend it not be used

when water is present. It should also be used with care at reduced
temperatures above 0.925.

Table 2-19: TRAPP Components (3.3 versions)
ID
Component Name ID Name Component Name Name
METHANE METHANE PROPYLENE PRLN
ETHANE ETHANE 1-BUTENE BUT1
PROPANE PROPANE cis-2-BUTENE BTC2
ISOBUTANE IC4 trans-2-BUTENE BTT2
n-BUTANE BUTANE ISOBUTENE IBTE
ISOPENTANE 2MB 1,3-BUTADIENE 13BD
n-PENTANE PENTANE 1-PENTENE PNT1
NEOPENTANE 22PR cis-2-PENTENE PTC2
n-HEXANE HEXANE trans-2-PENTENE PTT2
2-METHYLPENTANE 2MP 2-METHYL-1- 2BT1
BUTENE
3-METHYLPENTANE 3MP 3-METHYL-1- 3BT1
BUTENE
2,2-DIMETHYLBUTANE 22MB 2-METHYL-2- 2BT2
BUTENE
2,3-DIMETHYLBUTANE 23MB 1-HEXENE HXE1
n-HEPTANE HEPTANE 1-HEPTENE HPT1
n-OCTANE OCTANE PROPADIENE ALEN
n-NONANE NONANE 1,2-BUTADIENE 12BD
n-DECANE DECA BENZENE BNZN
n-UNDECANE UNDC TOLUENE TOLU
n-DODECANE DDEC m-XYLENE MXYL
n-TRIDECANE TRDC o-XYLENE OXYL
n-TETRADECANE TDCN p-XYLENE PXYL
n-PENTADECANE PNDC ETHYLBENZENE EBZN
n-HEXADECANE HXDC CARBON DIOXIDE CO2
n-HEPTADECANE HPDC CARBON CO
MONOXIDE
CYCLOPENTANE CP HYDROGEN H2
METHYLCYCLOPENTANE MCP HYDROGEN H2S
SULFIDE
CYCLOHEXANE CH OXYGEN O2
METHYLCYCLOHEXANE MCH NITROGEN N2

Table 2-19: TRAPP Components (3.3 versions)
ETHYLCYCLOPENTANE ECP SULFUR DIOXIDE SO2
ETHYLCYCLOHEXANE ECH WATER H2O
ETHYLENE ETLN
Reference
1 Leland, T. W., Robinson, J. S., and Suther G.A., 1968, Sta-

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

For petroleum fractions, viscosity prediction methods are usually
based on boiling point and specific gravity. The API Technical Data
Book (1978) expresses the Watson correlation in a nomograph
form. However, the graphical form is unsuitable for simulation pur-
poses and cannot be extrapolated. Abbott et. al., (1970, 1971) (Ref.
1) give a correlation which agrees with the API data quite well but
breaks down when extrapolated.The SimSci or Twu correlation
(Ref. 2) is based on a perturbation expansion method. Here, the
properties of a real system (petroleum fractions, in this case) are
expanded about the values of a reference system (chosen to be n-
alkanes). The kinematic viscosity of a petroleum fraction at 210 F is
expressed in the following manner:
Equation (2-342):
2
 450   o 450   1  2 f 2 
ln  2    ln 2   
 Tb   Tb   1  2 f 2 

Equation (2-343):
 SG 
2
f2  x SG  21.1141
Tb1/2
Equation (2-344):
56.7394
x  1.99873 
Tb1/2
Equation (2-345):
SG  SG  SG o

Similar equations for kinematic viscosity at 100 F are given below:
Equation (2-346):
2
 450   o 450   1  2 f1 
ln  1    ln 1   
 Tb   Tb   1  2 f1 
Equation (2-347):
 SG 
2
f1  1.33932 x SG  21.1141

Tb1/2
Equations (2-347) can compute the kinematic viscosities at the 2

temperaturest. A generalized relationship was developed by Wright
(and modified by Twu)(Ref. 3), given in equations (2-348) through
(2-350) below. These equations can be used together to compute the
relationship between viscosities at any two temperatures.
Equation (2-348):
ln  ln Z   A  B ln T 
Equation (2-349):
Z    0.7  e
 1.47 1.84 0.51 
2
Equation (2-350):
ln  ln Z1   ln  ln Z 2 
B
ln T1  ln T2

Equation (2-351):
ln  ln Z   ln  ln Z1   B  ln T  ln T1 
where:
 = kinematic viscosity
Reference
1 Abbott, M.M., Kaufman, T.G., and Domash, L., 1971, A

Correlation for Predicting Liquid Viscosities of Petroleum
Fractions, Can. J. Chem. Eng., 49, 379.
2 Twu, C.H., 1985, Internally Consistent Correlation for Pre-
dicting Liquid Viscosities of Petroleum Fractions, Ind. Eng.
Chem. Proc. Des. Dev., 24, 1287.
3 Wright, W.A., 1969, An Improved Viscosity-temperature
Chart for Hydrocarbons, J. of Materials, 4, 19.
Heavy Oil1 Correlation for Liquid Viscosity

Most earlier liquid viscosity methods produce poor predictions
when applied to heavy fractions. This is especially true at lower
temperatures where liquid viscosity may change dramatically with
small temperature changes. Simulation Sciences developed a corre-
lation that is now recommended for temperatures heavy oils and
bitumens. Viscosity is estimated at two reference (100F and 210F)
temperatures, then the viscosity-temperature relationship is extrap-
olated or interpolated, as required.
The HEAVY oils liquid viscosity method is a hybrid between the
LIBRARY and SIMSCI methods. Library components are treated
as individual components with viscosity contributions derived from
the saturated liquid (LIBRARY) viscosity correlations. In contrast,
individual petro component constants (Tc, Pc, etc.) are mixed
according to the SIMSCI method to represent a single lumped (typ-
ically heavy) component. This composite petro component is
treated mainly as in the SIMSCI method. An exception is that the
NBP is determined as the mean average of the lumped component.
The SIMSCI method would compute the NBP by mole averaging.
The viscosities of the library components and of the single lumped
component are combined using the Mehrotra2 mixing rule:

Equation (2-352):
M m ln  m  0.7    xi M i ln  i  0.7 
i
i = defined + lumped
where:
M, molecular weight
m (subscript) represents the mixture and
i (subscript) sums over all defined (library) component and the
single (lumped) petro component.
 is dynamic viscosity, mPa S
Reference
1 Gray, Murray R., Dekker, Marcel; Upgrading Petroleum

Residues and Heavy Oils; New York (1994).
2 Mehrotra, A.K.; Eastick, R.R; Svreck, W.Y; “Viscosity of
Cold Lake Bitumen and its Fractions”, Can. J. Chem. Eng.,
67: 1004-1009 (1989).
API Method for Liquid Viscosity

The API method used in PRO/II is very similar to the SIMSCI cor-
relation discussed above. Instead of using one reference fluid, two
reference fluids are used. Watson plots show that the logarithmic
function of viscosity at the same boiling point temperature is a lin-
ear function of API gravity. Hence, this relationship is extended as
follows:
Equation (2-353):
API  API r1
ln    ln  r1   ln  r1   ln  r 2  
r1  
API  API
r2
where:
= kinematic viscosity of the petroleum fraction
API = API gravity
Superscripts r1, r2 refer to reference fluids 1 and 2.

Since all the calculations are made at the same boiling point, equa-
tion (2-353) can be simplified based on the definition of Watson
characterization factor and of API gravity as:
Equation (2-354):
1/2  K 10 
 r2 
    r1 
r1
 
where:
K = the Watson Characterization factor.
The viscosity of the reference fluid (either fluid 1 or fluid 2) can be
expressed as:
Equation (2-355):
C2
ln  r   C1   C3 ln Tb   C4Tb  C5Tb3  C6Tb6
Tb
where:
C1, C2, C3, C4, C5, C6 = empirical constants.
Reference
1 Twu, C. H., 1986, A Generalized Method for Predicting

Viscosities of Petroleum Fractions, AIChE J., 32, 2091-
2094.
Also See:
Liquid Diffusivity
PRO/II's Dissolver unit requires the diffusivity of the solute in the
solvent liquid if the user does not supply mass transfer data. PRO/II
can calculate these diffusivities based on user-input data or can esti-
mate them from the Wilke-Chang correlation.
User-supplied Diffusivity Data

When the user supplies diffusivity data, the user must specify which
component (or components) is to be considered the solute. Diffusiv-
ity data can then be supplied for each solute in each solvent in the
following form:

Equation (2-356):
ln Dij  c1  c2 / T  c3 ln T
where:
Dij = diffusivity (in m2/sec) of solute i in solvent j
T = temperature in Kelvins
c1, c2, c3 = constants
For the diffusivity of a solute in a mixture of solvents, the following

mixing rule is used:
Equation (2-357):
ln Di , m   X j ln Dij
j
where:
Di,m = diffusivity (in m2/sec) of solute i in solvent mixture
Xj = mole fraction of solvent component j on a solute-free basis
In equation (27) the sum is over all solvent components j.
Wilke-Chang Correlation
Wilke and Chang (1955) developed a method for estimating the dif-
fusivity of a solute at infinite dilution in a binary mixture. SimSci
has adapted this method slightly and put it in multi-component
form. The Wilke-Chang correlation is of limited accuracy, but it
will generally provide a diffusivity that is good to within 50%. The
correlation should not be used in cases where the solute is water or
where the solute is electrolytic. The equation is as follows:
Equation (2-358):
1/2
7.4*102   j X j j M j  T
Di ,m 
mVi 0.6
where:
Di,m = diffusivity (in m2/sec) of solute i in solvent mixture
Xj = mole fraction of solvent component j on a solute-free basis

Mj = molecular weight of solvent component j
T = temperature in Kelvins
m= viscosity of solvent mixture in centipoise
Also see:
Special Methods for Surface Tension
Parachor Method (API 82 10A 3.2)

For mixtures of known composition at high pressures, surface ten-
sions may be calculated using the following equation:
Equation (2-359):
where:
σm = surface tension of the mixture, in dynes per centimeter
n = number of components in the mixture
Pi = parachor for component i.
ρL = density of the liquid mixture, in grams per millimeter
ρV = density of the vapor mixture, in grams per millimeter
ML = molecular weight of the liquid mixture
MV = molecular weight of the vapor mixture
xi = mole fraction of component i in liquid
yi = mole fraction of component i in vapor
API 82 10A 3.2 Surface Tension

This method is used to predict the surface tension of crude oils
and petroleum fractions.

Equation (2-360):
where:
σ = Surface tension of the liquid, in dynes per centimeter
Tc = Critical or pseudo critical temperature, in degrees Rankine
T = Temperature of system, in Rankine
K = Watson characterization factor
Reference
1 API Technical Data Book - Chapter 10, page no - 23, 1982.
NIST Transport Properties

NIST Transport Properties have three methods: NIST23, GERG,
and AGA8. NIST23 and GERG methods are used to calculate all
the transport properties and AGA8 is used to predict the vapor vis-
cosities and thermal conductivities.
NIST
The default REFPROP method (GERG or AGA8 as determined by
the REFPROP program) must be acquired separately from NIST.
GERG
The GERG method available as part of the REFPROP package
must be acquired separately from NIST.

Index
Numerics Additive Basis , 2-203

Adler , 2-83
Advanced Treatise , 2-205
1-BUTENE , 2-210
AH2O , 2-175
1-HEPTENE , 2-210
Ai , 2-175, 2-176, 2-194, 2-196
1-HEXENE , 2-160, 2-210
AIChE , 2-136, 2-197
1HEXENE , 2-160
AIChE J , 2-76, 2-81, 2-85, 2-91, 2-100, 2-112, 2-113,
1-PENTENE , 2-210
2-141, 2-143, 2-146, 2-168, 2-215
1T2C4MCP , 2-160
AIChE Meeting , 2-78
1T2MCP , 2-160
Aij , 2-135, 2-136, 2-139, 2-141, 2-143, 2-190
1-Trans-2 , 2-158
Aji , 2-99, 2-135, 2-136, 2-140
1-Trans-2-Cis-4-Tri , 2-158
Akad , 2-135
2-DIMETHYLBUTANE , 2-210
Al.Ref , 2-188, 2-190
2-METHYL-2-BUTENE , 2-210
ALCOHOL , 2-66, 2-68, 2-158, 2-159
2-METHYLPENTANE , 2-210
Alcohol data package , 2-158, 2-159
3-BUTADIENE , 2-210
Alcohol data package uses , 2-158
3-DIMETHYLBUTANE , 2-210
ALCOHOL databank , 2-159
3-METHYL-1-BUTENE , 2-210
Alcohol Dehydration Systems , 2-66, 2-68
3-Methylhexane , 2-160
Alcohol Package
3-METHYLPENTANE , 2-210 Table 1.2.8-1 Components Available , 2-159
6th World Congress , 2-77 ALEN , 2-210
Algebraic Representation , 2-135
Thermodynamic Properties , 2-135
A Alkanes , 1-7, 1-38
Alkanol , 2-172
A.S.M.E. , 2-166
Alkanolamine , 2-172
Acad , 2-138
Alkanolamines , 2-171, 2-172
According , 1-29, 1-40
Alpha formulation , 2-56, 2-57, 2-91, 2-93
characterization , 1-40
Alter , 1-44
Account , 2-129
dimerization , 2-129, 2-130 Amer , 2-140, 2-205
Acentric , 2-93, 2-94, 2-204 American Chemical Society , 2-99
Acentric factor , 1-2, 1-8, 1-9, 1-11, 1-12, 1-13, 1-16, American Petroleum Institute , 2-78, 2-81, 2-82
1-18, 2-75, 2-76, 2-78, 2-80, 2-83, 2-84, 2-94, 2-96, American Society , 1-25, 1-44
2-109, 2-110, 2-111, 2-129, 2-209 Testing , 1-25
ACH , 2-159 AMINE , 2-64, 2-65, 2-66, 2-172, 2-173, 2-174
ACS Symp , 2-99 Amine data package , 2-171
ACS Symposium Series , 2-197 Amine Package , 2-171
Activity Coefficients , 2-144, 2-197 Amine Systems , 2-62
Group Contribution Estimation , 2-144 Methods Recommended , 2-62
Activity-coefficient , 2-156 Amine Treating , 2-168, 2-174
Index-220
Better Data , 2-168, 2-174 ASME , 2-124
Amines , 2-49, 2-63, 2-65, 2-171, 2-172 ASOG , 2-144
Amines diethanolamine , 2-171 Assay Processing , 1-21, 1-22, 1-25, 1-40, 1-41
Amines MEA , 2-62 Assay streams , 1-22
Amines monoethanolamine , 2-171 Associating equation of state , 2-104
Amk , 2-146, 2-147, 2-148, 2-149 Association , 2-104, 2-105
Ammonia , 2-168 extent , 2-104, 2-105
Analytical Solution , 2-144 ASTM , 1-25, 1-29, 1-31, 1-33
following , 2-144 ASTM D1160 , 1-21
And/or , 2-95, 2-202 ASTM D2887 , 1-21
And/or vapor-liquid-liquid , 2-150 ASTM D323-73 , 1-42
Anderson , 2-143 ASTM D49 , 1-41
Andrade , 2-204, 2-205 ASTM D5191-91 , 1-42
Ann , 2-138 ASTM D86 , 1-21, 1-25, 1-46
Annual Book , 1-25 converting , 1-33
ASTM Standards , 1-25, 1-44 ASTM Standards , 1-25
Antoine , 1-4, 1-14 Annual Book , 1-25
API , 1-10, 1-12, 1-14, 1-16, 1-19, 1-20, 1-25, 1-26, 1-27, Azeotrope , 2-77
1-29, 1-31, 1-32, 1-33, 1-36, 1-38, 2-49, 2-58, 2-81, Azeotropes , 2-80
2-82, 2-125, 2-164, 2-204, 2-205, 2-206, 2-211,
azeotropic data , 2-151
2-214, 2-215
Azevedo , 2-54, 2-134, 2-156, 2-201
Flash point correlation , 1-46
API gravity , 1-12, 1-14, 1-36, 1-38, 2-214, 2-215
API liquid density , 2-49, 2-50, 2-81 B
API Method , 2-214
API Technical Data Book , 1-25, 1-33, 1-38, 1-42, 2-81,
Backfill , 2-151
2-124, 2-204, 2-205, 2-206, 2-211
PRO/II , 2-150, 2-151, 2-153
API/EPA , 2-165
Banks , 2-139
APINAPHTHA , 1-42, 1-44
Benedict-Webb-Rubin , 2-109, 2-110
Application Guidelines , 1-41, 2-75, 2-76, 2-77, 2-78,
Benedict-Webb-Rubin-Starling , 2-109, 2-124
2-80, 2-81, 2-82, 2-83
BENZENE , 2-210
application ranges , 2-76, 2-154
Bicarbonate , 2-171
Applications , 2-50
Carbamate Reversion , 2-172
Phase Equilibria , 2-54, 2-134
Bii , 2-128
Applied Hydrocarbon Thermodynamics , 1-20, 1-44
Bij , 2-100, 2-128, 2-141, 2-143, 2-184, 2-190
Applying , 1-6
setting , 2-143
Rackett , 1-12
Binary , 2-136
Aqueous Electrolyte Thermodynamics , 2-181
Thermodynamic Evaluation , 2-136
Handbook , 2-182
Binary Fill options , 2-150
Aqueous Liquid Phase , 2-177, 2-195, 2-196
binary interaction databank , 2-158, 2-163
Aqueous Phase Activities , 2-183, 2-184, 2-186, 2-187
Binary Mixtures , 2-136
Aqueous Solutions , 2-196
Two , 2-197 Bisulfide , 2-168, 2-171
Aqueous Solutions Containing Volatile Weak BK10 , 2-60, 2-61, 2-79
Electrolytes , 2-168 Black , 1-10
Aqueous Sour Water Systems , 2-168 Blending , 1-23
Aromatic Systems , 2-66, 2-67 Example , 1-23, 1-24, 1-25
PRO/II Component Reference Manual Index-221

Bluck , 2-101 fugacities , 2-127
Boston , 2-94, 2-134 fugacity , 2-50, 2-51, 2-52, 2-53, 2-88, 2-104, 2-106,
2-188, 2-189, 2-191
Boston-Mathias , 2-92
Calculation , 2-141
Braun K10 , 2-60, 2-79, 2-124
Multicomponent Phase Equilibria , 2-143
Brobst , 2-85
Calculation Methods , 2-124
Bromley-Zemaitis , 2-184
Calculations
Burkhart , 2-78 Flash Point , 1-45
Butane , 2-110 Cantalino , 2-149
Butterworth , 2-134 Carbamate , 2-172
BWR , 2-109 Carbamate Reversion , 2-171
BWRS , 2-63, 2-66, 2-67, 2-109, 2-110, 2-112 Bicarbonate , 2-172
Carbamates , 2-172
CARBON DIOXIDE , 2-159, 2-163, 2-169, 2-171,
C 2-210
Carbon Number , 1-2
C.A. Downey , 2-196 CAVETT , 1-5, 1-12
C2H4 , 2-193 CFCs , 2-69
C2H4O , 2-159 CH , 2-160, 2-163, 2-210
C2H6 , 2-163, 2-193 CH4 , 2-67, 2-163, 2-193
C2H6O2 , 2-163 Chang , 2-216
C3 , 1-4, 2-154, 2-163, 2-215, 2-216 Chao-Seader , 2-49, 2-75, 2-76, 2-77, 2-123
C3H6 , 2-193 Erbar Modification , 2-77
C3H8 , 2-163, 2-193 Chao-Seader K-value , 2-49
C4 , 1-4, 2-154, 2-215 characteristic volume , 2-83, 2-84, 2-85
C4-C5 , 2-80 Characterization , 1-6, 1-41, 2-60, 2-61
C4H10 , 2-163 according , 1-41
sets , 1-6
C4H10O3 , 2-163
Characterization-Lee-Kesler , 1-16, 1-19
C4H8O2SH2S , 2-159
Chemdist , 1-1
C5 , 1-4, 2-215
Chemical Abstract Number , 1-2
C5H10 , 2-160
Chemical Applications , 2-69
C5H12 , 2-159, 2-160, 2-163
Chemical Engineering Thermodynamics , 2-50, 2-134
C6 , 1-4, 1-39, 2-215
Chemical Engineers , 2-91
C6H12 , 2-160, 2-163
Chemical Thermodynamic Properties
C6H14 , 2-160, 2-163
NBS Tables , 2-196
C6H14O4 , 2-163
Chim , 2-168
C6H6 , 2-160, 2-163
Chlorofluorocarbons , 2-71
C7 , 1-4
choice , 2-92
C7H14 , 2-160, 2-163
Cis-2-PENTENE , 2-210
C7H16 , 2-160, 2-163
Clapeyron , 1-4
C7H8 , 2-160, 2-163
Classical Thermodynamics , 2-54, 2-134
C8 , 2-81 Nonelectrolyte Solutions , 2-50
C8H10 , 2-160, 2-163 Clausius-Clapeyron , 2-173
C8H16 , 2-163 Clausius-Clapyron , 1-12
Calculate , 1-41, 2-50, 2-88, 2-104, 2-126, 2-188, 2-190 CO , 2-62, 2-77, 2-79, 2-168, 2-190
Index-222
CO2 , 2-62, 2-63, 2-64, 2-76, 2-77, 2-79, 2-96, 2-125, Critical Review , 2-83
2-158, 2-159, 2-163, 2-165, 2-168, 2-170, 2-171, Equations , 2-83
2-172, 2-193, 2-210
Critical temperature , 1-2, 1-7, 1-9, 1-12, 1-15, 1-16,
Coal-tar Liquids , 1-20, 1-45 1-19, 2-56, 2-78, 2-82, 2-89, 2-105, 2-108, 2-109,
Coker fractionators , 2-60 2-110, 2-111, 2-129, 2-130, 2-154, 2-204
Complex Mixtures , 2-94 Critical volume , 1-2, 1-7, 1-13, 1-17, 2-85, 2-111,
2-129
Component Data , 1-1, 1-5, 2-204, 2-205, 2-206, 2-207
Cross-references , 1-1
Component Libraries , 1-1, 2-202, 2-204
Cubic , 2-91, 2-98, 2-100
Component Name , 2-210
New Generalized Alpha Function , 2-91
Component properties-extrapolation
cubic equation forms , 2-89
conventions , 1-3
Component properties-temperature correlation Cubic equation-of-state , 2-58
equations , 1-3 Cunningham , 2-94, 2-95, 2-101, 2-107
Component Solutions , 2-112 Cup
Components Available , 2-125 Closed cup , 1-45
Open Cup , 1-45
components in databank , 2-158, 2-163
Curl-Pitzer , 2-58, 2-60, 2-78, 2-80
Composition Curve
Ideal Liquid Mixtures , 2-205 Curves , 1-25
distillation cutpoints , 1-33
Composition-dependence , 2-101
TBP , 1-25
Compressed Liquids , 2-85
Cutpoint , 1-22, 1-23, 1-24, 1-40, 1-41
Compressibility , 2-54, 2-58, 2-80, 2-104, 2-110, 2-126,
2-128, 2-168, 2-190 Cutpoint Sets , 1-23
Compressibility Factors , 1-20 Cutpoints , 1-21, 1-22, 1-35
Defining , 1-22
Contents , 1-1, 1-21, 2-60
distillation curves , 1-33
Table , 1-1
set , 1-22, 1-23, 1-24, 1-34, 1-35
Convert
use , 1-24
ASTM D86 , 1-25
Cutpoints-application guidelines , 1-22
D86 , 1-25
TBP , 1-25 Cutpoints-multiple sets , 1-22
Coon , 2-94, 2-95, 2-101, 2-107 Cutpoints-secondary set , 1-22
Copeman , 2-94 CYCLOHEXANE , 2-160, 2-163, 2-210
Correlation , 1-47 CYCLOPENTANE , 2-160, 2-210
API Flash Point , 1-46
SIMSCI flash point , 1-47
Correlations , 2-211 D
Predicting Liquid Viscosities , 2-211
Corresponding States , 2-110 D.M. Rafal , 2-196
Multicomponent Mixtures , 2-110 D1160 Curves , 1-25
Corresponding States Correlation , 2-112 D2887 , 1-25, 1-27, 1-29, 1-30
Saturated Liquid Volume , 2-205 D2887 Curves , 1-25
Corresponding-states , 2-83 D2887 Simulated Distillation , 1-29
COSTALD , 2-66, 2-67, 2-73, 2-84, 2-85 D323 , 1-41
COSTALD liquid density , 2-66, 2-83 D323 RVP , 1-44
Critical compressibility factor , 1-2, 2-82 D4953 , 1-42, 1-44
Critical pressure , 1-2, 1-7, 1-12, 1-16, 2-76, 2-79, D5191 , 1-41, 1-44
2-129, 2-130
D86 Curves , 1-25
Critical Properties , 1-6, 1-12
Danner , 2-83, 2-97, 2-98

data estimation except , 2-69, 2-128
FILL , 2-152 Hayden-O Connell Method , 2-49
Databank , 1-1, 2-62, 2-154, 2-158, 2-163 Dimethylcyclopentane , 2-160
Henry s , 2-154 Dimethylhexane , 2-160
NRTL , 2-67, 2-68
Dimethylpentane , 2-160
databank components , 2-158, 2-163, 2-165, 2-168,
DIPA , 2-65, 2-66, 2-173
2-171
containing , 2-173
Databanks , 2-151, 2-153, 2-158
results , 2-63, 2-65
DEA , 2-65, 2-66, 2-171, 2-173
Dipole moment , 1-2, 2-129, 2-130
Deal , 2-144, 2-146
Dissociations , 2-171
De-asphalting , 2-60, 2-62
Dissolver , 2-215
Debye-Hckel , 2-184, 2-185
Distillation
Debye-Hückel , 2-184 curve cutpoints , 1-33
Dechema , 2-63 Distillation Calculations , 1-20
Defined Components , 1-3, 1-5 Physical Data , 1-20
Defining , 1-22 Distillation Curves
Cutpoints , 1-22 Interconversion , 1-25
pseudocomponent , 1-22 Types , 1-25
Density , 1-1, 1-3, 1-5, 1-6, 1-12, 1-16, 1-19, 2-49, 2-50, Distillation data-API 1963 method , 1-25
2-58, 2-69, 2-72, 2-73, 2-80, 2-81, 2-82, 2-83, 2-101, Distillation data-API 1987 method , 1-25
2-109, 2-110, 2-128, 2-158, 2-163, 2-165, 2-168,
Distillation data-ASTM D1160 , 1-25
2-171, 2-181, 2-184, 2-190, 2-196, 2-204, 2-208
Improved Correlation , 2-83 Distillation data-ASTM D2887 , 1-25
water , 1-15 Distillation data-ASTM D86 , 1-25
Density model , 2-83 Distillation data-Edmister-Okamoto method , 1-25
Departure-based , 2-57 Domash , 2-213
Derr , 2-144, 2-146 Dortmund modified UNIFAC
Des , 2-95, 2-98, 2-112, 2-129, 2-130, 2-139, 2-143, UFT2 , 2-148
2-147, 2-213 DSG , 1-6
Design Institute
Physical Property Data , 1-3
deviations , 2-99 E
equation , 2-99
parameters , 2-99 EBZN , 2-163, 2-210
DGA , 2-65, 2-66, 2-173 ECH , 2-163, 2-211
Diethylene , 2-64 Edmister , 1-13, 1-20, 1-33, 1-44, 2-77
Diethylene Glycol , 2-163 Edmister-Okamoto , 1-33
Diffusivities , 2-215 Edwards , 2-166, 2-168
Diffusivity , 2-202, 2-215 Eisenberg , 2-165, 2-168, 2-174
estimating , 2-216 El , 2-196
provide , 2-216
Electrolyte Mathematical Model , 2-175, 2-177
requires , 2-215
Electrolyte Solutions , 2-197
Diglycolamine , 2-171
Electrolyte Thermodynamic Equations , 2-180, 2-181,
Diisopropanolamine , 2-171
2-183, 2-184, 2-186, 2-187, 2-188, 2-190, 2-193,
Dimer , 2-129, 2-130, 2-189 2-194, 2-195, 2-196
Dimerization , 2-129, 2-188 Electrolytes , 2-197
Dimerize , 2-69 Electroneutrality Equation , 2-176, 2-178
Dimerizing , 2-49, 2-128
Index-224
Empirical Correlation , 2-128 Erbar-modified Grayson-Streed , 2-77
Second Virial Coefficients , 2-129 Estimates , 2-98, 2-215
Empirical Equation , 2-110 diffusivity , 2-215, 2-216
Thermodynamic Properties , 2-109 Gi , 2-98
Englewood Cliffs , 2-134, 2-156, 2-201 water/hydrocarbon , 2-98
Enthalpy , 1-3, 1-6, 1-12, 1-21, 1-40, 2-49, 2-50, 2-54, Ethanediol , 2-71
2-57, 2-60, 2-72, 2-73, 2-78, 2-80, 2-88, 2-104, Ethanolamine Process Simulated , 2-174
2-156, 2-158, 2-163, 2-165, 2-168, 2-171, 2-181,
Ethylbenzene , 2-163
2-188, 2-190, 2-193, 2-194, 2-195, 2-198
ETHYLCYCLOHEXANE , 2-163
Improved Prediction , 2-80
ETHYLCYCLOPENTANE , 2-211
Enthalpy-ideal-gas , 1-16, 1-19
Entropic , 2-138 ETHYLENE , 2-211
Ethylene Glycol , 2-163
Entropy , 2-49, 2-50, 2-57, 2-72, 2-73, 2-78, 2-80, 2-88,
2-137, 2-158, 2-163, 2-165, 2-168, 2-171, 2-188, ETLN , 2-211
2-190 EtSH , 2-168
Environmental Applications , 2-69 Excess Free Energy , 2-140
Equation New Expression , 2-139
API flash point , 1-46 Excess Gibbs Free Energy , 2-143
Nelson flash point , 1-47
New Expression , 2-143
SIMSCI flash point , 1-47
Extent , 2-104
Equation of state incorporating , 2-104
association , 2-104
equation of state water solubility method , 2-124 extent of association , 2-104
Equation-of-state , 1-10, 2-53, 2-63, 2-67, 2-68, 2-69,
Extrapolation Conventions , 1-3
2-70, 2-125, 2-128
Equations For Electrolyte LLE , 2-176
Equations For Solutions Involving F
Second Liquid Phase , 2-175
Equations of State , 1-6, 1-20, 2-49, 2-50, 2-54, 2-57,
FCCU , 2-60, 2-61
2-58, 2-60, 2-62, 2-69, 2-75, 2-82, 2-83, 2-88, 2-89,
2-91, 2-95, 2-96, 2-97, 2-98, 2-99, 2-100, 2-101, including , 2-60
2-104, 2-107, 2-109, 2-110, 2-124, 2-126, 2-128, Feeds , 1-22
2-129, 2-154, 2-156, 2-158, 2-163, 2-165, 2-168, flowsheet , 1-23, 1-24, 1-25
2-171, 2-181, 2-188, 2-190, 2-193, 2-195, 2-196 FILL , 1-5, 2-69, 2-200
Fill options , 2-120
Fill
Equilibrium constant K , 2-106 Equations of state , 2-120
Equilibrium constant Kij , 2-188 Liquid Activity methods , 2-150
Equilibrium Constants , 2-94, 2-104, 2-166, 2-167, Fill Options for _Solubility Data , 2-200
2-173, 2-176, 2-181, 2-189 Fitting
Equilibrium Expressions , 2-175, 2-178 Distillation Curves , 1-33
Equilibrium Flash Vaporization Calculations , 1-41 Fixed Properties , 1-3
Equilibrium Ratios , 2-80 Flash , 1-45
equilibrium reactions , 2-129, 2-171 Flash Point
Equimolar , 2-157 API Correlation , 1-46
Calculations , 1-45
Equlibrium , 2-173
Correlated Methods , 1-46
Erbar , 2-77, 2-124
Definition , 1-45
Erbar Modification , 2-77 Empirical methods , 1-46
Chao-Seader , 2-77 Index and User Mixing methods , 1-45
Erbar modification to Chao-Seader , 2-77 Library component Properties , 1-2
Erbar modification to Grayson-Streed , 2-77 Nelson Correlation , 1-47

open cup , 1-45 Fugacity fi , 2-154
SIMSCI Correlation , 1-47 Fundam , 2-91, 2-109
SIMSCI Method , 1-46
Fusion , 1-2
FloryHuggins Theory , 2-138
Flowrate , 1-40
Flowsheet , 1-22, 1-41 G
feeds , 1-25
Flowsheets , 1-33 Gallagher , 2-195
Fluid Mixtures , 2-91 GAMMA , 2-156
Fluid Phase Equil , 2-94, 2-95, 2-101, 2-103, 2-107, Gamma Method , 2-156
2-149
Gas Mixtures , 2-110
Fluid Phase Equilibria , 2-144 Volumetric Data , 2-113
Fluid Properties , 2-94 Gas Mixtures Containing Polar , 2-198
Fluid Thermodynamic Properties , 2-109 Thermodynamic Properties , 2-197, 2-198
Light Petroleum Systems , 2-109 Gas Processes , 2-60
Fluid-Phase Equilibria , 2-50, 2-200 Gas Processors Association , 2-168, 2-171
FluidPhase Equilibria , 2-154 Gaseous , 2-182
Molecular Thermodynamics , 2-134, 2-156
Gaseous Solutions , 2-89
Fluids , 2-91, 2-111, 2-112 Fugacities , 2-91
Gases , 2-205, 2-207, 2-208
Formation , 1-10, 1-13 Properties , 2-205
Heat , 1-10, 1-11, 1-12, 1-13, 1-15 Thermal Conductivity , 2-204
Fractionators , 2-60, 2-61 Gasoline-oxygenate , 1-42
Fredenslund , 2-109, 2-144, 2-146, 2-147, 2-148 General Cubic Equation , 2-89, 2-95, 2-101
FREE , 2-200, 2-201 State , 2-89, 2-95, 2-101
Free volume modification , 2-147 general cubic equation of state , 2-89, 2-95, 2-101
UNIFAC , 2-147 GeneralInformation , 1-1, 2-49, 2-72, 2-88, 2-123,
Free volume modification to UNIFAC 2-126, 2-158, 2-198, 2-202
UNFV , 2-147 Generalized Correlation , 2-75, 2-139
free volume modified UNIFAC Solvent Activities , 2-139
UNFV , 2-147 Vapor-Liquid Equilibria , 2-76
Free Water Decant , 2-123, 2-124 Generalized Correlation Methods , 2-57, 2-73, 2-75,
Frost-Kalkwarf , 1-4, 1-8 2-76, 2-77, 2-78, 2-79, 2-80, 2-81, 2-82, 2-83
Fugacities , 2-49, 2-51, 2-53, 2-70, 2-89, 2-126, 2-127, Generalized Information , 2-72
2-128, 2-132, 2-133, 2-134, 2-175 Generalized Method , 2-129, 2-211
calculating , 2-127 Predicting Second Virial Coefficients , 2-129
Gaseous Solutions , 2-89 Predicting Viscosities , 2-211
intead , 2-176 Generalized Thermodynamic Correlation Based on
terms , 2-176 Three-Parameter Corresponding States , 1-20,
Fugacity , 2-50, 2-54, 2-57, 2-69, 2-73, 2-75, 2-76, 2-77, 2-81, 2-110
2-88, 2-101, 2-104, 2-107, 2-126, 2-128, 2-129, Generating , 1-40
2-154, 2-175, 2-177, 2-188, 2-190, 2-193, 2-196, Pseudocomponent Properties , 1-40
2-198
calculate , 2-53, 2-88, 2-104, 2-188, 2-190 Generating Pseudocomponent Properties , 1-40
giving , 2-76 Gibbs , 2-101, 2-107, 2-136, 2-137, 2-141, 2-144, 2-181
represents , 2-76 Gibbs-Duhem , 2-187
Fugacity Coefficients , 2-198 form , 2-187
Generalized Correlation , 2-198 Gimi , 2-175
Index-226
Glushko , 2-197 Gyration , 2-130
GLYCOL , 2-63, 2-64, 2-163 Radius , 2-130
Glycol data package , 2-163
Glycol data package uses , 2-163
H
GLYCOL databank , 2-64, 2-163
Glycol Dehydration Systems , 2-64
H.K. Rasmussen , 2-144
Glycol Package , 2-164
H.P. , 2-197
Glycols , 2-49, 2-163
H2O , 2-77, 2-158, 2-163, 2-165, 2-166, 2-168, 2-172,
Glycols tri-ethylene , 2-64 2-175, 2-176, 2-177, 2-179, 2-193, 2-195
involving , 2-63, 2-64 correlating , 2-166
Gmehling , 2-147, 2-149 pressure , 2-195
Gomes , 2-54, 2-134, 2-156, 2-201 H2O-alcohol , 2-159
Goodwin , 2-95 oF , 2-158, 2-159
GPA Research Report RR-118 , 2-171 H2O-CO2-NACL , 2-177
GPA Sour Water Equilibria Correlation , 2-171 H2S , 2-62, 2-63, 2-64, 2-76, 2-77, 2-79, 2-96, 2-125,
GPA Sour Water Package , 2-168 2-158, 2-163, 2-165, 2-168, 2-170, 2-171, 2-172,
2-193, 2-210
GPSA Data Book , 2-124
H2S Volatility Data , 2-168
GPSWAT , 2-158, 2-168
H2S/C3H8 , 2-77
GPSWATER , 2-64, 2-65, 2-170
H2S-CO2-DEA-H2O , 2-165
GPSWATER data package , 2-168
H2S-CO2-MEA-H2O , 2-165
Gravity
specific , 1-15 Haar , 2-195, 2-198
Gravity data , 1-21, 1-36 Halogenated , 2-104
Grayson , 1-16, 2-72, 2-76, 2-77, 2-80 Handbook , 2-181

Aqueous Electrolyte Thermodynamics , 2-181
Grayson-Steeed , 2-124
Hankinson , 2-85
Grayson-Streed , 2-60, 2-61, 2-67, 2-76, 2-77, 2-78,
2-123, 2-124 Hanley , 2-208, 2-211
Grayson-Streed Erbar , 2-60 Hansen , 2-147
Groehling , 2-147 Harris , 2-141
Gross heating value , 1-2 Harvey , 2-99, 2-100
Group Contribution Estimation , 2-146 Hayden-O'Connell , 2-49, 2-69, 2-128, 2-129
Activity Coefficients , 2-144, 2-146 Hayden-O'Connell fu , 2-69
Group interaction data , 2-69, 2-144, 2-147 Hayden-O'Connell fugacity , 2-129
GroupContribution Method HCl , 2-71, 2-125
Polymer Solutions Using , 2-147 HClO , 2-193
Groups , 2-144, 2-145, 2-146 HCN , 2-65
Grulka , 2-139 Heat , 1-6, 1-12, 2-147, 2-156, 2-171, 2-181
GS , 2-60, 2-61, 2-62, 2-76 Formation , 1-6, 1-12
GS/GSE/IGS , 2-61, 2-62 Mixing , 2-148
GSE , 2-60, 2-61, 2-77 Mixing Calculations , 2-156
reaction , 2-172, 2-173, 2-181, 2-182
Guggenheim , 2-142
Heat of formation , 1-6, 1-12, 1-17
Guidelines , 2-135, 2-136, 2-137, 2-138, 2-139, 2-140,
2-141, 2-144, 2-199 Heat of Mixing Calculations , 2-156
Gunn , 2-112, 2-113 Heat of Reaction , 2-173, 2-182
Gupte , 2-107, 2-109 heat of reaction correction , 2-171
Heavy Petroleum , 1-20

HENRY , 2-68, 2-70, 2-155 Hydrocarbon Mixtures-Computer Program
Henry s , 2-154, 2-165 TRAPP , 2-211
databank , 2-155 Hydrocarbon Proc , 2-81
Henry s Law Option , 2-69 Hydrocarbon Processing , 2-168, 2-174
Henry's constants , 2-154, 2-155 Hydrocarbon-rich , 2-77, 2-97, 2-123, 2-124
Henry's Law , 2-56, 2-68, 2-70, 2-71, 2-154, 2-165, Hydrocarbons , 2-211
2-166, 2-169 Improved Viscosity-temperature Chart , 2-211
Henry's Law constants , 2-54, 2-165 Hydrocarbon-water , 2-77, 2-123
Henry's law gas solubility , 2-154 Hydrofiners , 2-60, 2-61
HEPTANE , 2-163 Hydrofluorocarbons , 2-71
Herning , 2-207 HYDROGEN , 2-210
HEXAMER , 2-70, 2-104, 2-105, 2-106, 2-107 Hydrogen deficiency number , 1-2
Hexamers , 2-69, 2-104 Hydrogen Fluoride , 2-104, 2-107
HF , 2-104 HYDROGEN SULFIDE , 2-163, 2-168, 2-171, 2-210
HF alkylation , 2-104
HF hexamerization , 2-106
High Pressure Crude Systems , 2-60
I
Methods Recommended , 2-60
High Pressure Crude Units , 2-61 IC4 , 2-163, 2-210
High Pressure Hydrocarbon-Hydrocarbon IC5 , 2-159, 2-163

Systems , 2-77 ID Name , 2-210
High Pressures , 2-207 IDEAL , 2-59, 2-67, 2-71, 2-73, 2-74, 2-75, 2-156
High Temperature , 2-76, 2-77 IDEAL and LIBRARY , 2-50, 2-73
Vapor-Liquid Equilibria , 2-77 Ideal Liquid Mixtures
Higher Polymer Solutions , 2-138 Composition Curve , 2-205
Highly Polar , 2-94 Ideal Vapor Enthalpy , 1-4
Highly Polar Asymmetric Systems , 2-99 Ideal-solubility , 2-198, 2-199
High-Pressure Aqueous Systems Containing IGS , 2-60, 2-61, 2-77
Gases , 2-100 IGS use , 2-60
High-Pressure Vapor-Liquid Equilibria , 2-112 Curl-Pitzer , 2-60
Hildebrand , 2-137, 2-138 Immiscible , 2-123
Hipkin , 2-80 Improved Accuracy , 2-80
HOCV , 2-70 Nomographs , 2-80
Hoftijzer , 2-168 Improved Correlation , 2-85
Holland , 2-91 Densities , 2-83, 2-85
Holmes , 2-140 Improved Equation , 2-83
Prediction , 2-83
HPDC , 2-210
Improved Grayson-Streed , 2-60, 2-77, 2-123
HPT1 , 2-210
Improved Prediction , 2-81
Huggins , 2-138
Enthalpy , 2-81
Hultgren G.O. 1958 , 2-110
Improved Viscosity-temperature Chart , 2-213
Huntjens , 2-168
Hydrocarbons , 2-213
Huron , 2-102, 2-103
Industrial Applications , 2-149, 2-197
Huron-Vidal , 2-103
Industry , 2-94
Huron-Vidal SRK and PR , 2-101
Infinite-dilution , 2-154, 2-173
Hydrocarbon Mixtures , 2-76
Infinite-pressure Gibbs , 2-102
Index-228
Inside/Out , 1-1 Kendall , 2-205
Intead , 2-175 kerosene water solubility method , 2-124
fugacities , 2-176 Kesler , 1-6, 1-10, 2-81, 2-112
Interaction Coefficients Keyes , 2-124
binary Fill options , 2-120, 2-150
K-factor , 2-125
Interconversion , 1-25
K-free , 2-201
Interconversion of Distillation Curves , 1-25
Kinematic , 2-211, 2-212, 2-213, 2-214
Internally Consistent Correlation , 2-213
Kister , 2-135
Predicting , 1-20, 1-45
Kistiakowsky , 1-15
Predicting Liquid Viscosities , 2-213
Kistiakowsky-Watson , 1-10
Intraphase , 2-175
Introduction , 1-1, 2-54, 2-103, 2-111, 2-134 Knapp , 2-112
Kolbe , 2-147
Ion Interaction Approach , 2-197
Krevelen , 2-165, 2-168
Ionic Chemical Systems , 2-69
Methods Recommended , 2-70, 2-71 Kusik , 2-187, 2-197
Ions , 2-172, 2-184, 2-185, 2-186, 2-196 K-value , 2-50, 2-54, 2-73, 2-75, 2-79, 2-124, 2-154,
2-156, 2-158
Isobutane , 2-163
compute , 2-155
ISOPENTANE , 2-159, 2-163
selected , 2-56
K-values , 2-49, 2-53, 2-60, 2-73, 2-74, 2-75, 2-77, 2-79,
2-97, 2-124, 2-125, 2-154, 2-158, 2-173
J Kwong , 2-91
J.Chem.Phys , 2-138
J.E. Cunningham , 2-91 L
J.H. Prausnitz , 2-137
J.M. Lichtenthaler , 2-154, 2-200 Larsen , 2-148
JANAF Thermochemical Tables , 2-197 Latent heat of vaporization , 1-6, 1-12, 1-18, 2-54, 2-73
Joback , 1-5 Lee , 1-5, 1-10, 1-16, 1-20, 2-81
John Wiley , 2-54, 2-134 Lee-Kesler , 1-6, 2-60, 2-73, 2-80, 2-81
Johnson , 1-16, 2-80 Lee-Kesler characterization , 1-17, 1-18
Johnson-Grayson , 2-80 Lee-Kesler-Plöcker , 2-110
Jones , 2-144, 2-146 Leiden , 2-91
Leland , 2-112, 2-208, 2-211
Lenior , 2-80
K LIBID , 2-159, 2-163
LIBRARY , 2-54, 2-202
K.H. Abrams , 2-196 use , 2-55, 2-56
Kabadi , 2-97, 2-98 LIBRARY enthalpies , 2-56, 2-57
Kabadi-Danner , 2-64, 2-193 Lichtenthaler , 2-54
Kabadi-Danner SRK , 2-97 Light Gases , 2-158
Kansas City , 2-78 Light Hydrocarbon Applications , 2-66
Kay s , 2-81 Light Hydrocarbons , 2-67, 2-109, 2-110
Keenan , 2-124 Light Petroleum Systems , 2-110
Kell , 2-195, 2-198 Fluid Thermodynamic Properties , 2-110
Kelvin , 2-68 Lightends , 1-21, 1-41
Kelvins , 2-181, 2-188, 2-190, 2-216, 2-217 Matching , 1-40

Lightends data , 1-39 Material Balance Equations , 2-179
Lightends-free , 1-39 Materials , 1-25, 2-213
Liquid Mathematical Models , 2-175, 2-181
vapor , 2-50 Mathias , 2-93, 2-94, 2-95
Liquid Activity Coefficient Methods , 2-50, 2-54, Mathias-Copeman , 2-93
2-69, 2-131, 2-135, 2-136, 2-137, 2-138, 2-139,
Maurer , 2-144
2-140, 2-141, 2-144, 2-147, 2-154, 2-156
Liquid Activity Methods MCH , 2-160, 2-163
Fill options , 2-150 MCP , 2-160, 2-210
Liquid activity methods , 2-71, 2-101, 2-147, 2-150, MDEA , 2-65, 2-66, 2-172, 2-173
2-154, 2-158 MEA , 2-65, 2-171, 2-173, 2-193
Liquid Diffusivity , 2-202, 2-215 Meissner , 2-187
Liquid Mixtures , 2-84, 2-85, 2-140 Melhem , 2-95
Thermodynamic Excess Functions , 2-140
Melhem-Saini-Goodwin , 2-93
Liquid molar volume , 1-2, 1-10, 2-52, 2-132, 2-137,
Melting temperature , 2-199
2-138, 2-139
Mercaptan , 2-168
Liquid Regions , 2-208
Mercaptans , 2-62, 2-96
Liquid Thermal Conductivity , 1-4, 2-203
MESH , 2-168
Liquid Viscosity , 1-4, 2-203, 2-204, 2-211
METHANE , 2-210
Special Methods , 2-211
Methods Recommended , 2-61, 2-62, 2-67, 2-68
LiquidLiquid Equilibria , 2-143
Amine Systems , 2-64, 2-65
Liquid-Liquid Equilibrium Equations , 2-178
Aromatic/Non-aromatic Systems , 2-66, 2-67
Liquids , 2-83 Environmental Applications , 2-71
Liquids on Reduced Temperature , 2-205 High Pressure Crude Systems , 2-60
LK , 1-6, 2-61, 2-80 Ionic Chemical Systems , 2-69
LKP , 2-110, 2-112 Low Pressure Crude Systems , 2-60
Lube Oil , 2-60, 2-62
LLE , 2-69
Natural Gas Systems , 2-62, 2-63, 2-64
LLE databank , 2-153
Reformers , 2-60
Local Composition , 2-140, 2-141 Solid Applications , 2-71
LongChain Compounds , 2-138 Sour Water Systems , 2-62
Low Pressure Crude Systems , 2-60 METHY , 2-208
Methods Recommended , 2-60 Methyl Mercaptan , 2-125
Low Pressure Crude Units , 2-60, 2-61 METHYLCYCLOHEXANE , 2-160, 2-163
Lube Oil , 2-60 METHYLCYCLOPENTANE , 2-160, 2-210
Methyldiethanolamine , 2-171
Lubricants , 1-25
Methylpentane , 2-160
Lyngby , 2-147 Misovich , 2-139
Lyngby modified UNIFAC
Mixing , 2-95, 2-139, 2-147
UFT1 , 2-147
Heats , 2-148
Rules , 2-95
M Mixing Calculations , 2-156

Heat , 2-156
mixing rules , 2-67, 2-69, 2-88, 2-91, 2-95, 2-97, 2-98,
Maddox , 2-174 2-99, 2-100, 2-102, 2-103, 2-104, 2-107, 2-154,
Main , 2-77, 2-171 2-187, 2-199, 2-204, 2-215
Margules , 2-135, 2-140 Mixtures , 2-78, 2-142, 2-198, 2-208
Margules Equation , 2-135, 2-136 Pseudo-Critical Constants , 2-78
Index-230
Statistical Thermodynamics , 2-208 N-alkanes , 2-211
Model , 2-178 Naphthalenes , 2-79, 2-80
Example , 2-178 Naphthenes , 2-125
modeling , 2-49 Natural Gas Processing , 2-62
Modifications , 2-147 Natural Gas Systems , 2-62
UNIFAC , 2-147, 2-148, 2-149 Methods Recommended , 2-62
Modifications to UNIFAC , 2-147 NBP , 1-5, 1-6, 1-11, 1-35, 1-37, 1-38, 1-39, 1-40
Modified , 2-92, 2-94, 2-95, 2-98 equal , 1-40
modified UNIFAC , 2-147 function , 1-6
UFT3 , 2-147 NBS Tables , 2-197
Modified UNIFAC Group Contribution Model , 2-148 Chemical Thermodynamic Properties , 2-196
Prediction , 2-148, 2-149 NBS Tech Note , 2-196
Modified UNIFAC Model , 2-149 NBS2 , 2-182
Molalities , 2-177 N-butane , 2-163
Molality , 2-175, 2-176, 2-182, 2-184 NC4 , 2-163
Molar Volume and Density , 2-196 NC5 , 2-160, 2-163
Molecular Thermodynamics , 2-54, 2-154, 2-201 NC6 , 2-160, 2-163
Fluid-Phase Equilibria , 2-54, 2-201 NC7 , 2-160, 2-163
FluidPhase Equilibria , 2-134, 2-156
N-DECANE , 2-210
Molecular weight , 1-1, 1-5, 1-6, 1-12, 1-21, 1-40, 2-58, N-DODECANE , 2-210
2-62, 2-147, 2-163, 2-215
Nelson flash point , 1-47
Molecular weight data , 1-22, 1-38
NEOPENTANE , 2-210
Molecular weight value , 1-38
New Alpha Function , 2-94, 2-101
Molecular-weight , 1-38
New Correlation , 2-85, 2-168
Molecule-molecule , 2-186
NH3 , 2-165, 2-166, 2-167, 2-168
Molecules , 2-208 Saturated Densities , 2-85
Different Sizes , 2-211
New Expression , 2-140, 2-141
Monomer-dimer , 2-127 Excess Free Energy , 2-139
Mueller , 2-112 Excess Gibbs Free Energy , 2-141
Multicomponent , 2-50, 2-96, 2-98, 2-99, 2-100, 2-135, New Generalized Alpha Function , 2-95
2-156, 2-187, 2-200, 2-215 Cubic , 2-92, 2-94, 2-95
Multicomponent Aqueous Solutions , 2-197 New Group-Contribution , 2-109
Multicomponent Equilibria , 2-140 New Mixing Rules , 2-101
Multicomponent Mixtures , 2-112 New Two-constant , 2-91
Corresponding States , 2-110, 2-112
Newman , 2-168, 2-197
Multicomponent Phase Equilibria , 2-141 NH3 , 2-125, 2-158, 2-165, 2-168, 2-170, 2-193
Calculation , 2-143
containing , 2-158
Multiple cutpoint , 1-22 involving , 2-168
M-XYLENE , 2-163, 2-210 New Correlation , 2-165
N-HEPTADECANE , 2-210
N-HEPTANE , 2-160, 2-210
N N-HEXADECANE , 2-210
N-HEXANE , 2-160, 2-210
NACLppt , 2-179
Ni , 2-57, 2-127, 2-134, 2-186, 2-188, 2-195
Nakamura , 2-190, 2-193
N-NONANE , 2-210
Nakamura Method , 2-188, 2-190
NOC , 2-145

N-OCTANE , 2-210 Orye , 2-140
NODIME , 2-139 OXYGEN , 2-210
NOG , 2-145, 2-146 OXYL , 2-163
Nomograph , 2-211 O-XYLENE , 2-163, 2-210
Nomographs , 2-79
Improved Accuracy , 2-79
Nonelectrolyte Solutions , 2-50 P
Classical Thermodynamics , 2-50
Non-hydrocarbon , 2-69, 2-76, 2-202 Panagiotopoulos-Reid , 2-98, 2-100
Nonideal Liquid Mixtures , 2-146 Panagiotopoulos-Reid SRK and PR , 2-98
Nonidealities , 2-70, 2-80, 2-126, 2-167, 2-168 Partington , 2-205
Nonideality , 2-56, 2-69, 2-99, 2-100, 2-133 Peng , 2-89, 2-91, 2-96
Non-ionic Chemical Systems , 2-69 Peng-Robinson , 2-61, 2-89, 2-90, 2-92, 2-94, 2-95,
Nonpolar Gas Mixtures , 2-207 2-96, 2-98, 2-99, 2-101, 2-123
Nonpolar Gaseous Mixtures , 2-112, 2-207 Peng-Robinson Huron-Vidal , 2-101
Nonpolar Substances , 2-208 Peng-Robinson modified , 2-99

Thermal Conductivity , 2-204 Peng-Robinson Panagiotopoulos-Reid , 2-98
Non-Random Two-Liquid , 2-49 PENTANE , 2-210
Normal boiling point , 1-2 Percent Distilled , 1-29, 1-33
Normal Pressures , 2-207 Perturbed-hard-sphere , 2-190
Nothnagel , 2-188, 2-193 following , 2-190, 2-191, 2-193
Nothnagel Method , 2-188 Petro , 2-91

UNIFAC structures , 2-67, 2-68
N-PENTADECANE , 2-210
PETRO Methods , 2-202, 2-204
N-PENTANE , 2-160, 2-210
PETROLEUM , 1-5
NRTL , 2-49, 2-69, 2-101, 2-140, 2-141, 2-158
databank , 2-68 Petroleum Components , 1-5, 1-6, 1-12, 1-16, 1-19
NRTL K-value , 2-158 Petroleum components-acentric factor , 1-6, 1-12,

1-16, 1-19
N-TETRADECANE , 2-210
Petroleum components-critical properties , 1-6, 1-12,
N-TRIDECANE , 2-210 1-16, 1-19
Number , 2-176, 2-177 Petroleum Fractions , 2-80, 2-211, 2-213, 2-215
NB , 2-176, 2-177 Equilibrium Flash Vaporization
N-UNDECANE , 2-210 Calculations , 1-44
Petroleum Products , 1-25, 1-42
Petroleum Refiner , 1-20, 1-44, 2-80
O Petroleum Refining , 2-78, 2-81, 2-82
Phase Equil , 2-91
O2 , 2-68, 2-77, 2-79, 2-96, 2-125, 2-159, 2-163, 2-210
Phase Equilibria , 2-50, 2-94, 2-148
OCTANE , 2-210 Applications , 2-54, 2-134
Oishi , 2-150 Phase-dependent , 2-194
Okamoto , 1-33 Phase-equilibrium , 2-88
Old Framework , 2-181 Phase-independent , 2-196
Olefinic , 2-202 Physical Property Data Service , 1-3
Order-of-magnitude , 2-147 Physics , 2-168
Organic Liquid Phase , 2-175, 2-193, 2-196 Pi , 2-175
Organic Phase Activities , 2-193 Pitzer , 2-112, 2-184, 2-186, 2-197
Index-232
Pitzer term , 2-184 PRO/II Help , 1-1
Plöcker , 2-111, 2-112 PRO/II Keyword Input Manual , 1-3
work , 2-111 PRO/II s databanks , 1-41, 2-129
Poling , 2-205 PRO/II Temperature-dependent Property
Polymer Solutions , 2-138 Equations , 1-3
Polymer Solutions Using , 2-150 Probability-curve , 1-34
maintain , 1-34
Polymer/solvent , 2-138
Poynting , 2-132, 2-133, 2-134 PROII databanks , 2-68
PROPADIENE , 2-210
Poynting correction , 2-52, 2-53, 2-69, 2-133, 2-134,
2-168, 2-170 PROPANE , 2-210
PR , 1-9, 2-61, 2-62, 2-63, 2-67, 2-69, 2-78, 2-89, 2-91, Properties , 2-204
2-96, 2-98, 2-101, 2-124 Properties From Structure , 1-5, 2-202
Prausnitz , 2-54, 2-99, 2-100, 2-112, 2-113, 2-129, 2-134, Property Generation– CAVETT Method , 1-12
2-140, 2-141, 2-142, 2-143, 2-144, 2-146, 2-150,
Property Generation– SIMSCI Method , 1-6
2-156, 2-168, 2-198, 2-199, 2-201, 2-204, 2-205
Property Generation–Lee-Kesler Method , 1-16, 1-19
Predicting , 1-16, 1-19, 1-41, 2-62, 2-196, 2-204
Internally Consistent Correlation , 1-20, 1-45 PROVISION Graphical User , 1-1
vapor-liquid-liquid , 2-64 PRP , 2-98
Vapor-Liquid-Solid Equilibria , 2-196 Pseudocomponent , 1-1, 1-5, 1-21, 1-22, 1-40, 2-82,
Predicting Liquid Viscosities , 2-211 2-83, 2-202
Correlation , 2-211, 2-213, 2-214 define , 1-22
Internally Consistent Correlation , 2-211 Pseudocomponent Properties , 1-40
Predicting Saturated Liquid Density , 2-82 Generating , 1-40
Predicting Second Virial Coefficients , 2-130 Pseudo-components , 2-125
Generalized Method , 2-130 Pseudocomponents , 1-1, 1-5, 1-21, 1-22, 1-23, 1-24,
Predicting Viscosities , 2-215 1-25, 1-33, 1-35, 1-38, 1-39, 1-40, 2-99, 2-202
Generalized Method , 2-215 Pseudo-critical , 2-112
Prediction , 1-20, 2-82, 2-147 Pseudo-Critical Constants , 2-78
Improved Equation , 2-82 Mixtures , 2-78
Modified UNIFAC Group Contribution Pseudocritical Constants , 2-113
Model , 2-147
Pseudoreduced , 2-76
Pseuodoreduced , 2-76
Pressure , 1-25, 2-104, 2-175, 2-195
760 , 1-26, 1-27, 1-29, 1-30, 1-31 Pure , 2-202
H2O , 2-195 PURE Methods , 2-202
HF , 2-104, 2-105, 2-106 P-XYLENE , 2-163, 2-210
Pressure-explicit , 2-128 Pytkowicz , 2-197
Pressure-independent , 2-193
PRH , 2-101
Primary TBP Cutpoint Set , 1-22
Q
PRLN , 2-210
QUADRATIC , 1-34, 1-36
PRM , 2-62, 2-64, 2-68, 2-70, 2-99
Quasichemical , 2-142
PRO/II Application Briefs Manual , 1-1
PRO/II back-calculates , 2-82
PRO/II Casebooks , 1-1 R
PRO/II databanks , 2-61, 2-62, 2-67, 2-82, 2-85
PRO/II Electrolytes , 2-175, 2-181, 2-184, 2-193, 2-198 RACKETT , 1-6, 2-58, 2-82, 2-196
PRO/II flowsheet , 2-70

applying , 1-12 Riedel , 1-4
use , 2-82 Rigorous Calculation , 2-174
Rackett liquid density , 2-82 Robinson , 2-89, 2-91, 2-96, 2-211
Rackett parameter , 1-2, 2-82 Roy , 2-208
Radius , 2-129 Roy-Thodos , 2-207
Gyration , 2-129 Rubin , 2-110
Radius of gyration , 1-2, 2-129
Rules , 2-78, 2-95
Rankine , 1-7, 1-11, 1-14, 1-15, 1-18, 1-29, 1-30, 1-37, Mixing , 2-95, 2-96
2-58, 2-73, 2-166 Stewart , 2-78
Raoult s , 2-73 RVP
Rasmussen , 2-109, 2-147 represents , 1-42
Reached.Estimation , 1-25
thermophysical , 1-25
Reaction , 2-171, 2-181 S
heat , 2-173, 2-181, 2-182
recommended ranges , 2-62, 2-75, 2-77, 2-78, 2-80, Saini , 2-95
2-81, 2-82, 2-83, 2-158, 2-163, 2-165, 2-168, 2-171 Salts , 2-100
Redlich , 2-91, 2-135 Sandler , 2-54, 2-134
Redlich-Kister , 2-157 Sato , 2-205
Redlich-Kister Expansion , 2-157 Satu , 2-204
Redlich-Kwong , 2-75, 2-89, 2-90, 2-91, 2-94, 2-95, Saturated Densities , 2-83
2-102, 2-104, 2-105 New Correlation , 2-83
Reference , 2-111 Saturated Liquid Density , 2-83
Refinery , 2-60 Saturated Liquid Enthalpy , 1-4
Reformers , 2-60, 2-61, 2-62 Saturated Liquids , 2-83
Saturated Nonpolar Liquids , 2-205
Regular Solution Theory , 2-137, 2-138
Saturated-liquid density , 2-74
Reid , 2-98, 2-99
Saturated-liquid enthalpy , 2-55, 2-57
Reid vapor pressure (RVP) , 1-41
Scatchard , 2-137
Reid vapor pressure (RVP)-APICRIDE method , 1-41
Scatchard-Hildebrand , 2-75
Reid vapor pressure (RVP)-APINAPHTHA
method , 1-41 Schiller , 2-147
Reid vapor pressure (RVP)-ASTM D323-73 Scott , 2-138

method , 1-41 Scrivner , 2-197
Reid vapor pressure (RVP)-ASTM D323-82 Seader , 2-72, 2-75, 2-76, 2-77
method , 1-41
Second Liquid Phase , 2-177
Reid vapor pressure (RVP)-ASTM D4953-91 Equations For Solutions Involving , 2-175
method , 1-41
Second Virial Coefficients , 2-128
Reid vapor pressure (RVP)-ASTM D5191-91
Empirical Correlation , 2-129
method , 1-41
Setschenow , 2-186
Reidel , 2-204, 2-205, 2-206
Shale Oils , 1-20
Reidel-Plank-Miller , 1-5
SimSci azeotropic databank , 2-151
Renon , 2-140, 2-141
SIMSCI characterization , 1-6
Renormalized , 2-201
k-free , 2-200 SIMSCI library , 1-1
required components , 2-129, 2-171 Sitzber , 2-135
Required Pure Component Properties , 2-135, 2-136, Skjold-Jørgensen , 2-147
2-137, 2-138, 2-139, 2-140, 2-141, 2-144
Index-234
SLE , 2-71 Specific gravity , 1-2, 1-6, 1-7, 1-11, 1-15, 1-22, 1-36,
SO2 , 2-71, 2-125, 2-193, 2-211 1-37, 1-38, 2-82, 2-85, 2-211
Soave , 2-92, 2-94, 2-96 Specific Heat , 2-204
Soave-Redlich Kwong , 2-96 Specific heat capacity , 1-16, 1-19
Soave-Redlich-Kwong , 2-49, 2-61, 2-96, 2-98, 2-99, Spencer , 2-83

2-100, 2-101, 2-123, 2-125, 2-188, 2-193 Spline , 1-34
Soave-Redlich-Kwong Huron-Vidal , 2-101 SRK , 1-11, 1-12, 2-57, 2-61, 2-62, 2-63, 2-66, 2-67,
Soave-Redlich-Kwong Kabadi-Danner , 2-97, 2-125 2-70, 2-83, 2-84, 2-92, 2-96, 2-97, 2-98, 2-101,
2-125, 2-164, 2-193
Soave-Redlich-Kwong modified , 2-99
SRK databank , 2-164
Soave-Redlich-Kwong Panagiotopoulos-Reid , 2-98
SRK HEXAMER , 2-104
Soave-Redlich-Kwong Panagiotoupolos-Reid , 2-98
SRK Method , 2-193
Soave-Redlich-Kwong SimSci , 2-100
SRK/PR , 2-61, 2-62
Solid , 2-182
SRKH , 2-101
Solid Applications
Methods Recommended , 2-69 SRKKD , 2-63, 2-64, 2-97
Solid Cp , 1-4 SRKM , 2-58, 2-62, 2-64, 2-66, 2-67, 2-70, 2-99, 2-100,
2-159, 2-163, 2-164, 2-167, 2-170, 2-171, 2-173
Solid Phase , 2-177, 2-194, 2-196
SRKM/PRM , 2-62, 2-63
Solid Thermal Conductivity , 1-4
SRKP , 2-98
Solid-Liquid Equilibria , 2-198, 2-199, 2-200
SRKS , 2-64, 2-66, 2-67, 2-69, 2-100, 2-107
Solubility Data , 2-198, 2-199, 2-200, 2-201
SRKS/SRKM , 2-69
Solubility Parameter , 1-2
Starling , 2-109, 2-110
Solubility parameter (Hildebrand) , 1-6, 1-16, 1-19,
2-138 Starling s BWRS , 2-110
solute components , 2-155 State , 1-11, 2-49, 2-51, 2-52, 2-53, 2-55, 2-56, 2-58,
2-59, 2-60, 2-63, 2-66, 2-67, 2-75, 2-83, 2-88, 2-89,
Solutions , 2-89, 2-135, 2-138, 2-139
2-90, 2-91, 2-92, 2-94, 2-95, 2-96, 2-97, 2-98, 2-99,
Classification , 2-135 2-100, 2-101, 2-102, 2-103, 2-104, 2-105, 2-106,
Thermodynamic Properties , 2-138 2-107, 2-108, 2-109, 2-110, 2-124, 2-125, 2-126,
Thermodynamics , 2-91 2-127, 2-128, 2-129, 2-131, 2-133, 2-154, 2-155,
Solvation , 2-130 2-156, 2-159, 2-163, 2-164, 2-167, 2-170, 2-171,
2-173, 2-181, 2-182, 2-183, 2-188, 2-190, 2-193,
Solve , 2-155
2-195, 2-196
C1 , 2-155
Associating Equation , 2-127
Solvent , 2-60, 2-62, 2-182 equation , 1-8, 1-9, 1-11, 1-12, 1-16, 1-17, 1-18,
Solvent Activities , 2-138, 2-150 1-20, 1-42, 1-43, 2-49, 2-52, 2-53, 2-55, 2-56,
Generalized Correlation , 2-138 2-58, 2-59, 2-60, 2-63, 2-69, 2-75, 2-76, 2-82,
Solvent De-asphalting Units , 2-60, 2-62 2-83, 2-88, 2-89, 2-90, 2-91, 2-92, 2-93, 2-94,
2-95, 2-96, 2-98, 2-99, 2-100, 2-101, 2-102,
SOUR , 2-62, 2-64, 2-65, 2-158, 2-165, 2-166, 2-167,
2-103, 2-104, 2-105, 2-106, 2-107, 2-108, 2-109,
2-168
2-110, 2-112, 2-124, 2-126, 2-127, 2-128, 2-129,
Sour Package , 2-165 2-131, 2-132, 2-133, 2-134, 2-154, 2-155, 2-156,
Sour water data package , 2-165 2-157, 2-159, 2-163, 2-164, 2-167, 2-170, 2-171,
2-173, 2-181, 2-182, 2-183, 2-188, 2-190, 2-193,
Sour Water EQuilibrium , 2-165
2-195, 2-196
Sour Water Systems , 2-64 General Cubic Equation , 2-89, 2-95, 2-101
Methods Recommended , 2-63, 2-65
Statistical Thermodynamics , 2-143, 2-211
Special Methods , 2-211 Mixtures , 2-208, 2-211
Liquid Viscosity , 2-211
Statistical-mechanical , 2-142
Special Methods for LiquidViscosity , 2-211
Steil , 2-204
Special Packages , 2-62, 2-158, 2-163, 2-165, 2-168,
2-171 Stewart , 2-78

Stiel , 1-15 Temperature-dependent Properties , 1-3, 1-10, 1-13
Stoichiometric , 2-175 Temperature-independent , 2-194, 2-196
Straightforward , 1-39, 2-82, 2-127 Terms , 2-175
Stream Average Properties , 2-202 fugacities , 2-175
Stream Property , 2-203 Ternary Liquid Systems , 2-136
Streed , 2-72, 2-76, 2-77 Tertiary amines , 2-171
Streed s , 2-76 Theory , 1-1, 2-80, 2-110, 2-112, 2-127, 2-129, 2-137,
2-138, 2-196, 2-200
Strong Electrolytes
Thermodynamic Properties , 2-196 Thermal Conductivity , 2-202, 2-205, 2-206, 2-208,
2-209, 2-211
Strongly Non-ideal Mixtures , 2-103
Determination , 2-206
Representing Vapor-Liquid Equilibria , 2-103
Thermal Constants , 2-197
Subcooled , 2-198
Thermodynamic , 2-89, 2-91
Subcritical , 1-3
Solutions , 2-91
SULFLN , 2-159
Thermodynamic Evaluation , 2-136
Sulfolane , 2-159
Binary , 2-136
SULFUR DIOXIDE , 2-211 Thermodynamic Excess Functions , 2-141
Supercritical Systems , 2-94 Liquid Mixtures , 2-141
Surface Tension , 1-4, 2-203 Thermodynamic Framework , 2-181, 2-193
Suther G.A. 1968 , 2-208 Thermodynamic Methods , 2-54, 2-59, 2-60
SWEQ , 2-165, 2-167, 2-168 Thermodynamic Methods-Chemical
uses , 2-165, 2-168 Applications , 2-69
Systems Containing Polar Components , 2-91 Thermodynamic Methods-Density , 2-58
Vapor-Liquid Equilibria , 2-94 Thermodynamic Methods-Enthalpy , 2-54
Thermodynamic Methods-Entropy , 2-57
Thermodynamic Methods-General Information , 2-49
T
Thermodynamic Methods-Natural Gas
Processes , 2-62
TBP , 1-21, 1-22, 1-25, 1-26, 1-27, 1-31, 1-33 Thermodynamic Methods-Phase Equilibria , 2-50
Convert , 1-26, 1-27, 1-29, 1-31
Thermodynamic Methods-Refinery & Gas
curves , 1-26, 1-27, 1-30, 1-31, 1-32, 1-33 Processes , 2-60
D86 , 1-25, 1-29, 1-31, 1-32, 1-33
Thermodynamic Properties , 1-16, 1-19, 2-109, 2-110,
Hg , 1-25, 1-26, 1-27, 1-29, 1-31 2-112, 2-135, 2-138, 2-196
resulting , 1-22 Algebraic Representation , 2-135
TBP Curves , 1-35 Empirical Equation , 2-109
TBP cutpoints , 1-21 Fluids , 2-110
sets , 1-21, 1-22 Gas Mixtures Containing Polar , 2-196
TBP Range , 1-22 Prediction , 1-16, 1-19
Solutions , 2-138
Tc , 1-7, 1-12, 1-15, 2-55, 2-56, 2-90, 2-104, 2-111
Strong Electrolytes , 2-196
TDCN , 2-210
Thermophysical , 1-6, 1-25, 2-50
Technical Data Book , 2-78, 2-81, 2-82
reached.Estimation , 1-25
Technical Gas Mixtures , 2-204
Third Generation Process Simulation , 2-94
TEG , 2-62, 2-163
Thomas , 2-204, 2-205
Temperature- dependent Properties , 1-3
Thomson , 2-84, 2-85
Temperature-dependent , 1-3, 2-88, 2-91, 2-95, 2-147
Three-parameter , 2-135, 2-147
incorporating , 2-147
Three-parameter corresponding-states , 2-80
Temperaturedependent , 2-141
TOLU , 2-160, 2-163, 2-210
Index-236
Torres-Marchal , 2-149 UNIQUAC , 2-67, 2-68, 2-69, 2-70, 2-141, 2-142, 2-143,
TR , 1-9, 2-55, 2-76, 2-78, 2-181, 2-194 2-144
UNIQUAC Equation , 2-142, 2-143, 2-144
Trans-2-BUTENE , 2-210
UNIWAALS , 2-70, 2-91, 2-107, 2-108
Trans-2-PENTENE , 2-210
UNIWAALS equation-of-state , 2-70
Transport Properties , 2-202, 2-204, 2-208, 2-211, 2-215
Transport properties-API method , 2-211 Unsaturated Hydrocarbons , 2-125
Use , 1-22, 1-37, 2-54, 2-61, 2-70, 2-71, 2-80, 2-82,
Transport properties-thermal conductivity , 2-208
2-165, 2-170
Transport properties-TWU method , 2-211 cutpoints , 1-22, 1-23, 1-24
Transport properties-viscosity , 2-204 LIBRARY , 2-55, 2-56
Transport properties-Wilke-Chang method , 2-215 PHI , 2-69, 2-70
TRAPP , 2-202 Rackett , 2-82, 2-83
Triethylene Glycol , 2-163 SimSci , 2-62
SWEQ , 2-165, 2-168
Triple Point Pressure , 1-2
three-parameter corresponding-states , 2-80
Triple-point temperature , 2-199
USER , 1-1
True Boiling Point , 1-21
User-supplied Diffusivity Data , 2-215
True vapor pressure (TVP) , 1-41
Utilities , 2-181
True vapor pressure (TVP)-application
guidelines , 1-41
Truncated Virial , 2-128, 2-129, 2-168 V
TVIRIAL , 2-128
TVP
van der Waals , 2-89, 2-90, 2-91, 2-95, 2-99, 2-107,
function , 1-42
2-108, 2-112, 2-142, 2-144, 2-145
TVP Methods , 1-43
van der Waals area and volume , 1-2, 2-142, 2-144
Two-Parameter Cubic , 2-89, 2-90
Van der Waals mixing , 2-112
Twu , 1-6, 1-10, 2-92, 2-94, 2-95, 2-100, 2-101, 2-104,
van Laar , 2-136, 2-140
2-106, 2-107, 2-211, 2-213, 2-215
Van Laar Equation , 2-136
Twu-Bluck-Coon , 2-113
Van Ness , 2-54, 2-134
Twu-Bluck-Cunningham-Coon , 2-92
Van Nostrand Reinhold Co , 2-138
Twu-Coon-Cunningham , 2-93, 2-94
Van t Hoff , 2-69, 2-198
Type , 1-25
Distillation Curves , 1-25 Van t Hoff SLE , 2-69
van't HoffEquation , 2-198, 2-199, 2-200
VANT HOFF Method , 2-71
U VAPOR , 2-194
Vapor and Solid Phases , 2-194
UFT1 , 2-151 Vapor fugacity , 2-49
UFT1 Lyngby , 2-147 Vapor Phase , 2-196
UFT2 Dortmund , 2-148 Vapor Phase Fugacities , 2-128, 2-130, 2-188, 2-190,
UFT3 , 2-149 2-193
UNDC , 2-210 Vapor Phase Imperfections , 2-168
UNFV , 2-149 Vapor pressure , 1-2, 1-3, 1-4, 1-10, 1-11, 1-12, 1-26,
2-52, 2-55, 2-74, 2-79, 2-83, 2-85, 2-96, 2-105,
UNIFAC , 2-69, 2-107, 2-144, 2-147, 2-154
2-132, 2-135, 2-136, 2-137, 2-138, 2-139, 2-140,
Free volume modification , 2-149 2-142, 2-155, 2-166
UNIFAC Group Contribution , 2-147 Vapor Pressure Calculations , 1-41
UNIFAC Structure Vapor Pressure Equations , 1-4, 1-16, 1-19
petro , 2-68

Vapor pressure-Antoine equation , 1-12 Wasserfach , 2-207
Vapor Thermal Conductivity , 1-4, 2-203, 2-207 WATER , 2-209, 2-211
Vapor Viscosity , 1-2, 1-4, 2-203, 2-204 Water
Vapor/liquid , 2-195 density , 1-15
Vaporization , 1-4, 1-10, 1-11, 1-12, 1-15, 2-55, 2-74 Water Activity , 2-187
latent heat , 1-6, 1-12, 1-18, 2-55, 2-57, 2-74 Water decant , 2-63, 2-123, 2-124
Vapor-Liquid Equilibria , 1-20, 2-75, 2-76, 2-77, 2-91, water partial pressure , 2-123, 2-124
2-109, 2-144, 2-168 Water/hydrocarbon , 2-97
Generalized Correlation , 2-75, 2-76 estimates , 2-97
High Temperature , 2-77
Water-hydrocarbon , 2-97, 2-98, 2-125
Systems Containing Polar Components , 2-94
Water-Hydrocarbon Phase Equilibria , 2-98
VaporLiquid Equilibria , 2-143, 2-147
Watson , 1-12, 1-16, 1-19, 2-124, 2-211
Vapor-Liquid Equilibrium Calculations , 2-129 expresses , 2-211
VaporLiquid Equilibrium XI , 2-140 function , 2-125
Vapor-liquid-liquid , 2-62 Watson characterization , 1-11, 2-215
predict , 2-63, 2-64
Watson K , 1-37, 2-68
Vapor-Liquid-Solid Equilibria , 2-197
Watson K-factor , 1-14, 1-37
Predicting , 2-197
WATSONK , 1-37
Vapor-phase fugacity , 2-181
WCO2 , 2-65
Vapor-phase nonidealities , 2-170
Webb , 2-110
Various Mineral Oils
Weidlich , 2-149
Specific Heat , 2-206
Weight-fraction , 1-35
Versatile Phase Equilibrium , 2-95
Vidal , 2-102, 2-103 WH2S , 2-65
Wien , 2-135
Virial , 2-128, 2-129, 2-130, 2-170, 2-188
Wilke , 2-216
Viscosity , 2-204, 2-205, 2-207, 2-208, 2-209, 2-211
Nonpolar Gas Mixtures , 2-204 Wilke-Chang , 2-215, 2-216
Technical Gas Mixtures , 2-207 Wilke-Chang Correlation , 2-215, 2-216
VL , 1-10 Wilke-Chang method , 2-215
VLE , 2-62, 2-69, 2-107, 2-147 WILSON , 2-69, 2-139, 2-140, 2-141, 2-165, 2-168
VLE databank , 2-153 Wilson Equation , 2-139, 2-140
VLLE , 2-123 Wilson Equation Used , 2-140
Vloeistoftoestand , 2-91 Predict Vapor Compositions , 2-140
Volume-averaged , 1-37 Winkle , 2-140
Volume-explicit , 2-127 Wiss , 2-135
Volume-fraction , 1-35 WNH3 , 2-65, 2-170
Volumetric , 2-112, 2-113 Wohl , 2-136
Volumetric Data , 2-110 Wohl s , 2-136
Gas Mixtures , 2-113 Work , 2-110
Volumetric Properties , 2-112 Plöcker , 2-110
Wright , 2-212, 2-213
W
Y
Walas , 2-134
Wamine , 2-65, 2-66 Yamada , 2-204, 2-205
Index-238
Yoon , 2-207 Z
Zipperer , 2-207

Volume2: Unit Operations
General Information
The PRO/II Reference Manual provides details on the basic equations and calculation techniques used in
the PRO/II simulation program and the PROVISION Graphical User interface. It is intended as a reference
source for the background behind the various PRO/II calculation methods.
What is in This Manual?

This volume of the PRO/II Reference Manual contains the correlations and methods used for the various
unit operations, such as the Inside/Out and Chemdist column solution algorithms.
For each method described, the basic equations are presented, and appropriate references provided for
details on their derivation. General application guidelines are provided, and, for many of the methods, hints
to aid solution are supplied.
Who Should Use This Manual?

For novice, average, and expert users of PRO/II, this manual provides a good overview of the calculation
modules used to simulate a single unit operation or a complete chemical process or plant. Expert users can
find additional details on the theory presented in the numerous references cited for each topic. For the nov-
ice to average user, general references are also provided on the topics discussed, e.g., to standard text-
books.
Specific details concerning the data entry steps required by the program can be found in the main PRO/II
Help. Detailed sample problems are provided in the PRO/II Application Briefs Manual, in the
\USER\APPLIB\ directory, and in the PRO/II Casebooks.
Finding What you Need

A Table of Contents in the electronic version of this manual includes hypertext links to the appropriate
chapters and sections. This provides quick access to information that may assist in preparing and entering
the required input data.
Chapter 3: Flash Calculations
PRO/II contains calculations for equilibrium flash operations

such as flash drums, mixers, splitters, and valves. Flash calcu-
lations are also used to determine the thermodynamic state of
each feed stream for any unit operation. For a flash calcula-
tion on any stream, there are a total of NC + 3 degrees of free-
dom, where NC is the number of components in the stream. If
the stream composition and rate are fixed, then there are 2
degrees of freedom that may be fixed. These may, for exam-
ple, be the temperature and pressure (an isothermal flash). In
addition, for all unit operations, PRO/II also performs a flash
calculation on the product streams at the outlet conditions.
The difference in the enthalpy of the feed and product streams
constitutes the net duty of that unit operation.
Basic Principles
Equilibrium Unit Operations
Basic Principles
Figure 1-1: Three-phase equilibrium flash
MESH Equations
Two-phase Isothermal Flash Calculations
PRO/II Unit Operations Reference Manual 1-241

Flash Tolerances
Bubble Point Flash Calculations
Dew Point Flash Calculations
Two-phase Adiabatic Flash Calculations
Water Decant
Three-phase Flash Calculations
MESH Equations
The Mass balance, Equilibrium, Summation, and Heat bal-
ance (or MESH) equations may be written for a three-phase
flash as:
Total Mass Balance:
Equation (1-1):
F  V  L1  L2
Component Mass Balance:

Equation (1-2):
Fzi  Vyi  L1 x1i  L2 x2i
Equilibrium:
Equation (1-3):
yi  K1i x1i
Equation (1-4):
yi  K 2i x2i
Equation (1-5):
K 2i
x1i  x2i
K1i
Summations:
Equation (1-6):
 y x
i
i
i
1i 0
Flash Calculations 3-242

Equation (1-7):
 y x
i
i
i
2i 0
Heat Balance:
Equation (1-8):
FH f  Q  VH v  L1 H1i  L2 H 2i
Also See:
Basic Principles
Two-phase Isothermal Flash Calculations

For a two-phase flash, the second liquid phase does not exist;
i.e., L2 = 0, and L1 = L in equations (1-1) through (1-8) above.
Substituting in equation (1-2) for L from equation (1-1), we
obtain the following expression for the liquid mole fraction,
xi:
Equation (1-9):
zi
xi 
V
 Ki  1 1
F
The corresponding vapor mole fraction is then given by:
Equation (1-10):
yi  K i xi
The mole fractions (xi and yi) sum to 1.0:

Equation (1-11):
x y
i
i
i
i  1.0
However, the solution of equation (1-11) often gives rise to

convergence difficulties for problems where the solution is
reached iteratively. Rachford and Rice in 1952 suggested that
the following form of equation (1-11) be used instead:

Equation (1-12):
 Ki  1 zi
 y x  
i i
V
 TOL
i i i
 Ki  1 1
F
Equation (1-12) is easily solved iteratively by a Newton-Raphson
technique, with V/F as the iteration variable.
Figure 1-1 shows the solution algorithm for a two-phase iso-

thermal flash, i.e., where both the system temperature and
pressure are given. The following steps outline the solution
algorithm.
1. The initial guesses for component K-values are obtained
from ideal K-value methods. An initial value of V/F is
assumed.
2. Equations (1-9) and (1-10) are then solved to obtain xi's
and yi's.
3. After equation (1-12) is solved within the specified toler-
ance, the composition convergence criteria are checked,
i.e., the changes in the vapor and liquid mole fraction for
each component from iteration to iteration are calculated:
Equation (1-13):
yi , ITER  yi , ITER 1
 TOL
yi
Equation (1-14):
xi , ITER  xi , ITER 1
 TOL
xi
4. If the compositions are still changing from one iteration to

the next, a damping factor is applied to the compositions
in order to produce a stable convergence path.
5. Finally, the VLE convergence criterion is checked, i.e.,
the following condition must be met:
Equation (1-15):
 y   x 
i i ITER    yi   xi  ITER 1  TOL

6. A check is made to see if the current iteration step, ITER,
is greater than ITERmax, the maximum number of itera-
tion steps. If ITER > ITERmax, the flash has failed to
reach a solution, and the calculations stop. If ITER
<ITERmax, the calculations continue.
7. Steps 2 through 6 are repeated until the composition con-
vergence criteria and the VLE criterion are met. The flash
is then considered solved.
8. Finally, the heat balance equation (1-8) is solved for the
flash duty, Q, once V and L are known.

Figure 1-1: Flowchart for Two-phase T-P Flash Algorithm

Figure 1-1: Flowchart for T-P Flash Algorithm {continued}
Also See:
Basic Principles
Flash Tolerances
The flash equations are solved within strict tolerances. Most
of these tolerances are built into the PRO/II flash algorithm
and cannot be modified by the user. However, the Composi-
tion Convergence Tolerance is not protected and may be
changed by users. Table 1-20 shows the values of the toler-
ances used in the algorithm for the Rachford-Rice equation (),

the composition convergence equations (1-13) and (4), and
the VLE convergence equation (1-15).
Table 1-20: Flash Tolerances
Equation Tolerance Basis
Rachford-Rice (1-12) 3.0e-8 absolute
Composition Convergence (1-13), (1-14) 3.0e-6 relative
VLE Convergence (1-15) 1.0e-5 absolute

Also See:
Basic Principles
Bubble Point Flash Calculations

For bubble point flashes, the liquid phase component mole
fractions, xi, still equal the component feed mole fraction, zi.
Moreover, the amount of vapor, V, is equal to zero. Therefore,
the relationship to be solved is:
Equation (1-16): 
K z   y
i
i i
i
i  1.0
The bubble point temperature or pressure is to be found by

trial-and-error Newton-Raphson calculations, provided one of
them is specified.
The K-values between the liquid and vapor phase are calcu-
lated by the thermodynamic method selected by the user.
Equation (1-16) can, however, be highly non-linear as a func-
tion of temperature as K-values typically vary as exp(1/T).
For bubble point temperature calculations, where the pressure
and feed compositions has been given, and only the tempera-
ture is to be determined, equation (1-16) can be rewritten as:
Equation (1-17):
 
ln   K i zi   0
 i 

Logarithmic equation (1-17) is more linear in behavior than
equation (1-16) which is a function of temperature, so a solu-
tion can be achieved more readily.
Equation (1-16) behaves in a more linear fashion as a function
of pressure, because the K-values vary as 1/P. For bubble
point pressure calculations, where the temperature and feed
compositions have been given, the equation to be solved can
be written as:
Equation (1-18):
 K z 1  0
i
i i

Also See:
Basic Principles
Dew Point Flash Calculations

A similar technique is used to solve a dew point flash. The
fractional amount of vapor, V/F, is equal to 1.0. Simplification
of the mass balance equations result in the following relation-
ship:
Equation (1-19):
z
i
i / K i   xi  1.0
i
For dew point pressure calculations, equation (1-19) can be

linearized by writing it as:
Equation (1-20):
 z 
ln   i   0
 i Ki 
For dew point temperature calculations, equation (1-19) may
be rewritten as:
Equation (1-21):
 zi 
  1  0
 i Ki 

The dew point temperature or pressure is then found by itera-
tive Newton-Raphson calculations using either equation (1-
20) or (1-21).
Also See:
Basic Principles
Two-phase Adiabatic Flash Calculations

For a two-phase, adiabatic (Q = 0) system, the heat balance
equation (1-8) can be rewritten as:
Equation (1-22):
Hv  V  Hl
1  1    TOL
Hf  F  Hf
An iterative Newton-Raphson technique is used to solve the

Rachford-Rice equation (1-12) simultaneously with equation
(1-22) using V/F and temperature as the iteration variables.
Also See:
Basic Principles
Water Decant
The water decant option in PRO/II is a special case of a three-
phase flash. If this option is chosen, and water is present in the
system, a pure water phase is decanted as the second liquid
phase, and this phase is not considered in the equilibrium
flash computations. This option is available for a number of
thermodynamic calculation methods such as Soave-Redlich-
Kwong or Peng-Robinson.
Note: The free-water decant option may only be used with the
Soave-Redlich- Kwong, Peng-Robinson, Grayson-Streed,
Grayson-Streed-Erbar, Chao-Seader, Chao-Seader-Erbar,
Improved Grayson-Streed, Braun K10, or Benedict-Webb-
Rubin-Starling methods. Note that water decant is
automatically activated when any one of these methods is
selected.

The water-decant flash method as implemented in PRO/II fol-
lows these steps:
1. Water vapor is assumed to form an ideal mixture with
the hydrocarbon vapor phase.
2. Once either the system temperature, or pressure is
specified, the initial value of the iteration variable, V/F
is selected and the water partial pressure is calculated
using one of two methods.
3. The pressure of the system, P, is calculated on a water-
free basis, by subtracting the water partial pressure.
4. A pure water liquid phase is formed when the partial
pressure of water reaches its saturation pressure at that
temperature.
5. A two phase flash calculation is done to determine the
hydrocarbon vapor and liquid phase conditions.
6. The amount of water dissolved in the hydrocarbon-
rich liquid phase is computed using one of a number of
water solubility correlations.
7. Steps 2 through 6 are repeated until the iteration vari-
able is solved within the specified tolerance.
Reference
1. Perry R. H., and Green, D.W., 1984, Chemical Engi-
neering Handbook, 6th Ed., McGraw-Hill, N.Y.
2. Rachford, H.H., Jr., and Rice, J.D., 1952, Journal of
Petroleum Technology, 4 sec.1, 19, sec. 2,3.
3. Prausnitz, J.M., Anderson, T.A., Grens, E.A., Eckert,
C.A., Hsieh, R., and O'Connell, J.P., 1980, Computer
Calculations for Multicomponent Vapor-Liquid and
Liquid-Liquid Equilibria, Prentice-Hall, Englewood
Cliffs, N.J.
Also See:
Basic Principles

Three-phase Flash Calculations
For three-phase flash calculations, with a basis of 1 moles/unit
time of feed, F, the MESH equations are simplified to yield
the following two nonlinear equations:
Equation (1-23):
f1  L1 , L2   a z
i
i i / d i  Tolerance
Equation (1-24):
f1  L1 , L2   b z
i
i i / di  Tolerance
where:
Equation (1-25):
ai  1  K1i 
Equation (1-26):
bi  1  K 2i  K1i / K 2i 
Equation (1-27):
di  K1i  ai L1  bi L2
Equations (1-23) through (1-26) are solved iteratively using a

Newton-Raphson technique to obtain L1 and L2. The solution
algorithm developed by SimSci is able to rigorously predict
two liquid phases. This algorithm works well even near the
plait point, i.e., the point on the ternary phase diagram where a
single phase forms.
Table 1-21 shows the thermodynamic methods in PRO/II
which are able to handle VLLE calculations. For most meth-
ods, a single set of binary interaction parameters is inadequate
for handling both VLE and LLE equilibria. The PRO/II data-
banks contain separate sets of binary interaction parameters
for VLE and LLE equilibria for many of the thermodynamic
methods available in PRO/II, including the NRTL and UNI-
QUAC liquid activity methods. For best results, the user
should always ensure that separate binary interaction parame-

ters for VLE and LLE equilibria are provided for the simula-
tion.
Table 1-21: VLLE Predefined Systems and K-value
Generators
K-value Generators VLLE Predefined Systems
K-value Method System
SRK1 AMINE SRK1 NRTL
SRKMNRTL SRKMUNIQUAC 
SRKKDUNIQUAC  SRKKDUNIFAC
SRKHUNIFAC SRKHUFT1 
SRKPUFT1  SRKPUFT2 
SRKSUFT2 SRKSUFT3
PR1 UFT3 PR1 UNFV 
PRMUNFV PRMVANLAAR 
PRHVANLAAR PRHMARGULES 
PRPMARGULES PRPREGULAR 
UNIWAALSREGULAR UNIWAALSFLORY
IGSFLORY IGSALCOHOL 
GSESOUR GSEGLYCOL 
CSE GPSWATER CSE SOUR
HEXAMERLKP AMINEGPSWATER 
HEXAMERLKP
1 VLLE available, but not recommended
Also See:
Basic Principles

Flash Drum
Valve
Mixer
Splitter
Flash Drum
The flash drum unit can be operated under a number of differ-
ent fixed conditions; isothermal (temperature and pressure

specified), adiabatic (duty specified), dew point (saturated
vapor), bubble point (saturated liquid), or isentropic (constant
entropy) conditions. The dew point may also be determined
for the hydrocarbon phase or for the water phase. The Upper
dew point may be determined for the total feed. In addition,
any general stream specification such as a component rate or a
special stream property such as sulfur content can be made at
either a fixed temperature or pressure. For the flash drum unit,
there are two other degrees of freedom which may be set by
imposing external specifications. Table 1-22 shows the 2-
specification combinations available for the flash unit opera-
tion.
Table 1-22: Constraints in Flash Unit Operation
Flash Operation Specification 1 Specification 2
ISOTHERMAL Temperature Pressure
DEW POINT Temperature  V/F=1.0
Pressure V/F=1.0
BUBBLE POINT Temperature  V/F=0.0
Pressure V/F=0.0
ADIABATIC Temperature  Fixed Duty
Pressure Fixed Duty
ISENTROPIC Temperature  Fixed Entropy
Pressure Fixed Entropy
UPPERDEWPOINT Temperature V/F=1.0
TPSPEC Temperature  General Stream
Pressure Specifications

Also See:

Valve
Figure 1-1: Valve Unit
The valve unit operates in a similar manner to an adiabatic

flash. The outlet pressure, or the pressure drop across the
valve is specified, and the temperature of the outlet streams is
computed for a total duty specification of 0. The outlet prod-
uct stream may be split into separate phases. Both VLE and
VLLE calculations are allowed for the valve unit. One or
more feed streams are allowed for this unit operation.
Also See:
Mixer
Figure 1-1: Mixer Unit
The mixer unit is, like the valve unit operation, solved in a
similar manner to that of an adiabatic flash unit. In this unit,
the temperature of the single outlet stream is computed for a
specified outlet pressure and a duty specification of zero. The
number of feed streams permitted is unlimited. The outlet
product stream will not be split into separate phases.

Also See:
Splitter
Figure 1-1: Splitter Unit
The temperature and phase of the one or more outlet streams

of the splitter unit are determined by performing an adiabatic
flash calculation at the specified pressure, and with duty spec-
ification of zero. The composition and phase distribution of
each product stream will be identical. One feed stream or a
mixture of two or more feed streams are allowed.
For a Splitter unit having M number of declared products, (M
– 1) product specifications are required. This properly implies
the Splitter requires a minimum of two product streams, and
every product stream except for one must have a product spec-
ification associated with it.
Also See:
Flash Calculations

Chapter 2: Isentropic Calculations
PRO/II contains calculation methods for the following single stage

constant entropy (isentropic) unit operations. These include:
 Compressors (adiabatic or polytropic efficiency specified)
 Expanders (adiabatic efficiency specified)
Compressor
Expander
General Information
PRO/II contains calculations for single stage, constant entropy
(isentropic) operations such as compressors and expanders. The
entropy data needed for these calculations are obtained from a num-
ber of entropy calculation methods available in PRO/II. These
include the Soave-Redlich-Kwong cubic equation of state, and the
Curl-Pitzer correlation method. Table 2-23 shows the thermody-
namic systems which may be used to generate entropy data. User-
added subroutines may also be used to generate entropy data.
Table 2-23: Thermodynamic Generators for Entropy

Generator Phase
Braun K10, CS, GS, GSE, CSE, IGS* VL
Lee-Kesler (LK) VL
LIBRARY L
AMINE, SOUR, GPSWATER, GLYCOL** VL
Soave Redlich-Kwong (SRK) VL
Peng-Robinson (PR) VL
SRK Kabadi-Danner (SRKKD) VL
SRK and PR Huron-Vidal (SRKH, PRH) VL
SRK and PR Panagiotopoulos-Reid (SRKP, PRP) VL
SRK and PR Modified (SRKM, PRM) VL
SRK SimSci (SRKS) VL
UNIWAALS VL
Benedict-Webb-Rubin-Starling (BWRS) VL

Table 2-23: Thermodynamic Generators for Entropy
Hexamer VL
* When any of these thermodynamic systems are chosen, the Curl-
Pitzer method is used to calculate entropies. For example, by
choosing the keyword SYSTEM=CS, Curl-Pitzer entropies are
selected.
** When any of these thermodynamic systems are chosen, the SRKM
method is used to calculate entropies. For example, by choosing the
keyword SYSTEM=AMINE, SRKM entropies are selected.
Once entropy data are generated (see Basic Principles in chapter 2

of the Component and Thermophysical Properties Reference Man-
ual.), the condition of the compressor outlet stream is computed.
Using these results, and a user-specified adiabatic or polytropic effi-
ciency, the compressor power requirements are computed.
Also See:
Isentropic Calculations
Compressor
Once entropy data are available, the condition of the compressor
outlet stream is computed. These results may be used alone, or in
conjunction with (optional) user-specified adiabatic or polytropic
efficiency to compute the compressor power requirements.
Basic Calculations
ASME Method
GPSA Method
Basic Calculations
For a compression process, the system pressure P is related to the
volume V by:
Equation(2-1):
PV n  constant
where n = isentropic coefficient
Isentropic Calculations 2-258

Figure 2-1 shows a series of these pressure versus volume curves as
a function of n.
Figure 2-1: Polytropic Compression Curve
The curve denoted by n=1 is an isothermal compression curve. For

an ideal gas undergoing adiabatic compression, n is the ratio of spe-
cific heat at constant pressure to that at constant volume, i.e.,
Equation(2-2):
n  k  CP / Cv
where:
k = ideal gas isentropic coefficient
Cp = specific heat at constant pressure
Cv = specific heat at constant volume
For a real gas, n > k.
The Mollier chart (Figure 2-2) plots pressure versus enthalpy, as
functions of entropy and temperature. This chart is used to show the
methods used to calculate the outlet conditions for the compressor
as follows:

Figure 2-2: Typical Mollier Chart for Compression
A flash is performed on the inlet feed at pressure P1, and tempera-

ture T1, using a suitable K-value and enthalpy method, and one of
the entropy calculation methods in Table 2-23. The entropy S1, and
enthalpy H1 are obtained at point (P1,T1,S1,H1).
The constant entropy line through S1 is followed until the user-
specified outlet pressure (P2) is reached. This point represents the
temperature (T2) and enthalpy conditions (H2) for an adiabatic effi-
ciency of 100%. The adiabatic enthalpy change Had is given by:
Equation(2-3):
H ad  H 2  H1
 If the adiabatic efficiency, ad, is given as a value less than

100%, the actual enthalpy change is calculated from:

Equation(2-4):
H ac  H ad *  ad
The actual outlet stream enthalpy is then calculated using:

Equation(2-5):
H 3  H1  H ac
 Point 3 on the Mollier chart, representing the outlet conditions

is then obtained. The phase split of the outlet stream is obtained
by performing an equilibrium flash at the outlet conditions.
 The isentropic work (Ws) performed by the compressor is com-
puted from:
Equation(2-6):
WS   H 2  H1  J   H ad  J
where:
J = mechanical equivalent of energy
In units of horsepower, the isentropic power required is:
Equation(2-7):
GHPad  H ad *778* F / 33000

Equation(2-8):
GHPac  H ac *778* F / 33000  GHPad *  ad

Equation(2-9):
HEADad  H ad *778
where:
GHP = work in horsepower
H = enthalpy change in BTU/lb
F = mass flow rate, lb/min
HEADad = Adiabatic Head, ft
The factor 33000 is used to convert from units of ft-lb/min to units

of horsepower.

The isentropic and polytropic coefficients, polytropic efficiency,
and polytropic work are calculated using one of two methods; the
method from the GPSA Engineering Data Book, and the method
from the ASME Power Test Code 10.
Also See:
ASME Method
The ASME method is more rigorous than the GPSA method, and
yields better answers over a wider rage of compression ratios and
feed compositions. For these reasons, it is now the default when no
preference is specified. The GPSA method was the default prior to
PRO/II version 4.1.
For a real gas, as previously noted, the isentropic volume exponent
(also known as the isentropic coefficient), ns, is not the same as the
compressibility ratio, k. The ASME method distinguishes between
k and ns for a real gas. It rigorously calculates ns, and never back-
calculates it from k.
Adiabatic Efficiency Given
Polytropic Efficiency Given

In this method, the isentropic coefficient ns is calculated as:
Equation(2-10):
nS  ln  P2 / P1  / ln V1 / V2 
where:
V1 = volume at the inlet conditions
V2 = volume at the outlet pressure and inlet entropy condi-

tions
The compressor work for a real gas is calculated from equation (2-
7), and the factor f from the following relationship:
Equation(2-11):
  nS 1 

WS  144  nS /  nS  1  fPV
1 1  2 1  S   1
 
P / P n
 

The ASME factor f is usually close to 1. For a perfect gas, f is
exactly equal to 1, and the isentropic coefficient ns is equal to the
compressibility factor k.
The polytropic coefficient, n, is defined by:
Equation(2-12):
n  ln  P2 / P1  / ln V1 / V3 

where:
V3 = volume at the outlet pressure and actual outlet enthalpy
conditions
The polytropic work, i.e., the reversible work required to compress
the gas in a polytropic compression process from the inlet condi-
tions to the discharge conditions is computed using:
Equation(2-13):
  n 1 

W p  144  n /  n  1  fPV
1 1  P2 / P1 
 
 n  1

 
where:
Wp = polytropic work
For ideal or perfect gases, the factor f is equal to 1.

The polytropic efficiency is then calculated by:
Equation(2-14):
Wp Wp Wp
p     ad
Wac Ws /  ad Ws
Note: This polytropic efficiency does not agree with the value cal-
culated using the GPSA method which is computed using p = {(n-
1)/n} / {(k-1)/k}

A trial and error method is used to compute the adiabatic efficiency,
once the polytropic efficiency is given. The following calculation
path is used:

2. The isentropic coefficient, isentropic work, and factor f are
computed using equations (2-6), (2-10), and (2-11).
3. An initial estimate is made for the isentropic efficiency, and
it is used to compute actual outlet conditions (i.e., at H3,
V3).
4. The polytropic coefficient, n, is calculated from equation
(2-12) using V3 (from above).
5. Using the values of f and n calculated from steps 1 and 3,
the polytropic work is calculated from equation (2-13).
6. Compute polytropic efficiency using equation (2-14).
7. If this calculated efficiency is not equal to the specified
polytropic efficiency within a certain tolerance, the isentro-
pic efficiency value is updated.
8. Steps 3 through 6 are repeated until the computed poly-
tropic efficiency equals the specified value.
Reference
American Society of Mechanical Engineers (ASME), 1965, Power
Test Code, 10, 31-33.
Also See: Isentropic Calculations
GPSA Method
The GPSA method is commonly used in the chemical process
industry, but is less rigorous than the default ASME method.
Note: The GPSA method was the default prior to PRO/II version
4.1. Currently, the ASME method is the default.


In this method, the adiabatic head is calculated from equations (2-3)
and (2-9). Once this is calculated, the isentropic coefficient k is
computed by trial and error using:
Equation(2-15):
 
HEADad   z1  z2  / 2  RT1 /  k  1 / k   P2 / P1 

 k 1 / k
 1


where:
Z1, Z2 = compressibility factors at inlet and outlet conditions.
R = gas constant
T1 = temperature at inlet conditions
This method of computing k produces inaccurate results when the

compression ratio (P2/P1) becomes low. PRO/II allows the user to
switch to another method to compute k if the compression ratio falls
below a certain set value.
If the calculated compression ratio is less than a value set by the
user (defaulted to 1.15 in PRO/II), or if k does not satisfy
.  k  166667
10 . , the isentropic coefficient, k, is calculated by
trial and error based on the following:
Equation(2-16): 
 k 1 / k 
T2   z1 / z2  T1  P2 / P1 
 
The polytropic compressor equation is given by:

Equation(2-17):
 
HEAD p   z1  z2  / 2  RT1 /  n  1 / n   P2 / P1 

 n 1 / n
 1

The adiabatic head is related to the polytropic head by:

Equation(2-18):
HEADad HEAD p

 ad p
The polytropic coefficient "n" is calculated from:

Equation(2-19):
n /  n  1
p 
k /  k  1
The polytropic coefficient, n, the polytropic efficiency, and the

polytropic head are determined by trial and error using equations

(2-17), (2-18), and (2-19) above. The polytropic gas horsepower
(which is reported as work in PRO/II) is then given by:
Equation(2-20):
GHPp  HEAD p * F / 33000

A trial and error method is used to compute the adiabatic efficiency,
once the polytropic efficiency is given. The following calculation
path is used:
9. Compute adiabatic head using equations (2-3) and (2-9).
10. Determine the isentropic coefficient, k, using equation (2-
15), or (2-16).
11. Check if 10.  k  166667
. , if so, go to step 4, else recalcu-
late k using temperature equation (2-16).
12. The polytropic coefficient, n, is then calculated from equa-
tion (2-19).
13. Compute polytropic head using equation (2-17).
14. Obtain adiabatic efficiency from equation (2-18).
Reference
GPSA, 1979, Engineering Data Book, Chapter 4, 5-9 - 5-10.
Also See:
Expander
General Information
Basic Calculations
General Information
The methods used in PRO/II to model expander unit operations are
similar to those described previously for compressors. The calcula-
tions however, proceed in the reverse direction to the compressor
calculations. Also, the expander model currently does not support
polytropic calculations.
Also See:

Basic Calculations
The Mollier chart shown in Figure 2-3 plots the pressure versus the
enthalpy, as a function of entropy and temperature. This chart is
used to show the methods used to calculate the outlet conditions for
the expander as follows:
Figure 2-3: Typical Mollier Chart for Expansion
 A flash is performed on the inlet feed at pressure P1, and tem-

perature T1, using suitable K-value and enthalpy methods, and
one of the entropy calculation methods in Table 2-23. The
entropy S1, and enthalpy H1 are obtained at point
(P1,T1,S1,H1).
 The constant entropy line through S1 is followed until the user-

specified outlet pressure (P2) is reached. This point represents
the temperature (T2) and enthalpy conditions (H2) for an adia-

batic efficiency of 100%. The adiabatic enthalpy change is
given by:
Equation(2-21):
H ad  H 2  H1
 If the adiabatic efficiency, ad, is given as a value less than
100%, the actual enthalpy change (ac) is calculated from:
Equation(2-22):
H ac  H ad *  ad
 The actual outlet stream enthalpy is then calculated using:
Equation(2-23): 
H 3  H1  H ac
 Point 3 on the Mollier chart, representing the outlet conditions

is then obtained. The phase split of the outlet stream is obtained
by performing an equilibrium flash at the outlet conditions.
 The isentropic expander work ( Ws ) is computed from:
Equation(2-24):
WS   H 2  H1  J   H ad  J
where:
J = mechanical equivalent of energy
In units of horsepower, the isentropic expander power output is:
Equation(2-25):
GHPad  H ad *778* F / 33000

Equation(2-26):
GHPac  H ac *778* F / 33000  GHPad *  ad

Equation(2-27):
HEADad  H ad *778
where:
GHP = work in horsepower
H = enthalpy change in BTU/lb

F = mass flow rate, lb/min
HEADAD = adiabatic head, ft
Factor 33000 converts from units of ft-lb/min to horsepower.

Also See:

If an adiabatic efficiency other than 100% is given, the adiabatic
head is calculated from equations (2-23), (2-24), and (2-27). Once
this is calculated, the isentropic coefficient k is computed by trial
and error using:
Equation(2-28):
 
HEADac   z1  z2  / 2  RT1 /  k  1 / k   P2 / P1 

 k 1 / k
 1

where:
z1, z2 = compressibility factors at the inlet and outlet condi-
tions
R = gas constant
T1 = temperature at inlet conditions
Polytropic Efficiency (not supported)
Note: The expander model currently does not support polytropic

calculations. However, the polytropic expansion equation is:
Equation(2-29):
 
HEAD p   z1  z2  / 2  RT1 /  n  1 / n   P2 / P1 

 n 1 / n
 1

Adiabatic head is related to polytropic head by:
Equation(2-30):
HEADad HEAD p

 ad p
Polytropic efficiency p, polytropic coefficient n, and isentropic

coefficient k are related the equation:

Equation(2-31):
n /  n  1
p 
k /  k  1
Equations (2-29), (2-30), and (2-31) may be solved using an itera-

tive trial-and-error approach to determine p, n, and k. The poly-
tropic gas horsepower output by the expander may be
considered to be the work. It can be computed by converting
polytropic head to horsepower using the equation:
Equation(2-32):
GHPp  HEAD p * F / 33000
Also See:

Chapter 3: Pressure Calculations
This chapter discusses pressure calculation methods for the pipe

and pump unit operations.
Pipes
Pumps
Pipes
General Information
Basic Calculations
General Information
PRO/II contains calculations for single liquid or gas phase or mixed
phase pressure drops in pipes. The PIPE unit operation uses trans-
port properties such as vapor and/or liquid densities for single-
phase flow, and surface tension for vapor-liquid flow. The transport
property data needed for these calculations are obtained from a
number of transport calculation methods available in PRO/II. These
include the PURE and PETRO methods for viscosities. Table 3-24
shows the thermodynamic methods which may be used to generate
viscosity and surface tension data.
Table 3-24: Thermodynamic Generators for

Viscosity and Surface Tension
Viscosity Surface Tension
PURE (V & L) PURE
PETRO (V & L) PETRO
TRAPP (V & L)
API (L)
SIMSCI (L)
PRO/II contains numerous pressure drop correlation methods, and
also allows for the input of user-defined correlations by means of a
user-added subroutine.
Also See:
Pressure Calculations

Basic Calculations
An energy balance taken around a steady-state single-phase fluid
flow system results in a pressure drop equation of the form:
Equation (3-1): 
 dP / dL t   dP / dL  f   dP / dL e   dP / dL acc
total friction elevation acceleration
The pressure drop consists of a sum of three terms:

The reversible conversion of pressure energy into a change in
elevation of the fluid,
The reversible conversion of pressure energy into a change in
fluid acceleration, and
The irreversible conversion of pressure energy into friction
loss.
The individual pressure terms are given by:
Equation (3-2):
 dP / dL  f  f  v 2 /  2 gc d 
Equation (3-3):
 dP / dL e  g  sin  / gc
Equation (3-4): 
 dP / dL acc   v / g c dv / dL
where:
l and g refer to the liquid and gas phases
P = the pressure in the pipe
L = the total length of the pipe
f = friction factor
 = fluid density
v = fluid velocity
gc = acceleration due to standard earth gravity
Pressure Calculations 3-272

g = acceleration due to gravity
= angle of inclination
(dP/dL)t = total pressure gradient
(dP/dL)f = friction pressure gradient
(dP/dL)e = elevation pressure gradient
(dP/dL)acc = acceleration pressure gradient
For two-phase flow, the density, velocity, and friction factor are
often different in each phase. If the gas and liquid phases move at
the same velocity, then the "no slip" condition applies. Generally,
however, the no-slip condition will not hold, and the mixture veloc-
ity, , is computed from the sum of the phase superficial veloci-
ties:
Equation (3-5):
vm  vsl  vgl
where:
sl = superficial liquid velocity = volumetric liquid flow rate/
cross sectional area of pipe
gl = superficial gas velocity = volumetric gas flow rate/cross

sectional area of pipe
Equations (2), (3), and (4) are therefore rewritten to account for
these phase property differences:
Equation (3-6):
 dP / dL  f  f tp tp vtp2 / 2 g c d
Equation (3-7):
 dP / dL e  g tp sin  / g c
Equation (3-8):
 dP / dL acc  tp vtp / g c dvtp / dL

where:
tp = fluid density =1HL+gHg

HL,Hg = liquid and gas holdup terms subscript tp refers to the
two-phases.
Also See:
Pressure Drop Correlations

The hybrid pressure drop methods available in PRO/II each uses a
separate method to compute each contributing term in the total pres-
sure drop equation (1). These methods are described below.
Beggs-Brill-Moody (BBM)
Beggs-Brill-Moody High Velocity (BBMHV)
Beggs-Brill-Moody-Palmer (BBP)
Dukler-Eaton-Flanigan (DEF)
Mukherjee-Brill (MB)
Gray MethodOliemens Method
Hagedorn-Brown (HB)
Beggs-Brill-Moody (BBM)
This method is the default method used by PRO/II, and is the rec-
ommended method for most systems, especially single phase sys-
tems. For the pressure drop elevation term, the friction factor, f, is
computed from the relationship:
Equation (3-9):
f / f n  f tp / f n  exp  s 
The exponent s is given by:

Equation (3-10):
s  y /  0.0523  3.182 y  0.8725 y 2  0.01853 y 4 

Equation (3-11):
s  ln  2.2e y  1.2  , 1  e y  1.2

Equation (3-12):
y  ln  L / H L2 
where:
fn = friction factor obtained from the Moody diagram for a
smooth pipe.
L = no-slip liquid holdup = vsl / (vsl + vsg)
vsl = superficial liquid velocity
vsg = superficial gas velocity
The liquid holdup term, HL, is computed using the following corre-
lations:
Equation (3-13):
H L 0   aLb / N Fr
c

H L  H L0 when   0
H L  H L 0 when   0
where:
Equation (3-14):
  1  1  L  ln  d  Le N LVf N Frg  sin 1.8   0.333sin 3 1.8  
where:
NFr = Froude number
NLV = liquid velocity number
a, b, c, d, e, f, g = constants
The BBM method calculates the elevation and acceleration pressure
drop terms using the relationships given in equations (3) and (4) (or
equations (7) and (8) for two-phase flow).
Beggs-Brill-Moody High Velocity (BBMHV)

The high-velocity version of the Beggs-Brill-Moody correlation is a
good correlation for all pipe lines, especially at high velocities. It
differs from the BBM method only in the correction factor calcula-
tions. The correction factor calculations for BBMHV are:

Equation (3-15):
2
 v  vm
Ek   m  when  0.95
 vsonic  vsonic
else
Ek  0.95
vm = mixture velocity
vsonic = sonic velocity of the fluid
P
v sonic = g c   ---
  s
gc = 32.2 (in FPS), or 1.0 (in SI)
 = ratio of specific heats of the fluids
P = pressure at prevailing conditions
= density at prevailing conditions
Beggs-Brill-Moody-Palmer (BBP)
This method uses the same elevation, and acceleration correlations
described above for the Beggs-Brill-Moody (BBM) method. The
equation for the friction pressure drop term is the same as that given
for the BBM method in equations (9) through (12). For this method,
however, the Palmer correction factors given below are used to cal-
culate the liquid holdup.
Equation (3-16):
H L  0.541H L , BBM  0
H L  0.918H L , BBM  0
where:
HL,BBM = liquid holdup calculated using the BBM method
Dukler-Eaton-Flanigan (DEF)
This method uses the Dukler correlation to calculate the friction
term. The friction factor is given by:
Equation (3-17):
f / f n  1  y / 1.281  0.478 y  0.444 y 2  0.094 y 3  0.0084 y 4

Equation (3-18):
y   ln  L 
Equation (3-19):
f n  0.0056  0.5 N Re
where:
NRe = Reynolds number
The liquid holdup, HL, used in calculating the mixture density, , in

the friction term is computed using the Eaton correlation. In this
correlation, the holdup is defined as a function of several dimen-
sionless numbers.
The elevation term is calculated using equation (3). The mixed den-
sity, , however, is calculated not by using the Eaton holdup, but by
using the liquid holdup calculated by the Flanigan correlation:
Equation (3-20):
H L  1/ 1  0.326v1.06
sg 
The acceleration term is calculated using the Eaton correlation:

Equation (3-21):
Wl  vl   Wg  vg 
2 2
 dP 
  
 dL  acc 2 g c qm L
where:
W = mass flow rate
v = fluid velocity
vsg = superficial gas velocity
qm = mixture flow rate
subscripts g and l refer to the gas and liquid phases
Mukherjee-Brill (MB)
The Mukherjee-Brill method is recommended for gas condensate
systems. In the MB method, a separate friction pressure drop term is

given for each region of flow. Figure shows the various flow pat-
terns which the MB method is able to handle.
Figure 1: Various Two-Phase Flow Regimes
Figure 2: Various Two-Phase Flow Regimes
For stratified flows in horizontal pipes:

Equation (3-22):
 dp / dL  f  f  g vg2 / 2 g c d
For bubble or slug flows:

Equation (3-23):
 dP / dL  f  f  m vm2 / 2 g c d
For mist flows:

Equation (3-24):
 dP / dL  f  ff fr  g vg2 / 2 g c d
where:
ffr = factor calculated from a correlation
For bubble, slug, and mist flows, the elevation pressure drop is
computed using equation (7), but for stratified flows, the fluid den-
sity used is the gas phase density.
The acceleration pressure drop term is given by:
Equation (3-25):
 dP / dL acc   vmvsg g tp / g c P   dP / dL t

where:
vs = slip velocity
The density, tp, is equal to the gas density for stratified flows only.
A separate expression is used to calculate the holdup for each flow
pattern. These are given as:
 < 0 Bubble, Slug, Mist flow
Equation (3-26):
 N 0.371771 
H L  e H 2 , H 2  H1  GV0.393962 
 N LV 
Equation (3-27):

H1  0.51664  0.789805sin   0.551627sin 2   15.519214 NLV
2
 < 0 Stratified flow

Equation (3-28):
 N GV
0.079961

H L  e , H 2  H1  0.604887 
H2
 N LV 
Equation (3-29):

 H1  1.330282  4.171584s in   4.171584sin2   56.262268NLV
2
 0 (all flow patterns)

Equation (3-30):
 N 0.475686 
H L  e H 2 , H 2  H1  GV0.288657 
 N LV 
Equation (3-31):
H1  0.380113  0.129875s in   0.119788sin2   2.343227 NLV

2
where:
Nlv = liquid viscosity number
Gray Method
The Gray method has been especially developed for gas condensate
wells, and should not be used for horizontal piping. The recom-
mended ranges for use are:
 Angle of inclination,  =  70 degrees
 Velocity, v < 50 ft/s,
 Pipe diameter, d < 3.5 inches
 Liquid condensate loading ~ 50 bbl/MMSCF
The friction pressure drop term is computed from equations (2) or
(6), where the friction factor used is obtained from the Moody
charts. The elevation term is calculated using equations (3) or (7),
while the acceleration term is given by equation (24).
The liquid holdup term, HL is given by:
Equation (3-32):
HL  1 Hg

1
1 eA
Hg 
R 1
Equation (3-34):
B1
  205  
A1  2314  N v 1  
  Nc 
Equation (3-35):
  0.730 R  
B1  0.0814 1  0.05554 ln 1  
  R  1  
Equation (3-36):
VsL
R
Vsg
Equation (3-37):
 m2 vsm
2
Nv 
g L   L   g 
Equation (3-38):
g  l   g  D 2
ND 
L
Equation (3-39):
 0 q0  0.617 w qw
L 
q0  0.617 qw
where:
 = surface tension
q0 = in situ oil volumetric flow rate
qw = in situ water volumetric flow rate
qm = mixture volumetric flow rate
ND = diameter number

L and g refer to the liquid and gaseous phases
Oliemens Method
This method uses the Eaton correlation previously described above
to calculate the liquid holdup. The friction factor is obtained from
the Moody diagrams, and the friction pressure term is computed
using:
Equation (3-40):
 dP / dL  f  fG 2 /  2 g c d eff OLI 144 

Equation (3-41):
G  q1 1  qg  g / 1  BL  A
Equation (3-42):
OLI  tp / 1  BL 
Equation (3-43):
BL  H L  H Lns
where:
G = mass flux
HLns = no-slip liquid holdup
OLI = Oliemens density
deff = effective diameter
A = pipe cross sectional area

L and g refer to the liquid and gas phases respectively
The acceleration term is set equal to zero, while the elevation pres-
sure drop term is computed using:
Equation (3-44):
 dP / dL e   s g sin  / g c144
 s  1 H1   g H g ,  0
 s   g ,   0 and H L  1.0
Equation (3-45):
 s  1 ,   0 and H L  1

where:
 = angle of inclination
subscripts L and g refer to the liquid and gas phases respec-
tively.
Hagedorn-Brown (HB)
This method is recommended for vertical liquid pipelines, and
should not be used for horizontal pipes. The liquid holdup term is
calculated from a correlation of the form:
Equation (3-46):
H L  function of  N LV , N GV , N D 
where:
NLV , NGV , ND are the dimensionless liquid velocity number, gas
velocity number, and diameter number.
The friction factor is obtained from the Moody diagrams, and the
friction pressure term is computed using equations (2) or (6),
depending on whether there is single- or two-phase flow.
Reference
1. Beggs, H. D., An Experimental Study of Two-Phase Flow

in Inclined Pipes, 1972, Ph.D. Dissertation, U. of Tulsa.
2. Beggs, H. D., and Brill, J. P., A Study of Two-Phase Flow
in Inclined Pipes, 1973, Trans. AIME, 607.
3. Moody, L. F., Friction Factors for Pipe Flow, 1944, Trans.
ASME, 66, 671.
4. Palmer, C. M., Evaluation of Inclined Pipe Two-Phase Liq-
uid Holdup Correlations Using Experimental Data, 1975,
M.S. Thesis, U. of Tulsa.
5. Mukherjee, H. K., An Experimental Study of Inclined Two-
Phase Flow, 1979, Ph.D. Dissertation, U. of Tulsa.
6. Gray, H. E., Vertical Flow Correlation in Gas Wells, 1974,
in User Manual: API 14B, Subsurface Controlled Safety
Valve Sizing Computer Program.
7. Flanigan, O., Effect of Uphill Flow on Pressure Drop in
Design of Two-Phase Gathering Systems, 1958, Oil & Gas
J., March 10, 56.

8. Eaton, B. A., The Prediction of flow Patterns, Liquid
Holdup and Pressure Losses Occurring During Continuous
Two-Phase Flow in Horizontal Pipes, 1966, Ph.D. Disserta-
tion, U. of Texas.
9. Dukler, A.E., et al., Gas-Liquid Flow in Pipelines, Part 1:
Research Results, Monograph NX-28, U. of Houston.
10. Hagedorn, A.R., and Brown, K.E., Experimental Study of
Pressure Gradients Occurring During Continuous Two-
Phase Flow in Small Diameter Vertical Conduits, 1965, J.
Per. Tech., Apr., 475-484.
Also See:
Pumps
General Information
Basic Calculations
General Information
The PUMP unit operation in PRO/II contains methods to calculate
the pressure and temperature changes resulting from pumping an
incompressible fluid.
Also See:
Basic Calculations
The GPSA pump equation is used to relate the horsepower required
by the pump to the fluid pressure increase:
Equation (3-47):
HP  qP / 1714.3e 
where:
HP = required pump power, in horsepower
q = volumetric flow rate, gal/min.
P = pressure increase, psi

e = fraction efficiency (by default, input values are entered as
percentages)
The factor 1714.3 converts the pump work to units of horsepower.
The work done on the fluid calculated from (1) above is added to
the inlet enthalpy. The temperature of the outlet fluid is then
obtained by performing an adiabatic flash.
Note: The PUMP unit should only be used for incompressible flu-
ids. Compressible fluids may be handled using the COMPRESSOR
unit operation.
Reference
GPSA Engineering Data Book, 9th Ed., 5-9
Also See:

Chapter 4:Distillation and Liquid-Liq-
uid Extraction Columns
The PRO/II simulation program is able to model rigorous and short-

cut distillation columns, trayed and packed distillation columns
(random and structured packing), as well as liquid-liquid extraction
columns.
Rigorous Distillation Algorithms
ELDIST Algorithm
Rate-based Segment Modeling using RATEFRAC®
Column Hydraulics
Shortcut Distillation
Liquid-Liquid Extractor
Column Tray Efficiency Calculations

General Information
General Column Model
Mathematical Models
Inside Out Algorithm
Chemdist Algorithm
Reactive Distillation Algorithm
Initial Estimates
General Information
This chapter presents the equations and methodology used in the
solution of the distillation models found in PRO/II. It is recom-
mended reading for those who want a better understanding of how
the distillation models are solved. This chapter also explains how
the intermediate printout relates to the equations being solved.All of
the distillation algorithms in PRO/II are rigorous equilibrium stage

models. Each model solves the heat and material balances and
vapor-liquid equilibrium equations. The features available include
pumparounds, five condenser types, generalized specifications, and
interactions with flow sheeting unit operations such as the Control-
ler and Optimizer. Reactive distillation is available for distillation
and liquid-extraction. Automatic water decant is available for
water/hydrocarbon systems.
Modelling a distillation column requires solving the heat and mate-
rial balance equations and the phase equilibrium equations. PRO/II
offers four different algorithms for modeling of distillation columns:
 the Inside/Out (I/O) algorithm,
 the Sure algorithm,
 the Chemdist algorithm, and
 the ELDIST algorithm.
For electrolyte systems the Eldist algorithm is available, and for liq-
uid- liquid extractors the LLEX algorithm should be used. Eldist,
Chemdist, the LLEX, and RATEFRAC also allow chemical reac-
tion. Eldist is used when equilibrium electrolytic reactions are pres-
ent. Chemdist and LLEX allow kinetic, equilibrium (non-
electrolyte) and conversion reactions to occur on one or more
stages. RATEFRAC allows kinetic and equilibrium to occur on one
or more stages. This does not support conversion reactions.
For most systems, SimSci recommends using the I/O algorithm.
When more than one algorithm can be used to solve a problem, the
I/O algorithm will usually converge the fastest. The I/O algorithm
can be used to solve most refinery problems, and is very fast for
solving crude columns and main fractionators. The I/O algorithm
also solves many chemical systems, and when possible should be
the first choice for systems with a single liquid phase.
The Sure algorithm in PRO/II is the same time proven algorithm as
in PROCESS. This algorithm is particularly useful for hydrocarbon
systems where water is present. It is the best algorithm to solve eth-
ylene quench towers which have large water decants in the upper
portion of the tower. The Sure algorithm is also appropriate for
many other refining and chemical systems.
Chemdist is a new algorithm developed at SimSci for the simulation
of highly non-ideal chemical systems. Chemdist is a full Newton-
Raphson method, with complete analytic derivatives. This includes
Distillation and Liquid-Liquid Extraction Columns 4-288

composition derivatives for activity and fugacity coefficients.
Chemdist allows two liquid phases to form on any stage in the col-
umn, and also supports a wide range of two liquid phase condenser
configurations. Chemdist with chemical reactions allows In-Line
Procedures for non-power law kinetic reactions.
Eldist is an extension of Chemdist for modeling distillation of aque-
ous electrolyte mixtures. The aqueous chemistry is solved using
third party software from OLI Systems. The electrolyte calculation
computes true vapor-liquid equilibrium K-values, which are con-
verted to apparent vapor-liquid equilibrium K-Values. Eldist then
uses these in the vapor-liquid equilibrium calculations.
Also See:
General Column Model

A schematic diagram of a complex distillation column is shown in
Figure 4-1. A typical distillation column may have multiple feeds
and side draws, a reboiler, a condenser, pumparounds, and heater-
coolers. The column configuration is completely defined; the num-
ber of trays and the locations of all feeds, draws, pumparounds and
heater-coolers. Note that the optimizer can change feed, draw and
heater-cooler locations.

Figure 4-1: Schematic of Complex Distillation Column
Trays are numbered from the top down. The condenser and reboiler
are treated as theoretical stages, and when present the condenser is
stage one.
There are no “hard limits” on the number of feeds, draws, pumpar-
ounds etc. This results from the PRO/II memory management sys-
tem.
Table 4-25 shows the features available with each algorithm. Pump-
arounds can be used for liquid and/or vapor. The return tray can be
above or below the draw tray. Note that when the pump around
return is mixed phase (liquid and vapor) that both the vapor and the
liquid are returned to the same tray.
PRO/II provides hydrodynamic calculations for packing supplied
by Koch-Glitsch, LP (formerly supplied by Norton Co.) and Sulzer
Brothers. Both rating and design calculations are available. In rating

mode, the diameter and height of packing are specified and the
pressure drop across the packed section is determined. In design
mode, the height of packing and the pressure drop are specified, and
the packing diameter is calculated.
Tray rating and sizing is also available and may be performed for
new and existing columns with valve, sieve and bubble cap trays.
Valve tray calculations are done using the methods from Glitsch.
Tray hydraulics for sieve trays are calculated using the methods of
Fair and for bubble cap trays with the methods of Bolles. Rating
and design calculations are available.
The I/O and Sure algorithms provide a free water decant option.
This is used in refinery applications to model water being decanted
at the condenser or at other stages in the distillation column.
Table 4-25: Features Overview for Each Algorithm

I/O Sure Chem LLE Eldist EIO Ratefra
dist X c
Pumparounds Y Y N N N Y Y
Packed Column Y Y Y N N Y Y
Tray Rating/Sizing Y Y Y N N Y Y
Two Liquids on any tray N Y Y — N N N
Free Water Decant Y Y N — N Y Y
Tray Efficiency Y N Y(2) N Y(2) Y Y
Solids Y Y Y N (1) Y Y
LS Components N N N N Y Y Y
Electrolytes N N N N Y N Y
Kinetic Reaction N N Y Y N N Y
Equilibrium Reaction N N Y Y N N Y
Conversion Reaction N N Y Y N N Y
Thermo Simphon
Y N N N N Y N
Reboiler
Reboiler Y Y Y N Y Y Y
Side Column Y Y N N N Y N
(1) Eldist predicts solids precipitation on stages, but does not allow solid
formation for mass balance purposes.

(2) Only vaporization efficiencies available.

Side draws may be either liquid or vapor, and the location and phase
of each must be specified. Solid side draws are not allowed. There
may be an unlimited number of products from each stage.
Feed tray locations are given as the tray number upon which the
feed is introduced. A feed may be liquid, vapor or mixed phase.
PRO/II also allows for different conventions for mixed phase
(vapor/liquid) feeds. The default convention NOTSEPARATE
introduces both the liquid and the vapor to the same stage. SEPA-
RATE places the liquid portion of the feed on the designated feed
tray and the vapor portion of the feed on the tray above the desig-
nated feed tray.
A pump around is defined as a liquid or vapor stream from one tray
to another. The return tray can be either above or below the pump
around draw tray. The pump around flow rate can be specified or
calculated to satisfy a process requirement. If a heater/cooler is used
with the pump around, it must be located on the pump around return
tray. The pump around return temperature, pressure, liquid fraction,
and temperature drop will be computed if it is not specified.
Heater/coolers may be located on any tray in the column. A heater/
cooler is treated only as a heat source or sink. Rigorous models of
external heat exchangers are available via the attached heat
exchanger option.
Feed rates, side draw rates and heater/cooler duties may be either
fixed or computed. For each varied rate or duty, a corresponding
design specification must be made.
Also See:
Mathematical Models
There are many different approaches to solving the distillation
equations. This is evident from the large number of articles on the
subject in the chemical engineering literature. There are many
classes of distillation problems; wide and narrow boiling, azeo-
tropic, homogeneous and heterogeneous liquid phases, electrolytic
and reactive. Unfortunately, no one algorithm is yet available which
can reliably solve all of these problems. PRO/II provides different
algorithms which excel in solving certain classes of problems and
often provide solution capability over a very wide range of prob-
lems. Eldist is designed to solve a specific class of problems,

namely electrolytic systems. The LLEX (liquid-liquid extractor) is
for liquid-liquid extraction systems.
Also See:
Inside Out Algorithm

The Inside/Out (I/O) column algorithm in PRO/II is based on an
article by Russell in 1983. The I/O column algorithm contains a
number of novel features which contribute to its excellent conver-
gence characteristics. The algorithm is partitioned into an inner and
outer loop. In the inner loop, the heat, material and design specifica-
tions are solved. Simple thermodynamic models for enthalpy and
vapor liquid equilibrium (VLE) K-values are used in the inner loop.
This, along with the form of the simple model and the choice of
primitive variables, allows the inner loop to be solved quickly and
reliably. In the outer loop, the simple thermodynamic model param-
eters are updated based on the new compositions and the results of
rigorous thermodynamic calculations. When the rigorously com-
puted enthalpies and K-values match those of the simple thermody-
namic models, and the design specifications are met, the algorithm
is solved.Inner Loop
The primitive variables in the inner loop are the stripping factors
and side stream withdrawal factors. The inner loop equations are
the stage enthalpy balances and the design specifications. The strip-
ping factor here is defined as:
Equation (4-1):
KV 
Sj   b 
 L j
where:
Sj = the Stripping Factor for stage j
V = the net vapor leaving the stage

L = the net liquid leaving the stage
Kb = the base component K-value from the simple K-value
model (see equation (4-11))
The inner loop solves the system of equations:

Equation (4-2):
  LSS  
H1  f  S1 , S 2 ,...., S n ,   0
  L k 
  LSS  
H 2  f  S1 , S 2 ,...., S n ,   0
  L k 
........................................................
  LSS  
H n  f  S1 , S2 ,...., Sn ,   0
  L k 
  LSS  
SPk  f  S1 , S 2 ,...., S n ,   0
  L k 
In equation (2) Hj is the heat balance for stage j:

Equation (4-3):
  LSS     VSS  
H j  H Lj L j 1      H j V j 1  
V
 
  L  j    V  j 
NF NQ
 H Lj 1 L j 1  H Vj 1V j 1   H iF Fi  Qi  0
i 1 i 1
and SPK is a design specification equation.

This system of equations is solved using the Newton-Raphson
method. The first Jacobian matrix is obtained by finite difference
approximation. This Jacobian is then inverted, and at subsequent
iterations the inverse Jacobian is updated using Broyden's method.
To evaluate the errors in the enthalpy and specification equations
for a given set of stripping factors, the component flows and stage
temperatures must be computed for the given stripping factors and

simple model parameters. Figure 4-1 shows a schematic diagram of
a simple stage.
Figure 4-1: Schematic of a Simple Stage for I/O

Writing the material balance for this stage in terms of net liquid and
vapor flow rates results in:
Equation (4-4):
LSS VSS
f j = – l j – 1 + l j 1 +  ---------- + v j 1 +  ---------- – vj + 1
 Lj   Vj 
j j
where:
l = the component liquid rate, moles/time
v = the component vapor rate, moles/time
f = the component feed rate, moles/time
Given the equilibrium relationship it is possible to remove v from
equation (4). This is done as follows:

Equation (4-5):
K ij v j lij
vij  yij v j  K ij xij v j 
Lj
where K is the vapor liquid equilibrium fugacity ratio. Now the

component mass balance can be written as:
Equation (4-6):
  LSS    KijVj    VSS     Kij 1Vj 1 

f j  lij 1  lij 1       1      lij  
  L  j   Lj    V  j    Lj 1 
If K is assumed constant, equation (5) results in a linear system of
equations for component i which form a tridiagonal system:
Equation (4-7):
 Bi ,1 Ci ,1   li,1   fi ,1 
 1 B Ci,2  l  f 
 i ,2   i ,2   i,2 
 1 Bi ,3 Ci ,3   li,3   fi ,3 
   
 . . .  .  . 
 . . .  .  . 
   
 . . .  .  . 
 1 Bi,n1 Ci ,n1  li ,n1   fi,n1 
   
 1 Bi,n   li ,n   fi,n 
where B and C are given by:

Equation (4-8):
  LSS    K ijV j    VSS  

Bij  1        1    
  L  j   L j    V  j 
Equation (4-9):
K V 
Cij    ij 1 j 1 
 L j 1 
 
Side stream withdrawal factors are defined as:

Equation (4-10):
 LSS 
RL j  1   
 L j
 VSS 
RV j  1   
 V j
The vapor equilibrium K-value simple model is given by:

Equation (4-11):
K ij   ij K b
where ij is the relative volatility for component i on stage j and Kb

is the base component K-value modeled by:
Equation (4-12):
1 1 
ln  K b   A  B   ref 
T T 
In equation (4-12) Tref is a reference temperature. Using this defini-
tion of the simple K-value model and the side stream withdrawal
factors, the material balance () can be rewritten as:
Equation (4-13):
fij  lij 1  lij  RLj  aij S j RVj   lij 1  aij 1S j 1 
The set of equations defined by (4-13) still form a tridiagonal

matrix so that equation (4-7) still applies. Bij and Cij from (4-8) and
(4-9) now become:
Equation (4-14):
Bij  RLj   ij S j RVj

Cij   ij 1S j 1
Outer Loop
The outer loop in the Inside/Out algorithm updates the simple ther-
modynamic model parameters and checks for convergence. In the
inner loop, the distillation equations are solved for the current sim-
ple thermodynamic models. The convergence check in the outer
loop therefore compares the rigorously computed enthalpies and

VLE K-values from the new compositions resulting from the inner
loop calculations.
The simple model used for VLE K-values is given by equations
(11) and (12). The initial value of Kb on each stage j is computed
by:
Equation (4-15):
ln  K b    wi ln  K i 
i
ti
wi 
t i
i
  ln K i 
ti  yi
1
 
T  
The simple K-values can be calculated very quickly for a given
temperature. Also, once new molar flows are computed in the inner
loop, a new bubble point temperature can be easily computed. Once
the molar flows are computed, the mole fractions are obtained from:
Equation (4-16):
lij
xij 
l i
ij
and substituting equation (11) into the bubble point equation:

Equation (4-17):
 y  K
i
ij
i
x 1
ij ij
Equation (4-18):
1
Kb 
 xi
i i
Once Kb has been determined, equation (4-12) can be arranged so

that the bubble point temperature can be solved for directly. The
bubble point expression is:

Equation (4-19):
1
 ln  K b  A  1 
T bubble
  ref 
 B T 
The simple enthalpy models are of the form:

Equation (4-20):
H v  H v0  H v
H L  H L0  H L
where:
Hv = the vapor enthalpy
HL = the liquid enthalpy
H0V = the vapor ideal gas enthalpy
H0L = the liquid ideal gas enthalpy
Hv = the vapor enthalpy departure from the ideal gas enthalpy
HL = the liquid enthalpy departure from the ideal gas

enthalpy
The simple model for the enthalpy departure is given by:
Equation (4-21):
H v  A  B T  T ref 
H L  C  D T  T ref 
where the departures are modeled in terms of energy per unit mass.
The I/O algorithm has four different levels of intermediate iteration
printout. These are None, Part, Estimate, and All. None results in no
iteration printout. Part results in partial intermediate printout, and is
useful to monitor the progress of the algorithm toward solution.
Estimate should be used to debug a non-converged column. Esti-
mate prints the initial column estimate and more information on
actual equation errors to help determine what the convergence diffi-
culty is. All prints out the column temperature, liquid and vapor
profiles at each iteration and the same comprehensive intermediate
printout as Estimate.

With Partial intermediate printout, the following information is pro-
vided at each iteration:
ITER 1 E(K)= 1.0717E-01 E(ENTH+SPEC)=1.392E-03 E(SUM)=
3.159E-01
INNER 0 : E(ENTH+SPEC) = 1.104E-02
INNER 1 : E(ENTH+SPEC) = 1.854E-04 ALPHA = 1.0000
ITER 2 E(K)= 1.137E-02 E(ENTH+SPEC) = 1.854E-04 E(SUM) =
2.454E-02
INNER 1 : E(ENTH+SPEC) = 7.476E-06 ALPHA = 1.0000
The error E(ENTH+SPEC) is the sum of the enthalpy balance and
specification errors and is used to determine convergence of the
inner loop. The inner loop convergence tolerance for
E(ENTH+SPEC) is:
Table 4-26:
Iteration E(ENTH+SPEC) Tolerance
1 0.01
0.001, (if E(ENTH+SPEC) error from iteration 1
2
was below 0.001, then the tolerance = 2.0E-5)
3 2.0E-5
E(ENTH+SPEC) is the most important number to watch for column

convergence.
The second most important number to watch for information about
column convergence is alpha, the damping factor. The damping fac-
tor alpha is applied to the correction to the stripping factors and side
stream withdraw factors. An alpha value of 1.0 corresponds to no
damping and indicates that convergence is progressing well. Low
alpha values indicate that the full correction to the stripping factors
resulted in an increase in the inner loop enthalpy and specification
equations. A line search is performed using a progressively smaller
step size until the inner loop equation errors are reduced. This may
be due to a poor approximation to the Jacobian matrix, a very poor
starting estimate, or infeasible design specifications.
The E(K) error is the average error between the K-values predicted
using the simple thermodynamic model and the rigorously com-
puted K-values using the compositions and temperatures resulting
from the inner loop calculations. A large E(K) indicates highly
composition sensitive K-values.
The error sum E(SUM) is the sum of the enthalpy, specification and
the bubble point errors. This value is not used in the convergence

check. E(SUM) is a good indicator of how convergence is progress-
ing, and is similar to the ERROR SUM for the Sure Algorithm.
With Estimate and All iteration printout levels, the following inter-
mediate printout results:
ITER 1 E(K)= 1.017E-01 E(ENTH+SPEC)= 1.392E-03 E(SUM)= 3.159E-
01
COMPONENT ERROR: AVG = 4.491E-02 MAX(T 1 )= 1.814E-01
ENTHALPY ERROR: AVG = 0.000E+00 MAX(T 4, LIQ)= 0.000E+00
K-VALUE ERROR: AVG = 1.017E-01 MAX(T 1, C 1 )= 3.31OE-
01
SPEC ERROR : AVG = 1.134E-02 MAX(SPEC 1 ) = 2.267E-02
HBAL ERROR : AVG = 5.368E-03 MAX(TRAY 2 ) = -1.230E-02
TEMP CHANGE: AVG = 8.500E-01 MAX(TRAY 1 ) = -2.461e+00
INNER 1: E(ENTH+SPEC) = 1.854E-04 ALPHA - 1.0000
SPEC ERROR : AVG = 1.886E-04 MAX(SPEC 1 ) = 3.756E-04
HBAL ERROR : AVG = 9.114E-05 MAX(TRAY 3 ) = 2.182E-04
TEMP CHANGE: AVG = 1.257E-01 MAX(TRAY 1 ) = -2.431E-01
ITER 2 E(K)= 1.137E-02 E(ENTH+SPEC)= 1.854E-04 E(SUM)=2.454E-
02
COMPONENT ERROR: AVG = 5.068E-03 MAX(T 1) =1.026e-02
ENTHALPY ERROR: AVG = 0.000E+00 MAX(T4, LIQ) =0.999E+00
K-VALUE ERROR: AVG = 1.137E-02 MAX(T1, C 2) =2.268E-02
SPEC ERROR : AVG = 6.25E-04 MAX(SPEC 1)= -1.247E-03
HBAL ERROR : AVG= 2.799E-04 MAX(TRAY 2 )= 5.961E-04
TEMP CHANGE: AVG= 3.719E-02 MAX(TRAY 1 )=-8.621E-02
INNER 1 : E(ENTH+SPEC)= 7.476E-06 ALPHA = 1.0000
SPEC ERROR : AVG = 8.569E-06 MAX(SPEC 1)= -1.587E-05
HBAL ERROR : AVG = 3.191E-06 MAX(TRAY 2)= 9.271E-06
TEMP CHANGE: AVG = 7.271E-03 MAX(TRAY 1)= 1.253E-02
Reference
Russell, R.A., A Flexible and Reliable Method Solves Single-tower
and Crude-distillation -column Problems, 1983, Chem. Eng., 90,
Oct. 17, 53-9.
Also See:
Chemdist Algorithm
The Chemdist algorithm in PRO/II is a Newton based method
which is suited to solving non-ideal distillation problems involving
a smaller number (10 vs. 100) of chemical species. These condi-
tions are generally encountered in chemical distillations as opposed
to crude fractionation where the I/O algorithm would be a better
choice. Chemdist is designed to handle both vapor-liquid and

vapor-liquid-liquid equilibrium problems as well as chemical reac-
tions.
Figure 4-1: Schemactic of a Simple Stage for Chemdist

Basic Algorithm
Basic Algorithm
Figure 4-1 shows a schematic of an equilibrium stage for the case of
two phase distillation with no chemical reaction. The equations
which describe the interior trays of the column are as follows:
Component Mass Balance:

Equation (4-22):
M ij  exp  X ij  Li  exp Yij  Vi  exp  X i 1, j   Li 1  LDi 1 

 exp Yi 1, j  Vi 1  Vi D1   f i ,Lj  fiV1
i  1, NT ; j  1, NC
Energy Balance:
Equation (4-23):

Vapor-Liquid Equilibrium:
Equation (4-24):
Qij  Yij  X ij  ln  K ij  , i  1, NT ; j  1, NC
Summation of Mole Fractions:

Equation (4-25):
NL
Si  1   exp  X ij  i  1, NT
j 1
Equation (4-26):
NC
Si'  1   exp Yij  i  1, NT
j 1
where:
Fi =total feed flow to tray i
Li =total liquid flow from tray i
Vi = total vapor flow from tray i
Qi = heat added to tray i
Ti = temperatures of tray i
Xi,j = ln(xi,j) natural log of the liquid mole fractions
Yi,j = ln(yi,j) natural log of the vapor mole fractions
NC = number of components
NT = number of trays
subscripts:
i = tray index
j = component index
superscripts:
F = refers to a feed
D = refers to a draw

L = refers to a liquid property
V = refers to a vapor property
other:
^ refers to properties on a molar basis
lower case letters refer to component flows
upper case letters refer to total flows or 
transformed variables
The unknowns, alternatively referred to as iteration or primitive
variables:
(X,Y,L,V,T)i, where i=1,NT are solved for directly using an aug-
mented Newton-Raphson method. Specification equations involv-
ing the iteration variables are added directly to the above equations
and solved simultaneously.
The modifications of the Newton-Raphson method are twofold. The
first is a line search procedure that will, when possible, decrease the
sum of the errors along the Newton correction. If this is not possi-
ble, the size of the increase will be limited to a prescribed amount.
The second modification limits the changes in the individual itera-
tion variables. Both of these modifications can result in a fractional
step in the Newton direction. The fractional step size, is reported in
the iteration summary of the column output. Note that an  of 1
indicates that the solution procedure is progressing well and that, as
the solution is approached,  should become one. In the case of
very non-linear systems which may oscillate, the user can restrict
the step size by specifying a damping factor which reduces the
changes in the composition variables. A cutoff value is used by the
algorithm so that when the value of the sum of the errors drops
below the given level, the full Newton correction is used. This
serves to speed the final convergence.
The iteration history also reports the largest errors in the mass bal-
ance, the energy balance, and the vapor-liquid equilibrium equa-
tions. Given a good initial estimate, these should decrease from
iteration to iteration. However, for some systems, the errors will
temporarily increase before decreasing on the way to finding a solu-
tion. The user can limit the size of the increase in the sum of the
errors.
All derivatives for the Jacobian matrix are calculated analytically.
User-added thermodynamic options that are used by Chemdist must

provide partial derivatives with respect to component mole frac-
tions and temperature. Chemdist uses the chain rule to convert these
to the needed form.
Vapor-Liquid-Liquid Algorithm
The equations describing the VLLE system are derived by substitut-
ing the bulk liquid flows and transformed bulk liquid mole frac-
tions, Li and Xi,j, for the single liquid phase flows and the
transformed liquid mole fractions, Li and X ij , in the above equa-
tions (22-26).
That is, Li becomes Li and Xi,j becomes X ij
where:
Equation (4-27):
X ij  ln  lij'  lij"  /  L'ij  L"ij  

Equation (4-28):
Li  L'i  L"i
and:
L'ij , L"ij = total liquid flows of the first and second liquid phases,
respectively.
l ij' , l ij"
= component liquid flows in the first and second liquid
phases, respectively.
The new equations which are identical in form to those listed in the
basic algorithm section above, equations (22-26), will not be
repeated here. The K-values which are used in the VLE equations
are calculated by performing a LLE flash. That is, the K-value is
evaluated at the composition of one of the liquid phases produced
by the LLE flash. Chemdist uses the K-value derivatives with
respect to the two liquid phases, the chain rule, and the definition of
a total derivative to calculate the derivatives of the VLE equation
with respect to the bulk liquid flow and composition. That is, the
bulk liquid flows are subject to the all of the constraints imposed by
the LLE equations.
The equations are solved in a two-step approach. After initialization
and calculation of the Jacobian matrix, the Newton-Raphson algo-
rithm calculates new values for the iteration variables (X,Y,L,V,T)i.

The resulting tray temperatures and composition of the bulk liquid
phases are used in performing liquid-liquid equilibrium flash calcu-
lations. If a single liquid phase exists, the calculations proceed as in
the basic algorithm. If a second liquid phase is detected, the liquid
compositions of the two liquid phases are used to calculate the K-
values and the derivatives with respect to each liquid phase. Using
the chain rule and the definition of a total derivative, these composi-
tion derivatives are used to calculate the derivative of the VLE
equations with respect to the bulk liquid phase. A new Jacobian
matrix is calculated and the Newton-Raphson algorithm calculates
new values for the iteration variables. The cycle repeats until con-
vergence is achieved.
This approach is not as direct as using the individual component
compositions for each liquid phase. However, it results in more sta-
ble performance of the Newton-Raphson algorithm because a sec-
ond liquid phase is not continually appearing and disappearing.
Liquid draws are dealt with in terms of bulk liquid properties (i.e.,
other than for a condenser, it is not possible to directly specify the
selective withdrawal of any one liquid phase).
Reference:
1. Bondy, R.W., 1991, Physical Continuation Approaches to

Solving Reactive Distillation Problems, paper presented at
1991 AIChE Annual meeting.
2. Bondy, R.W., 1990, A New Distillation Algorithm for Non-
Ideal System, paper presented at AIChE 1990 Annual
Meeting.
3. Shah, V.B., and Bondy, R.W., 1991, A New Approach to
Solving Electrolyte Distillation Problems, paper presented
at 1991 AIChE Annual meeting.
Also See:
Reactive Distillation Algorithm

The Chemdist, LLEX, and RATEFRAC algorithms in PRO/II sup-
port both liquid and vapor phase chemical reactions. Since reactive
distillation is an extension of the basic chemicals distillation algo-
rithm, the reader should be familiar with this material before pro-
ceeding. In general, the extensions of the Chemdist, LLEX, and
RATEFRAC algorithms for reactive distillation are suited to the

same size systems, i.e., distillation systems which have a smaller
number (10 vs. 100) of chemical species. Larger systems can be
simulated, but a large number of calculations can be expected.
Basic Algorithm
Kinetic Reaction Homotopy (Volume Based)
Basic Algorithm
Figure 4-1 shows a schematic of an equilibrium stage for the case of
two phase distillation with chemical reaction. The equations which
describe the interior trays of the column on which reactions occur
are essentially the basic equations which have terms added for gen-
eration and consumption of chemical species. The equilibrium
equations will be affected only indirectly through the formation or
disappearance of chemical species. Similarly, the energy balance
equation is affected through the enthalpies of the species enthalpies.
If two chemicals react to form a third and produce heat in doing so,
then the enthalpy of the reaction product must be low enough to
account for the disappearance of the moles of the reacting species
and the heat of reaction.
Figure 4-1: Reactive Distillation Equilibrium Stage

The mass balance equations are the only equations which must have
consumption and production terms added. The new equation is:

Equation (4-29):
where ε = molar rate of equilibrium reaction

The kinetic rates of reaction are given by:
Equation (4-30):
A- V  A  a  B  b K
r k = k 0 exp  – ------
 RT
where:
V = the reaction volume
A, B = denote chemical species A and B
a,b = the stoichiometric coefficients of chemical species A and
B in the stoichiometric equation, respectively
exp(-A/RT) = the Arrhenius rate expression for temperature
dependence
 = denotes the product of the concentrations of the chemicals
raised to their stoichiometric coefficients.
The only place the reaction volume is used in the distillation calcu-
lations is in the kinetic rate expression (equation (30)). It is
extremely important that the tray reaction volumes are consistent
with the volume basis used in determining the kinetic rate expres-
sion. If the reaction is a homogeneous liquid phase reaction, and the
rate expression is based on liquid phase reactions done in a CSTR,
then the liquid volume should be used. This volume corresponds to
the liquid volume on the tray and in the downcomer. Do not use the
entire mechanical volume between trays unless the rate expression
was determined from pilot plant data and the entire volume was
used to characterize the rate equation. Similarly, if the reaction is
catalyzed by a metal on a ceramic support and the rate equation was
based on the entire cylindrical volume of the packed bed holding
the catalyst, then this should be used.

Since the enthalpy basis in PRO/II is on a pure chemical basis, it is
unsuitable for keeping track of enthalpy changes due to reactions.
Therefore, reactive distillation converts chemical enthalpies to an
elemental basis before simulating the tower. After the simulation is
complete, the product stream enthalpies are recalculated using the
standard PRO/II basis. While this is mostly hidden from the user, it
does impact the reporting overall column enthalpy balance and is
the reason for reporting multiple enthalpy balances. This does not
impact the accuracy of the solution.
Chemdist, LLEX, and RATEFRAC support any type of reaction
which can be entered through the Reaction Data section or
described using an in-line procedure. Various reaction parameters
may be varied from the flowsheet using calculators and DEFINE
statements. Any set of mixed reactions may be assigned to trays in
the distillation column.
Chemdist, LLEX, and RATEFRAC support single tray distillation
columns. By using this feature, Chemdist and RATEFRAC may be
used as a two-phase reactor model which produces vapor and liquid
streams in equilibrium. In addition, the bottoms product rate may be
set to zero so that a boiling pot reactor can be modeled. As part of
this functionality, a single non-volatile component may be speci-
fied. The non-volatile component is typically a catalyst which may
used in the kinetic reaction rate expressions.
Kinetic Reaction Homotopy (Volume Based)

The solution of the Mass, Equilibrium, Summation, and Enthalpy
balance equations can be a difficult task for non-ideal chemical sys-
tems. The addition of reaction terms further complicates the chal-
lenge. Chemdist, LLEX, and RATEFRAC both have a homotopy
procedure to simplify obtaining a solution to reactive distillation
columns. The basic procedure is straightforward:
 Start with a set of equations to which you know the answer.
 Then modify the equations a little and solve them.
 Modify them again and re-solve using the last solution.
Eventually, the equations will be deformed into the equations to
which you want the answer.
This procedure has a formalized mathematical basis with the theo-
retical underpinnings beginning as early as 1869 (Ficken, 1951).
Mathematically, a homotopy is a deformation or bending of one set

of equations that are difficult to solve, f{x} = 0, into a set whose
solution is known or easily found, g{x}=0. A new set of equations,
referred to as the homotopy equations, is constructed from f{x} and
g{x}. The homotopy equations are what enable us to move
smoothly from the easy problem to the difficult problem. The most
general conditions for the homotopy equation are:
Equation (4-31):
H  x, t  some function of f  x and g  x  0
such that:
Equation (4-32):
H  x 0 , 0  g  x 0   0
H  x  , 0  f  x    0
The simplest transformation is a linear homotopy. In this case, the

homotopy equation becomes:
Equation (4-33):
H  x, t  tf  x  1  t  g  x  0
In equation (4-33), t is varied from zero to 1. The first challenge is

choosing the proper homotopy, the second is determining the
sequence of t that allows you to move from the simple equations to
the difficult equations.
The methods for tracking the homotopy path from 0 to 1 are classi-
fied as either “simple”, discrete methods, or “continuation”, differ-
ential methods based on the integration of an initial value method.
Currently, the reactive distillation algorithm in PRO/II uses a “clas-
sical” homotopy with a set of predefined steps. In most cases
involving reaction, this approach is sufficient.
The reactive distillation algorithm uses a physical homotopy with
the reaction volume being linked directly to the homotopy parame-
ter. That is, initially, the reaction volume is zero and the “simple”
set of equations corresponds to the basic distillation problem. At the
final point, the reactive volume is equal to the specified volume and
the equations are the full set describing reactive distillation. This

homotopy is only used for those systems using a reaction volume.
These are the most difficult systems to solve.
The actual function used to increase the reaction volume is a combi-
nation of functions. Initially, there may not be any products present
in the tower and the reaction may proceed very quickly. Therefore,
the volume is initially increased on a log fraction basis which very
gradually introduces the reaction. After the products begin to accu-
mulate on the trays, the reaction volume is increased linearly. The
transition between the two modes is at 25%.
Summarizing, if the reaction homotopy is used, the initial problem
is solved with no chemical reaction on the trays. After the solution
is reached, the reaction volume is increased by a small amount and
the problem is resolved using the no reaction solution as a starting
point. After the solution is reached, the reaction volume is again
increased and the problem is resolved. This continues until the reac-
tion volume has been fully introduced. The number of increments
and the initial volume may be specified by the user.
If the steps are small or the problem is not particularly difficult, the
problems at each volume are solved in a small number of iterations.
Even with this, the distillation equations are being solved at each
volume step and it may take quite a few iterations to solve. Other
authors report increases in solution times from 30% to 300%
depending on the difficulty of the problem. In fairness, if the prob-
lem takes 3 times as long using the homotopy, the engineer devoted
a great deal of time generating the initial estimates in order to get
any solution. In many cases, there is no choice.
Reference
1. Bondy, R.W., Physical Continuation Approaches to Solv-

ing Reactive Distillation Problems, paper presented at 1991
AIChE Annual meeting.
2. Ficken, F.A., 1951, The Continuation Method for Func-
tional Equations, Communications on Pure and Applied
Mathematics, 4.
Also See:

Initial Estimates
As previously mentioned, initial column profiles are needed for
solution of the column heat, mass, equilibrium, and performance
specification balances. These may either be provided by the user, or
generated internally by PRO/II using an initial estimate generator.
User-provided Estimates
Temperatures
Liquid and Vapor Profiles
Liquid and Vapor Mole Fractions
Estimate Generator
Recommendations
User-provided Estimates
Ideally, the only estimates the user has to provide is either the over-
head rate or the bottoms rate with the product information. On the
other extreme, the user can provide the complete estimates for the
temperature, flow rates, and composition profiles. PRO/II's initial
estimate generation (IEG) algorithms generate these numbers rela-
tively well and the user need not provide any initial estimates
except for difficult simulations.
PRO/II could interpolate the temperature, liquid and vapor rates,
and phase compositions estimates, if the end point values for these
variables are available. These end point values could either be pro-
vided by the user or estimated by PRO/II. When these values are
provided by the user, we require that the user provide at least two
endpoint values (first and last theoretical stage). The first theoreti-
cal stage is the condenser or the top tray for the “no condenser”
case. The last theoretical stage is the reboiler or the bottom tray for
the “no reboiler” case.
Temperatures
Tray temperatures are relatively easy to estimate. The reboiler and
condenser temperatures represent the bubble points and/or dew
points for the products. These may be estimated by the user or cal-
culated using the shortcut fractionator model.
The top and bottom tray temperatures may be estimated by addition
or subtraction of a reasonable temperature difference from the con-
denser and reboiler temperatures.

For complex fractionators, the product draw temperatures are usu-
ally known or can be estimated from the product ASTM distilla-
tions.
Liquid and Vapor Profiles

For most columns, the vapor and/or liquid profiles are more diffi-
cult to estimate. Moreover, they are generally more influential than
temperatures in aiding or hindering the solution.
Estimates for the overhead or the bottoms products are provided
with the product information; in addition, rates for the side draw
products are also provided by the user.
For columns with condensers, it is important to provide an estimate
of the reflux, either as the liquid from tray one or the vapor leaving
tray two (the top product plus reflux). For simple columns with liq-
uid or moderately vaporized feeds, constant molar overflow may be
assumed and the vapor from the reboiler tray 6 assumed to be the
same as the tray 2 vapor. The reboiler vapor may also be provided
by giving an estimate of the liquid leaving the tray above the
reboiler.
For columns in which the feed has high vapor rate, there will be a
sharp break in the vapor profile at the feed tray. For such columns at
least four vapor rates should be provided: top tray, feed tray, tray
below feed, and bottom tray.
For columns in which the reflux is to be used as a performance
specification, the reflux should be set at the specification value in
the estimate, enhancing convergence.
The effect of side draws must be considered for complex fraction-
ators. It is usually safe practice for such columns to add the side
product rates and multiply by two to estimate a top reflux rate.
For columns having steam feeds, the steam flow must be included
in the vapor estimates. An estimate of the decanted water should
also be included with the product information.
Note: In general, convergence is enhanced when the reflux quantity

is estimated generously.
Liquid and Vapor Mole Fractions

PRO/II generates reasonable profiles for liquid and vapor mole
fractions, using one of the initial estimate models selected by the

user. The user could provide the mole fraction profile to aid the con-
vergence.
Estimate Generator
The temperature, rate, and composition profiles not provided by the
user are generated by PRO/II using one of the built-in estimate gen-
erator models. When using the estimate generator, product rates are
still provided with the product information.
Various models used for the estimate generation are shown below in
Table 4-27 with the column algorithm.
Table 4-27: Default and Available IEG Models

Algorithm/
IEG Method I/O Chemdist SURE LLEX ELDIST
Simple Defa Default Defaul Defaul Yes*

ult t t
Conventional Yes Yes Yes
Refining Yes Yes Yes
Electrolyte Default*
* For electrolytic systems, simple IEG is same as electrolyte IEG.

The estimate generator will work for most columns, regardless of
complexity or configuration. Of course, for simulations in which a
column model is being used to simulate a combination of unit oper-
ations (columns, flash drums, etc.), the estimate generator should
not be used since it sets up profiles corresponding to a conventional
distillation situation. Furthermore, use of the estimate generator is
not meant to provide the most optimum starting point (although this
may often be the case) but rather to provide a starting point with a
high probability of reaching solution.
The Simple estimate generator computes tray flows from constant
molar overflow and the temperatures and mole fractions from L/F
flashes.
The Conventional estimate generator uses the Fenske method to
determine product mole fractions as follows:
 Perform shortcut Fenske calculations to determine the product
splits and compositions. The flows from the product informa-
tion are used to initiate the shortcut calculations and, when pos-

sible, the performance specifications desired for the rigorous
solution will be used for specifications. Note that only specifi-
cations pertaining to the product rates or compositions have
any meaning for the shortcut model, i.e., rigorous specifica-
tions such as tray temperatures and tray flows (including
reflux) have no meaning. When rigorous specifications cannot
be used, the initial estimate generator will use alternate specifi-
cations selected in this order: the rate from the product infor-
mation, and a fractionation index (Fenske trays) equal to
approximately 1/2 of the column theoretical trays.
 Based on the shortcut results the product temperatures are cal-
culated. Any user-provided temperatures are used directly.
 The column liquid loading is calculated by using the reflux
estimate provided by the user. Note that an L/D ratio of 3.0 is
assumed if no reflux quantity is provided.
 A column heat balance is performed. If side coolers are present
and duties have been provided, the flow profiles are appropri-
ately adjusted.
The Refining estimate generator uses the Fenske method just like
the conventional estimate generator. The four steps described above
for the conventional method are repeated here. In addition, the bot-
tom tray temperature is adjusted for the effect of stripping stream, if
present. Adjustment is also made for inter-linked columns if pres-
ent.
In light of the above procedure it is good practice to:
Recommendations
 Provide reasonable estimates with the product information.
 Provide a reasonable reflux estimate.
 Provide temperature guesses for sub-cooled products (the esti-
mate generator would use the saturated values).
 Provide the side cooler/heater estimates, if possible.
Also See:
Distillation and Liquid-Liquid Extraction Columns

ELDIST Algorithm
The ELDIST algorithm in PRO/II is a combination of a Newton-
based method which is used in Chemdist for solving MESH equa-
tions and the solution of liquid phase speciation equations described
in Section - Electrolyte Mathematical Model.
Basic Algorithm
Basic Algorithm
Column mesh equations are solved by a Newton-Raphson algo-
rithm in the outer loop while liquid phase speciation along with K-
value computations are handled by the inner loop, as shown in Fig-
ure 4-1.
Figure 4-1: ELDIST Algorithm Schematic

Inner Speciation Loop
Input to the inner loop model are temperature, pressure, and
component mole fractions for liquid and vapor phase. Tempera-
ture, pressure, and liquid phase mole fractions are needed for
speciation calculations and for computation of liquid phase

fugacities. Vapor phase mole fractions, along with the above
information, are needed for K-value and K-value derivatives
computations.
To better describe the liquid phase speciation concept, consider
the aqueous system of components H2O, CO2, and NaCl. If
Encl. precipitation is not allowed then there are eight unknowns
for a given system. These are:
MolesH2O, MHion, MOHion, MHCO3, MNaion, MClion and
MCO2aq
(M is molality (moles per kg solvent) of a component or an ion)

There are three independent equilibrium equations:
Equation (4-34):
 Hion * mHion *  OHion * mOHion

K H 2Oaq 
aH 2Oaq
Equation (4-35):
 Hion * mHion *  HCO ion * mHCO ion

K H 2Oaq  3 3
 CO aq * mCO aq * aH Oaq
2 2 2
Equation (4-36):
 Hion * mHion *  HCO ion * mHCO ion

K HCO3ion  3 3
 HCO ion * mHCO ion

3 3
where:
 =activity coefficients
K = equilibrium constants
Activity coefficients and equilibrium constants are functions of
temperature, pressure and molarities of components or ions.
In addition, there are four independent atom balance equations and
one electroneutrality equation.
Sodium Balance:
Equation (4-37):
NaCl  in   mNaion * MolesH 2O * MWH 2O /1000  0

Chlorine Balance:
Equation (4-38):
NaCl  in   mClion * MolesH 2O * MWH 2O /1000  0
Carbon Balance:
 
CO2  in  mCO3ion  mHCO3ion  mCO2aq * MolesH2O * MWH2O /1000  0
H+ Balance:
Equation (4-40):

H 2O  in   MolesH 2O  MolesH 2O * MWH 2O /1000 

* mCO3ion  mOHion  mHCO3ion  0 
Electroneutrality Equation:
Equation (4-41):
 mHion  mNaion    M HCO ion  2mCO ion  mOHion  mClion   0

3 3
The inside loop solves these eight equations for eight unknowns
using Newton's method. Once these unknowns are computed, and
true (aqueous) mole fractions of aqueous components are deter-
mined, all ions are combined to translate them in terms of aqueous
mole fractions of the original components. These components are
referred to as Reconstituted Components. Overall mole fractions for
these components would be the aqueous mole fractions (true mole
fraction) plus reconstitution of ions. Hence, for a given set of input
liquid mole fractions (x), the inside loop returns two sets of liquid
mole fractions, namely the true mole fractions (x), and the reconsti-
tuted mole fractions (xRC).
Once the speciation equations are solved, vapor-liquid equilibrium
constants (K-values) and its derivatives are computed as a function
of T, P, Xt, and y.
Outer Newton-Raphson Loop

Outer loop model is solved by the Newton-Raphson algorithm.
There are 2NC+3 equations and 2NC+3 unknowns on each theoret-
ical tray.
Independent variables on each tray are:
Table 4-28:
a. Natural log of liquid mole fractions, ln(x) NC
b. Natural log of vapor mole fractions, ln(y) NC
c. Tray liquid rate L 1
d. Tray vapor rate V 1
e. Tray temperature T 1
2NC + 3
The equations to be solved on each tray are:
Component Balance: (NC)

Equation (4-42):
mb  n, j   x  n  1, j  L  n  1  y  n  1, j  V  n  1
 f  n, j   y  n, j  V  n   SV  n    x  n, j   L  n   SL  n  
Vapor-Liquid Equilibrium: (NC)

Equation (4-43):
vle  n, j   ln  y  n, j    ln  k  n, j  x  n, j    0
Energy Balance: (1)

Equation (4-44):
Eb  n   F  n  Hf  n   V  n  1 H  n  1  L  n  1 h  n  1
 V  n   SV  n   H  n    L  n   SL  n   h  n   Q  n   0
Summation x: (1)

Equation (4-45):
 
SX  n     x  n, j    1  0
 j 
Summation y: (1)
 
SY  n     y  n, j    1  0
 j 
Reference:
1. Shah, V.B., Bondy, R.W., A New Approach to Solving

Electrolyte Distillation Problems, paper presented at 1991
AIChE annual meeting.
2. 2.OLI Systems Inc., 1991, PROCHEM User's Manuals,
Version 9, Morris Plains, NJ.
Also See:
ELDIST Algorithm
Rate-based Segment Modeling using RATEFRAC®

Introduction
Segments and Packed Towers
Rate-based Tray or Segment Diagram
Variables
Equations
Equilibrium Relationships
Vapor Liquid Equilibrium Relationships
Calculations for Mass Transfer Rate

Introduction
RATEFRAC® is a rigorous rate based distillation model. The algo-
rithm is based on the work of Krishnamurthy and Taylor [ref 1].
Rate based models use mass and heat transfer rate expressions to
compute the actual mass transfer as opposed to equilibrium based
models, which assume that the liquid and vapor leaving a stage are
in equilibrium.
Because RATEFRAC® is based on mass transfer, any column inter-
nal modeled requires specific mass transfer correlations for the
internal. Different correlations have been implemented for valve,
sieve and bubble cap trays as well as for random and structured
packing.
RATEFRAC® uses a modified Newton-Raphson algorithm for
solving the model equations. RATEFRAC® requires approximately
two and a half times as many variables and equations as an equilib-
rium stage model, making RATEFRAC® solution times longer than
solving a comparable equilibrium stage tower.
Segments and Packed Towers

When modeling packed towers, the tower diameter and height of
packing are used to determine the interfacial area available for mass
and heat transfer. Because RATEFRAC® does not use theoretical
stages, the packed tower is divided up into 'segments' to calculate
the heat and mass transfer for a given height of packing. For exam-
ple, if a packed section with 30 ft of packing is being modeled using
10 segments, each segment represents 3 ft of packing. A good rule
of thumb to use when determining segment height is that each seg-
ment should be approximately 1 HETP.
When modeling a distillation tower using ProVision, the user first
enters the number of theoretical stages when specifying the tower.
If a RATEFRAC® tower with packing is being modeled, this value
is used internally as the number of segments. When the number of
segments is specified, the default algorithm is the IO algorithm.
Rate-based Tray or Segment Diagram

In a classical equilibrium stage model, the liquid and vapor leaving
the stage are assumed to be in thermodynamic equilibrium. In the
rate based model shown in Figure 4-1, the liquid and vapor leaving
the stage are not in thermodynamic equilibrium. In fact, it is possi-
ble for the liquid to be sub-cooled and the vapor to be superheated.

If the vapor is below the equilibrium dew point, this implies that
mist formation could occur at this location in the tower and further
analysis is required..
Figure 4-1: Non-Equilibrium Segment Model

Note: The bulk liquid and vapor phases are modeled separately and
have their own compositions, flow rates and temperatures. Also
note that liquid and vapor feeds are fed to same phase.
Note: In PRO/II heat entering is positive and leaving is negative.
Variables
Each non equilibrium (rate based) tray or segment introduces
5*NOC + 3 equations and variables (where NOC is the number of
components). The equilibrium stage model used by RATEFRAC®
uses only 2*NOC+1 equations and variables. Because of the
increased number of equations and variables, RATEFRAC® must

invert a larger matrix at each iteration than an equivalent equilib-
rium stage model.
The variables for a non equilibrium stage are as follows:
Table 4-29: Variables for non-equilibrium stage

Description Symbol Number of
Variables
Bulk Liquid Phase Mole Fractions xbulk NOC

Bulk Vapor Phase Mole Fractions ybulk NOC
Interface Liquid Mole Fractions xint NOC
Interface Vapor Mole Fractions yint NOC
Molar Flux across interface N NOC
Bulk Liquid Temperature TL 1
Bulk Vapor Temperature TV 1
Interface Temperature Tint 1
Equations
Vapor Phase Component Material Balances
Liquid Phase Component Material Balances
Vapor Phase Enthalpy Balance
Calculation of Partial Molar Enthalpy
Liquid Phase Enthalpy Balance: (1 Equation)
Vapor Phase Component Material Balances

The vapor and liquid phase equations are written in terms of total
component molar flow rates. Total flow rates are chosen as inde-
pendent variables instead of net flow rates to allow for total pump-
arounds and total draws from stages. The original paper by
Krishnamurthy and Taylor [ref 1] used net liquid and vapor compo-
nent rates as independent variables.
NOC equations per segment; where NOC is the number of compo-
nents.
For a non-equilibrium segment:

Equation (4-47):
vi , j  N i , j  vi , j 1 1  rv j 1    viF, j   viPA
,j
NF NPA
i = 1..NOC, j = 1..NT
where
i is the component
j is the segment
Total vapor flow rate of component i leaving
vi , j
segment j
Molar flux term. Transfer of component i on seg-

Ni, j ment j between phases. This is a variable on each
segment. It has been randomly presumed that the
transfer from vapor to liquid is positive. The
shifting of material from liquid to vapor will
automatically be considered as negative quanti-
ties.
Flow rate of component i leaving segment j +1 *
vi , j 1
in the vapor phase
Pump around
PA
Flow rate of component i entering segment j as

viF, j an external feed
Flow rate of component i entering segment j as a

viPA
,j pump around Stream
Vapor side draw ratio for stage j+1

rv j 1
NF Number of feeds
NPA Number of pumparounds
NOC Number of components
NT Number of trays or segments

Liquid Phase Component Material Balances
NOC equations per segment where NOC is the number of
components.
For a non-equilibrium segment:
Equation (4-48):
li , j  N i , j  li , j 1 1  rl j 1    liF, j   liPA
,j
NF NPA
i = 1..NOC, j = 1..NT
where
li , j Total Flow rate of component i leaving segment j

in the liquid phase
li , j 1 Total Flow rate of component i leaving segment

j-1 in the liquid phase
rl j 1 Liquid side draw ratio for stage j-1
Ni, j Molar flux term for component i on segment j.

Refer equation 1 for more details
Flow rate of component i entering segment j as

liF, j
an external feed
Flow rate of component i entering segment j as a

liPA
,j
pump around
Vapor Phase Enthalpy Balance

For any non-equilibrium segment:
Equation (4-49):
 
v
NOC
i, j H j   N i , j H i , j  q vj    vi , j 1   svi , j 1  H j 1
NOC  NOC NOC 
   PA 
    viF, j H Fj      viPA
, j H j   Q j
v
NF  NOC  NPA  NOC  NQ

Where
Enthalpy of mixture on segment j

Hj
Vapor phase partial molar enthalpy of component

H i, j
i on segment j
Heat transferred by conduction from vapor phase

v
qj on segment j
Equation (4-50):
qvj  htcjv T jv  T jI 
v Heat-transfer coefficient of vapor phase on seg-

htcj
ment j.
v Vapor Temperature
Tj
I Interface Temperature
Tj
H j 1 Enthalpy of vapor mixture on segment j+1
Enthalpy of feed(s) entering segment j

HFj
pa Enthalpy of interconnecting stream(s) to segment

Hj j
v Heat added to/removed from segment j

Qj
Calculation of Partial Molar Enthalpy

Partial molar enthalpies are obtained using finite difference deriva-
tives. One of the benefits of using component molar flows as
opposed to mole fractions as independent variables is that perturb-
ing mole numbers leads to derivatives that are easier to calculate
then when using mole fractions.
Equation (4-51):
Total Enthalpy  nT H j

Equation (4-52):
   nT H j  
H i, j   , k  1..c, k  i
 ni , j T , P , n
k
Partial Molar Enthalpy

H j 
H j  nT   , k  1..c, k  i
 ni , j T , P ,n
k
Note: Thermodynamic subroutines in PRO/II expect compositions

in terms of mole fractions.
 (H j ) 
  is determined by perturbing ni , j
  ni , j 
( n i, j  i , j 
x i, j  when i is perturbed (  i , j 
nT , j   i , j 
( n k, j 
x k, j  when i  k , k  1..c
nT , j   i , j 
The enthalpy balance is given by

Equation (4-54):
 
 v
NOC
i, j  N i , j  H i , j  q vj    vi , j 1   svi , j 1  H j 1
 NOC NOC 
   PA 
    viF, j H Fj      viPA
, j H i, j   Q j
v
NF  NOC  NPA  NOC  NQ

Liquid Phase Enthalpy Balance: (1 Equation)
For any non-equilibrium segment:
Equation (4-55):
 
l
NOC
i, j h j    li , j 1   sli , j 1  h j 1   N i , j h j 1 q j
 NOC NOC  NOC
   PA 
    liF, j h Fj      liPA
, j hj    Q j   Q j
L L
NF  NOC  NPA  NOC  NQ E
where
hj Enthalpy of liquid mixture on segment j
Enthalpy of liquid mixture on segment j-1

h j 1
Liquid phase partial molar enthalpy of compo-

hi, j
nent i on segment j (see also equation 23)
Heat transferred by conduction to liquid phase on

L
qj segment j
Equation (4-56):
q Lj  htcjL T jI  T jL 
L Heat-transfer coefficient of liquid phase on seg-

htcj ment j
I Interface Temperature
Tj
L Liquid Temperature
Tj
Enthalpy of feed(s) entering segment j as liquid

hF j
pa Enthalpy of liquid interconnecting stream(s) to

hj
segment j
L Heat added to/removed from segment j

Qj
Lpa Heat added to/removed from segment j from

Qj
pumparounds

The liquid phase enthalpy balance is given by
Equation (4-57):
L
  lij – Nij hij =   lij – 1 – slij – 1 hij – 1 + q j
NOC NOC
 F  F  PA PA  L
+     l ij h j +    l ij h ij –  Q j +

NF NOC
  NPA  NOC  NQ
LPA
Q j
Equilibrium Relationships
Rate Relationships in the Vapor Phase

For any segment j:
Equation (4-58):
yiI, j  K iI, j xiI, j

i=1..NOC, j=1..NT
Which gives NOC (number of components) equations per stage.
where:
y I i, j Mole fraction of component i on segment j

(interface vapor composition)
x I i, j Mole fraction of component i on segment j

(interface liquid composition)
K I i, j Vapor-liquid equilibrium constant
In general,
The K-values are functions of the interface temperature, vapor
phase mole fractions and the liquid phase mole fractions

Equation (4-59):
K iI, j  f Ti ,I j , yiI, j , xiI, j 
Rate Relationships in the Vapor Phase

NOC-1 equations where NOC is the number of components.
For any non-equilibrium segment,
Equation (4-60):
Ni , j  Niv, j  Niv, j T jv , T jI , ykjI , ykjbulk , ykjbulk

1 , N kj , kikj , k  1, 2...noc, a j 
v
The transfer rates N vij are functions of
where:
Binary i-k mass transfer coefficients on segment

k v ikj
j
aj Interfacial area between phases in contact on

segment j
Interfacial vapor composition on segment j

y I kj
Bulk vapor composition on segment j

y bulk kj
Tvj Bulk vapor temperature on segment j
TIj Interface temperature on segment j
y bulk kj 1 Bulk vapor composition on segment j+1
N kj Mass transfer rates on segment j
k Component index
Ni, j Mass transfer rate considered as a variable

N iv, j Vapor phase mass transfer rate calculated from
generalized Maxwell-Stefan multi component
Interface Energy Balance Equation: (1 Equation)

Liquid Rate Expressions
Summation of Mole Fractions: (1 Equation for Each Phase)
N
NOC
i. j H i , j  q vj  N
NOC
i. j hi , j  q Lj
Equation (4-62):
N i. j H i , j  htcjv T jv  T jI   N i. j hi , j  htcjL T jI  T jL 
NOC NOC
Liquid Rate Expressions

NOC-1 equations where NOC is the number of components.
Equation (4-63):
Ni , j  NiL, j  NiL, j TjL , TjI , xkjI , xkjbulk , ykjbulk

1 , N kj , kikj , k  1, 2...noc, a j 
L
The transfer rates N Li,j are functions of
k L ikj Binary i-k mass transfer coefficients on segment j

(liquid phase).These are specific to each column
internal, ie sieve/valve/bubble cap tray or random or
structured packing.
aj Interfacial area unavailable for heat and mass trans-
fer
x I kj Interfacial liquid composition on segment j
x bulk kj Bulk liquid composition on segment j

TLj Bulk liquid temperature on segment j
TIj Interface temperature on segment j
x bulk kj 1 Bulk liquid composition on segment j-1
N kj Mass transfer rates on segment j
k Component Index
Ni, j Transfer rate of component i on segment j as a vari-

able
N Li, j Mass transfer rate of component i calculated based

on multi component mass transfer theory
Summation of Mole Fractions: (1 Equation for Each Phase)

Interface Liquid phase mole fractions:
Equation (4-64):
x
NOC
L
i, j  1.0 i  1, 2....NOC
Interface Vapor phase:

Equation (4-65):
y
NOC
I
i, j  1.0 i  1, 2....NOC
Calculations for Mass Transfer Rate

Vapor phase
Liquid phase
Heat Transfer Coefficients
Diffusion Coefficients

Vapor phase
(i) Exact method

Equation (4-66):
N iv, j  J iv, j  yibulk

, j NTj i  1, 2...NOC
where:
J vi, j Diffusion flux of component i on segment j
NTj Total mass transfer rate on segment j
y bulk i , j Bulk vapor phase mole fraction of component I on

segment j
The diffusion fluxes are obtained by solving Maxwell-Stefan equa-

tions. See Krishna and Standart [8, 9].
Equation (4-67):
J  y  yI 
1 1
L
  B v    v  exp  v    I  bulk
j j j j j
The above system of equations give diffusion fluxes for NOC-I

components on segment j.
where:
( Jv) j Vector of diffusion fluxes in the vapor

phase on segment j
B v 1
j
Matrix of multi component mass
transfer coefficients on segment j.
  exp  I 
v
j
v 1
Correction factors for finite mass
transfer fluxes. Elements of the matrix
  are given by equations (24 &
v
25)
y bulk Composition of vapor based on aver-

aging procedure used

Interface vapor composition
yI
Elements of multi component mass-transfer coefficients matrix

[B v] j:
For any segment j:
Equation (4-68):
Equation (4-69):
 1 1 
Bin   yibulk
,j    i  1, 2.....  NOC  1 , i  n
 kin , j kic , j 
where:
Diagonal element
Bij
Off-diagonal element
Bin
k ic , j Binary mass transfer coefficient for the binary

pair i and c on segment j. The binary mass trans-
fer coefficients have interfacial area terms in-
built in k ic , j
kin , j Binary mass transfer coefficient for the binary

pair i and n on segment j. The binary mass
transfer coefficients have interfacial area terms
in-built in k in,j
y bulk ij y bulk nj Mole fractions of species i and n respectively on

segment j in the bulk vapor phase.
Elements of the matrix [  v]j:

Equation (4-70):
Ni , j c N n, j
i, j   i  1, 2....  NOC  1
kic , j n 1 kin , j
n i
Equation (4-71):

  1 1 
 in   N i , j    i  1, 2.....  NOC  1 , i  n
 kin , j kic , j 
where:
Diagonal element
 ij
 in
Transfer rate of component i on segment j

Ni, j
Transfer rate of component n on segment j

N n, j
(ii) Effective diffusivity method

N i , j  J iv, j  yiave
, j NTj
where:
Average composition of species i between bulk

y ave i , j vapor phase and interface on segment j
Equation (4-73):
, j  yi , j
yibulk I
y ave
i, j 
2
The diffusion flux of any component i is proportional to only its
own concentration gradient. Thus:

Equation (4-74):
 eieffv  1 y  yiI, j 
1
J iv, j  kieff
v
 ieff
v bulk
i, j
Liquid phase
Equation (4-75):
N iL, j  J iL, j  xiI, j NTj i  1, 2....  NOC  1
where:
Transfer rate of species i on segment j calculated

N Li, j using liquid properties
Diffusion flux of component i on segment j

J Li, j
Liquid phase mole fraction of component i on seg-

x I i, j ment j (interface composition)
Total transfer rate on segment j

NTj
The diffusion fluxes are obtained by solving generalized Maxwell-

Stefan equations.
Equation (4-76):
L L –1 –1 I bulk
 J  j =  B  j    j    j  exp     j  exp    –  I  j   x – x j
The above system of equations furnished diffusion fluxes for NOC -

1 components on segment j
Elements of the matrix B
L
  j :
For any segment j:
Equation (4-77):
xijI C xnI , j
Bi , j   i  1, 2....  NOC  1
kiC n 1 kin , j
n i

Equation (4-78):
where
Bij Diagonal element
Bin Off-diagonal element
Mole fractions of species i and n at the liq-

x I i, j x I n, j
uid interface on segment j
k ic , j Binary mass transfer coefficient for the

binary pair i and c in the liquid phase on
segment j. The binary mass transfer coeffi-
cients have interfacial area terms in-built in
.
k ic , j
k in , j Binary mass transfer coefficient for the

binary pair i and n in the liquid phase on
segment j.
Elements of the matrix [r]j :

Equation (4-79):
 ln i
in   in  xi i, n  1, 2...  NOC  1
xn
where:
 in kronecker delta = 1.0 when i = n

kronecker delta = 0.0 when i = n
Activity coefficient of component i
Elements of the matrix  j :

L
 
Equation (4-80):
Ni , j NOC N n, j
i, j   i  1, 2....  NOC  1
kic , j n 1 kin , j
n i
Equation (4-81):
 1 1 
 in   N i , j    i  1, 2.....  NOC  1 , i  n
 kin , j kic , j 
where
Diagonal element
ij
 in
Transfer rate of species i on segment j

Ni, j
Note: All terms are calculated based on liquid properties
(iii) Effective Diffusivity Procedure

Equation (4-82):
N iL, j  J iL, j  xiave

, j N Tj i  1, 2....  NOC  1

where
Average mole fraction of species i on

xavei, j segment j and is computed between
interface and bulk compositions

x ave i , j x I i , j  x bulk i , j
2
Equation (4-83):
   ln yi  j 
  ieff  j  eieff  1 j  xiI, j  xibulk
,j 
1
J iL, j  kieff
L
1  xi
 x 
 i 
where:
Effective liquid phase mass transfer

k Lieff coefficient of species i in the multi com-
ponent mixture
Correction factor associated with finite

  j e
ieff
ieff
1 1
j transfer rates
For ideal systems:

ieff eieff  eieff  1 x ,j 

1
J iL, j  kieff
L I
i, j  xibulk
NT
ieff  L
kieff
The effective mass transfer coefficient k L ieff is calculated using

an appropriate effective diffusivity approach.
Effective diffusivity procedure to compute k ieff

Vapor phase
(a) For any segment j
Equation (4-85):

where
k v ieff , j Vapor phase effective mass transfer coeffi-

cient of species i on segment j
k
v
ic , j
Vapor phase binary mass transfer coefficient
of species i and C forming the binary pair on
segment j
k v in , j Vapor phase binary mass transfer coefficient

of the binary pair i and n on segment j
y ave i , j Average mole fraction of component i on

segment j
y ave n , j Average mole fraction of species n on seg-

ment j
y ave i , j y I i , j  y bulk i , j
2
y I i, j Mole fraction of species i at vapor interface

on segment j
y bulk i , j Mole fraction of species i in the bulk vapor

phase on segment j
(b) The interfacial area available for mass transfer in packed col-
umns is calculated using [ref 2].
Equation (4-86):
  0.05 0.2 
0.75

aw  a 1  exp  Re0.1 Fr We 
 
L L L
 c 
where
ReL L
apL

PrL a  L2
g L2
WeL L2
a p  L
L Liquid superficial mass velocity -This

velocity is based on tower cross-sectional
ap Specific surface area of the packing
L Liquid Viscosity
g Acceleration due to gravity
L Liquid Density
 Surface tension
 c Critical surface tension of the packing

material
aw Wetted interfacial area
(c) The liquid phase mass transfer coefficients in packed columns

are calculated using [ref 2]
Equation (4-87):
 L   L 1/3  L2/3
 ScinL   a p d 1p 
1/ 2 0.4
 in
k   0.0051
 g  L  aw  L

where
kinL Binary mass transfer coefficient for the

binary pair and in the liquid phase
d 1 Nominal diameter of packing or packing

size
ScinL Schmidt number for the binary pair i and n

in the liquid Phase
ScinL  L /  L Din 
L Liquid Viscosity
L Density of the liquid mixture
Din Binary Maxwell-Stefan diffusion coefficient

for the binary pair i and n
Heat Transfer Coefficients
The CHILTON-COLBURN equation is used to evaluate heat
transfer coefficients.
Equation (4-88):
htc
kav  Sc   pr 
2/3 2/3

Cpmix
where
k av Average binary mass transfer coefficients
Sc Schmidt number
Sc  mix /  mix Dav 
 mix Mixture viscosity

 mix Mixture density
Dav Average diffusivity
htc Heat transfer coefficient
C mix Molar heat capacity
r Prandtl number
r
c mix  mix / ktmix
c mix
Mass heat capacity
k tmix Mixture thermal conductivity
Diffusion Coefficients
Vapor Phase Binary Diffusion Coefficients

Binary diffusion coefficients for the vapor phase are calculated
using the Fuller method [ref 3 and 4].
Equation (4-89):
0.000143T 1.75
DAB  2
P M AB   v  A    v  B 
1/3 1/3
 
where
P Pressure
M A, M B Molecular weights
M AB
2  1
MA  MB

1 1

T Temperature
D AB Binary Diffusion Coefficients
V Atomic Diffusion Volume Defined in

Table 4-30
Table 4-30: Atomic Diffusion volume

Atom or Group Diffusion Volume
C 15.9
H 2.31
O 6.11
N 4.54
F 14.7
Cl 21.0
Br 21.9
I 29.8
S 22.9
Aromatic Ring -18.3
Heterocyclic Ring -18.3
Liquid Binary Diffusion Coefficients

Liquid Binary Diffusion Coefficients are calculated using the
Wilke-Chang correlation [ref 5].
Equation (4-90):
B M B T
o
DAB  7.4*108
 BVA0.6

where:
o Diffusion coefficient of species A (the solute)

D AB
present in low concentration
B Association factor from the following Table 4-31
Table 4-31: Association Factor

Water 2.26
Methanol 1.9
Ethanol 1.5
Unassociated Solvents 1.0
MB Molecular weight of species B
T Temperature
 Viscosity of solvents B
Liquid Multicomponent Diffusion Coefficients

The Wilke Chang equation provides binary diffusion coefficients in
a binary mixture at infinite dilution. Taylor and Krishna provide an
expression to compute binary diffusion coefficients in a multi com-
ponent mixture. The expression used is equation 4.2.18 in [6].
Equation (4-91):
DA, B   DAB   D  
o 1 xB  xi  /2 o 1 xi  x j /2
BA
Reference
1. R. Krishnamurthy, R. Taylor, “A non equilibrium stage model
of multi component separation processes. Part 1: model
description and method of solution”, AIChEJ., Vol 31(1985),
pp. 449-456.
2. Onda, K., Takeuchi, H., and Okumoto, Y. J., Journal of Chemi-
cal Eng, Japan, 1(1) 56, (1968).

3. Fuller, E.N., P.D. Schettler and J.C. Giddings, Ind. Eng. Chem.
Vol 58, No. 5, May 1966 pages 19-27.
4. Fuller, E.N., N.K. Ensley and J. C. Giddings, Journal of Physi-
cal Chemistry, Vol 75, No. 11, Nov 1969, pages 3679-3685.
5. Wilke, C.R. and P. Chang, AIChE J, Vol 1, pg 264, 1955.
6. Reid, Robert C, Prausnitz, John M and Poling, Bruce E., The
Properties of Gases and Liquids, Fourth Edition, McGraw-Hill,
Inc, ISBN 0-07-051799-1.
7. Taylor, Ross and R. Krishna, Multicomponent Mass Transfer,
1993, John Wiley & Sons, ISBN 0-471-57417-1.
8. Krishna, R. and G.L. Standart, AIChE Journal, 22, 1976, pg 383
9. Krishna, R. and G.L. Standart, Chem Eng Comm, 3, 1979, pg
201
Column Hydraulics
General Information
Tray Rating and Sizing
Random Packed Columns
Structured Packed Columns
General Information
PRO/II contains calculation methods for rating and sizing trayed
distillation columns, and for modeling columns packed with ran-
dom or structured packing. Trayed columns are preferable to
packed columns for applications where liquid rates are high, while
packed columns are generally preferable to trayed columns for vac-
uum distillations, and for corrosive applications. All tray rating and
packed column calculations require viscosity data. A thermody-
namic method for generating viscosity data from Table 4-32 should
therefore be selected by the user for these applications.
Viscosity
Method Phase
PURE V, L, VL
PETRO V, L, VL
TRAPP V, L, VL

Viscosity
SATD V, L, VL
U1, U2, U3,
V, L, VL
U4, or U5
BW V
KVIS L
LBC L
TWUB L
APIT L
Tray Rating and Sizing

Columns containing valve, sieve, or bubble cap trays may be mod-
eled by PRO/II using a number of proven methods. Methods devel-
oped by Glitsch are used to compute the capacity or flood point, and
the pressure drop for valve trays. For sieve or bubble cap trays, the
capacity is computed by using 95 and 85% of the valve capacities
respectively. The tray pressure drop is calculated by the Fair
method for sieve trays, and by the method of Bolles for bubble cap
trays.
Capacity
Pressure Drop
Capacity
The capacity of a trayed column is defined in terms of a vapor flood
capacity factor, at zero liquid load, CAF0. Nomographs are used to
obtain the capacity factors based on tray spacing and vapor density.
Foaming on trays is taken into account by using a so-called “system
factor”. Table 4-33 shows the system factors to be used to correct
the vapor capacity factors.
Table 4-33: System Factors for Foaming Applications

System Factor
Absorbers (over 0 F) .85
Absorbers (below 0 F) .80
Amine Contactor .80
Vacuum Towers .85

Table 4-33: System Factors for Foaming Applications
Amine Stills (Amine Regenerator) .85
H2S Stripper .85
Furfural Fractionator .85
Top Section of Absorbing Type Demethanizer/
.85
Deethanizer
Glycol Contactors .50
Glycol Stills and Glycol Contactors in Glycol
.65
Synthesis Gas
CO2 Absorber .80
CO2 Regenerator .85
Caustic Wash .65
Caustic Regenerator, Foul Water, Sour Water Stripper .60
Alcohol Synthesis Absorber .35
Hot Carbonate Contactor .85
Hot Carbonate Regenerator .90
Oil Reclaimer .70

For sizing an existing trayed column, or for calculating the percent
of flood for a given column diameter, the column vapor load is
used. The vapor load may be determined by using:
Equation (4-92):
Vload  ACFS  G /   L  G  
0.5
where:
Vload = vapor load capacity
ACFS = actual vapor volumetric flow rate
G = vapor density
L =liquid density
Pressure Drop
For valve, sieve, or bubble cap trays the total tray pressure drop is a
sum of the dry tray pressure drop, and the pressure drop due to the
liquid holdup on the trays:

Equation (4-93):
P  Pdry  Pl
where:
P = total pressure drop, inches liquid
Pdry = dry tray pressure drop, inches liquid
Pl = pressure drop through the liquid on the trays, inches liq-
uid
The dry tray pressure drop is obtained from nomographs relating
the pressure drop to the weight of the valves at low vapor flow
rates, and to the square of the vapor velocity at high vapor flow
rates.
For sieve trays, the method of Fair is used to calculate the dry tray
pressure drop, which is given by:
Equation (4-94):
Pdry  0.186 / Cv2  G /  L  vG2
where:
Cv = discharge coefficient
vG = superficial vapor velocity
For bubble cap trays, the dry tray pressure drop is calculated by the
method of Bolles:
Equation (4-95):
Pdry  1.20  G /   L  G  
0.2
hsh vG0.4  K 2 G /  L vG2
where:
hsh =bubble cap slot height
The dry cap coefficient, K2, in equation (4) is a function of the ratio
of the annular to riser areas.
For valve trays, the pressure drop through the liquid is given by:

Equation (4-96):
Pl  0.4  L / lw   hw 
2/3
 
where:
L = total liquid flow rate, gpm
lw = weir length, inches
hw = weir height, inches
The pressure drop through the liquid on the sieve or bubble cap tray
is given by:
Equation (4-97):
Pl   hds
For sieve trays,

Equation (4-98):
hds  hw  how  hhg / 2
For bubble cap trays,

Equation (4-99):
hds  hs  how  hhg / 2
where:
hds = calculated height of clear liquid over trays (dynamic seal)
hw = weir height
hs = static slot seal (weir height minus height of top slot above
plate floor)
how = height of crest over weir
hhg = hydraulic gradient across plate
The dimensionless aeration factor, , in equation (4-97) is a

function of the superficial gas velocity.
Also See:
Column Hydraulics

Random Packed Columns
Capacity
Pressure Drop
Efficiency
Columns containing conventional randomly oriented or dumped
packing such as Raschig rings, Berl saddles, and Pall rings may be
modeled by PRO/II. Table 4-34 shows the random packing types
supported by PRO/II.
Table 4-34: Random Packing Types, Sizes, and Built-in Packing Factors
(ft2/ft3)
T Random (mm.) 6.3 9.5 12.7 15.9 19 25.4 31.7 38.1 50.8 76.2 88.9
Y Packing (in) 0.25 0.375 0.5 0.62 0.75 1.0 1.25 1.5 2.0 3.0 3.5
PE Type (size) 5 #25 #40 #50 #70
#15
IMTPR
1 51 41 24 18 12
(Metal)
Hy-Pak TM
2 45 29 26 16
(Metal)
Super Intalox
R
3 60 30
Saddles
(Ceram)
Super Intalox
4 Saddles 40 28 18
(Ceram)
Pall Rings
5 95 55 40 26 17
(Plastic)
Pall Rings
6 81 56 40 27 18
(Metal)
Intalox
7 Saddles 725 1000 580 145 92 52 40 22
(Ceramic)
Raschig Rings
8 1600 1000 580 380 255 179 125 93 65 37
(Ceramic)
Raschig Rings
9 700 390 300 170 155 115
(1/32" Metal)
Raschig Rings
10 410 300 220 144 110 83 57 32
(1/16" Metal)

Table 4-34: Random Packing Types, Sizes, and Built-in Packing Factors
(ft2/ft3)
Berl Saddles
11 900 240 170 110 65 45
(Ceramic)
IMTP and Intalox are registered marks of Koch-Glitsch, LP. Hy-Pak is a trademark of Koch-
Glitsch, LP (formerly trademarked or registered by Norton Company).
Table 4-35: Koch-Glitch Random Packing Types
T Koch-Glitch Available sizes
Y Random Packing
P Type
E
12 Snowflake (Plastic) one size
Cascade Mini-Ring inches 1.0 1.5 2.0 2.5 3.0 4.0 5.0
13
(metal) mm 25.4 38.1 50.8 63.5 76.2 101.6 127
Cascade Mini-Ring inches 2.0
14
(plastic) mm 50.8
inches 0.625 1.0 1.5 2.0 3.5
15 FlexiRing (Metal)
mm 15.88 25.4 38.1 50.8 88.9
FlexiRing inches 0.625 1.0 1.5 2.0 3.5 40
16
(Plastic) mm 15.88 25.4 38.1 50.8 88.9 101.6
Super Intalox inches 1.0 2.0 3.0
17
Saddles(Plastic) mm 25.4 50.8 76.2
Flexi Saddles inches 1.0 1.5 2.0 3.0
18
(Ceramic) mm 25.4 38.1 50.8 76.2
IMTP (Metal) inches one size
19
#25 mm
20
#40 mm
21
#50 mm
22
#60 mm
23
#70 mm
Hy-Pak inches 1.0 1.5 2.0
24
(Metal) mm 25.4 38.1 50.8

inches 2.0
25 Beta Rings (Plastic)
mm 50.8
Flexi Saddles LPD inches 1.0 1.5 3.0
26
(ceramic) mm 25.4 38.1 76.2
INTALOX inches 2.0
27
ULTRA-A (Metal) mm 50.8
INTALOX inches 2.0
28
ULTRA-L (Metal) mm 50.8
INTALOX inches 2.0
29
ULTRA-T (Metal) mm 50.8
INTALOX inches 2.0
30
ULTRA-O (Metal) mm 50.8
Capacity
The capacity of a randomly packed column is determined by its
flood point. The flood point is defined as the point at which the
slope of the pressure drop curve goes to infinity, or the column effi-
ciency goes to zero. For random packing, the flood point as given
by the superficial vapor velocity at flood, vGf, is determined by
Eckart's correlation:
Equation (4-100):
vGf2 FP L0.2 G /  L g c  function  L' / G  G /  L  

0.5
 
where:
vGf = superficial vapor velocity at flood
Fp = packing factor
 = w/L
w = density of water
G = density of vapor
L = density of liquid
gc = gravitational constant
L = liquid viscosity
L’ = liquid mass flux

G’ = vapor mass flux
Alternately, the flood point may be supplied by the user.
Pressure Drop
The column pressure drop may be calculated by one of two meth-
ods. The Norton method uses a generalized pressure drop correla-
tion:
Equation (4-101):
  G  L  G  
0.5
P  function1  FP vL0.1vG2  ,   
   L  G  G   L  
where:
L = L/L = liquid kinematic viscosity
The Tsai method uses the following correlation for computing pres-
sure drop:
Equation (4-102):
 C 2 F v L   0.5 
P  function2  s P L ,  G  
 g c G  L  


where
Cs = operating capacity factor
0.5
  
Cs  vG  G 
 L  G 
However, there are no published packing factors for the Tsai

method. Therefore the Norton packing factors are utilized by PRO/
II when equation (10) is used.
Efficiency
The column efficiency may be measured by the Height Equivalent
to a Theoretical Plate (HETP). The HETPs for most chemical sys-
tems are generally close in value for a fixed packing size, regardless
of the application. By default, therefore, the HETP values are deter-
mined by a “Rules-of-thumb” method suggested by Frank. Only the

RATEFRAC® algorithm uses non-theoretical trays and reports
HETP. None of the other column algorithms compute the HETP or
use any user-supplied value for HETP.
If Norton (now Koch-Glitsch, LP) IMTP packing is used, an alter-
nate method may be used to compute the HETP values. In this
method, more rigorous calculations are made based on the size of
the packing and the total vapor and total liquid leaving a packed
stage. The height of a vapor phase transfer unit is given by:
Equation (4-103):
  D '  a  z p 1/3 
   /  737.34GL f  f  f 
0.5 b
H G    t
   ScG
0.3048   3.048 
  
where:
HG = height of vapor phase transfer unit, m
 = packing parameter
Dt’ = lesser of column diameter or 0.6096 m (2 ft)
zp = height of packed bed, m
ScG = gas phase Schmidt number =G /GDG
DG = gas phase diffusion coefficient, m2/s
GL = liquid mass velocity based on column cross section, kg/

m.s
f = (L/w)0.16
f = (L/w)-1.25
f = (L/w)-0.8
a = 1.24 for ring packing, 1.11 for saddle packing

b = 0.6 for ring packing, 0.5 for saddle packing
The height of a liquid phase transfer unit is given by:

Equation (4-104):
H L  C fl  z p / 3.048   ScL 
0.15 0.5
where:
 = packing parameter
Cfl = function of Fr
Fr = vG /vGf at constant L/V
vG = superficial vapor velocity, m/s
vGf = superficial vapor velocity at flood, m/s
ScL = liquid phase Schmidt number = L/LDL
DL = liquid diffusion coefficient, m2/s
The HETP is then computed from:

Equation (4-105):
HETP   H G   H L  ln  /    1 
where:
 = ratio of slope of equilibrium line to operating line = mV/L
Packing factors for the various random packing types are given in
Table 4-34.
Also See:
Column Hydraulics
Structured Packed Columns

Capacity
Pressure Drop
Efficiency
Columns containing various structured packing manufactured by
Sulzer Brothers of Switzerland can be simulated using PRO/II. Col-
umn pressure drop, capacity, and efficiency for the 12 different

types of Sulzer packing given in Table 4-36 are computed using
correlations supplied by Sulzer.
Table 4-36: Types of Suzer Packing Available in PRO/II

Type Description Applications
MELLAPAK 64X 64 m2/m3
MELLAPAK 64Y
125 m2/m3, sheet metal, very
high capacity. Suitable for
extremely high liquid loads Basic chemicals
where separation efficiency Ethylbenzene/
MELLAPAK 125X requirements are low.
MELLAPAK 125Y Configuration angle of X types
styrene
30 degree to vertical, Y types 45. Fatty acids, e.g., tall
Use X types for higher capacity, oil
Y types for higher separation
efficiency.
Cyclohexanone/ -ol,
MELLAPAK 170Y 170 m2/m3, sheet metal, high
Caprolactam
capacity, moderate separation
MELLAPAK 170X Vacuum columns in
efficiency.
refineries
MELLAPAK 2Y
2 m2/m3
MELLAPAK 2X
MELLAPAKPLUS 202Y 202 m2/m3
250 m2/m3, sheet metal,
MELLAPAK 250X
moderate capacity, high C3 splitter, C4 splitter
MELLAPAK 250Y
separation efficiency.
350 m2/m3, sheet metal,
MELLAPAK 350X Absorption/ desorption
moderate capacity, high
MELLAPAK 350Y columns
separation efficiency.
352 m2/m3, more efficient
MELLAPAKPLUS 352Y surface utilization with lower
pressure drop.
500 m2/m3, sheet metal, limited
capacity, very high separation
MELLAPAK 500X
efficiency. Suitable where
MELLAPAK 500Y
column weight is of overriding
importance.

602 m2/m3, more efficient
MELLAPAKPLUS 602Y surface utilization with lower
pressure drop.
MELLAPAK 750Y 750 m2/m3
N125Y (Plastic) 125 m2/m3
N250X (Plastic)
250 m2/m3
N250Y (Plastic)
N252y (Plastic) 252 m2/m3
MELLAGRID 64X 64 m2/m3
MELLAGRID 90X 90 m2/m3
MELLAGRID 64Y 64 m2/m3
MELLAGRID 40Y 40 m2/m3
Metal wire gauze, high capacity, Fine chemicals, Isomers,
BX high separation efficiency even at Perfumes, Flavors, Pilot
BXPlus small liquid loads. CY offers columns. Increased
CY maximum separation efficiency, performance of existing
lower capacity than BX. columns.
BXPFP
MELLACARBON 250Y 250 m2/m3
MELLACARBON 350Y 350 m2/m3
Sulzer structured packing available in PRO/II include 9 types of

corrugated sheet metal known as MELLAPAK, 2 types of metal
gauze known as BX and CY, and a ceramic KERAPAK packing.
Capacity
The capacity of a packed column is generally limited by the onset of
flooding, or maximum column vapor load. The flooding point,
however, is difficult to measure. For structured packing, the limit of
capacity is generally used to indicate the flood point. The limit of
capacity (100% capacity) is defined as the vapor load that corre-
sponds to a column pressure drop of 12 mbar/m.
Furthermore, the column capacity is expressed in terms of the
capacity factor. The capacity factor or load factor, cG, of the vapor
phase is defined as:
Equation (4-106):
cG  VG  G /   L  G  
1/2

where:
VG = superficial vapor velocity, m/s
G = vapor density, kg/m3
L = liquid density, kg/m3
Capacity correlations are obtained by plotting the experimental

capacity data on a so-called Souder diagram. On this diagram, the
capacity factor is plotted versus the flow parameter, , which is
defined as:
Equation (4-107):
  L / G  G /  L 
1/2
where:
L = liquid flow, kg/s
G = vapor flow, kg/s
The liquid phase capacity factor, cL, is defined by:
Equation (4-108):
cL  VL   L /   L  G  
1/2
where
VL = superficial liquid velocity, m/s
cL is related to the vapor capacity factor by:
Equation (4-109):
cG1/2  mcL1/2  n
where m and n are constants.

The straight line correlations given in (17) were obtained for two
separate hydraulic regimes:
Low liquid loads, (cL)1/2 < 0.07 (m/s)1/2
High liquid loads, (cL)1/2 > 0.07 (m/s)1/2
The capacity correlations have been shown to predict the column

capacity within an accuracy of 6%.
Pressure Drop
The pressure drop model used in PRO/II for structured packing is a
sum of three separate correlations as shown in Figure 4-1.
Figure 4-1: Pressure Drop Model

The F-factor in Figure 4-1 is defined as:
Equation (4-110):
F  factor  VG  G 
1/2
Region I is for columns operating below 50% capacity. In this

region the wetted wall column model is used to obtain a straight-
line relationship between the logarithm of the pressure drop and the
logarithm of the F-factor. At the end of region II (and the beginning
of region III), where the capacity limit is reached, the pressure drop
is obtained from the capacity correlation. Finally, the correlation in
region II is modeled by using a quadratic polynomial to join regions
I and III. At the juncture of regions I and II, the polynomial approx-
imation has the same slope as the wetted wall correlation in region
I. It should be noted that the pressure drop correlations for all Sulzer
packing types were developed without considering the liquid vis-
cosity.
Efficiency
The column efficiency or separation performance for Sulzer pack-
ing is measured by the number of theoretical stages per meter

(NTSM). The NTSM is therefore the inverse of the height equiva-
lent of a theoretical plate (HETP). The NTSM is defined as:
Equation (4-111):
NTSM  ShG DG aI / d hVG
where:
ShG = Sherwood number of the vapor phase = kG d h / DG
DG = diffusion coefficient of the vapor phase
aI = interfacial area per unit volume of packing, m2/m3
dh = hydraulic diameter of packing, m
kG = vapor phase mass transfer coefficient
The mass transfer in Sulzer packing has been modeled by neglect-

ing the liquid phase mass transfer coefficient, kL. This was done
because the value of the vapor phase mass transfer coefficient, kG,
is most often much less numerically than kL. Experimental data
were used to obtain the following relationship for the Sherwood
number:
Equation (4-112):
ShG  ReGm ScG1/3
The relationship for the interfacial area is given by:

Equation (4-113):
aI    LVL 
0.2
For metal packing types such as the MELLAPAK series, the factor
m in equation (20) usually has a value of 0.8. For gauze packing
such as BX or CY, the factor m has a value closer to 1, i.e., indepen-
dent of the liquid load. This is because gauze packing are more
completely wetted, regardless of the liquid load, while for metal
packing the wetted area increases with increasing liquid load. The
NTSM correlations are obtained by substituting equations (20) and
(21) into equation (19).

Reference:
1. Spiegel, L., and Meier, W., Correlations of Performance

Characteristics of the Various Mellapak Types (Capacity,
Pressure Drop and Efficiency), 1987, Paper presented at the
4th Int. Symp. on Distillation and Absorption, Brighton,
Eng. (Sulzer ChemTech Document No. 22.54.06.40).
2. Separation Columns for Distillation and Absorption, 1991,
Sulzer Chemtech Document No. 22.13.06.40.
3. Ballast Tray Design Manual, 1974, Glitsch Bulletin No.
4900-5th Ed.
4. Tsai, T. C., Packed Tower Program has Special Features,
1985, Oil & Gas J., 83(35), Sept., 77.
5. Perry, R. H., and Chilton, C. H., 1984, Chemical Engineer's
Handbook, 6th Ed., Chap. 18, McGraw-Hill, N.Y.
6. Vital, T. J., Grossell, S. S., and Olsen, P. I., Estimating Sep-
aration Efficiency, 1984, Hydrocarbon Processing, Dec.,
75-78.
7. Bolles, W. L., and Fair, J. R., Improved Mass-transfer
Model Enhances Packed-column Design, 1982, Chem.
Eng., July 12, 109-116.
8. Intalox High-performance Separation Systems, 1987, Nor-
ton Bulletin IHP-1. (Now part of Koch-Glitsch, LP)
9. Frank, O., 1977, Chem. Eng., 84(6), Mar. 14, 111-128.
Also See:
Column Hydraulics
General Information
Fenske Method
Underwood Method
Kirkbride Method
Gilliland Correlation

Distillation Models
Simple Columns
Complex Columns
Refinery Heavy Ends Columns
Troubleshooting
General Information
PRO/II contains shortcut distillation calculation methods for deter-
mining column conditions such as separations, minimum trays, and
minimum reflux ratios. The shortcut method assumes that an aver-
age relative volatility may be defined for the column. The Fenske
method is used to compute the separations and minimum number of
trays required. The minimum reflux ratio is determined by the
Underwood method. The Gilliland method is used to calculate the
number of theoretical trays required and the actual reflux rates and
condenser and reboiler duties for a given set of actual to minimum
reflux ratios. Finally, the Kirkbride method is used to determine the
optimum feed location.
The shortcut distillation model is a useful tool for preliminary
design when properly applied. Shortcut methods will not, however,
work for all systems. For highly non-ideal systems, shortcut meth-
ods may give very poor results, or no results at all. In particular, for
columns in which the relative volatilities vary greatly, shortcut
methods will give poor results since both the Fenske and Under-
wood methods assume that one average relative volatility may be
used for calculations for each component.
Fenske Method
The relative volatility between components i and j at each tray in
the column, is equal to the ratio of their K-values at that tray, i.e.:
Equation (4-114):
yiN / xiN K iN
 N
i, j  N N  N
yj / xj Kj
where:
y = mole fraction in the vapor phase
x = mole fraction in the liquid phase

subscripts i, j refer to components i and j respectively
superscript N refers to tray N
For small variations in volatility throughout the column, an average
volatility, may be defined. This is taken as the geometric average of
the values for the overhead and bottoms products:
 iave
, j   i , j i , j
1 N
The minimum number of theoretical stages is then given by:

Equation (4-116):
xi , D x j , B
log
x j , D xi , B
N min 
log  iave
,j
where:
subscripts B, D refer to the bottoms and distillate respective.
Also See:
Underwood Method
The values of the relative volatilities of the feed components deter-
mine which components are the light and heavy key components. It
is recommended that the most volatile component found in mean-
ingful concentrations in the bottom product is selected as the light
key component. Similary, the least volatile component found in
meaningful concentrations in the overhead product is selected as the
heavy key component.
The relative volatility of each component can therefore be
expressed in terms of the volatility of the heavy key, i.e.,
Kj
j 
K hk

where:
J refers to any component, and hk refers to the heavy key com-
ponent
For components lighter that the heavy key, J > 1, and for compo-
nents heavier than the heavy key, J < 1. for the heavy key compo-
nent itself, J = 1.
The Underwood method is used to determine the reflux ratio requir-
ing an infinite number of trays to separate the key components. For
a column with infinite trays, the distillate will exclude all compo-
nents heavier than the heavy key component. Similarly, the bottoms
product will exclude all components lighter than the light key.
Components whose volatilities lie between the heavy and light keys
will distribute between the distillate and bottoms products. An
equation developed by Shiras et al. can be used to determine if the
selected keys are correct. At minimum reflux ratio:
xJD, D  J  1 xhk , D  hk   J xhk , D

D D
 
xJF, F  hk  1 xhkF , F  hk  1 xhkF , F
If the value of the ratio given by equation (5) is less than -0.01 or
greater than 1.01 for any component J, then that component will
likely not distribute between both products. Therefore to test if the
correct key components are selected, equation (5) should be applied
to those components lighter than the light key, and heavier than the
heavy key. If they fail the test described above, then new key com-
ponents should be selected.
It should be noted that an exact value of Rmin is not needed. This
value is necessary only to provide an estimate of the product com-
position, and to determine if the specified reflux ratio is reasonable.
The Underwood equations assume a constant relative volatility, as
well as a constant liquid/vapor rate ratio throughout the column.
The first equation to be solved is:
Equation (4-119):
N  J xJ , F
1  q   
i 1  J  

Equation (4-120):
HG  H F
q
Hv
where:
q = thermal condition of feed
= heat to convert to saturated vapor/heat of vaporization
HG = molar enthalpy of feed as a saturated vapor
HF = molar enthalpy of feed
Hv = molar latent heat of vaporization
xJ,F = mole fraction of component J in feed
 = a value between the relative volatilities of the light and

heavy 
keys, i.e., hk (=1) < < lk
The second equation to be solved is:

Equation (4-121):
N  J xJ , D
 Rmin ,1  
j 1  J  
where:
Rmin = minimum reflux ratio = (L/D)min
xJ,D = mole fraction of component J in distillate
The algorithm used to solve for Rmin is given in Figure 4-1.

Also See:

Figure 4-1: Algorithm to Determine Rmin

Kirkbride Method
The optimum feed tray location is obtained from the Kirkbride
equation:
Equation (4-122):
m B x  xlk , B 
2

log    0.206 log  hk , F
  
 p  D xlk , F  xhk , D  
 
where:
m = number of theoretical stages above the feed tray
p = number of theoretical stages below the feed tray
Also See:
Gilliland Correlation
The Gilliland correlation is used by PRO/II to predict the relation-
ship of minimum trays and minimum reflux to actual reflux and
corresponding theoretical trays.
The operating point selected by the user (expressed as either frac-
tion of minimum reflux or fraction of minimum trays) is selected as
the mid-point for a table of trays and reflux. Based on the corre-
sponding reflux ratio, the column top conditions are calculated and
the associated condenser duty determined.
The reboiler load is computed from a heat balance. Note that the
selection of the proper condenser type is vital to accurate calcula-
tion of heat duties. Also, the condenser type selected will have no
effect whatsoever on the separations predicted. Figure 4-1 shows

the condenser types available in PRO/II for the shortcut distillation
model. Water may be decanted at the condenser.
Figure 4-1: Shortcut Distillation Column Condenser Types

Also See:
Distillation Models
There are two shortcut distillation models available in PRO/II, as
shown in Figure 4-1. In the first method (CONVENTIONAL),
which is the default, total reflux conditions exists in the column. In
the second method (REFINE), the shortcut column consists of a

series of one feed, two product columns, starting with the bottom
section. In this model, there is no reflux between the sections.
Figure 4-2: Shortcut Distillation Column Models

Simple Columns
Simple columns are defined as columns in which a single feed loca-
tion may be defined, located somewhere between the reboiler and
condenser. Obviously, absorbers and strippers do not meet these cri-
teria and it is recommended that only the rigorous distillation
method (see Section-Rigorous Distillation Algorithms) be used for
these types of columns.
Moreover, it is not possible to predict extractive distillation or any
separation in which K-values vary widely with composition, since
such columns violate the Fenske and Underwood assumptions. For
example, calculation of the stages and reflux for a propylene-pro-
pane splitter by shortcut methods will give very poor results since
for this type of column the relative volatility varies from 1.25 in the
reboiler to 1.07 in the condenser. Thus, the Fenske method will
greatly under-predict the minimum trays required and the Under-
wood method will under-predict the minimum reflux required for
the separation.
For simple columns, in which the relative volatilities do not vary
greatly and in which equal molal overflow is approached, the short-
cut calculations allow bracketing a reasonable design base.
An operating point expressed as either fraction of minimum reflux
or trays may be selected by the user. This is a design parameter and
usually a matter of personal preference or company standards.
However, a value of 1.5 times minimum reflux or two times mini-
mum trays will usually give a reasonable basis for a simple column.
Selection of the separation key components is a primary importance
for the Underwood method. It is extremely important that the light
and heavy keys be distributed in both products, with their distribu-
tion defining a sharp separation. This may mean that the keys must
be “split”, with middle component(s) which distribute loosely in
both products allowed to float as required to meet the sharp separa-
tion of the keys. Incorrect selection of keys can give poor and
meaningless results, moreover, this can result in failure of the
Underwood calculations. As a general rule of thumb, the more non-
ideal a column, the more the Underwood method will under-predict
the reflux requirements.
The column heat requirements will be predicted based on the con-
denser type selected. For sub-cooled condensers, it is necessary to
define the temperature to insure that the sub cooling effect is con-
sidered.

For type 2 condensers (mixed-phase) the separation into vapor and
liquid products should not be attempted in the shortcut model, since
this would require two specifications (for a flash drum). Separation
into liquid and vapor products is accomplished by sending the
shortcut overhead product (mixed-phased) to an equilibrium flash
drum calculation. When the column overhead is known to contain
water, it is important that the estimated overhead product rate
include both water and hydrocarbon product.
While any type of product specification may be used to define the
split, the Underwood calculations will only be useful when the
specifications describe a sharp split between a light and heavy key.
If the number of Fenske trays (fractionation index) is given in lieu
of a specification, this may also invalidate the Underwood calcula-
tions.
If desired, the user may supply estimates of the Fenske trays
required for the separation. For columns in which there are a large
number of trays, this will speed convergence.
Complex Columns
For complex columns (in which there are more than two products) it
becomes impossible to select key components to define the frac-
tionation within the various sections. For such columns, the separa-
tion is defined indirectly in terms of stream properties. The PRO/II
program allows a wide variety of such properties.
As mentioned above, two models are available for complex col-
umns. For the CONVENTIONAL model, Fenske relationships
defining the column sections (each section having two products) are
solved simultaneously, thus the interaction of reflux between the
sections is considered. For the REFINE model, each section is
solved independently, starting from the bottom. This model closely
approximates typical oil refinery columns in which total liquid
draws are sent to side strippers and little (if any) liquid is returned to
the next lower tray.
As the number of products increases, the difficulty in definition of
nonconflicting specifications also increases. There are often upper
and lower limits for each specification. For example, the total prod-
uct rate cannot exceed the feed rate. Furthermore, for specifications
such as ASTM/TBP temperatures, the selection of the components
to represent the feed streams can be very important. For example, it
would not be reasonable to attempt to separate ten components into
six products, etc. Care should be exercised that the specifications

define rates for all products (either directly or indirectly). For illus-
tration, consider the following example shown in Figure 4-3:
Figure 4-3: Shortcut Column Specification

For this column, four specifications are required. Selection of two
specifications each for products A and C would satisfy this require-
ment, however, it might not be sufficient to define stream B. There-
fore, a better set of specifications would include values for all the
products, A, B and C. As a general rule, it is best that specifications
omissions be limited to the top stream.
Specifications may be grouped into two general categories:
 Bulk properties: Gravities, Rates (mole, volume, weight)
 Intensive properties: ASTM/TMP Distillations, Component
rates/ purities, Special properties
As a general rule, fractionation indices may be defined in conjunc-
tion with bulk properties, but will not work well when used with
intensive properties. For intensive properties, the additional flexi-
bility of allowing PRO/II to calculate the Fenske trays is highly
desirable.
The nature of the Fenske calculations necessitates judgment when
using specifications such as ASTM/TBP distillation points. End
points and initial points may be distorted by the Fenske model

because of the infinite reflux assumption, resulting in “trimming” of
the stream tails (initial points too high, end points too low). More-
over, the component selection may also greatly affect the initial and
end points. For these reasons, it is recommended the 5% and 95%
points be chosen in lieu of initial and end points.
Refinery Heavy Ends Columns

The second model is extremely useful for prediction of yields and
analyzing data for crude units, vacuum units, cat fractionators, bub-
ble towers, etc. There are generally two possible situations when
dealing with such columns:
1. Yields are to be predicted, based on a given feed composi-
tion.
2. Operating data are to be checked by comparison of the pre-
dicted product properties with the actual product properties.
The operating product rates are used for this case.
The selection of components cannot be over-emphasized for such
studies. While minimization of component numbers is desirable for
simulation cost reduction, sufficient components must be included
to enable accurate simulation. In particular, for case a), the yields
predicted can be greatly influenced by the components chosen. For
case b), it is a relatively simple matter to adjust the components
used as required to more accurately predict product properties. For
case a), this a more complex task with judgment necessarily applied
in light of the simulation requirements. The standard cuts used by
PRO/II have been developed for crude unit simulation and will give
good results. It is generally recommended that compromises to the
standard cuts be made in the heavier components (above 800 F)
where possible.
For series of columns, the shortcut model itself can be important.
For the crude-vacuum unit combination shown in Figure 4-4, the
system may be simulated as one column or two. It is usually better
to use two shortcuts, since the crude unit products will be well
defined while the vacuum products may be somewhat nebulous. In
this way, the crude unit yields will not be affected by errors in defi-
nition of the vacuum unit yields and bulk properties may then be
described for the vacuum unit to aid solution. On the other hand, if
definitive vacuum product specifications are available, the single
unit model can insure more accurate vacuum unit yields.

Figure 4-4: Heavy Ends Column

The crude-pre-flash system shown in Figure 4-5 presents a different
case.
Figure 4-5: Crude-Pre-Flash System

For this case, common products will be produced on both units and
a single column model attempting to represent all the products is

difficult (if not impossible). For systems such as this it is much bet-
ter to always use a two column model.
The sections in actual distillation columns are interlinked through
both feeds and liquid refluxes. Refluxes at each section are gov-
erned by heat balances around that section and the entire system.
Although some adjustment in reflux is possible, there is an upper
limit to the number of trays which can be present in any section. For
a crude column, this is usually around 6 to 8 theoretical trays. This
is because the heavy-end mixtures have wide boiling ranges. Once
the product rates are fixed, each mixture can only have limited bub-
ble point ranges. In other words, the fractionation within each sec-
tion is restricted and depends to a large extent on the overall heat
balance.
The Fenske model is useful in defining the fractionation require-
ments within each section. While the fractionation index (Fenske
trays) is only qualitatively definitive, it is useful in evaluating the
feasibility of desired separation.
The fractionation index is approximately equivalent to the number
of theoretical trays times the reflux ratio; thus, the theoretical stages
required for a given separation may be estimated. (These trays must
then be adjusted accordingly to correspond to actual trays).
Experience has shown that the fractionation indices fall into certain
ranges for refinery columns. Table 4-37 below illustrates typical
values:
Table 4-37: Typical Values of FINDEX

Crude Typical FINDEX
LSR - Naphtha 5-7
Naphtha - Kero 4-5
Kero - Diesel 2.5 - 3.5
Diesel - Gas Oil 2 - 2.5
Gas Oil - Topped Crude 1.25 - 1.75
Cat Fractionators
Gasoline - Light Cycle 5-7
Light Cycle - Heavy Cycle 1.5 - 2.5
Heavy Cycle - Clarified Oil 1.1 - 1.5
Vacuum Units
Overhead - Light Gas Oil 2 - 2.5

Table 4-37: Typical Values of FINDEX
Light Gas Oil - Heavy Gas Oil 1.25 - 1.75
Heavy Gas Oil - Resid 1 - 1.5
Values of fractionation indices differing greatly from the above val-

ues suggest impossibilities or conflicts in the product specifications
used for the model.
When it is desired to use the shortcut model to verify yields and
properties, it is suggested that the product yields and/or gravities be
used in conjunction with the typical fractionation induces shown
above. It is interesting to note that values selected anywhere within
the ranges given will produce nearly identical products. This also
illustrates rather graphically the controlling effect of product draw
rate versus trays for such columns.
When using the shortcut model for rate prediction it is recom-
mended that fractionation indices not be used in conjunction with
intensive properties. Definition of the fractionation with FINDEX
may very well result in a case that is impossible to converge.
For yield prediction, a combination of product ASTM 95% temper-
atures and gaps works very well for crude units. For the topped
crude, a gap of 100 to - 150 F with the gas oil usually gives a rea-
sonable operation, or the gravity of the topped crude may also be
used for a specification.
Also See:
Troubleshooting
Simple Columns
Simple columns are defined as consisting of one feed and two prod-
ucts, with reboilers and condensers. Systems with two overhead
products (partial condensers) are simulated with one combined
overhead product, with the separation to vapor and liquid products
being accomplished in an ensuing flash drum.
Troubleshooting is usually simple for such columns. Fenske calcu-
lation failures are usually caused by:
 Impossible or conflicting specifications which result in impos-
sible material balances. (In particular, look for this situation
when component mole fractions are specified).

 User specified fractionation index (minimum Fenske trays) for
which it is impossible to meet other specifications.
 Poor product rate estimates – in particular, caused by not
accounting for water in the top product.
Underwood calculation failures are caused by incorrect separation
key selection. Possible causes are:
Heavy and light key components which both distribute to the same
product.
Heavy and light key components which do not define a sharp sepa-
ration. (For this case “split” keys must be defined.)
Note: The trial calculations for the shortcut fractionator will be

printed when a PRINT statement with the keyword TRIAL is
included in the SHORTCUT unit operation. This may be used to
help diagnose Fenske failures.
Complex Columns
For complex columns (more than two products), a series of two
product columns are used to represent the separations with the feed
introduced into the bottom section. The default model type one con-
siders the effect of reflux between the sections; model two assumes
to reflux between the sections. The second model type is very use-
ful for simulation of petroleum refinery “heavy ends” columns.
For these columns, it is impossible to select key components to
define the fractionation within the various sections. Therefore, the
separations must be indirectly defined using product stream proper-
ties. As the number of products increase, it becomes increasingly
difficult to define non-conflicting product specifications. There are
also usually upper and lower limits for each specification based on
material balance considerations and feed representation. Care must
be exercised to define specifications which result in unique rates for
all products (either directly or indirectly).
Calculation failures are always related to specifications. Some pos-
sible problems include:
 Conflict of fractionation indices with intensive stream property
specifications. In general, this combination of specifications
should be avoided and fractionation index used only in con-
junction with stream bulk properties such as rates and gravities.

 Specifications which do not result in a unique rate for each
product stream.
 Component definition which does not allow the desired separa-
tions to be accomplished (either too few components or incor-
rect component boiling point ranges).
 Distortion of ASTM/TBP initial and endpoints by the Fenske
model because of the infinite reflux assumption. (5% and 95%
specifications are much better than initial and endpoint specifi-
cations.)
Since the solution of the entire system of two product sections is
iterative and simultaneous, it is possible that a poor specification in
one section may result in a seeming problem for another section.
Usually there is a single specification which “binds” the system and
prevents solution.
Inspection of the trial calculated results will often reveal the interac-
tions of the specifications, and hence, the incompatibility. For
petroleum refinery “heavy ends” calculations, the predicted frac-
tionation indices may be evaluated in the light of typical values for
such columns. (See Table 4-38.)
Examination of the component distribution to the various product
streams in the stream printout is useful for checking the component
definition for “reasonableness”. For the most accurate simulation of
crude units, the standard cut ranges should be used. Cut ranges may
be broadened to reduce the simulation cost, however, Table 4-38
illustrates the effect of changing the cut ranges on the product yields
for a typical crude unit.
Table 4-38: Effect of Cut Ranges on Crude Unit Yields

Incremental Yields from Base
 Base Case 1 Case 2 Case 3 Case 4 Case 5
Product Case* % % % % %
Bbls/ Increa Increa Increa Increa Increa
Day se se se se se
Overhead 23159 -2.4 -0.3 - - -
Naphtha 23285 +6.2 +0.4 -0.3 - -
Kerosene 16232 -8.2 +0.3 +1.7 - +0.7
Diesel 19149 -0.2 -0.6 -0.2 +0.9 -2.1
Gas Oil 11002 +11.2 -15.4 -16.5 -16.9 -6.4

Table 4-38: Effect of Cut Ranges on Crude Unit Yields
Incremental Yields from Base
Topped
42173 1.8 +3.6 +3.8 +4.0 +2.3
Crude
Total 135000
No. Comps 46 36 49 45 39 37
No. of Cuts
100-600 - - - - - 20
600-800 - - - - - 5
100-800 28 15 38 34 28 -
800-1200 8 - 4 4 4 5
800-1500 - 15 - - - -
1000-1500 - - 1 1 1 -
1200-1500 4 - - - - 1
Note: For all cases, yields were predicted, based on product 95% points and 
5-95 gaps.

* Standard cuts
It is recommended that a systematic approach be taken when debug-

ging shortcut columns. Trial printouts will often reveal clues to the
limiting specification. Increasing the number of calculation trials is
never a good strategy, since solution will normally be reached well
within the default number of trials (20).
Reference
1. Treybal, R. E., Mass Transfer Operations, 3rd Ed., Chap. 9,

McGraw-Hill, N.Y.
2. Fenske, M.R., 1932, Ind. Eng. Chem., 24, 482.
3. Underwood, A.J.V., 1948, Chem. Eng. Prog, 44, 603.
4. Gilliland, E.R., 1940, Ind. Eng. Chem., 32, 1220.
5. Ludwig, E.E., 1964, Process Design for Chemical and Pet-
rochemical Plants, Vol. 2, pp. 26, 27, Gulf Publishing.
6. Kirkbride, C.G., 1944, Petrol. Refiner, 23, p. 32.
Also See: Shortcut Distillation

General Information
Basic Algorithm
General Information
Liquid-liquid extractions are modeled in PRO/II using the general
trayed column model in conjunction with the LLEX algorithm. The
LLEX algorithm in PRO/II is a Newton based method which is
suited to solving non-ideal distillation problems involving a smaller
number (10 vs. 100) of chemical species. LLEX is designed to solve
liquid-liquid equilibrium problems with more than one equilibrium
stage.
Basic Algorithm
Figure 4-6 shows a schematic of an equilibrium stage with a lighter
liquid (denoted as liquid-1) and a heavier liquid (liquid-2) in equi-
librium.
Figure 4-6: Schematic of a Simple Stage for LLEX

The equations which describe the interior trays of the column are as
follows (with all rates, compositions, and enthalpies expressed on a
molar basis):

Component Mass Balance Equations:
Equation (4-123):
M i , j  exp  X iI, j  LIi  exp  X iII, j  LIIi  exp  X iII1, j  LIIi 1  LDII
i 1 
 exp  X i 1, j  LIi 1, j  Fi , j i  1, NT
Energy Balance Equation:

Equation (4-124):
Ei  LIi HiI  LIIi HiII   LIIi 1  LDII

i 1  Hi 1   Li 1  Li 1  Hi 1  Qi  Fi Hi
II I DI I
i  1, NT
Liquid-Liquid Equilibrium Equations:

Equation (4-125):
LLEi , j  X iI, j  X iII, j  ln  K i , j  i  1, NT and j  1, NC
Summation of Mole Fractions:

Equation (4-126):
Si  1   exp  X iI, j  i  1, NT
Equation (4-127):
Si'  1   exp  X iII, j  i  1, NT
where:
Fi = total feed flow to tray i
LiI = total liquid-1 flow from tray i
LiII= total liquid-2 flow from tray i
Qi = heat added to tray i
Ti = temperatures of tray i
XIi,j = ln(xIi,j) = natural log of the liquid-1 mole fractions
XIIi,j = ln(xIIi,j) = natural log of the liquid-2 mole fractions

Ki,j = liquid-liquid equilibrium constant for component j, on
tray i
NC = number of components
NT = number of trays
subscripts:
i refers to the tray index
j refers to the component index
superscripts:
D = refers to a draw
L = refers to a liquid-1 property
L = refers to a liquid-2 property
I = refers to a liquid-1 phase
II = refers to a liquid-2 phase
The unknowns, alternatively referred to as iteration or primitive
variables:
(XI, XII, LI, LII, T)i where i = 1, NT
are solved for directly using an augmented Newton-Raphson
method. Specification equations involving the iteration variables
are added directly to the above equations and solved simultane-
ously.
The modifications of the Newton-Raphson method are twofold. The
first is a line search procedure that will, when possible, decrease the
sum of the errors along the Newton correction. If this is not possi-
ble, the size of the increase will be limited to a prescribed amount.
The second modification limits the changes in the individual itera-
tion variables. Both of these modifications can result in a fractional
step in the Newton direction. The fractional step size, , is reported
in the iteration summary of the LLEX output.
Note: An  of 1 indicates that the solution procedure is progress-

ing well and that, as the solution is approached, should become
one.

For highly non-linear systems which may oscillate, the user can
restrict the step size by specifying a damping factor which reduces
the changes in the composition variables. A cutoff value is used by
the algorithm so that when the value of the sum of the errors drops
below the given level, the full Newton correction is used. This
serves to speed the final convergence.
The iteration history also reports the largest errors in the mass bal-
ance, the energy balance, and the liquid-liquid equilibrium equa-
tions. Given a good initial estimate, these should decrease from
iteration to iteration. However, for some systems, the errors will
temporarily increase before decreasing on the way to finding a solu-
tion. The keyword ERRINC limits the size of the increase in the
sum of the errors.
All derivatives for the Jacobian matrix are calculated analytically.
User-added thermodynamic options that are used by LLEX must
provide partial derivatives with respect to component mole frac-
tions and temperature. LLEX uses the chain rule to convert these to
the needed form.
Reference
1. Bondy, R.W., A New Distillation Algorithm for Non-Ideal

System, paper presented at AIChE 1990 Annual Meeting.
2. Shah, V.B., and Kovach, J.W. III, Bluck, D., A Structural
Approach to Solving Multistage Separations, paper pre-
sented at 1994 AIChE Spring meeting.
Column Tray Efficiency Calculations

The purpose of tray efficiency calculations is to reduce the fraction-
ation effectiveness of individual trays. These tray efficiencies are
not the same as overall efficiencies. PRO/II column models support
three formulations for efficiency: Murphree, Vaporization, and
equilibrium efficiencies.
Condenser and reboiler trays automatically have efficiencies of
unity, regardless of the efficiency specified by the user. When the
efficiency is not equal to 1.0, by definition the affected phases are
not in phase equilibrium. This includes the vapor phase (Muphree
efficiency) or the vapor and liquid phases (equilibrium and vapor-
ization efficiencies). This often causes inconsistencies in the
reported results. Users should note and account for the following
possible situations.

• For columns without condensers, the overhead vapor is
not at the dew point. Depending upon the specified effi-
ciencies, the overhead fluid may be either superheated or
in the two-phase region.
• Columns with condensers may exhibit condensing curves
that cannot be matched by an HCURVE unit. This occurs
when the tray two vapor is not in equilibrium, because the
HCURVE uses a series of equilibrium flashes to generate
its condensing curve.
• Product draws from trays having equilibrium or vaporiza-
tion efficiencies not equal to 1.0 will not be at a dew or
bubble point.
Murphree Efficiency
Vaporization Efficiency
Equilibrium Efficiency
Equilibrium and Vaporization Efficiencies Together
Murphree Efficiency
This is the most common form of tray efficiency, and is supported
by the IO and enhanced IO algorithms. The RATEFRAC® algo-
rithm supports Murphree tray efficiencies only on equilibrium
stages; not on non-equilibrium rate-based segments. Murphree effi-
ciencies may be greater than 1.0 for a given component or group of
components. The equation for Murphree efficiency has the form:
Equation (4-128):
 i ,n   i ,n 1
EiM, n 
 i*,n   i ,n 1
where:
EMi,n is the Murphree tray efficiency for component i on tray n
i,n = Vapor phase mole fraction of component i on tray n
*i,n = Equilibrium mole fraction of component i on tray n over

the actual liquid composition.

Vaporization Efficiency
The IO, Enhanced IO, LLEX, and CHEMDIST algorithms support
vaporization efficiency. IN the LLEX model, the vaporization effi-
ciencies change the distribution between the liquid phases. The
RATEFRAC® algorithm also supports Vaporization tray efficien-
cies, but only on equilibrium stages; not on non-equilibrium rate-
based segments. The equation for vaporization efficiency is:
Equation (4-129):
K ieff,n
,n 
Eivap
K ieq,n
where:
Evapi,n = Vaporization efficiency for component i on tray n
Keffi,n = The effective K-value for component i on tray n
Keqi,n = The equilibrium K value, based upon the liquid com-

position for component i on tray n.
Equilibrium Efficiency
Only the IO and Enhanced IO algorithms support equilibrium effi-
ciency. The equation form is:
Equation (4-130):
K ieff,n  1
Eieq, n 
,n  1
K ivap
Equilibrium and Vaporization Efficiencies Together

The IO and Enhanced IO algorithms support using both equilibrium
and vaporization efficiencies at the same time on the same trays for
the same components. The equation used for this option is:
Equation (4-131):
K ieff, n   K ieq, n  1.0  Eieq, n  1.0  Eivap

,n

Also See:


Chapter 5: Heat Exchangers
Process heat transfer equipment may be simulated in PRO/II using

one of three heat exchanger models
Simple Heat Exchangers
Zones Analysis
Rigorous Heat Exchanger
LNG Heat Exchanger
Air Cooled Heat Exchanger
Furnace Model

General Information
Calculation Methods
General Information
Heat exchangers are used to transfer heat between two process
streams, or between a process stream and a utility stream such as air
or steam. For all three heat exchanger models, the following basic
design equation holds:
Equation (5-1):
 U  U o T  A
where:
q = heat transferred in elemental length of exchanger dz
Uo = overall heat transfer coefficient
T = overall bulk temperature difference between the two
streams
A = element of surface area in exchanger length dz

Once an appropriate mean heat-transfer coefficient, and tempera-
ture difference is defined, equation (5-1) may be re-written for the
entire exchanger as follows:
Equation (5-2):
Q  U om Ao Tm  H out  H in
where:
Q = total exchanger heat duty
Uom = overall mean heat-transfer coefficient
Ao = total exchanger area
Tm = mean temperature difference

Also See: Simple Heat Exchangers
Calculation Methods
The simple heat exchanger model in PRO/II may be used to simu-
late heat exchange between two process streams, heat exchange
between a process stream and a utility stream, or to heat or cool a
single process stream. The simple model does not rigorously rate
the exchanger, i.e., pressure drops, shell and tube side heat transfer
coefficients, fouling factors are not calculated.
Heat Exchangers 5-390

Figure 5-1: Heat Exchanger Temperature Profiles
For counter current or co-current flows as shown in Figure 5-1, the

appropriate expression for the mean temperature difference is the
logarithmic mean, i.e.: For counter-current flows,
Equation (5-3):
Tlm  LMTD 
T 1
in  Tout
2
  Tout1  Tin2 
 T1 T 2 
ln  in1 out2 
 Tout  Tin 
For co-current flows,
Equation (5-4):
Tlm  LMTD 
T 1
in  Tin2   Tout
1
 Tout
2

 T1 T 2 
ln  1in in2 
 Tout  Tout 
where:
Tlm = LMTD = logarithmic mean temperature difference
superscript 1 denotes one side of the heat exchanger

superscript 2 denotes the other side of the heat exchanger
In actual fact, the flows are not generally ideally counter-current or
cocurrent. The flow patterns are usually mixed as a result of flow
reversals (e.g., in exchangers with more than one tube or shell pass),
bypassed streams, or streams which are not well mixed. F-factors
have been derived by Bowman et. al. to account for these non-ideal
flow patterns and are used in PRO/II to correct equations (5-3) and
(5-4). For multipass heat exchangers, where the ratio of shell passes
to tube passes given is not 1:2 (e.g., for a 2 shell- and 6 tube-pass
exchanger), the F-factors actually used are those computed for
exchangers with the ratio of one shell to two tube passes (i.e., for 2
shell- and 4 tube passes).
The method used by PRO/II to determine the heat transferred when
using utility streams is given by:
 For water and air cooling utility streams, the only heat transfer
considered is sensible heat, i.e.,
Equation (5-5):
Q   H out  H out  w, a  hA Tout  Tin 
where:
h = sensible heat transfer coefficient
H = enthalpy of utility stream
 For steam or refrigerant utilities, only latent heat is considered
in the heat transfer. Either the saturation temperature (Tsat) or
saturation pressure (Psat) must be supplied.
Equation (5-6):
Q  m
where:
m = mass flowrate of utility stream
 = latent heat at Tsat
 Product stream liquid fraction (hot or cold side)

 Product stream temperature approach to the bubble or dew
point (hot and cold side)

Any one of the following specifications may be made in PRO/II:
 Overall exchanger heat duty
 Product stream temperature (hot or cold side)
 Hot side outlet to cold side inlet temperature approach
 Hot side inlet to cold side outlet temperature approach
 Hot side outlet to cold side outlet temperature approach
 Minimum internal temperature approach
 Overall heat transfer coefficient (U) and area (A) given
Also See:
Zones Analysis
General Information
Calculation Methods
General Information
Conventionally for a simple heat exchanger, the logarithmic mean
temperature difference is calculated using the stream temperatures
at the inlet and outlet of the unit (equations (5-3) and (5-4) in the
previous section - Simple Heat Exchangers). Optionally, PRO/II
can compute a duty-averaged LMTD. This option becomes increas-
ingly useful when phase changes occur along the length of the
exchanger. Under these conditions, the LMTD calculated as
described for the simple heat exchanger may often be inadequate
because of the non-linearity of the enthalpy-temperature character-
istics of the stream changing phase. Zone analysis may therefore be
extremely useful for locating internal temperature pinches.
Also See:
Zones Analysis
Calculation Methods
In this method, the heat exchanger is divided into a number of
zones, and the heat exchanger design equation is then applied to
each zone separately. The number of zones may be specified by the
user, or be automatically selected by PRO/II. Automatic selection

by PRO/II ensures that all the phase changes are located on the zone
boundaries. No zone should account for more than 20% of the total
heat exchanger duty; therefore, a minimum of 5 zones is required.
PRO/II may use up to a maximum of 25 zones.The design equation
for the heat exchanger is given by:
Equation (5-7):
Q  U om Ao LMTDzones  H out  H in
For a total of n zones, LMTD zones is calculated from the individ-

ual zones values as a weighted LMTD:
Equation (5-8):
Q
LMTDzones  n
Qi

i 1 LMTDi
where:
Q = total exchanger duty
Qi = heat duty in zone i
LMTDi = logarithmic mean temperature difference for zone i
The LMTD values for the individual zones are computed using the
temperatures of the streams entering and leaving each zone.
For counter-current flows in zone i,
Equation (5-9):
LMTD 
T 1
in ,i  Tout
2
,i    Tout ,i  Tin ,i 
1 2
i
 T1 T 2 
ln  in1,i out2,i 
 Tout ,i  Tin ,i 
For co-current flows in zone i,
Equation (5-10):
LMTD 
T 1
in ,i  Tin2,i   Tout
1
,i  Tout ,i 
2
i
 T1 T 2 
ln  1in ,i in2,i 
 Tout ,i  Tout ,i 

For all the heat exchanger specifications described above, except
for the minimum internal temperature approach, the zones analysis
is independent of the calculation of the overall heat duty. In these
cases, by default, the LTMD zones value is calculated and reported
after the equations for the exchanger have been solved, but is not
used in heat transfer calculations. The user may, however, specify
that the zones analysis be done at calculation time, i.e., while PRO/
II is solving the design equations. This option is, however, neither
necessary nor recommended in these cases.
For minimum internal temperature approach specifications, how-
ever, zones analysis is required at calculation time in order to accu-
rately identify pinch points. Under these conditions, the weighted
LMTD is used in equation (5-7).
Also See:
Zones Analysis
Example
An example of a zones analysis of a counter-current heat exchanger
is given next, and shown in Figure 5-1.
Figure 5-1: Zones Analysis for Heat Exchangers

Consider a counter-current heat exchanger with a hot side contain-
ing a superheated hydrocarbon-water vapor mixture which enters at
temperature Th(in) (point 1). The hot fluid changes phase when it
cools down to Th(dew hc), the dew point of the hydrocarbon. A
zone boundary is created at this phase change. As the stream contin-

ues to cool, it changes phase yet again when it reaches the aqueous
dew point Th(dew aq). Again, a zone boundary is created here.
After further cooling, another phase change occurs at Th(bub), the
bubble point of the stream, and continues to cool until it reaches
Th(out) (point 2).
The cold side containing a sub-cooled liquid enters at temperature
Tc(in) (point 3), and is heated to the bubble point, Tc(bub). A zone
boundary is created at this point. The cool stream is further heated
until it reaches the aqueous dew point, Tc(dew aq). It is heated even
further until it reaches the hydrocarbon dew point, Tc(dew hc).
Finally, it is heated until the final temperature of Tc(out) (point 4) is
reached. Based on phase change points alone, the maximum num-
ber of zones which may be created is seven as shown in Figure 5-1.
Additionally, PRO/II will further subdivide these zones into smaller
zones of equal DT. The calculation procedure is then as follows:
 The ends of the exchanger constitute the overall zone boundar-
ies, and the total exchanger heat duty is calculated. If the over-
all U and A values are specified, the overall duty is estimated.
 The duty for each zone is calculated, and then the corrected
LMTD values for each zone are obtained. Equation (5-8) is
then used to determined the weighted average LMTD value for
the exchanger.
 The heat transfer coefficients are calculated for each zone.
 The areas for each zone are determined using the zone values
for U, Q, LTMD, and equation (5-9) or (5-10), and then are
summed to give the heat transfer area for the entire exchanger.
Reference
Bowman, R. A., Mueller, and Nagle, 1940, Trans. ASME, 62, 283.
Also See:
Zones Analysis
Heat Exchangers

General Information
Heat Transfer Correlations
Calculation of Bundle weight, Shell weight (dry) and Shell weight
(with water)
Fouling Factors
General Information
PRO/II contains a shell-and-tube heat exchanger module which will
rigorously rate most standard heat exchangers defined by the Tubu-
lar Exchanger Manufacturers Association (TEMA). Shell and tube-
side heat transfer coefficients, pressure drops, and fouling factors

are calculated. The TEMA types available in PRO/II are given in
Figure 5-2.
Figure 5-2: TEMA Heat Exchanger Types

Heat Transfer Correlations
The two phase heat transfer coefficient may be determined by one
of two methods; Modified Chen Vaporization method (newly
added), or HEX5 method (existing method). These two methods
differ in the calculation of boiling and condensing film coefficients.
The Modified Chen Vaporization method is the default method used
by PRO/II and it includes predictions for sub-cooled and film boil-
ing. Condensation methods account for flow regimes and gravity
versus shear effects.
HEX5 method is supported for the backward compatibility.
The two phase heat transfer coefficient method is effective only
when change occurs on either shell side or tube side or both sides.
For the phase change case, the Modified Chen Vaporization and
HEX5 methods will result in different heat transfer coefficients. For
the no phase change case, both Modified Chen Vaporization and
HEX5 methods will give the same heat transfer coefficients.
Shell Side
The basic correlations used for phase change (i.e Modified Chen
Vaporization method, or HEX5 method) or no phase change cases
are as follows:
The heat transfer coefficient for an ideal tube bank, Hideal, is
obtained from the following relationships:
Equation (5-11):
0.8
0.037 N Re G N Pr
N Nu (tur ) 
1  2.443N Re G  N Pr2/3  1
0.1
Equation (5-12):
N Nu (lam )  0.664 N Re
0.5 1/3
G N Pr
Equation (5-13):
N Nu (bund )  0.3   N Nu ( lam )  N Nu ( tur ) 

2 2 0.5
Equation (5-14):
kN Nu ( bund )
hideal 
L

where:
NReG = Reynolds number, as defined by Gnielinski
NReG = WL
 F DS lb b
c
b
NPr = Prandlt number = --------
k
W = total mass flow rate in shell side
c = specific heat of fluid
F = shell void fraction

Ds = shell inside diameter
lb = baffle spacing
b = fluid viscosity at bulk temperature

NNu = Nusselt number
k = thermal conductivity of shell side fluid

L = effective length of shell
Subscripts tur, and lam refer to the turbulent and laminar flow
regimes, and bund refers to the tube bundle.
Alternatively, the user may supply the shell side heat transfer coeffi-
cient directly.
The Bell-Delaware method is used to compute the correction fac-
tors for shell side heat transfer coefficient.
The Bell-Delaware method accounts for the effect of leakage
streams in the shell side. The shell side heat transfer coefficient is
given by:
Equation (5-15):
h  hideal J c J l J b J s J r
where:
h = average shell side heat transfer coefficient
hideal = shell side heat transfer coefficient for an ideal tube bank

Jc = correction factor for baffle cut and spacing
Jl = correction factor for baffle-leakage effects
Jb = correction factor for bundle bypass flow effects
Js = correction factor for inlet and outlet baffle spacing
Jr = correction factor for adverse temperature-gradient build-up
The correction factor, Jc, is a function of the fraction of the total

tubes in the cross flow; Jl is a function of the tube-to-baffle leakage
area, and the shell-to-baffle leakage area; Jb is a function of the
fraction of cross flow area available for bypass flow and the Reyn-
olds number; Js is a function of the baffle spacing; Jr is a function of
the number of baffles.
For detailed correlations related to Modified Chen Vaporization and
HEX5 methods, please refer to “Shell side” on page 599.
Tube side
The basic correlations used for phase change (i.e Modified Chen
Vaporization method, or HEX5 method) or no phase change cases
are as follows:
For turbulent flow in circular tubes, the tube side heat transfer coef-
ficient is obtained from the Sieder-Tate equation:
Equation (5-16):
0.14
hD 0.8 1/3   w 
N Nu   0.023 N Re N Pr  
k  b 
where:
w = fluid viscosity at the wall temperature
The above relationship holds for the following flow regimes:
Equation (5-17):
N Re  10000
0.7  N Pr  700
L
 60
D
where:

NNu = Nusselt number
DW
NRe = Reynolds number = -----------
At b
NPr = Prandlt number
L = tube length
D = effective tube diameter
W = total mass flow rate in tube side
At = cross sectional tube area
For laminar flow regimes, NRe þ 2000, a different relationship is

used for the heat transfer coefficient, depending on the value of the
Graetz number. The Graetz number, NGz, is defined as:
Equation (5-18):
D
N Gz  N Re N Pr  
L
For NGz < 100, a relationship first developed by Hausen is used:
Equation (5-19):
0.14
0.085 N Gz  b 
N Nu  3.66  2/3  
1  0.047 N Gz  w 
For NGz > 100, the Sieder-Tate relationship is used:
Equation (5-20):
0.14
 b 
N Nu  1.86 N 1/3
  Cadj
 w 
Gz
where:
gc = Gravitational constant, 4.18x108
 b  w = fluid density at bulk temperature (b) and wall tem-

perature (w)

1
 --- 
3
C adj = 0.87  1.0 + 0.015N 
Gr
 
3
 D b gc  
N Gr = --------------------------
-
2

b
2 2
b – w
 = ----------------------
-
2 w
For transition flow regimes where 2000 < NRe < 10000, the tube
side film coefficient is obtained by interpolation between those val-
ues calculated for the laminar and turbulent flow regimes:
Equation (5-21):
htrans 
 hturb  hlam  N Re  2000   h
lam
8000
where:
htrans = heat transfer film coefficient for the transition regime
hturb = heat transfer film coefficient for the turbulent flow

regime
hlam = heat transfer film coefficient for the laminar flow regime
The user may also supply the film coefficients directly.

For detailed correlations related to Modified Chen Vaporization and
HEX5 methods, please refer to “Tubeside” on page 611.
Also See:

Shell Side
Tube Side

Shell Side
The shell side pressure drop may be determined by one of two
methods; the Bell-Delaware method, or the stream analysis method.
The Bell-Delaware method, which is the default method used by
PRO/II, uses the following procedure.
First, the pressure drop for an ideal window section is calculated
using the following correlations:
For NRe < 100,
Equation (5-22):
26bW  N cw lb  W2
Pwi   '  2 

g c  Sm S w      Do Dw  g c  Sm S w  
0.5 0.5
For NRe > 100,

Equation (5-23):
W 2  2  0.6 N cw 
Pwi 
2 gc Sm S w 
The pressure drop for an ideal cross flow section is then calculated:
Equation (5-24):
0.14
4 f W 2 Nc  w 
Pbi  k  
2  g c Sm2  b 
where:
Pwi= pressure drop for an ideal window section
Pbi= pressure drop for an ideal cross flow section
μb= viscosity of shell side stream at fluid temperature

μw= viscosity of shell side stream at wall temperature
W = shell side stream flow rate
lb=central baffle spacing
fk = the friction factor for the ideal tube bank calculated at the
shell side Reynolds number

gc = gravitational force conversion factor = 4.18 x 108 lbm-ft/
lbf-hr
Nc = number of tubes in one cross flow section
Ncw = number of cross flow rows in each window
Sm = minimum cross sectional area between rows of tubes for

flow normal to tube direction
Sw = cross sectional area of flow through window
Do = tube outside diameter
Dw = equivalent diameter of a window
p' = tube pitch, center-to-center spacing of tubes in tube bundle

 = fluid density
The actual shell-side pressure drop is obtained by accounting for the
effects of bypasses and leakages, and is given by:
Equation (5-25):
 N 
Ps   N b  1 Pbi Rb  N b Pwi  Rl  2Pbi RB Rs 1  cw 
 Nc 
where:
Ps = actual shell side pressure drop
Nb = number of segmental baffles
Rb = bundle bypass flow correction factor
Rl = baffle leakage effects correction factor
Rs = correction factor for unequal baffle spacing effects
The stream analysis method, proposed in 1984 by Willis and John-

son, is an iterative, analytical method. At each iteration the cross
flow resistance, Rc, the window flow resistance, Rw, the tube to
baffle resistance, Rt-b, the shell to baffle resistance, Rs-b, the leak-
age resistance, Rl, the flow rate through the windowed area, Ww,
the cross flow pressure drop, Pc, the window pressure drop, Pw,
and the cross flow fraction, Fc are calculated as follows:

Equation (5-26):
Rc  function  Dc , tube bank layout ,  , Sc 

Equation (5-27):
 0.6856 S w 
1.9 exp  
 Sm 
Rw 
2  S w2

Equation (5-28):
R t-b = func(tube-to-baffleclearance,tube-to-baffleleakage area, ρ,μ)

Equation (5-29):
R s- b=func(shell-to-baffleclearance,shell-to-baffle leakage area, ρ,μ)

Equation (5-30):
Rt  func  Rt b , Rs b 
Equation (5-31):
W
Ww  0.5
 R  Rc 
1  w 
 Rl 
Equation (5-32):
Pc  RcWw2
Equation (5-33):
Pw  RwWw2
Equation (5-34):
 Pc / Rc 
0.5
Fc 
W
where:
Sc = cross flow area
Dc = cross flow equivalent diameter

Iterations are stopped once the value of Fc meets the following cri-
terion:
Equation (5-35):
Fc ,iter  Fc ,iter 1
 0.01
Fc ,iter
The shell side end space pressure drops at the inlet and outlet of the
exchanger, Ps,in, and Ps,out, and the actual shell side pressure
drop, Pss, are then calculated using the equations:
Equation (5-36):
Ps ,in  Rs ,inWin2

Equation (5-37):
Rs ,in  function  Rc , lb , S m , S w ,  
Equation (5-38):
Ps ,out  Rs ,outWout

2
Equation (5-39):
Rs ,out  function  Rc , lb , S m , S 2 ,  
Equation (5-40):
Ps ,in   N b  1 Pc  Pw   Ps ,out

Pss 
gc
where:
Ps,in = mean shell side end space pressure drop at exchanger
inlet
Ps,out = mean shell side end space pressure drop at exchanger
outlet
Rs,in = end space resistance at exchanger inlet
Rs,out = end space resistance at exchanger outlet
¯¯¯¯¯= (overstrike) denotes an average

Tube Side
The tube side pressure drop may be determined by one of two meth-
ods; BBM (Beggs-Brill-Moody) method (newly added), or HEX5
method (existing method).The BBM method is the default method
used by PRO/II. Please refer Section “Pipes” for further details of
BBM.
HEX5 method is supported for the backward compatibility and the
following equations used in the HEX5 method.
The tube side pressure drop, Pts, is calculated as the sum of the
pressure drops in the tubes plus the pressure drops in the return
bends:
Equation (5-41):
FGt2 Ln
Pt 
4.35*109 Di S p c
Equation (5-42):
2nGt2
Pr 
 2.741*10 S 
6 2
p
Equation (5-43):
Pts  Pt  Pr
where:
Pt = pressure drop in tubes
Pr = pressure drop in return tubes
Pts = total pressure drop in the tube side
c = fluid viscosity factor
F = friction factor
Gt = mass flux
L = tube length
n = number of tube passes

Di = tube inner diameter
Sp = specific gravity of fluid
The friction factor, F, and viscosity factor, c are computed using

different correlations for each flow regime:
For turbulent flows, NRe > 2800,
Equation (5-44):
0.14
 
c   b 
 2 
Equation (5-45):
log F  0.2643log N Re  2.5103
For laminar flows, NRe < 2100,

Equation (5-46):
0.25
 
c   b 
 2 
Equation (5-47):
log F  0.9952 log N Re  0.31537
For transition flow regimes, 2100 < NRe < 2800, F and c are
obtained by interpolation between the laminar and turbulent values:
Equation (5-48):
c 
 c ,tur  c ,lam   N Re  2100 
 c ,lam
700
Equation (5-49):
F
 Ftur  Flam  N Re  2100   F
lam
700
Calculation of Bundle weight, Shell weight (dry) and Shell weight

(with water)
Bundle weight
Shell weight (dry)

Shell weight (with water)
Bundle weight
Equation (5-50):
AS  AT / N S / N P
Equation (5-51):
W  3.63  0.924 log  AS /10.765 

Equation (5-52):
W   2.205 / 489.54  DT exp W 
Shell weight (dry)

Equation (5-53):
A  12 L / Di   2.5
0.537
Equation (5-54):
B   Di 
1.611
Equation (5-55):
C  1.2  25600.0 / PSD 

0.537
Equation (5-56):
Z  AB / C
Equation (5-57):
WS   2.205*63.0545 / 489.54  DS Z
Shell weight (with water)
Equation (5-58):
VS  L  Di / 2  /144.0
2
For kettle reboilers, the shell weight with water is calculated

assuming that the tube bundle diameter is 60 percent of the
shell diameter. The Volume of shell (VS) is calculated as fol-
lows:

Equation (5-59):
C  2.0a tan  0.96 

Equation (5-60):
Y1  0.5C1  Di / 2 
2
Equation (5-61):
Y2  0.192  Di / 2 
3
Equation (5-62):
Y3    Di / 2   Y1  Y2
2
Equation (5-63):
VS  L Y3 /144.0 
Equation (5-64):
VT  LN  d o2  di2  /  4*144.0 

Equation (5-65):
WW  DW VS  VT 
Equation (5-66):
WSW  WB  WS  WW
where:
AS = Area per shell (ft3)AT = Total Area (ft3)
di = Tube inside diameter (inch)

do = Tube outside diameter (inch)
Di = Shell inside diameter (inch)
DS = Density of shell material (lb/ft3)
DT = Density of tube material (lb/ft3)
DW = Density of water (62.4 lb/ft3)
NS = Number of shells in series
NP = Number of shells in parallel

PSD = Shell side design pressure (psia)
VS = Volume of shell (ft3)
VT = Volume of tubes (ft3)
WB = Bundle weight (lb)
WS = Shell weight dry (lb)
WSW = Shell weight with water (lb)
WW = Water weight (lb)
Fouling Factors
In most exchanger applications, the resistance to heat transfer
increases with use as a result of scaling caused by crystallization or
deposition of fine material. These factors may or may not increase
the pressure drop in the exchanger. For both the tube side and shell
side, the user may input separate factors to account for thermal and
pressure drop resistances due to exchanger fouling. Thermal fouling
resistances cannot be calculated analytically. Tables for thermal
heat transfer coefficients (the inverse of thermal resistances) for a
number of common industrial applications may be obtained from
standard references on heat exchangers such as Perry's handbook,
or the book by Kern.
PRO/II also allows the user to account for the effect of fouling on
pressure drop by inputting a thickness of fouling layer.
Reference
1 Perry, R. H., and Chilton, C. H., 1984, Chemical Engineers

Handbook, 6th Ed.
2 Kern, 1950, Process Heat Transfer, McGraw-Hill, N.Y.
3 Gnielinski, V., 1979, Int. Chem. Eng., 19(3), 380-400.
4 Willis, M. J. N., and Johnston, D., 1984, A New and Accu-
rate Hand Calculation Method for Shell side Pressure Drop
and Flow Distribution, paper presented at the 22nd Heat
Transfer Conference, Niagara Falls, N.Y.
Also See:

Heat Exchangers
LNG Heat Exchanger

General Information
Calculation Methods
Zones Analysis
General Information
The PRO/II LNG (Liquefied Natural Gas) heat exchanger model is
also called a “Cold Box”. It simulates the exchange of heat between
any number of hot and cold streams. An advantage of this type of
exchanger is that it can produce close temperature approaches
which is important when cooling close boiling point components.
Typically, LNG exchangers are used for cryogenic cooling in the
natural gas and air separation industries.
Calculation Methods
The LNG exchanger is divided into hot or cold “cells” representing
the individual cross-flow elements. Cold cells represent areas where
streams are cooled, while hot cells represent areas where streams
are heated. The following assumptions apply to the LNG heat
exchanger:
 Each LNG exchanger must have at least one hot and one
cold cell.
 The exchanger configuration is ignored.
 At least one cell does not have a product specification and
all unspecified cells leave at the same temperature. Equa-
tion (5-67) applies to every cell in the LNG exchanger.
Equation (5-67):
 qcell  H out  H in  mC p Tout  Tin 
where:
qcell = heat transferred in exchanger cell
Hout = enthalpy of stream leaving the cell
Hin = enthalpy of stream entering the cell

The following specifications may be set for a LNG cell:
 Outlet temperature, Tout.
 Cell duty, dqcell.
 Phase of outlet stream.
 Hot-cold stream temperature approaches.
 Minimum internal temperature approach (MITA).
Note: The last three specifications listed above (outlet phase, tem-
perature approach, and MITA) can only be accomplished using a
feedback controller unit.
Figure 5-1: Algorithm used to solve an LNG exchanger

Also See:

LNG Heat Exchanger
Heat Exchangers
Zones Analysis
When phase changes occur within the LNG heat exchanger, PRO/II
can perform a Zones Analysis to locate and report any internal tem-
perature pinches or crossovers. For the LNG exchanger, the UA and
LMTD for the exchanger are calculated using the composite hot and
cold streams.
Note: See Zones Analysis, for more details.
Also See:
LNG Heat Exchanger
Heat Exchangers
Air Cooled Heat Exchanger

General Information
Air Side Pressure Drop Correlations
Air Side Film Coefficient Correlations
General Information
Air Cooled Heat Exchanger (ACE) is Heat Transfer equipment,
which uses air as the cooling fluid. Air cooled Heat exchangers are
used in many process industries, especially in Petro chemical indus-
tries.
Air Cooled Heat Exchanger have two sides, one is tube side, which
is a process side and the other one is shell side, which is basically
air side. Air is supplied to the unit operation using fans.
Two calculation options available in PRO/II for simulating Air
Cooled Heat Exchanger are
1 Rating mode
2 Design mode
Air Side Pressure Drop Correlations

1) Bare Tubes

2) Finned Tubes
1) Bare Tubes
Equation (5-68):
N R N EU FR WF2
ps 
1.2*1011
Equation (5-69):
F2
 
N EU  N EUI  W 
  
Equation (5-70):
N EUI  N EUK AK1

Equation (5-71):
0.256
F2  0.776( 0.545 NRe )
if W  
0.196
 0.968 ( 1.076 N Re )
if W  
Equation (5-72):
WF DOT
N Re 
12K
Equation (5-73):
  
C  1  
 4 pt / DOT 
Equation (5-74):
DOT  DO  2tf1
A) In-line arrangement:
For 2.9 < NRe 2 x 103
Equation (5-75):
E1  0.272
1.02
86.7 
N Re
E2  0.263 
N Re

For 2x103 < NRe 2.01 x 106
Equation (5-76):
1.0*1010
9.27 *106 
N Re
2.49*103 
N Re
E1  0.267 
N Re
2.74*1013
3.12*10  10
N Re
1.24*10 
7
N Re
1.97 *103 
N Re
E2  0.235 
N Re
For 6.9 < NRe 8.010 x 103

Equation (5-77):
1.83*104
6.01*103 
N Re
6.46*102 
N Re
5.66*101 
N Re
E3  0.188 
N Re
For 799 < NRe 2.01 x 106

Equation (5-78):
E3  0.247  5.96*107 N Re  1.50*1012 N Re

2
 1.37 *1018 N Re
3
 3.96*1025 N Re
4
E4  0.177  3.11*107 N Re  1.77 *1012 N Re

2
A1  1.009 F30.744
A2  1.007 F30.655
A3  1.004 F30.539
0.0265
0.297 
F3
A4  1.218 
F3
For NRe 1.0 x 106

Equation (5-79):
AK1  A4
For 1.0x105 < NRe 1.0 x 106

Equation (5-80):
 A4  A3   N Re  1.0*105 
AK1  A3 
106  105
For 1.0x104 < NRe 1.0 x 105
Equation (5-81):
 A3  A2   N Re  1.0*104 
AK1  A2 
105  104
For 1.0x103 < NRe 1.0 x 104
Equation (5-82):
 A2  A1   N Re  1.0*103 
AK1  A1 
104  103

For NRe 1.0 x 103
Equation (5-83):
AK1  A4
NR
1 2 3 4 5
FR1 3.3405 2.4903 2.0068 1.7551 1.6041
FR2 1.2497 1.1897 1.1397 1.1048 1.0838
FR3a 1.895 1.1575 1.02 1.025 1.02
FR4a 2.6543 1.8216 1.5325 1.1480 0.9139
NR
6 7 8 9 10
FR1 1.5034 1.4315 1.3775 1.3356 1.3021
FR2 1.0698 1.0598 1.0524 1.0466 1.0419
FR3a 1.0167 1.0143 1.0125 1.0111 1.01
FR4a 0.3704 0.4603 0.5278 0.5803 0.6222
For NRe 1.0 x 106

Equation (5-84):
FR  FR 4 a

For 1.0x104 < NRe 1.0 x 106
Equation (5-85):
 FR 4a  FR 3a   N Re  1.0*104 
FR  FR 3a 
106  104
For 1.0x102 < NRe 1.0 x 104

Equation (5-86):
 FR 3a  FR 2   N Re  1.0*102 
FR  FR 2 
105  104
For 10 < NRe 1.0 x 102

Equation (5-87):
 FR 2  FR1   N Re  1.0*102 
FR  FR1 
102  101
For NRe 10

Equation (5-88):
FR  FR1
B) Staggered arrangement:
For 2.9 < NRe 2 x 103
Equation (5-89):
3
3  2.41  10 
– 1.55  10 +  -------------------------
2  N Re 
3.35  10 + ------------------------------------------------------------------
2 N Re
2.47  10 + ------------------------------------------------------------------------------------------------- -
N Re
E 1 = 0.795 + ---------------------------------------------------------------------------------------------------------------------------------
-
N Re
For 2 x 103 < NRe 2.01 x 106

Equation (5-90):
5.49*1012
1.32*1010 
N Re
9.84*106 
N Re
3.39*103 
N Re
E1  0.245 
N Re

For 2.9 < NRe 2 x 103
Equation (5-91):
5.74*102
4.26*104 
N Re
97.3 
N Re
1.11*10  2
N Re
E2  0.683 
N Re

For 2 x 103 < NRe 2.01 x 106
Equation (5-92):
4.82*1012
1.04*1010 
N Re
7.58*106 
N Re
2.48*103 
N Re
E2  0.203 
N Re

For 6.99 < NRe 101.0
Equation (5-93):
 – 126.0 – 582.0 -------------

 N Re 
44.8 +  -------------------------------------
 N Re 
 
E 3 = 0.713 + ------------------------------------------------------------
N Re

For 100 < NRe 1.000 x 104
Equation (5-94):
3.80*108
8.80*106 
N Re
7.17 *104 
N Re
3.03*102 
N Re
E3  0.343 
N Re

For 1.000 x 104 < NRe 2.01 x 106
Equation (5-95):
8.72*1015
1.65*1012 
N Re
7.92*107 
N Re
1.81*103 
N Re
E3  0.162 
N Re
For 99 < NRe 5.000 x 103

Equation (5-96):
8.62*107
1.92*10  6
N Re
1.48*10 
4
N Re
98.9 
N Re
E4  0.330 
N Re

For 5.000x103 < NRe 2.000 x 106
Equation (5-97):
4.63*1014
2.51*10  11
N Re
5.07 *10 
7
N Re
4.98*103 
N Re
E4  0.119 
N Re

Equation (5-98):
pt
F3 
pl
Equation (5-99):
A1  0.93F30.48 if F3  1.6
 F30.048 if F3  1.6
For 1.6 < F3

Equation (5-100):
A2  0.951F30.284
0.113
0.55 
F3
0.708 
F3
A3  1.28 
F3
A4  2.016  1.675F3  0.949 F32  0.234 F33  0.021F34
For F3  1.6
Equation (5-101):
0.113
0.55 
F3
0.708 
F3
A2  1.28 
F3
A3  2.016  1.675F3  0.949 F32  0.234 F33  0.021F34
For 105 < NRe

Equation (5-102):
AR1  A4

For 104 < NRe  105

Equation (5-103):
 A4  A3   N Re  104 
AR1  A3 
105  104

For 103 < NRe  104
Equation (5-104):
 A3  A2   N Re  103 
AR1  A2 
104  103
For 102 < NRe  103
Equation (5-105):
 A2  A1   N Re  102 
AR1  A1 
103  102
For NRe  102
Equation (5-106):
AR1  A1


NR
1 2 3 4 5
FR1 0.8089 0.8841 0.9227 0.9421 0.9536
FR2 0.2595 0.4946 0.6562 0.7422 0.7937
FR3 0.450 0.6701 0.780 0.8351 0.8680
FR4 1.1593 1.1044 1.0696 1.0522 1.0418
FR5 1.50 1.335 1.230 1.1725 1.1380
NR
6 7 8 9 10
FR1 0.9614 0.9669 0.9710 0.9742 0.9768
FR2 0.8281 0.8527 0.8711 0.8854 0.8969
FR3 0.890 0.9057 0.9175 0.9267 0.9340
FR4 1.0348 1.0298 1.0261 1.0232 1.0209
FR5 1.115 1.0986 1.0863 1.0767 1.069
For 105 < NRe

Equation (5-107):
FR  FR 5
For 104 < NRe  105

Equation (5-108):
 FR 5  FR 4   N Re  104 
FR  FR 4 
105  104
For 103 < NRe  104
Equation (5-109):
 FR 4  FR 3   N Re  103 
FR  FR 3 
104  103

For 102 < NRe  103

Equation (5-110):
 FR 3  FR 2   N Re  102 
FR  FR 2 
103  102

For 10 < NRe  102
Equation (5-111):
 FR 2  FR1   N Re  102 
FR  FR1 
102  101

For NRe  10
FR  FR1
Both in-line and staggered arrangement

Staggered arrangement
Equation (5-113):
B1  1.25
Equation (5-114):
B3  2.0
Equation (5-115):
B2  1.5
Equation (5-116):
E2  E2
Equation (5-117):
E1  E1
Equation (5-118):
E3  E3

Equation (5-119):
ptc  1.25 if pt  1.25

= 2.0 if pt  2.0
= pt if pt  1.25 and pt  2.0
In-line arrangement
Equation (5-120):
B1  1.5
Equation (5-121):
B2  2.0
Equation (5-122):
B3  2.5
Equation (5-123):
E1  E2
Equation (5-124):
E2  E3
Equation (5-125):
E3  E4
 E2 if E3  104
N EUK  E3 if ptc  B3
( E3  E2 )( ptc  E2 )

 E3  if ptc  B2 and ptc  B3
( E3  E2 )
( E2  E1)( ptc  E1)

 E3  if ptc  B1 and ptc  B2
( E2  E1)
 E1 if ptc  B1


2) Finned Tubes
Equation (5-127):
ps  ps K1
Equation (5-128):
K f Gs2YC1C2
ps 
5.22 1010 sDv
Equation (5-129):
K1  0.42 N Re
0.075
1
In-line arrangement
K1  1.0 Staggered arrangement
Equation (5-130):
0.00806
Kf  0.1321
N Re1
Equation (5-131):
W
Gs 
AF
Equation (5-132):
0.4
 12 Dv 
C1   
 pt 
Equation (5-133):
0.6
Y 
C2   l 
 pt 
Equation (5-134):
4( XYZ  N TTLTV )
Dv 
ABX
Equation (5-135):
ABX  TL N T DO F

Equation (5-136):
Equation (5-137):

s
62.5
Equation (5-138):
W
WF 
 AF
Equation (5-139):
WF Dv
N Re1 
K
Equation (5-140):
  2 N F H FTF )
N TTL ( DOT
AF  XZ 
12 N R
Equation (5-141):
where
ABX = Area of bundle (ft2)
AF = Effective cross-sectional area of bundle (ft2)
DOR = Tube root OD (inch)
DOT = Tube outside diameter + fouling layer thickness (inch)
 = Tube root diameter + fouling layer thickness (inch)

DOT
DO = Tube outside diameter (inch)
DV = Volumetric hydraulic diameter
FR = Row correction factor

FR1 = Row correction factor at Reynolds number of 10
FR3a = Row correction factor at Reynolds number of 104
FR4a = Row correction factor at Reynolds number of 106
F2 = Factor for influence of fluid-property variation
GS = Mass velocity (lb/hr-ft2)
HF = Fin height (inch)
K1 = Correction factor for in-line arrangement
Kf = Friction factor
NEU = Euler number
NF = Number of fins per inch
NR = Number of tube rows per bundle
NRe = Reynolds number
NRe1 = Reynolds number based on hydraulic diameter
NT = Number of tubes per bundle
pt = Transverse pitch (inch)
pl = Longitudinal pitch (inch)
s = Specific gravity
tfl = Air side fouling layer thickness (inch)
TF = Fin thickness (inch)
TL = Tube length (ft)

WF = Air flow rate weight (lb/hr)
X = Bundle width (ft)

Y = Bundle height (ft)
Z = Bundle length (ft)
ps = Air side pressure drop
 = Air viscosity (lb/ft-hr)
K = Air kinematic viscosity (ft2/hr)
W = Air viscosity at wall temperature (lb/ft-hr)
 = Air density (lb/ft3)
Air Side Film Coefficient Correlations

Equation (5-142):
H air  H C  H R AT  H W AW AT
Equation (5-143):
 (1   t )( gTC4   gTW4 )

HR 
2(TC  TW )
Equation (5-144):
3
 T 
H W  9.46  W 
 1000 
Calculation of HC
1) Bare Tubes
2) Finned Tubes
1) Bare Tubes
Equation (5-145):
12N Nu(cal) K air

HC 
DOT
Equation (5-146):
N Nu(cal)  N Nu(row) F1 F2

Equation (5-147):
N Nu(row)  0.3  ( N Nu(lam)

2
 N Nu(tur)
2
)0.5
Equation (5-148):
N Nu(lam)  0.664 N Re
0.5
N Pr0.33
Equation (5-149):
0.8
0.037 N Re N Pr
N Nu(tur)  0.1
1  2.443N Re ( N Pr0.667  1)
Equation (5-150):
WF DOT
N Re 
12 k
Equation (5-151):
W
WF 
 ZXC
Equation (5-152):
  
C  1  
 4 pt / DOT 
Equation (5-153):
DOT  Do  2tfl
Equation (5-154):
N Pr
F1  0.25
N Pr  N Pr(wall)
N Pr(wall)
N Pr
 0.11
N Pr  N Pr(wall)
N Pr(wall)
Equation (5-155):
1  ( N R  1) F3
F2 
NR

Equation (5-156):
0.667
F3  1  Staggered arrangement
pl
 p 
0.7  l  0.3 
 1  pt  Inline arrangement
2
1.5  pl 
C   0.7 
 pt 
Equation (5-157):
pl
pl 
DOT
Equation (5-158):
pt
p t 
DOT
Equation (5-159):
2Y ( X  Z )
AW 
 N T DOTL
Equation (5-160):
AT  1.0
2) Finned Tubes
Equation (5-161):
12N Nu(cal) K air

HC 

DOT
Equation (5-162):
N Nu(cal)  N Nu(row) F2

Equation (5-163):
0.2 0.18 0.14
 p   D   DOT
 
N Nu(row)  0.19  t   OT   
0.65
N Re N Pr0.333
 pl   N F   HF 
Staggered arrangement
 N 0.625 
 0.3  Re0.375 
( N Pr )0.333
F
 F 
Inline arrangement
Equation (5-164):
pl
pl 

DOT
Equation (5-165):
( N R  1)
F 2  0.5 
NR
Equation (5-166):
pt
pt 

DOT
Equation (5-167):
  DOR  2tfl
DOT
Equation (5-168):
WF DOT
N Re 
12k
Equation (5-169):
W
WF 
 AF
Equation (5-170):
  2 N F H FTF )
N TTL ( DOT
AF  XZ 
12 N R

Equation (5-171):
A1
FF 
A2
Equation (5-172):
A1  A3  A4
Equation (5-173):
A2  0.2618 Do
Equation (5-174):
  DOR (1  A5 )  ( DOR  2 H F ) A5 
A3 
12
Equation (5-175):
A4 

2 N F ( DOR  2 H F ) 2  DOR
2

48
Equation (5-176):
A5  N FTF
Equation (5-177):
A6  0.2618 Di
Equation (5-178):
2Y ( X  Z )
AW 
 N T DORTL
Equation (5-179):
DOR
AT 
Di FF
Equation (5-180):
A1
FF 
A6
AF = Effective cross-sectional area of bundle (ft2)
AT = Area Bare tube/Area tube + Fin ratio
AW = Area refractory /Area bare tube ratio

CPair = Air specific heat (Btu/lb-F)
Di = Tube inside diameter (inch)
Do = Tube outside diameter (inch)
DOR = Tube root OD (inch)
DOT = Tube outside diameter + fouling layer thickness
= Tube root diameter + fouling layer thickness

F1 = Adjust factor for heating/cooling
F2 = Adjustment for number of rows
F3 = Tube correction factor
Hair = Air side mean heat transfer coefficient (Btu/hr-ft2-R)
HC = Convective heat transfer coefficient (Btu/hr-ft2-R)
HF = Fin height (inch)
HR = Gas radiation coefficient (Btu/hr-ft2-R)
HW = Refractory wall radiation coefficient (Btu/hr-ft2-R)
Kair = Air thermal conductivity (Btu/hr-ft-F)
NF = Number of fins per inch
NNu(cal) = Nusselt number, calculated
NNu(lam) = Nusselt number, laminar
NNu(row) = Single row Nusselt number
NNu(tur) = Nusselt number, turbulent
NPr = Prandtl number, Air
NPr(wall) = Air Prandtl number at wall temperature
NR = Number of tube rows per bundle
NRe= Reynolds number, Air

NT = Number of tubes per bundle
pl = Longitudinal pitch (inch)
pt = Transverse pitch (inch)
tfl = Air side fouling layer thickness (inch)
TC = Mean air temperature (Rankine)
TF = Fin thickness (inch)
TL = Tube length (ft)
TW = Tube wall temperature (Rankine)
W = Air flow rate per bundle (lb/hr)

X = Bundle width (ft)
Y = Bundle height (ft)
Z = Bundle length (ft)
εt = Emissivity (0.9)
εg = Emissivity (0.17)
μ = Air viscosity (lb/ft-hr)
μk = Air kinematic viscosity (ft2/hr)
ρ = Air density (lb/ft3)
σ = Stefan-Boltzmann constant (0.1714× 10-8 Btu/hr-ft2-R4)

Furnace Model
Figure 5-1: Typical Furnace Configuration

General Information
The furnace model (FURNACE) often is also called a fired heater,
fire box, or tube-still heater. Similar to a heat exchanger, it models a
two-sided unit operation that exchanges heat between the two sides.
A typical configuration is shown in Figure 5-1(5-1).Process fluid
passes through a set of tubes and the utility fluid passes through
enclosures (the fire box) that surround the tubes. There is no mixing
or other mass transfer between the two sides. Unlike other heat
exchanger models, the utility (or combustion) side always models
an air-fuel mixture that undergoes combustion modelled using a
pre-defined set of reactions. Heat always transfers from the com-
bustion side to heat the process fluid. No reactions occur on the pro-
cess side.
The model is suitable for simulating a variety of related types of
heat-transfer equipment, particularly still-tube heaters and some
water-tube boilers. It is not suitable for modelling still-tube reac-
tors, since the process-side does not support reactions. Input data is
similar to that of the simple heat exchanger model (see HX earlier
in this chapter), in that it does not include detailed specifications for
the physical configuration of the equipment.
Major Specifications
Modes of Operation
The furnace model makes no explicit distinction between rating and
design modes. However, depending upon the data supplied by the
user, the simulation solves implicitly on one or the other of these
modes.
Design mode: Supply operating values for the following measur-
able parameters:
 Process-side outlet temperature or duty (not both).
 Tube skin temperature.
 Wall temperature.
 Ambient temperature (with wall temperature, for heat loss).
The model computes the heat transfer coefficients for radiation,
conduction through the tube walls, and conductive heat losses
through the furnace walls.

Rating mode: Supply operating values for heat transfer coeffi-
cients:
 Gas-to-tube heat transfer coefficient.
 Tube-to-process fluid heat transfer coefficient.
 Gas-to-wall heat transfer coefficient.
 Wall-to-atmosphere heat transfer coefficient.
The model calculates the process duty and outlet temperature.
In addition to the wall-to-atmosphere coefficient, the model
expects a value for the ambient atmospheric temperature.
Process Outlet Pressure Specification

Three options are available for specifying the final outlet pressure
of the process fluid. Specify one of the following:
 Outlet pressure (a single operating value)
 Process-side pressure drop (a single operating value)
 Pressure equation (specify the reference flow rate, refer-
ence pressure drop, and up to 3 equation constants A,B,C)
Equation (5-181):
C
P  Flow 
 A B 
Pref  Flowref
 
When no pressure specification is present, the default is dP = 0,
which sets the process outlet pressure to the inlet pressure.
Additional Operating Constraints

The model allows users to impose optional constraints that help
keep the solution within a reasonable operating range. In actual
plant equipment, kilns often operate up to 2500F, while furnaces
typically operate no hotter than 4000F. Available temperature con-
straints include:
 Maximum tube skin temperature
 Maximum temperature difference between the tube skin
temperature and the average tube temperature.
Supplying one of the two values is sufficient, since each may be
computed from the supplied value of the other. These values essen-

tially are estimates or guidelines, and valid solutions may exceed
these limits. When the solution results exceed either limit, PRO/II
issues a warning (not an error). Specifying both constraints further
decreases the degrees of freedom, and increases the probability of
generating this warning.
Initial Estimates
Users may supply actual operating values or initial estimates for the
following parameters.
 Bridge wall temperature (average)
 Percentage of duty lost through furnace walls
 Tube skin temperature (average)
 Process outlet temperature
When both the estimate and operating values are missing for one of
these parameters, the model generates an estimate for the missing
value.
Equations in the Furnace Model

After user-supplied data are applied and initial estimates are avail-
able, the furnace unit operation populates an equation-based model
of the problem. It employs a closed-form non-linear solver instead
of an iterative algorithm to reach a solution. This is a close analog
of the open-form model available in ROMEO, the Rigorous On-line
Modeling program offered by SimSci-Esscor.
Elemental Composition of Combustion Reactants in the Fuel

The simultaneous solution of the equation set incorporates the following
constraints.
• All carbon, hydrocarbons, and carbon monoxide in the

feed to the combustion chamber combust
• to form only water and carbon dioxide.
• Sulfur and hydrogen sulfide combust completely to form
only sulfur dioxide and water.
• Nitrous compounds in the combustion feed undergo con-
version to N2.
• There is no recirculation of the flue gas through the com-
bustion chamber.
General form:
Equation (5-182):

Rr = Rfuel * Xr / War
Where:
Rr = Molar flow rate of reactant “r” in the feed to the combus-
tion side.
Rfuel = Molar flow rate of total merged feed to combustion side
Xr = Mole fraction of reactant “r” in the feed to the combustion
side.
War = Atomic weight of reactant “r”
Only nitrogen, oxygen, carbon, hydrogen, sulfur, and argon partici-
pate in the combustion process. All library components that consist
only of these elements are decomposed to obtain the available
amount of reactants. The model analyzes the chemical formulae of
these components to determine the stoichiometric content of each
reactant. The decomposition process reduces binary molecules O2,
N2, and H2 to their elemental forms. Renormalization of the feed
redefines the composition using the reactant species in place of the
decomposed components. The model treats non-library and other
components in the feed as inert species that do not participate in
combustion, and they exit intact in the flue gas. Additionally, solids
and assay components should not be present in the combustion -side
fluid.
Air is a unique component that receives special consideration.
When argon is present, it displaces a fraction (0.00934) of the nitro-
gen from air. In addition, the decomposition of air releases its water
content as water vapor. When analysis determines insufficient oxy-
gen is available to achieve complete combustion, the model intro-
duces additional nitrogen and oxygen (simulating air) to eliminate
the oxygen deficiency. It also issues a warning to notify the user of
this action.
The following relationships determine the stoichiometric amount of
each reactant available in the combustion-side feed.
RN = Rfuel * XN / 14.0067 Moles of atomic nitrogen.
RO = Rfuel * XO / 15.9994 Moles of atomic oxygen.
RO2 = Rfuel * XO2 / 31.999 Moles of molecular oxygen.
RC = Rfuel * XC / 12.01115 Moles of carbon.
RH = Rfuel * XH / 1.00797 Moles of atomic hydrogen.
RS = Rfuel * XS / 32.064 Moles of sulfur.

RAr = Rfuel * XAr / 39.948 Moles of argon.
Amount of Each Combustion Product in the Flue Gas

The following equations define the formation of combustion prod-
uct components. All of the product components ( CO2, SO2, O2,
N2 and H2O ) must be present in the component slate used by the
simulation. Combustion may release water from the air in the fuel
mixture.
RCO2 = RC
RH2O = 0.5 * RH + RAir * XH2O/Air
RSO2 = RS
RO2 = 0.5 * RO + RAir * XO2/Air – RC – 0.25 * RH – RS
RN2 = 0.5 * RO + RAir * XN2/Air
Where:
RCO2 = Moles of carbon dioxide in the flue gas
RH2O = Moles of water in the flue gas
RSO2 = Moles of sulfur dioxide in the flue gas
RO2 = Moles of molecular oxygen in the flue gas
RN2 = Moles of molecular nitrogen in the flue gas
RAir = Mole flow rate of air
XH2O/Air = Mole fraction of water in air
XO2/Air = Mole fraction of molecular oxygen in air
XN2/Air = Mole fraction of molecular nitrogen in air
Flue Gas Rate and Composition

The mole flow rate of the flue gas is the sum of all the component
mole rates:
Equation (5-183):
Rflue = ( Rp ) + ( Rn )
Where:
Rflue = Mole flow rate of flue gas
Rp = Moles of combustion product p

Rn = Moles of inert component n
Component fractions are the products of dividing each component
flow by the total flow:
Xi = Ri / Rflue
Where:
Xi = mole fraction of any component i
Ri = mole rate of any component i
Combustion Side Energy Balances

Equation (5-184):
dHfiring = - Rfuel * Hcombust fuel
Where:
dHfiring = Firing duty
Hcombust fuel = total heat of combustion of the fuel.
Flue gas duty is computed from:

Equation (5-185):
Qflue = Rair * (Hin air – Ht0 air) + Rfuel * (Hin fuel – Ht0 fuel)
- Rfuel * Hcombust fuel
Where t0 is the reference temperature for computing adiabatic heats
of combustion. Typically, the furnace sums the lower heating values
(LHV’s) of the reacting species to obtain Hcombust. Hcombust is
applied to the fuel at the reference temperature of the LHV’s. The
topic “Reactor Heat Balances” in chapter 7 describes the procedure
for applying the heat of combustion to reach the final outlet
temperature and enthalpy. The overall energy balance for the com-
bustion process is:
Equation (5-186):
dHfiring - Hfuel + Qflue = 0
Where:
Hfuel = initial enthalpy of the fuel feed
Adiabatic flame enthalpy:

Equation (5-187):

Hadia flame = Ht0 in flue + Qflue / Rflue
Heat Loss through Wall to Atmosphere via Radiant Heating

Equation (5-188):
Qloss rad = HTCgas-wall * (Tradgas4 – Twall4)
Equation (5-189):
%dHloss rad = Qloss rad / dHfiring
Equation (5-190):
Qloss atm = HTCwall-atm * (Twall – Tatm)
Combustion-Side Duty
Equation (5-191):
Hcombust = Qprocess + Qloss
LMTD Calculations
dT1 = Ttskin avg – Tproc in
dT2 = Ttskin avg – Tproc out
dTlo = min(dT1, dT2),
dThi = max(dT1, dT2)
Tratio = dTlo / (dThi)2
Equation (5-192):
LMTD = (dTlo - dThi ) / log(Tratio )
Approximate formulations are substituted as appropriate to

avoid divide by zero and log( 0 ).
Process-Side Calculations
The process side of the furnace is much simpler (from a calculation
viewpoint) than is the combustion side. The process stream under-
goes simple heating with no reactions. In a rating mode, once the
heat duty from the combustion side is available on the process side,
it is not difficult to calculate the final outlet conditions.
In a design mode, the user supplies either process outlet tempera-
ture or duty. It then requires only a straightforward application of a
temperature-pressure (T, P) flash or a pressure-enthalpy (P,Q) flash

at the specified outlet pressure to obtain the duty or temperature and
final phase state of the process fluid.
Radiant Gas Temperature
Equation (5-193):
Tradgas = Tbridge wall + 0.25 *(Tadia – T0) * Qprocess / Qflue
Tube to Process Fluid Heat Transfer

Equation (5-194):
Qprocess = HTCtube-proc * LMTD
Equation (5-195):
dTskin = Tskin max – Tskin avg
where Tskin max is an optional constraint provided by the user.

Chapter 6: Reactors
PRO/II offers the following chemical reactors:

 Conversion Reactor (operates at a desired conversion level)
 Equilibrium Reactor
 Gibbs Free Energy Minimization Reactor
 Ideal Mixed Flow Reactor (Continuous Stirred Tank Reactor)
 Ideal Tubular Reactor (Plug Flow reactor or PFR)
Reactor Heat Balances
Conversion Reactor
Equilibrium Reactor
Gibbs Reactor
Continuous Stirred Tank Reactor (CSTR)
Plug Flow Reactor (PFR)
Reactor Heat Balances

The heats of reaction for all reactors are determined in one of two
ways:
 The user may supply the heat of reaction for each stoichiomet-
ric reaction in the Reaction Data section. This heat must be
given at a reference temperature and phase, either vapor or liq-
uid. PRO/II will not accept a mixed-phase reference basis.
 If the heat of reaction is not supplied, the heat of reaction will
be calculated from heat of formation data. PRO/II has heat of
formation data available for all library components at 25C,
vapor phase. PRO/II will estimate the heats of formation for all
PETRO components. The heat of formation data may be over-
ridden for all LIBID and PETRO components. If NONLIB
components are used, the heat of formation data should be pro-
vided by the user at the same reference conditions as all other
components.

Once the heat of reaction data are supplied, PRO/II calculates the
total enthalpy change along the reaction path shown in Figure 7-1.
Calculations proceed as follows.
a) The reactants are brought to the reference temperature and
phase. The enthalpy difference, H2-H1 is calculated by the
prevailing enthalpy calculation methods for that reactor.
b) The total heat of reaction, ∆Hr, is then calculated by summing

all the individual heats of reaction occurring in the reactor.
Figure 6-1: Reaction Path for Known Outlet Temperature and

Pressure
c) The reactor effluents are brought to the outlet thermal condi-
tions resulting in H4.
Equation(6-1):
Duty   H 2  H1   H r   H 4  H 3 
The total reactor duty is the sum of the individual path duties. This
process is completely independent of enthalpy datum, hence users
can supply enthalpy values at any arbitrary datum with good results.
For vapor phase reactions, the reference pressure is taken as 1 atm.
Should the reference phase condition (checked by the flash opera-
tion) be found to be liquid for either the reactants or products, the
pressure is lowered further until only vapor is present. Similarly, for
the liquid phase reactions, the reference pressure of reactants or
products is increased until only liquid is present.
Reactors 6-448
When the ADIABATIC option is active, duty may be supplied on
the OPERATION statement. (Unlike the FLASH unit operation, the
reactor also has reference state enthalpies H2 and H3 and heat of
reaction Hr which can be changed, and which will change the outlet
enthalpy. An adiabatic reactor will actually be a fixed-duty reactor.)
The outlet temperature is determined by trial and error to satisfy the
duty.
The reactor duty can be calculated from equation (6-1).
The heat balance will be printed in the reactor summary if the
PRINT PATH statement is input.
Also See:
Reactors
Heat of Reaction
The heat of reaction may be furnished by the user as a function of
the moles of base component reacted. Alternatively, the heat of
reaction will be computed by PRO/II if not supplied, through the
following relationship:
Equation(6-2):
H r   H f , products  H f , reactants
where:
Hf = heat of formation of each component at 25 C
Heat of formation data are available in the component databank for

library components and can be estimated for petroleum components
using internal correlations. For NONLIBRARY components this
data must be furnished.
Conversion Reactor
Shift Reactor Model
Methanation Reactor Model
The CONREACTOR unit operation is a simple conversion reactor.
No kinetic information is needed nor are any reactor sizing calcula-
tions performed. The desired conversion of the base component is
specified and changes in the other components will be determined

by the corresponding stoichiometric ratios. Conversions may be
specified as a function of temperature, as follows:
Equation(6-3):
Fractional Conversion  Co  C1T  C2T 2
where:
T is in problem temperature units
C0, C1, C2 are constants
The fractional conversion could be based either on the amount of

base component in the feed to the reactor (feed-based conversion)
or on the amount of base component available for a particular reac-
tion (reaction-based conversion). The former concept is suitable for
specifying conversions in a system of parallel reactions, whereas
the latter definition is more appropriate for sequential or series reac-
tions. PRO/II will select feed-based conversion as the default con-
version basis for single, parallel and series-parallel reactions.
Reaction-based conversion is the default conversion basis for series
reactions. If specified explicitly, the method (FEED or REAC-
TION) selected with the CBASIS keyword will be used. In any
case, the fractional conversion value input with the CONVERSION
statement will be understood to have as its basis the default or input
CBASIS, whichever is applicable.
The reactor may be operated isothermally at a given temperature,
adiabatically (with or without heat duty specified), or at the feed
temperature. For adiabatic reactors, heat of reaction data must be
given or should be calculable from the heat of formation data avail-
able in the component library databank. Temperature constraints
can be specified. For isothermal reactors, the heat of reaction data is
optional. If supplied, the required heat duty will be calculated.
An unlimited number of simultaneous reactions may be considered.
The conversion reactor can also be used to model shift and metha-
nation reactors. In this case, fractional conversions can be specified
for the shift and methanation reactions.
Also See:
Reactors
Reactors 6-450
Shift Reactor Model
The purpose of the shift reactor model is to simulate the shift con-
version of carbon monoxide into carbon dioxide and hydrogen with
steam:
Equation(6-4):
CO  H 2O  CO2  H 2

Also See:
Conversion Reactor

Methanators are used to convert the excess CO from the shift reac-
tion into methane. The reactor model is similar to the shift reactor
but both the methanation and shift reactions take place simultane-
ously.
Equation(6-5):
CO  3H 2  CH 4  H 2O
CO  H 2O  CO2  H 2
Also See:
Conversion Reactor
Equilibrium Reactor
The EQUREACTOR unit operation is a simple equilibrium reactor.
No kinetic information is needed nor are any reactor sizing calcula-
tions performed. Equilibrium compositions are calculated based on
equilibrium constant data. Approach data, if specified, are used to
compute approach to equilibrium.
The reactor may be operated isothermally at a given temperature,
adiabatically (with or without heat duty specified), or at the feed
temperature. For adiabatic reactors, heat of reaction data must be
given or should be calculable from the heat of formation data avail-
able in the component library databank. Temperature constraints
can be specified. For isothermal reactors, the heat of reaction data is
optional. If supplied, the required heat duty will be calculated.

A single reaction is considered for the stoichiometric and simulta-
neous equilibria of two reactions are computed for the methanator
model.
For chemical equilibrium calculations in PRO/II, ideal behavior is
assumed for reaction in either the liquid or vapor phase.
For a reaction,
Equation(6-6):
aA  bB  cC  dD
The equilibrium constant is:
For liquid with “Activity” as activity base:
Equation(6-7):
c d
C D
K eq = ------------------
-
a b
A B
for vapor or liquid with “Fugacity” as activity base:
Equation(6-8):
c d
fC fD
K eq = ---------------
a b
fA fB
for vapor or liquid with “Molar Concentration” as activity base:
Equation(6-9):
c d
CC CD
K eq = ------------------
-
a b
CA CB
for vapor or liquid with “Mole Fraction” as activity base:
Equation(6-10):
c d
xC xD
K eq = -----------------
a b
xA xB
where:
p = the partial pressure of the component
α = the activity of the component
Reactors 6-452
f = the fugacity of the component in either liquid or vapor
C = the molar concentration of the component in liquid
x = the mole fraction of the component in liquid
Note: Keq is dimensionless for liquid phase reactions and has the
dimension of (pressure unit) with = c + d - a - b for vapor phase
reactions
The temperature dependency of the equilibrium constant is

expressed as:
Equation(6-11):
B
ln  Keq   A   C  ln T   DT  E T 2  F T 3  GT 4  H T 5
T
where:
Keq = reaction equilibrium constant
A-H = Arrhenius coefficients

T = absolute temperature
When no approach data are given, all reactions go to equilibrium by
default. The approach to equilibrium can be given either on a frac-
tional conversion basis or by a temperature approach. The conver-
sion itself can be specified as a function of temperature.
When the temperature approach is given, Keq is computed at T,
where:
T = Treaction - ∆T(endothermic reactions)
T = Treaction + ∆T(exothermic reactions)
Based on the value of Keq, conversion of base component and
product compositions can be calculated.
If the approach to equilibrium is specified on a fractional conver-
sion basis, the conversion of the base component B, is given by:
Equation(6-12):
CB   BF  BR     BF  BE 
where:

BR = moles of component B in the product
BF = moles of component B in the feed
BE = moles of component B at equilibrium
= specified approach to equilibrium
= C0 + C1T + C2T2
The coefficients C0, C1, and C2 may appear in any combination,

and missing values default to zero. For a fixed approach, C1 and C2
are zero. When no approach data are given, reactions attain equilib-
rium, and C0 = 1.0, C1 = 0.0, and C2 = 0.0.
The equilibrium reactor can also be used with specialized reactor
models for shift and methanation reactions.
Shift Reactor Model
Calculation Procedure for Equilibrium
Also See:
Equilibrium Reactor
Shift Reactor Model

The purpose of the shift reactor model is to simulate the shift con-
version of carbon monoxide into carbon dioxide and hydrogen with
steam:
Equation(6-13):
CO  H 2O  CO2  H 2
Just as in the Stoichiometric Reactor, the desired conversion is

determined from an equilibrium model for the shift reaction. PRO/
II has incorporated the National Bureau of Standards data for equi-
librium constants. This can be represented by:
Equation(6-14):
B
ln  K eq   A 
T
Reactors 6-454
where:
A and B are functions of temperature
T = absolute temperature, R
and
Equation(6-15):
P CH4 P H2 O
K eq = -----------------------
-
3
P CO P H2
where:
p = partial pressure in any units
If desired, users may override the NBS data and supply their own
constants A and B in the above equations.
The approach to equilibrium can also be indicated either on a frac-
tional conversion basis or by a temperature approach.

Also See:
Equilibrium Reactor

Methanators are used to convert the excess CO from the shift reac-
tion into methane. The reactor model is similar to the shift reactor
but both the methanation and shift reactions take place simultane-
ously. It can also be used to model the reverse reaction viz., steam
reforming of methane to yield hydrogen. These are:
Equation(6-16):
CO  3H 2  CH 4  H 2O
CO  H 2O  CO2  H 2
Just as for the shift reaction, the National Bureau of Standards data
are available for methanation reaction. The methanation equilib-
rium is given by:
Equation(6-17):
PCH 4 PH 2o
K eq
PCO PH32

where:
p = partial pressure in psia
Also See:
Equilibrium Reactor
Calculation Procedure for Equilibrium

For adiabatic, equilibrium models, the calculation procedure is as
follows:
1 Assume an outlet temperature.
2 Determine the equilibrium constant at the assumed temper-
ature plus the approach to equilibrium.
3 Calculate the product compositions from Keq for the reac-
tion.
4 Calculate the conversion and adjust by the fractional
approach to equilibrium.
5 Calculate the enthalpy of products and perform an adiabatic
flash to determine the outlet temperature.
6 If the calculated and assumed temperatures do not agree,
repeat the calculations with the new temperature.Only one
approach to equilibrium, i.e., either a temperature approach
or a fractional conversion approach, is allowed.
Also See:
Equilibrium Reactor
Gibbs Reactor
General Information
Mathematics of Free Energy Minimization
General Information
The Gibbs Reactor in PRO/II computes the distribution of products
and reactants that is expected to be at phase equilibrium and/or
chemical equilibrium. Components declared as VL or VLS phase
type can be in both chemical and phase equilibrium. Components
declared as LS or S type are treated as pure solids and can only be
Reactors 6-456
in chemical, but not phase, equilibrium. The reactor can be at either
isothermal or adiabatic conditions. Reaction and product specifica-
tions can be applied to impose constraints on chemical equilibrium.
Available constraints include fixed product rates, fixed percentage
of feed amount reacted, global temperature approach, and reaction
extent or temperature approach for each individual reaction. The
mathematical model does not require the knowledge of reaction
stoichiometry from the user except when the reaction extent or a
temperature approach is to be specified for the individual reaction.
Mathematics of Free Energy Minimization

Objective Function of Gibbs Free Energy Minimization
Solution of Gibbs Free Energy Minimization
Phase Split
Objective Function of Gibbs Free Energy Minimization

The objective function which is to be minimized is composed of
two parts. The first is the total Gibbs free energy of the mixture in
all phases.
Equation(6-18):
NS G OC NP NC G
G
  j n cj   jp n jp
RT j 1 RT p 1 j 1 RT
where:
NS = number of solid components
NP = number of fluid phases
NC = number of fluid components
Gj0C = Gibbs free energy of solid component at standard state
Gjp = Gibbs free energy of fluid component at reactor temper-

ature and pressure
T = reactor temperature
njC = number of moles of solid component
njp = number of moles of fluid component

In the design equation (6-18), the Gibbs free energy is represented
by a quadratic function.
Equation(6-19):
1
G  N   G  n   GT  n  N  n    N  n   2G  N  n 
T
2
When a temperature approach is applied for all reactions (global
approach) or for individual reactions (individual approach), the
standard state free energies of formation are modified in a way that
the relation between the reaction equilibrium constant and change
of Gibbs free energy of formation is satisfied (see equation ()). The
standard state Gibbs free energy is defined as at reactor tempera-
ture, 1 atm, and ideal gas state for all fluid components, and at reac-
tor temperature, 1 atm, and solid state for all solid components
Equation(6-20):

K j = exp   – G j    RT  
j = 1  NR
where:
NR = number of reactions
∆Gj = change of Gibbs free energy of formation at modified

temperature T'
T' = T + ∆T
∆T = temperature approach
The second part of the objective function is the conservation of ele-
ment groups and mass balance equations created from the con-
straints on chemical equilibrium. For each element group, the
output flow rate has to be equal to the feed flow rate, i.e.:
Equation(6-21):
NS NP NC
bk   m jk n   m jk nmp
c
j k  1,..., NE
j 1 p 1 j 1
Reactors 6-458
where:
bk = feed quantity of element group k
NE = number of element groups

mjk = number of element group k contained in component j
If the product rate of a component is fixed, either by the constraint

of fixed product rate or by the fixed percentage of feed amount
reacted, the additional mass balance constraint can be written as:
Equation(6-22):
d j  n cj j  1,..., NSFIX
NP
d j   n jp j  1,..., NCFIX
j 1
where:
dj = specified or derived fixed product rate
NSFIX = number of solid components with fixed product rate

NCFIX = number of fluid components with fixed product rate
If a reaction has a specified reaction extent, the additional mass bal-
ance constraint is:
Equation(6-23):
NS NR  NS
 NP 
 r   arj  ncj  nj    arj   n jp  n 0j  r  1,..., NR
j 1 j 1  p i 
where:
r = fixed reaction extent

arj = matrix element derived from the inverse of stoichiometric
coefficient matrix
From equations (6-18), (6-21), (6-22), and (), the overall objective
function for the minimization of Gibbs free energy can be expressed
as equation (6-24):

Equation(6-24):
In equation (6-24) above, 's are the Lagrange multipliers for the
conservation of elemental groups and various mass balance equa-
tions.
Solution of Gibbs Free Energy Minimization

The necessary conditions for a minimum value of F(n) are:
Equation(6-25):
F  n 
0 j  1,..., NS
ncj
F  n 
0 j  1,..., NC ; p  1,..., NP
n cjp
F  n 
0 k  1,..., NE
 k
F  n 
0 r  1,..., NR
 r
F  n 
0 j  1,..., NSFIX
 j
F  n 
0 j  1,..., NCFIX
 j
Note that since these are the necessary, but not the sufficient, condi-
tins for Gibbs free energy minimization, a local minimum Gibbs
free energy can be obtained. Multiple solutions may be found when
multiple fluid phases coexist in the mixture. Providing different ini-
tial estimates for different runs can be used as a way to check
whether solution corresponding to a local minimum Gibbs free
energy has been reached.
Reactors 6-460
The new solution point in each calculation iteration is determined
by:
Equation(6-26):
N '  n    N  n
where:
n = the solution point from previous iteration
N' = the new solution point from equations (6-25)

 = step size parameter
The parameter is adjusted to ensure the new solution point, N' will
further minimize Gibbs free energy. A Fibonacci search procedure
is applied when  is close to zero. When a Fibonacci search is per-
formed, the thermophysical properties of the reactor mixture can be
either based on the same properties from the final result of the pre-
vious iteration or updated at each searching step of a new .
The convergence criterion is based on the relative or absolute
change of Gibbs free energy and the relative change of component
product rate between two consecutive iterations:
Equation(6-27):
G r  G r 1   if G r 1   2
or
Equation(6-28):
G r  G r 1
 if G r 1   2
G r 1
and
Equation(6-29):
r r 1
ncj  ncj r r 1
c r 1
 if ncj  ncj  0.01
n j
and

Equation(6-30):
n rjp  n rjp1
 if n rjp  n rjp1  0.01
n rjp1
The variable  is the convergence tolerance, which is defaulted to

1.0E-4 and can be specified by the user. The precision limit for a
component product flow rate in any phase is 0.01. For any change
in the product rate less than this value, the solution will be consid-
ered to be converged.
Phase Split
When a fluid phase condition of either vapor, liquid, vapor-liquid,
liquid-liquid, or vapor-liquid-liquid, is specified for the reactor, the
Gibbs free energy of fluid components is calculated based on the
specified fluid phases. On the other hand, if the fluid phase is
unknown or not specified for the reactor, phase split trials can be
performed to evaluate the number of fluid phases in the reactor. The
starting iteration number and the frequency of phase split trial can
be adjusted by the user. In each phase split trial, a new fluid phase is
added to the current fluid phases. If the Gibbs free energy is
reduced as a result of adding this new phase, the new fluid phase is
accepted.
The reactor modeling generally follows the algorithm described in
the papers of Gautam et al. (1979) and White et al. (1981). Addi-
tional information can be found in the book by Smith (1991).
Reference
1 Gautam, R., and Seider, W.D., 1979, Computation of Phase

and Chemical Equilibrium, Part I, AIChE J., 25, 991-999.
2 Gautam, R., and Seider, W.D., 1979, Computation of Phase
and Chemical Equilibrium, Part II, AIChE J., 25, 999-1006.
3 White, C.W., and Seider, W.D., 1981, Computation of
Phase and Chemical Equilibrium, Part IV, AIChE J., 27,
466-471.
4 Smith, W.R., and Missen, R.W., 1991, Chemical Reaction
Equilibrium Analysis: Theory and Algorithm, Krieger Pub-
lication Company, Malabar, Florida.
Also See:
Reactors 6-462
Gibbs Reactor

The Continuous flow Stirred Tank Reactor (CSTR) is a commonly
used model for many industrial reactors. The CSTR assumes that
the feed is instantaneously mixed as it enters the reactor vessel.
Heating and cooling duty may be supplied at user's discretion. A
schematic of a CSTR is given in Figure 6-2:
Figure 6-2: Continuous Stirred Tank Reactor

Design Principles
Multiple Steady States
Boiling Pot Model
CSTR Operation Modes
Also See:
Reactors

Design Principles
The steady-state conservation equations for an ideal CSTR with M
independent chemical reactions and N components (species) can be
derived as:
Mass balance:
Equation(6-1):
M
Fj  Fjf    ij i T , P, C1 , C2 ,..., CN  V
j 1
Energy balance:
Equation(6-2):
 N   N  M
  Fjf  H T f     Fjf  H T     H i   jV  Q  0

*
 j 1   j 1  i 1
where:
Cj = exit concentration of jth component
Fj = mole rate of component j in product
Fjf = mole rate of component j in feed
P = reactor pressure
ij = stoichiometric coefficient of jth species for ith reaction
V = volume of the reacting phase



j = rate of ith reaction
H(T) = molar enthalpy of product

H(Tf) = molar enthalpy of feed
Tf = feed temperature
T = reactor temperature
Hi = molar heat of reaction for the ith reaction
Q* = heat removed from the reactor

In PRO/II, only power law models for kinetics are provided. How-
ever, any kinetic model can be introduced through the user-added
Reactors 6-464
subroutines feature in PRO/II. For further details, refer to Chapter 7
of the PRO/II User-added Subroutines User's Manual. The result-
ing general expression for the rate of the ith reaction is:
Equation(6-3):
 E   N
i  Ai exp   i  T  C j j
 RT  j 1
where:
Ai = Arrhenius frequency factor
Ei = activation energy, energy/mol
R = gas constant
T = temperature
 = temperature exponent
Cj = concentration of jth species
N = total number of reacting components
j = exponents of concentration

i
= reaction rate for reaction i.
For multiple, simultaneous reactions, the overall reaction rate for
each reacting component is:
Equation(6-4):
M
 E   N
*j    ij Ai exp   i  T  C j j
i 1  RT  j 1
where:
*j = net rate of production of species j.
Solution of a CSTR involves the simultaneous solution of the mass
and energy balance equations (6-1) and (6-2).
Also See:

Multiple Steady States
Adiabatic, exothermic reactions in CSTR’s may have two valid
steady state solutions, as illustrated in (6-3).
Figure 6-3: Thermal Behavior of CSTR

The qr line represents heat removal and is linear with increase in
temperature. The qg curve represents heat generation. At low tem-
peratures, the curve increases exponentially with temperature due to
increased reaction rate. As the reactants are exhausted, the extent of
reaction levels off. Thus, there are three places where the two
curves intersect. The top and bottom intersections represent stable
solutions. The middle one represents the “ignition” temperature.
Reactors above that temperature tend to stabilize at the high reac-
tion rate and reactors below that temperature tend to stabilize at the
low reaction rate.
In the PRO/II CSTR unit operation, either solution is possible and
there is no built-in logic to ascertain that the correct solution is
found. The final solution can be influenced by the addition of an
initial estimate on the OPERATIONS statement. Generally, the
CSTR will find the high temperature solution if the initial estimate
is above the ignition temperature and the low temperature solution
for initial estimates below the ignition temperature.
For some exothermic reactions and for all endothermic reactions
there may be only one intersection between the heat generation and
heat removal curves, indicating only one steady state. PRO/II read-
ily finds this solution.
Reactors 6-466
Also See:
Boiling Pot Model

When the CSTR is operated as a boiling pot reactor, the reactions
take place in the liquid phase, and the vapor product, in equilibrium
with the reacting liquid, is drawn off.From a degree of freedom
analysis for the boiling pot reactor,
Variables:T, P, Q, F, Xj, Yj, V Total = 2N + 5
Equations:Material Balance, equation (6-1)
K j  yj / xj
x y j j 1
Total = 2N + 3
Reaction rate, equation (6-3)
Energy balance, equation (6-2)
The degrees of freedom or the number of variables to be fixed is 2.
The rest of the variables or unknowns are then calculated by solving
the model equations. Since the pressure P is fixed by the CSTR
input, the user can choose to fix one of the other variables T, Q, or
V. This leads us to the discussion on the possible operational modes
of the CSTR.
Also See:
CSTR Operation Modes

The possible operational modes for the CSTR are:
 adiabatic (fixed or zero heat duty).
 isothermal (fixed temperature)
In addition, for the boiling pot model, there is another optional
mode of operation,
 isometric (fixed volume of reacting liquid phase).
The reactor volume is required for the vapor and liquid models. The
pressure specification is fixed for all three models when input
explicitly as the operating pressure or pressure drop, or when calcu-
lated as the pressure of the combined feed to the reactor.

Also See:

The plug flow reactor is an idealized model of a tubular reactor.
Whereas the feed mixture to a CSTR reactor gets instantaneously
mixed, the fluid elements entering the plug flow reactor are
assumed to be unmixed in the direction of the flow. Since each ele-
ment of feed spends the same time in the reactor, the plug flow reac-
tor is also a convenient method of modeling a batch reactor (on a
spatial basis instead of on a time variable basis). A schematic dia-
gram of a plug flow reactor is shown in Figure 6-4.
Figure 6-4: Plug Flow Reactor
Design Principles
PFR Operation Modes
Available Methods
Also See:
Reactors
Design Principles
The steady state mass and energy balance for the one-dimensional
PFR for M simultaneous reactions can be derived as follows:
Reactors 6-468
Mass balance:
Equation(6-5):
d i
G  i 1 ,  2 ,...,  M , P, T 
dz

Energy balance:
Equation(6-6):
dT
G  J * 1 ,  2 ,... M , P, T   Q
dz
where:
G = mass flow per unit area through the reactor
 = extent of reaction per unit mass
i = rate or reaction for the ith reaction
* = total reaction rate of whole system

z = axial distance from the inlet of the reactor
T = temperature at a distance z from the inlet
Equation(6-7):
Q
Q

C P
where
Q* = heat transferred to or from the reactor per unit area

P = pressure
J = heat transfer ratio,
Equation(6-8):
 H R 
  
 CP 
where

C = mean heat capacity of the species in the reactor
P

HR = total heat of reaction
Equations (6-5) and (6-6) may be combined to eliminate the reac-

tion rate term to give:
Equation(6-9):
dT d Q
J 
dz dz G
or
Equation(6-10):
z Q
T  To  J    dz
0 G
where:
T  To ,   0 at z  0
are the initial conditions.

There are now various cases that may arise.
I Temperature programmed reactor.
(a) Isothermal. If T (z) = T, then equation (6-5) can be inte-
grated by standard numerical methods.
(b) If T (z) is specified, i.e., a profile for T is given, then equa-
tion (6-5) can be solved by numerical quadratures.
II Heat control programmed.
(a) Adiabatic. If Q(z) = 0 we have the constancy of (T - J), and
equation (6-5) can be written as a function of only.
(b) If Q(z) 0  z L, is specified (profile of heat transfer given),
equations (6-5) and (6-6) must be solved simultaneously.
III Heat control governed by a further equation.
In this case we have to consider the physical form of the cooling or
heating supplied. If Tc(z) is the coolant temperature at position z,
the heat transfer equation can be written as Q* = h* (Tc - T), which
leads to another series of sub-cases.
(a) Tc constant. In this case the differential equations for and T

can be integrated together. This could also be done if Tc were
specified as afunction of z.
Reactors 6-470
(b) Tc governed by a further differential equation. Here, the
issues to be considered are: the form of coolant flow (cocur-
rent or countercurrent) and whether the cold feed itself is to
be used as the coolant.
Also See:
PFR Operation Modes

PRO/II supports these modes of plug flow reactor operation:
 adiabatic, with or without heat addition/removal
 thermal, with the option of indicating temperature and pres-
sure profiles
 cocurrent flow
 countercurrent flow (the outlet temperature of the cooling
stream is required).
The thermal mode of operation is the default.
There are two methods of numerical integration available in PRO/
II. The Runge-Kutta method is the default method, and is preferred
in most cases. When sharply varying gradients are expected within
the reactor, the Gear method, which has a variable integration step
size, may be preferred.
For exothermic reactions, two valid solutions (the low conversion
and the high conversion) are possible. The plug flow reactor model
in PRO/II is not equipped to find the hot spot or ignition tempera-
ture. The user can manipulate the exit cooling temperature for coun-
tercurrent reactors or stream product temperature for auto thermal
reactors to get either the low conversion or the high conversion
solution.
Reference
Smith, J.M., 1970, 2nd Ed., Chemical Engineering Kinetics,
McGraw-Hill, NY.
Also See:

Available Methods
A. Packed bed model of plug flow reactor
The pressure drop through packed beds will be calculated using the
ERGUN equation. User supplied data includes the particle size,
shape factor (alternately supplied by designating the packing as
spherical or cylindrical) and void fraction. These parameters will be
made available to the Procedure section.
B. Theoretical background for the Ergun equation.

Implementing the ERGUN equation in the Plug Flow reactor for the
calculation of pressure drop of a single-phase fluid flowing through
the packed catalyst bed. The Ergun equation has the form:
Equation(6-11):
DP  G  1     
   3  150 1     1.75G 
DL   g c D p      Dp 
where:
P = pressure, lb/ft2
 = Porosity = volume of void / total bed volume
1   = volume of solid / total bed volume

gc = 32.174 lbm.ft/s2.lbf (conversion factor)
DP = diameter of particle in the bed, ft
m = Viscosity of fluid passing through the bed, lbm/ft.h

L = length down the reactor, ft
u = superficial velocity, ft/h
r = Fluid density, lb/ft3
G = ru = superficial mass velocity, lbm./ft3
For packed pipe, the fluid must be either all liquid or all vapor. For
liquid, the density can be considered incompressible over the length
of a finite segment.This means equation (6-5) can be used directly.
For all vapor, the density varies owing to changes in pressure, tem-
perature and reaction. Assuming that the compressibility factor
Reactors 6-472
change is negligible over the length of a finite segment we can
develop the following:
As the reactor is operated at steady state the mass flow rate at any
point down the reactor, m(kg/s) is equal to the entering mass flow
rate, m0 (equation of continuity).
m0 = m
r0v0 =  v
Since volume of the fluid is changing with temperature and pres-
sure, we have
Equation(6-12):
v  vo 1   AXA  Po P T To 
(Here volume change is given for single reaction)

Equation(6-13):
vo  To   1   P
  o   o    
v  T   1   A   Po
From equation (6-5) and (6-7) we have:
Equation(6-14):
dP  G  1      PT
   3  150 1     1.75G  o 1   A X
dL   o g c DP      Dp  To P
Where,
 A = Fractional change in volume of the system between no

conversion to Complete conversion.
xA = Fractional conversion of A
Equation (6-14) can be used to calculate pressure along the length

of the reactor using the Runge-Kutta, Gear or LSoda integration
methods.
C. User specified pressure drop in packed pipe

The existing pressure drop entries currently in place for the open
pipe will be implemented for packed pipe. This includes specifica-
tion of pressure drop, the outlet pressure and a defined pressure pro-
file.

D. Open pipe pressure drops
The pressure drop for each integration interval will be calculated
via the currently exiting pipe unit operation. The minimum pressure
drop method required is Beggs-Brill-Moody (BBM). However, it's
likely that providing all of the pressure drop models will be simple
to implement once BBM is supplied. This includes access to the
UAS pressure drop calculations.
Also See:
Reactors 6-474
Chapter 7:Solids Handling Unit Oper-
ations
The equations used by the following types of solids handling equip-
ment are discussed in this chapter.
Dryer Rotary Drum Filter

Filtering Centrifuge Countercurrent Decanter
Dissolver Crystallizer
Melter/Freezer
Dryer
Rotary Drum Filter
Filtering Centrifuge
Countercurrent Decanter
Dissolver
Crystallizer
Melter/Freezer
Dryer
General Information
Calculation Methods
General Information
PRO/II has the capability of simulating a simple continuous solids
dryer in which the drying gas and solid streams flow counter-cur-
rent to each other. The liquid (typically water) content of the solid
stream is reduced by contact with the hot gas stream. The dryer unit
is simulated in much the same way as the flash drum unit is. If the
stream composition and rate are fixed, then there are 2 degrees of
freedom that may be fixed. Any one of the following combination
of specifications may be used when defining the dryer unit opera-
tion:
DRYER
SPECIFICATION 1 SPECIFICATION 2
OPERATION

ISOTHERMAL TEMPERATURE PRESSURE
ISOTHERMAL TEMPERATURE DP
ADIABATIC TEMPERATURE FIXED DUTY
PRESSURE FIXED DUTY
DESIGN TEMPERATURE GENERAL DESIGN
Specification
DESIGN PRESSURE GENERAL DESIGN
Specification
DESIGN DP GENERAL DESIGN
Specification
A design specification may be the amount of feed vaporized, or the

moisture content of the solids product, or a rate or fraction (or PPM)
specification on either product stream.
Calculation Methods
The design specification is used along with mass balance equations
to calculate the operating dryer temperature or pressure (the other is
specified). A two-phase (VL) flash is performed to determine the
vapor and liquid phase distributions. The details of the calculation
flash algorithm may be found in Chapter 1, Flash Calculations.
Also See:
Dryer
Rotary Drum Filter

General Information
Calculation Methods
General Information
In solid-liquid separations, horizontal rotary drum filters are often
used to decrease the liquid content of a stream containing solids.
For a given filter diameter and width (rating calculations), PRO/II
will compute the pressure drop, cake thickness, average cake satu-
ration, as well as determine the rates of the solid cake and filtrate
product streams. For design calculations, PRO/II will determine the
drum diameter and width required for a given pressure drop.
Solids Handling Unit Operations 7-476

Calculation Methods
As a solid-liquid mixture is filtered, a layer of solid material, known
as the filter cake, builds up on the filter surface. Vacuum filtration is
used to drain liquid through the filter cake. An important character-
istic of the filter cake is its permeability. The permeability is
defined as the proportionality constant in the flow equation for lam-
inar flow due to gravity through the bed. The permeability is a func-
tion of the characteristics of the cake, such as the sphericity and size
of the cake particles and the average porosity of the cake, and is
given by:
Equation(7-1):
K  g c d p2  A B 
where:
K = permeability of filter cake
gc = acceleration due to gravity
dp = diameter of cake particle
 = average porosity of filter cake

A,B are constants
The values of the constants A and B in equation (7-1) are functions
of the ratio of particle sphericity to the cake porosity.
a


A and B assume different values in different sphericity ranges:
For  > 1.5,
Equation(7-2):
A  exp  2.49160  0.2099 

B  exp 1.74456  0.2085 
For < 1.5,

Equation(7-3):
 0.4942 
A  exp 1.8780 
  
 0.5144 
B  exp 1.1069 
  
The pressure drop across the filter cake is then given by:
Equation(7-4):
2 L L Skc
Pc 
 D 2W 2 Atot2
where:
L = liquid volumetric flow rate through the cake
L = liquid viscosity
S = rate of dry solids in the feed

kc = cake resistance
 = angle of filtration
D = diameter of filter drum
W = width of filter drum
 = drum rotational speed in rad/s =2(RPM)/60
RPM = rotational speed of drum in revolutions/min
Atot = total filter area =2DW
The actual pressure drop across the drum filter is then given by:
Equation(7-5):
 
1/ 1 C f 
Pact  Pc 
where:
Cf = filter cake compressibility factor
The value of the filter cake compressibility factor can vary from 0
for an incompressible cake to 1.0 for a highly compressible cake.
Industrially, the value of Cf is typically 0.1 to 0.8.

The filter bed thickness is given by:
Equation(7-6):
S
t
 D W  s 1   
2
The filter bed will never become completely dry, but will always
contain a certain amount of liquid which cannot be removed by fil-
tration. This liquid remains in the spaces between particles, and is
held in place by the surface tension of the liquid. This residual cake
saturation is a function of a dimensionless group known as the cap-
illary number, Nc. The capillary number is given by:
Equation(7-7):
 P 
K   L  act 
t 
Nc  

where:
L = liquid density
The residual cake saturation, s0 is calculated based on the value of

the capillary number:
For 0.002 < Nc < 0.03,
Equation(7-8):
s0  101.80.299log Nc
For Nc > 0.03,

Equation(7-9):
s0  102.7590.957 log Nc
For Nc < 0.002,

Equation(7-10):
The average level of saturation in the cake is a function of the filter

pressure drop as well as cake characteristics such as the cake drain
number, drain height, and thickness. The cake drain number and
height are calculated from the cake permeability, and the liquid den-
sity and surface tension:

Equation(7-11):
L
Nc  K

0.275
hD 
ND
The average cake saturation is given by:

Equation(7-12):
 2.993  0.036 z 2 y  0.055 z 2  0.274 z 

sav  exp  
2
 0.756 zy  0.099 zy  0.500 y  0.172 y 
2
where:
t
z
hD
 Pact  
2
1/3 
y  ln  0.453K 1   
  t L  

For design calculations, an iterative method solution method is

used, in combination with the equations given above, to calculate
the filter diameter and width required to produce a specified pres-
sure drop.
Reference
1 Treybal, R. E., 1980, Mass-Transfer Operations, 3rd Ed.,
McGraw-Hill, N.Y.
2 Dahlstrom, D.H., and Silverblatt, C.E., 1977, Solid/Liquid
Separation Equipment Scale Up, Uplands Press.
3 Brownell, L.E., and Katz, D.I., 1947, Chem. Eng. Prog.,
43(11), 601.
4 Dombrowski, H.S., and Brownell, L.E., 1954, Ind. Eng.
Chem., 46(6), 1207.
5 Silverblatt, C.E., Risbud, H., and Tiller, F.M., 1974, Chem.
Eng., 127, Apr. 27.
Also See:
Rotary Drum Filter
Solids Handling Unit Operations

General Information
Calculation Methods
General Information
An alternate solid-liquid separating unit to the rotary drum filter is
the filtering centrifuge. In this type of unit, the solid-liquid mixture
is fed to a rotating perforated basket lined with a cloth or mesh
insert. Liquid is forced through the basket by centrifugal force,
while the solids are retained in the basket. PRO/II contains five
types of filtering centrifuges as indicated in Table 7-39.
Table 7-39: Types of Filtering Centrifuges

Available in PRO/II
Type Description
WIDE Wide angle. Half angle of basket cone > angle of
repose of solids.
DIFF Differential scroll. Movement of solids from filter
basket controlled by a screw.
AXIAL Axial vibration. High frequency force applied to the
axis of rotation.
TORSION Torsional vibration. High frequency force applied
around the drive shaft.
OSCIL Oscillating. A low frequency force is applied to a
pivot supporting the drive shaft.
Calculation Methods
For rating applications, the basket diameter, rotational speed in rev-
olutions per minute, and centrifuge type are specified. The centrifu-
gal force is then computed using:
Equation(7-13):
r 2
g cent 
gc
where:
gcent = centrifugal force
r = radius of centrifuge basket

 = rotational speed, rad/s =2(RPM)/60

RPM = rotational speed of basket in revolutions/min
If Centrifuge type is not given and RPM value is not supplied then
the RPM is calculated based on expression 8-14 and a centrifugal
force of 1200 kg-m/sec2 .
The amount of solids remaining the basket is computed from:
Equation(7-14):
M s    r 2  rcake
2
 hs 1   
where:
Ms = mass of solids remaining in the basket
rcake = radius of inner surface of filter cake
h = height of basket
s = solid density
 = average filter cake porosity

The thickness of the filter cake is given by:
Equation(7-15):
tcake  r  rcake
The surface area of the filter basket, and the log-mean and arithme-
tic mean area of the filter cake are given by:
Equation(7-16):
2 htcake
Acake ,lm 
ln  r / rcake 
Acake ,mean    r  rcake  h
Afilter  2 rh
where:
Acake,lm = log-mean surface area of filter cake
Acake,mean = arithmetic mean surface area of filter cake
Afilter = surface area of filter basket

The drainage of liquid through the filter cake of granular solids in a
filtering centrifuge is a result of two forces; the gravitational force,
and the centrifugal force in the basket, and is given by:
Equation(7-17):
K  d p2 
A B 
where:
K = permeability of filter cake
dp = diameter of cake particle
A,B are constants. The values of the constants A and B in equation


(7-17) are a function of  = --- , the ratio of the cake sphericity to

the cake porosity.
A and B are given by:

For  > 1.5,
Equation(7-18):
A  exp  2.49160  0.2099 

B  exp 1.74456  0.2085 
For  < 1.5,

Equation(7-19):
 0.4942 
A  exp 1.8780 
  
 0.5144 
B  exp 1.1069 
  

The residual cake saturation, a result of small amounts of liquid
held between the cake particles by surface tension forces, is a func-
tion of a dimensionless group known as the capillary number, Nc.
The capillary number is given by:

Equation(7-20):
K  L g cent
Nc 
g c
where:
L = liquid density
= liquid surface tension

The residual cake saturation, s0 is then calculated based on the
value of the capillary number:
For 0.002 < Nc < 0.03,
Equation(7-21):
s0  101.80.299log Nc

For Nc > 0.03,
Equation(7-22):
s0  102.7590.957 log Nc
For Nc < 0.002,

Equation(7-23):
s0  0.072
The cake drain number and height are calculated from the cake per-
meability, centrifugal force, and the liquid density and surface ten-
sion:
Equation(7-24):
K  L g cent
ND 
gc 
0.275
hd 
ND
The average cake saturation is then given by:

Equation(7-25):
t h  h
sav  s0  cake D   D
 tcake  tcake
where:
sav = average filter cake saturation
The corresponding moisture content of the filter cake, Xcake, is cal-

culated using:
Equation(7-26):
   L
X cake  sav 
1     s
Finally, the actual rate of filtrate through the basket is given by:
Equation(7-27):
 F feed  W liq –  F feed  W sol + F inert X cake 

F filtr = ----------------------------------------------------------------------------------------------------------
-
PL
where:
Ffiltr = rate of filtrate
Ffeed = total mass rate of feed to centrifuge
Wliq= weight fraction of liquid in feed
Wsol = weight fraction of solid in feed
Winert = total mass rate of inert components in feed
The maximum filterate flowrate is given by :

Equation(7-28):
Acake ,lm K
 L 2  r 2  rL2   m
Acake,mean Afilter
Fmax 
2 L K c M s
where:
FMax = maximum filterate flowrate

= angular velocity
Kc= cake resistance
Km= filterate medium resistance
Note: The maximum flowrate is compared with the actual flowrate

in each design iteartion.
For design calculations, an iterative method solution method is

used, in combination with the equations given above, to calculate
the filter diameter required to produce a specified filtrate flow.
Reference
1 Treybal, R. E., 1980, Mass-Transfer Operations, 3rd Ed.,
McGraw-Hill, N.Y.
2 Grace, H.P., 1953, Chem. Eng. Prog., 49(8), 427.
3 Dombrowski, H.S., and Brownell, L.E., 1954, Ind. Eng.
Chem., 46(6), 1207.
Also See:
General Information
Calculation Methods
Calculation Scheme
General Information
Mixtures of solids and liquids may be separated by counter-current
decantation (CCD). This unit operation consists of several settling

tanks in series. A typical stage of the counter-current decantation
system is shown in Figure 7-1.
Figure 7-1: Countercurrent Decanter Stage

If the purpose of the CCD unit is to obtain a thickened underflow,
then the tank is referred to as a thickener. The solid-liquid mixture
flows in a counter current path to a dilute liquid wash stream. In
each tank, the solids from the slurry feed settle under gravity to the
bottom of the tank. The clarified overflow is transferred to the pre-
vious tank for use as the wash liquid, while the underflow from the
tank is transferred to the next tank in the series. The feed to the first
tank in the series therefore consists of the slurry feed and the over-
flow from the second tank, while the feed to the last tank consists of
the liquid wash (typically water), and the underflow slurry from the
second to last tank. If the purpose of the CCD unit is to obtain a
clear overflow, then the tank is referred to as a clarifier.
Calculation Methods
The equations describing the model are as developed below.
Total Mass Balance:

Equation(7-29):
U N  TS / PS

Equation(7-30):
ON  U N 1  ON 1  U N
where:
U = decanter underflow rate from a stage
PS = solid fraction in underflow
TS = total solids flow through CCD
O = total overflow rate from a stage
Subscripts N, N-1, N+1 refer to stage N, and the stages below
and above stage N.
Component Balance:
Equation(7-31):
xiU, NU N 1  xiO, N 1ON 1  U N xiU, N  ON xiO, N
where:
xU = composition of underflow from a stage
xO = composition of overflow from a stage

The mixing efficiency for each stage, EN, is given by:
Equation(7-32):
xiU, N 1
EN 
xiO, N
Mixing efficiency generally is a function of temperature and com-

position. However, in PRO/II, it is assumed that the mixing effi-
ciency is constant for each stage. This assumption, along with the
fixing of the ratio of the overflow solids concentration to the under-
flow solids concentration, de-couples the solution of equations (7-
29) through (7-32), and enables the equations to be solved simulta-
neously.
Equations (7-29) through (7-32) may be re-written as:
Equation(7-33):
b1 xiU,1  1 xiU,2  Fi ,1 for stage1

Equation(7-34):
 N xiU, N 1   N xiU, N   N xiU, N 1  Fi , N for stages 2 to N-1

Equation(7-35):
 N xiU, N 1   N xiU, N  Fi , N for stage N
where:
Equation(7-36):
U1  O1 R1 
 R2  1 O2U1
Y1
1 
D1
Equation(7-37):
O2 R2
1 
D1
Equation(7-38):
F1C fi ,1C
Fi ,1 
D1
Equation(7-39):
D1  O1  R1  1
Equation(7-40):
 N  1
Equation(7-41):
 R N + 1 – 1 O N + 1 U N
U N + O N R N – ------------------------------------------------- -
yN
N = -------------------------------------------------------------------------------------
DN
Equation(7-42):
yN  U N
Equation(7-43):
ON 1 RN 1
N 
DN

Equation(7-44):
FNC fi ,CN
Fi , N 
DN
Equation(7-45):
DN  U N 1   RN  1 ON
Equation(7-46):
1
RN 
EN
The underflow and overflow stream temperatures from each stage
are the same and are assumed equal to the stage temperature, i.e.,
the stage is in thermal equilibrium.
Also See:
Calculation Scheme
For the rating calculations, the total mass balances are solved easily
once the total solids and percent solids underflow at each stage are
specified. The calculation procedure is given below.
First the underflow rates are calculated from equation (7-29). The
wash water rate to the last stage is known, and the last stage over-
flow rate is then calculated using:
Equation(7-47):
ON  F2  U N 1  U N
The remaining overflow rates are then calculated from the last stage
backwards to the first stage using equation (7-30).
Once UN and ON are calculated for all stages, the component bal-
ance equations are then solved using the Thomas algorithm, a ver-
sion of the Gaussian elimination procedure. This method of solving
the tri-diagonal equations (7-33) through (7-34) avoids matrix
inversion, buildup of truncation errors, and avoids negative values
of xi, N being produced. The tri-diagonal equations can be reduced
to:

Equation(7-48):
1 p1 0 0 . . . 0   xi ,1   qi ,1 
0    
 1 p2 0 . . . 0   xi ,2   qi ,2 
. . . . . . . .  .   . 
    
. . . . . . . .  .   . 

. . . . . . . .  .   . 
    
. . . . . . . .  .   . 
0 0 0 0 . . . pN 1   xi , N 1   qi , N 1 
    
 0 0 0 0 . . . 1   xi , N   qi , N 
where:
Equation(7-49):
1
p1 
1
Equation(7-50):
Fi ,1
qi ,1 
1
Equation(7-51):
N
pN 
 N   N pN 1
Equation(7-52):
Fi , N   N qN 1
qi , N 
 N   N pN 1
The solution of this matrix results in the immediate solution of the
last stage composition xi, N, using the last row of the matrix, i.e.,
Equation(7-53):
xi , N  qi , N
The compositions on other stages are then obtained by backward

substitution:
Equation(7-54):
xi , N 1  qi , N 1  pN 1 xi , N

For the design mode calculations, the number of stages is not given,
but a recovery specification is made on either the overhead or
underflow product. In this case, PRO/II will begin the calculations
described above by assuming a minimum number of stages present.
If the design specification is not met, the number of stages will be
increased, and the design equations re-solved until the specification
is met.
Reference
1 Scandrett, H.E., “Equations for Calculating Recovery of
Soluble Values in a Countercurrent Decantation Washing
System”, 1962, Extractive Metallurgy of Aluminum, 1, 83.
Also See:
Dissolver
General Information
Particle Size Distribution
Material and Heat Balances
Solution Procedure
General Information
Dissolution of solids into liquid solutions is a mass transfer opera-
tion which is widely used in the chemical industry in both organic
as well as inorganic processes. A unit operation that utilizes mass
transfer controlled dissolution is the stirred tank dissolver. The con-
tents of the stirred tank dissolver are well-mixed using an agitator,
and when it is operated in a continuous manner, the unit can be
called a continuous stirred tank dissolver or CSTD. The PRO/II dis-
solver is of the CSTD type.

Figure 7-2: Continuous Stirred Tank Dissolver
Development of the Dissolver Model

The dissolution of a solute from the solid particle into the surround-
ing liquid can be modeled as the rate of decrease in volume of the
solid particle:
Equation(7-55):
 
 p  V p t  V p t t   Ap k L   L S  C   t
where:
p = density of solid particle, kg/m3
Vp = volume of particle, m3
Ap = surface area of particle, m2
kL = liquid phase mass transfer coefficient, kg/m2-sec
L = liquid density, kg/m3

S = solubility, kg solute/kg liquid
C = liquid phase concentration of solute, kg/m3

t = time, sec
As t 0, equation (7-55) becomes:
Equation(7-56):
dV p
p  Ap k L   L S  C 
dt
Equation(7-57):
4
V p   r 3 , Ap  4 r 2
3
where:
r = radius of solid particle, m and
Equation(7-58):
dr
p  kL   L S  C 
dt
Equation (7-58) describes the mass transfer rate per unit area as
dependent on two factors; the mass transfer coefficient and concen-
tration difference. The mass transfer coefficient is the liquid phase
coefficient, since diffusion of the solute from the particle surface
through the liquid film to the bulk of the liquid solution is the dom-
inant or rate-controlling step. The concentration difference is the
difference between the equilibrium concentration at the solid-liquid
interface and the solute concentration in the dissolver liquid.
Integrating equation (7-58) for constant kL,
Equation(7-59):
kL
r   pL S  C  
p
represents the change in particle size due to the dissolution process.

The following simplifying assumptions are used in the development
of the dissolver model:
 The solid particles are spherical in shape.
 There is no settling, breakage, or agglomeration of solid parti-
cles.
 The liquid in the dissolver follows a continuous stirred tank
type flow, whereas the solid particles are in plug flow. As a

result, the temperature and liquid phase concentration in the
dissolver are uniform, and all the solid particles have the same
residence time.
 The dissolution of a single solid component only is modeled,
and the presence of “inert” components has no effect on the dis-
solution process.
Also See:
Dissolver
Mass Transfer Coefficient Correlations

The liquid phase mass transfer coefficient kL is a function of vari-
ous quantities such as diffusivity of solute in liquid solution, impel-
ler power and diameter, and physical properties of the solid
component and liquid. For large particles, the coefficient has been
found to be independent of particle size, whereas for smaller parti-
cles, the coefficient increases with decreasing particle size.The fol-
lowing correlation has been proposed by Treybal for liquid phase
mass transfer in solid-liquid slurries:
For dp < 2 mm,

Equation(7-60):
0.17
 di 
ShL  2  0.47 Re 0.62
p   ScL0.36
 dt 
For dp > 2 mm,

Equation(7-61):
ShL  0.222 Re3/4 1/3

p ScL
where:
dp = solid particle diameter, m
ShL = liquid phase Sherwood number, dimensionless
Rep = particle Reynolds number, dimensionless
di = impeller diameter, m
dt = dissolver tank diameter, m
ScL = liquid phase Schmidt number, m

This is the default correlation used in the dissolver model for calcu-
lating the mass transfer coefficient.
If detailed mass transfer data are available, the following correla-
tion can be selected by specifying the parameters a, b, and dcut:
For dp < dcut,

Equation(7-62):
a b
kL   0.1733
dp dp
where:
a, b are mass transfer coefficient parameters
dcut = solid particle cut-off diameter, m
When the mass transfer coefficient is a function of particle size,

equation (7-58) can be integrated as:
Equation(7-63):
r2 dr
    L S  C  /  p
r1 kL
using numerical quadrature.
Note: Both r (radius) and dp (diameter) are used for particle size
here, but inter-conversion between r and dp is done in the program.
Also See:
Dissolver
Particle Size Distribution

For a solid represented by a discrete particle size distribution, r1f,
r2f, .....rif and m1f, m2f, ..... mif are the particle sizes and mass flow
rates of the feed solids, and r1p, r2p, ..... rip is the particle size dis-
tribution of the solids in the product. For the case of constant kL,
from equation (7-59)
Equation(7-64):
kL
rip  rif    L S  C 
p

and the rate of dissolution is:
Equation(7-65):
 r 
3

   1   ip   mif
i 
r 
  if  
   
3
 kL
  1  1 
 r
  L S  C       mif
i 
   p if  

Material and heat balances around the dissolver as well as vapor-
liquid equilibrium have to be satisfied. The equilibrium solid solu-
bility, S, is also determined. These equations, many of them in sim-
plified form, are given below:
Overall
Equation(7-66):
F EB
where:
F = mass rate of feed, kg/sec
E = mass rate of overhead product, kg/sec
B = mass rate of bottoms product, kg/sec
Component
solute,
Equation(7-67):
Fsolute  Esolute  Bsolute
solvent,
Equation(7-68):
Fsolvent  Esolvent  Bsolvent
inerts,

Equation(7-69):
Fi  Ei  Bi , i  1, 2,..., N
where:
solute refers to the solute component
solvent refers to the solvent component
i refers to the inert component
Solid-liquid Solute Balance

Equation(7-70):
Fsolute  Fsolute
Liq
 PF
Equation(7-71):
Bsolute  Bsolute
Liq
P
where:
Liq
Fsolute = mass rate of solute component in feed liquid, kg/sec
PF = mass rate of solid in feed, kg/sec
Liq
Bsolute = mass rate of solute component in bottoms product liquid,
kg/sec
P = mass rate of solid in bottoms product, kg/sec
Solute Vapor Balance

Equation(7-72):
 E 
Esolute  Ysolute   MWsolute
 MWvapor
 
where:
MWsolute = molecular weight of solute component kg/kgmol
MWvapor = molecular weight of overhead product, kg/kgmol
E = mass rate of overhead product, kg/sec

Y = mole fraction in overhead product

Heat Balance Equation
Equation(7-73):
Heat Duty = Product Enthalpy - Feed Enthalpy
Phase Equilibria
Solid-liquid Phase Equilibrium
Equation(7-74):
X solute  f1  temperature 
Vapor-liquid Phase Equilibrium

Equation(7-75):
Yi  f 2  X i 
Residence Time
Equation(7-76):
 V /Q
where:
 = residence time in the dissolver, sec
V = operating volume of the dissolver, m3

Q = volumetric rate of bottoms product, m3/sec
Concentration
Equation(7-77):
C  Cf   / Q
Solution Procedure
The solution procedure or algorithm using the above equations per-
forms sequential calculations of the solid-liquid problem through
mass transfer kinetics and vapor-liquid equilibrium calculations
along with heat and material balances. This iteration loop is
repeated until product stream compositions do not change and con-
vergence is obtained.

Reference
1 Parikh, R., Yadav, T., and Pang, K.H., 1991, Computer
Simulation and Design of a Stirred Tank Dissolver, Pro-
ceedings of the European Symposium on Computer Appli-
cations in Chemical Engineering, Elsevier.
2 Treybal, R.E., 1980, Mass Transfer Operations, 3rd Ed.,
McGraw Hill, N.Y.
Also See:
Dissolver
Crystallizer
General Information
Crystallization Kinetics and Population Balance Equations
Solution Procedure
General Information
The crystallizer is used for separation through the transfer of the
solute component from a liquid solution to the solid phase. The
crystallization process depends on both phase equilibria as well as
kinetic or non-equilibrium considerations.Solid-liquid equilibrium
is defined in terms of solubility, which is the equilibrium composi-
tion of the solute in a liquid solution containing the solvent compo-
nent. Solubility is a function of temperature, and is calculated from
either the van't Hoff equation or user-supplied solubility data. The
solubility is rigorously calculated if electrolyte thermodynamic
methods are used. Crystallization can occur only in a supersaturated
liquid solution. A supersaturated liquid is one in which the solute
concentration exceeds the equilibrium solubility at the crystallizer
temperature. Supersaturation is generally created by cooling the liq-
uid and/or evaporation of the solvent. Additionally, for crystalliza-
tion systems where evaporation of solvent occurs, the vapor phase
and liquid solution satisfy vapor-liquid equilibrium.
The quantity of crystals formed depends on the residence time in
the crystallizer and is determined by the kinetics of the crystalliza-
tion process. Crystals are generated from supersaturated solutions
by formation of nuclei and by their growth. The primary driving

force for both nucleation and crystal growth is the degree of super-
saturation. In addition, nucleation is also influenced by mechanical
disturbances such as agitation, and the concentrations and growth of
solids in the slurry. These rate relationships are normally expressed
as power law expressions, which are similar to equations for power
law kinetics used for chemical reactions. The constants in the two
rate equations are the nucleation rate constant and growth rate con-
stant.
The heat effect associated with the crystallization process is
obtained from the input value of the heat of fusion of the solute
component. This, along with the enthalpies of the feed and product
streams, will determine the heating/cooling duty required for the
crystallizer. This duty is generally provided by an external heat
exchanger across which a T is maintained. The feed consisting of
the fresh feed and recycled product slurry is circulated through the
heat exchanger to the crystallizer. If the external heat exchanger
option is not turned on in the input file, the duty is assumed to be
provided by an internal heater/cooler.
Figure 7-3: Crystallizer

All crystallizers have some degree of mixing supplied by an agitator
and/or pumparound. The limiting case is ideal mixing, where condi-
tions in the crystallizer are uniform throughout, and the effluent
conditions are the same as those of the crystallizer contents. Such a
unit is commonly known by the name of Mixed Suspension Mixed
Product Removal (MSMPR) crystallizer or Continuous Stirred
Tank Crystallizer (CSTC). A further assumption made in the devel-
opment of the crystallizer model is that breakage or agglomeration
of solid particles is negligible.

Crystallization Kinetics and Population Balance Equations
Growth Rate:
Equation(7-78):
G  kG S GEXP
where
G = growth rate of crystals, m/sec
kG = growth rate constant, m/sec
eq
X solute – X solute
S = supersaturation ratio= ------------------------------------------
eq
X solute
Xsolute = Actual mole fraction of solute in liquid
Xeqsolute = Equilibrium mole fraction of solute in liquid at the

crystallizer temperature.
GEXP = Exponential factor for growth rate applied to super-
saturation ratio.
Nucleation Rate:
Equation(7-79):
Bo   k B M TBEXP1  S BEXP 2  G BEXP 3  RPM BEXP 4 
where:
Bo = crystal nucleation rate, number/sec.m3
kB = nucleation rate constant
MT = magma density, i.e., concentration of crystals in slurry,

kg crystals/m3 slurry
RPM = impeller speed, revolutions/min
BEXP1, BEXP2, BEXP3, BEXP4 = exponents

Nuclei Number Density:
Equation(7-80):
Bo
no  
G
where:
no = nuclei number density, number/m/m3 slurry
 = liquid volume fraction in slurry, m3 liquid/m3 slurry

Population Balance Equations:
For discrete particle size distribution for crystals, number density
n(r) can be expressed as a histogram with m divisions and rk as the
average particle size of the kth division. A typical example is shown
in Figure 7-4.
Making a balance on the number density of the crystals in the crys-
tallizer,
Equation(7-81):
dn
q f n f  qn  GV
dr
where:
q = volumetric rate of bottoms product slurry, m3/sec
qf = volumetric rate of feed, m3/sec
V = operating volume of crystallizer, m3
r = characteristic length of crystal, m

V
Residence time is defined as:  = ---
q
Figure 7-4: Crystal Particle Size Distribution
By rearranging equation (7-81), multiplying by the integrating fac-

r / G
tor e , and integrating, we get:
Equation(7-82):
 Gr  q f 1 r
   q G  f dr
d  e n   n e G
For the kth division,

Equation(7-83):
rk 1  rk
qf  rk 1  rk

n  rk   n  rk 1  e G
 n fk  1  e G 
q  
Using the initial condition: n(ro) = no at ro = 0,

Equation(7-84):
 r1
qf   r1

k  1, n(r1 )  no e G
 n f ,1 1  e G 
q  
Equation(7-85):
r1  r2
qf  r1  r2

k  2, n(r2 )  no e G
 n f ,2 1  e G 
q  
  r1 q f   r1
  r1  r2 q f  r1  r2

  no e G  n f ,1 1  e G   e G  n f ,2 1  e G 
 q    q  
r2
qf   r1Gr2 r2
  r1  r2

 no e G
  n f ,1  e  e   n f ,2  1  e G  
G
q      
For any k, the generalized expression is:
Equation(7-86):
 rk
qf k r1Grk rt 1  rk

n(rk )  no e G
  n f ,1  e  e G 
q t 1  
For feed containing no solids, equation (7-86) simplifies to:
Equation(7-87):
 rk
n(rk )  no e G
The magma density, MT (the weight concentration of crystals in

slurry) is calculated from the third moment of the particle size dis-
tribution,
Equation(7-88):

M T   c kv  r 3 ndr
0
where:
c = density of crystals, kg crystal/m3 crystal
kv = crystal shape factor = 1 for cubic crystals, /6 for spheri-

cal crystals
For the case of no solids in feed, the magma density is:

Equation(7-89):
M T  6  c kv no  G 
4
Also See:
Crystallizer

These equations are given in simplified form below:
Overall
Equation(7-90):
F EB
where:
F = feed rate, kg/sec
E = overhead product rate, kg/sec
B = bottom product rate, kg/sec
Component
Equation(7-91):
F solute = E solute + B solute

Equation(7-92):
F solvent = E solvent + B solvent

Equation(7-93):
F i = E i + B i i = 1 2  N
where: subscripts solute, solvent, and i refer to the solute, sol-
vent and inert components, respectively.
Solid-liquid Solute Balance

Equation(7-94):
Fsolute  Fsolute
Liq
 PFc
Equation(7-95):
Bsolute  Bsolute
Liq
 Pc

where:
Liq
F solute = component rate of solute in feed liquid, kg/sec
c
P F = component rate of solute in crystallizer feed, kg/sec
Liq
B solute = solute component rate in bottoms liquid, kg/sec
c
P = solute component crystal rate in bottoms product, kg/sec
Solute Vapor Balance

Equation(7-96):
 E 
Esolute  Ysolute   MWsolute
 MWvapor
 
where:
Ysolute = vapor phase mole fraction of solute
MWvapor = molecular weight of overhead product, kg/kgmol
MWsolute = molecular weight of solute, kg/kgmol
Heat Balance Equation

Equation(7-97):
Heat Duty = Product Enthalpy - Feed Enthalpy
Phase Equilibria
Solid-liquid Phase Equilibrium
Equation(7-98):
X solute  f1  temperature 
where:
eq
X solute = equilibrium mole fraction of solute in crystallizer liquid
at crystallizer temperature.
Vapor-liquid Phase Equilibrium

Equation(7-99):
Yi  f 2  X i 

where:
Yi = vapor phase mole fraction of component i
Xi = liquid phase mole fraction of component i
Solution Procedure
The solution procedure for the crystallizer model uses the above
equations to perform solid-liquid calculations through crystalliza-
tion kinetics in a supersaturated liquid solution, and VLE calcula-

tions, along with material balances. The algorithm used is shown in
Figure 7-5.
Figure 7-5: MSMPR Crystallizer Algorithm
Reference
1 Treybal, R.E., 1980, Mass Transfer Operations, 3rd Ed.,
McGraw Hill, N.Y.

Melter/Freezer
General Information
Calculation Methods
General Information
Solid melting and freezing units are important operations in many
industries, including food, glass, and edible oil manufacture. Solid
components in a mixture may be melted and transformed into a liq-
uid component, and liquid components may be frozen and trans-
formed into solids in the PRO/II melter/ freezer unit operation.
Calculation Methods
The operating temperature and pressure of the melter/freezer is
specified by the user. The unit may operate in one of two modes:
 The temperature is specified and PRO/II determines which
components are to undergo phase transformation based on the
normal melting temperature of each component
 The component and fraction to be frozen or melted is specified.
This is the only criteria used for determining which compo-
nents undergo phase transformation. The melting temperature
is ignored for the calculations, and components not specifically
given by the user do not undergo a solid-liquid phase change.
The resulting product streams are then flashed isothermally at the
given temperature and pressure conditions to determine their ther-
modynamic properties. Only the distribution between vapor and liq-
uid (and/or water) phases is considered in the flash calculations.
True solid-liquid equilibrium is not considered.

The calculation scheme for this unit operation is shown in Figure 7-
6.

Figure 7-6: Calculation Scheme for Melter/Freezer
Also See:
Melter/Freezer

Chapter 8: Utilities
This section describes a number of supplemental calculation meth-

ods available in PRO/II. These calculations are performed after the
process flow sheet has solved, and therefore do not affect the flow
sheet convergence.
Phase Envelope
Heating / Cooling Curves
Binary VLE/VLLE Data
Hydrates
Check Solids
Exergy
Phase Envelope
General Information
Calculation Methods
General Information
The PHASE ENVELOPE module generates a phase envelope or
constant liquid fraction curve (in tabular or plot form) for streams
using the Soave-Redlich-Kwong or Peng-Robinson equation of
state methods.
Note: The phase envelope module is currently limited to the Soave-
Redlich-Kwong and Peng-Robinson thermodynamic methods only.
Up to five separate curves or tables may be specified for each phase
envelope module. Figure 8-1 shows a typical phase envelope:

Figure 8-1: Phase Envelope
Calculation Methods
Flash computations often fail at the critical conditions. However,
for the Phase Envelope module, the true critical point, criconden-
therm, cricondenbar, and points of the phase envelope are deter-
mined with the method of Michelsen. This method provides a direct
solution for the mixture critical point, and encounters no difficulties
in the critical region. Regions of retrograde condensation are also
accurately predicted.
Note: Water will always be treated as a regular component in PRO/

II for phase envelope calculations, regardless of whether water is
declared as a decanted phase or not.
Reference
1 Michelsen, M.L., 1980, Calculations of Phase Envelopes
and Critical Points for Multi-component Mixtures, Fluid
Phase Equil., 4, pp. 1-10.
2 The Phase Envelope calculations are always performed
after the flow sheet has fully converged, and therefore does
not affect the convergence calculations. Also, like the
Utilities 8-514
HCURVE, this unit is not accessible via the CONTROL-
LER, MVC, or CASESTUDY.
Also See:
Phase Envelope
Utilities

General Information
Calculation Options
Critical Point and Retrograde Region Calculations
VLE, VLLE, and Decant Considerations
Water and Dry Basis Properties
GAMMA and KPRINT Options
Availability of Results
General Information
The HCURVE module provides a variety of options to calculate and
report properties of process streams in a PRO/II simulation. In gen-
eral, a heating/cooling curve is generated for a process stream
between two defined points or states: the user must provide infor-
mation that defines both the initial point and end point of the pro-
cess stream being investigated. The physical state of the stream
must be fully defined at these two limiting points. The information
presented here is intended to extend user understanding and provide
insight into the capabilities and limitations of the HCURVE mod-
ule. Several different types of curves may be requested, and each
type of curve offers a number of options for defining the end-point
states of the stream. Examples of data that sufficiently define a
stream state include:
 Specifying both temperature and pressure, or
 Specifying enthalpy content and either temperature or pressure.
The stream itself always supplies all composition information.

Also See:
Calculation Options
Any number of heating / cooling curves may be requested in each
HCURVE unit, but you must identify the process stream for each
curve. Alternatively, instead of explicitly identifying a process
stream, the HCURVE module allows you to specify a stream by
describing a configuration of a unit operation such as a heat
exchanger, flash drum, or distillation column. For example, you
may elect to instruct the HCURVE module to generate a curve with
points spaced at equal temperature and pressure increments
between the inlet and outlet conditions on the hot side of a heat
exchanger in the simulation. When using any of these options, the
end-point states of the desired stream are obtained from the con-
verged solution of the unit operation, and in general cannot be mod-
ified by supplying additional input data for the curve.All
calculations use the standard thermodynamic, flash, and transport
techniques discussed in earlier sections of this manual and in the
PRO/II Keyword Input Manual and PROVISION User's Guide. A
single thermodynamic method set is used in each HCURVE mod-
ule. When more than one thermodynamic method set is present in
the simulation, a unit-specific method may be used to choose the
one set that will be used for all curves in the HCURVE module.
When the unit-specific method is not specified, the default thermo-
dynamic data set will be used.
The GAMMA option available for most heating cooling curves is
valid only when the thermodynamic method set being used employs
a liquid activity K-value method.
Also See:
Critical Point and Retrograde Region Calculations

The extreme phase discontinuities inherent at the critical point pose
particularly severe calculation situations for dew and bubble curve
generation, although all curve calculations experience some diffi-
culties in this region. Generally, it is not uncommon for flash calcu-
lations to fail as the curve crosses the critical point. That model can
compute a complete phase diagram, including the critical point, and
Utilities 8-516
correctly finds both solutions when retrograde phenomena are pres-
ent.
Figure 8-2: Phenomenon of Retrograde Condensation

Many systems, commonly encountered in natural gas applications,
exhibit a phase behavior known as “retrograde condensation” as
illustrated in Figure 8-2. That is, above the critical pressure in the
two-phase region, it is possible for the condensate to vaporize as the
temperature is decreased. For such systems, it often is possible to
obtain two different valid solutions for the dew point temperature at
a fixed pressure, depending on how the curves are initialized and
the size of the temperature increments. Experience has shown that
the Peng-Robinson (PR) K-value generator is somewhat more sta-
ble when predicting dew points in the retrograde region than is the
Soave-Redlich-Kwong equation of state.
Also See:
VLE, VLLE, and Decant Considerations

The HCURVE module currently does not perform rigorous liquid-
liquid equilibrium calculations. Systems exhibiting two liquid
phases may be modeled only using “free water” thermodynamic
method sets with the DECANT=ON option of the WATER state-

ment activated (either explicitly or by default). In the HCURVE
module, only a single liquid phase appears in the results produced
by all rigorous VLLE K-value methods and VLE K-value methods
that do no decant free water.
Also See:
Water and Dry Basis Properties

HCURVE tables report several properties on a “DRY BASIS.” Dry
basis is meaningful only when using a free-water decanting K-value
method with the decant option activated (see VLE, VLLE, and
Decant Considerations above). In this situation, dry basis means
free water has been ignored during the calculation of the (dry) prop-
erties. This strategy applies only to liquid phase calculations; prop-
erties of vapor, even vapor containing water, are not affected. In the
typical case, solubility and miscibility of water in the non-aqueous
liquid phase are not considered when performing water decanting.
This means, in almost all cases, that dry properties are calculated on
a completely water-free basis that ignores all dissolved or entrained
water as well as any “free” water. In a completely analogous man-
ner, properties reported for the “WATER” liquid phase are only
meaningful when a free-water decanting K-value method is
used.When using a non-decanting VLE K-value method, at most a
single liquid phase is reported. When using a (non-decanting) rigor-
ous VLLE K-value method, the HCURVE module ignores the liq-
uid-liquid phase split and again handles all liquid as a single phase.
In both of these cases, the (reported) single liquid phase always
includes all of the liquid water that is present. This means that prop-
erties of the “decant” liquid are meaningless, and typically are
reported as zero, missing, or “N/A” (i.e., not applicable).
Also See:
GAMMA and KPRINT Options

The PROPERTY statement allows the user to stipulate sets of
properties that will be reported for every heating/cooling curve gen-
erated in an HCURVE module. The GAMMA and KPRINT
options allow the user to request property reports for individual
heating cooling curves. The GAMMA option is a super-set of the
KVALUE option; that is, GAMMA prints all the same information
Utilities 8-518
as the KVALUE option and adds more data to the report. For this
reason, there is no benefit to including both options for a single
heating/cooling curve.Both GAMMA and KVALUE generate a
report for each component in the stream at each point of the heating/
cooling curve. Table 8-1 summarizes the information reported at
each point.
Table 8-1: GAMMA and KPRINT

Report Information
Property GAMMA KPRINT
Point ID number X X
Temperature X X
Pressure X X
Component name X X
Component composition in vapor X X
Component composition in liquid X X
Component equilibrium K-value X X
Component name X
Component gamma (activity coefficient) X
Component vapor pressure X
Pure component fugacity coefficient X
Component Poynting correction X
Component vapor fugacity coefficient X
Availability of Results
Heating/Cooling units always perform their calculations during the
output pass of the flow sheet convergence module whenever PRO/II
executes. This means that HCURVE modules are not considered
until after the completion of all calculations needed to solve the
flow sheet. For this reason, the following applies to data generated
by HCURVE units:
 HCURVE data are not available to CONTROLLERs or OPTI-
MIZERs to control or modify flow sheet calculations,
 HCURVE data are not accessible through the SPECIFICA-
TION feature
 HCURVE data cannot be used to affect flow sheet convergence
calculations.
However, HCURVE results are stored in the problem database files
and appear in the standard output reports of the simulation. In addi-
tion, HCURVE results may be retrieved through facilities of the
PRO/II Data Transfer System (PDTS) for use in user-written appli-

cations (see the PRO/II Data Transfer System User's Guide). Also,
a small subset of the HCURVE data is included in the export file
created by using the DBASE option.
The DBASE DATA=PC1 option creates an ASCII database file
that includes selected data for each heating/cooling curve generated
by every HCURVE unit in the problem flow sheet. A typical exam-
ple of the HCURVE data included in the .ASC file is shown in
Table 8-2.
Table 8-2: Sample HCURVE .ASC File

13 F100 0 0 12
228.00 1000.00 281.89 108.45 0.00000E+00 390.34
21.325 4.7685 0.00000E+00 0.81725 0.18275 0.00000E+00
232.00 1000.00 220.65 227.53 0.00000E+00 448.18
16.231 9.8631 0.00000E+00 0.62201 0.37799 0.00000E+00
236.00 1000.00 162.69 339.24 0.00000E+00 501.93
11.598 14.496 0.00000E+00 0.44446 0.55554 0.00000E+00
240.00 1000.00 115.57 430.33 0.00000E+00 545.90
7.9673 18.126 0.00000E+00 0.30533 0.69467 0.00000E+00
244.00 1000.00 79.685 500.58 0.00000E+00 580.26
5.3071 20.787 0.00000E+00 0.20339 0.79661 0.00000E+00
248.00 1000.00 52.146 555.42 0.00000E+00 607.57
3.3549 22.739 0.00000E+00 0.12857 0.87143 0.00000E+00
252.00 1000.00 30.150 600.03 0.00000E+00 630.18
1.8744 24.219 0.00000E+00 0.718E+01 0.92817 0.00000E+00
256.00 1000.00 11.608 638.20 0.00000E+00 649.81
0.69776 25.396 0.00000E+00 0.267E+01 0.97326 0.00000E+00
258.77 1000.00 0.00000E+00 662.26 0.00000E+00 662.26
0.00E+00 26.094 0.00000E+00 0.000E+00 1.0000 0.00000E+00
260.00 1000.00 0.00000E+00 664.14 0.00000E+00 664.14
0.00E+00 26.094 0.00000E+00 0.000E+00 1.0000 0.00000E+00
This data in the table above should be interpreted as follows:

@DBHCRV HC00 ISO 13 F100 0 0 12
Utilities 8-520
The statement above identifies the data as an isothermal (ISO) heat-
ing/cooling curve generated by HCURVE unit HC00 for stream
F100. The remaining entries on this line are included for use by
PRO/II utility functions such as IMPORT, and are not described
here.
The subsequent lines of information in Table 8-3 present a limited
subset of data generated for this stream by the HCURVE calcula-
tions. Each point of the curve is summarized on two lines of the list-
ing. Table 8-3 interprets the data for a typical point of the curve.
Table 8-3: Data For an HCURVE Point
----------- Enthalpy, K*Kcal/h -------------
Temp C Pres mmHg liquid vapor water (decant) total
228.00 1000.00 281.89 108.45 0.00000E+00 390.34
----- mole rate, Kg mole/hr -- ----- Mole Fraction (wet) ------
liquid vapor water(decant) liquid vapor water(decant)
21.325 4.7685 0.00000E+00 0.81725 0.18275 0.00000E+00
All the data are expressed in the dimensional units used to supply
input data in the original problem definition. For example, Table 8-
3 indicates temperature is presented in degrees Celsius. Alterna-
tively, if the dimensional unit of temperature in the original input
file had been, for example, Rankine, then the temperatures pre-
sented in Table 8-2 and Table 8-3 would represent Rankine temper-
atures. This reasoning also applies to the enthalpy and rate data.
Note: The information available in the .ASC file always is limited
to the data shown in Table 8-3, regardless of the type of heating/
cooling curve or the printout options included in the HCURVE unit.
Also See:

General Information
Input Considerations
Output Considerations
General Information
The Binary VLE/VLLE Data module (BVLE) may be used to vali-
date binary vapor-liquid or vapor-liquid-liquid equilibrium data for
any given pair of components. This unit operation generates tables
and plots of K-values and fugacity coefficients versus liquid and
vapor composition at a specified temperature or pressure. A number
of plot options are available.Any thermodynamic VLE or VLLE K-
value method may be used to validate the VLE or VLLE data. For
liquid activity thermodynamic methods, the following are calcu-
lated by the BVLE module:
 K-values
 Liquid activity coefficients
 Vapor fugacity coefficients
 Vapor pressures
 Poynting correction.
For non-liquid activity methods such as the SRK cubic equation of
state, the following are calculated by the BVLE module:
 K-values
 Liquid fugacity coefficients
 Vapor fugacity coefficients.
Only selected input and output features of the Binary VLE / VLLE
Data module are discussed in this reference manual.
The BVLE unit operation does not affect flow sheet convergence. It
is always executed during the output calculations phase of simulator
execution, after the flow sheet has fully converged, and therefore
does not affect the convergence calculations. Also, like the
HCURVE, this unit is not accessible via the CONTROLLER,
MVC, or CASESTUDY.
Also See:
Utilities 8-522
One feature worth discussing further is the XVALUE option of the
EVALUATE statement. Quite often, tables of generated data
bracket, but do not exactly match, points of great interest such as
experimental compositions. The XVALUE option allows the user to
specify exact component mole fraction values so these points can be
very closely investigated.The XVALUE entry accepts liquid/vapor
mole fractions for component i, one of the two components
declared on the COMP entry (on the same EVAL statement). If
only one value is given, it is assumed to be the starting value, with
the number of points determined by the DELX and POINTS
entries. If two values are given, they are assumed to be the starting
and terminal values, with the number of points to generate specified
by the POINTS entries. The default starting and ending (mole frac-
tion) values are 0.0 and 1.0. When three or more points are sup-
plied, only those specific points are generated.
Also See:
Output Considerations
Results of each EVALUATE statement are printed as tables or
optional plots. The format of the report tables changes depending
upon whether the thermodynamic methods set that is being used is
able to predict two liquid phases (VLLE) or only a single liquid
phase (VLE). The tables of results are clearly labeled and only two
additional notes are presented here:
1 In the mole fraction results tables, X(1) in the header repre-
sents the molar liquid fraction and Y(1) represents the
molar vapor fraction of component one. X(2) and Y(2)
identify the same quantities for the second component of
the binary. In VLLE results listings only, the first and sec-
ond liquid phase columns are distinguished by asterisks.
For example, X(1)* represents mole fractions of compo-
nent 1 in the first liquid phase while X(1)** is used for frac-
tions of component 1 in the second liquid phase. Since at
most only a single vapor phase exists, asterisks never
appear with vapor data headings (such as Y(1) or Y(2)).
2 In VLLE results listings of activity coefficients and vapor
fugacity coefficients, an additional column appears labeled
Distribution Coefficient. The distribution coefficients are
liquid-liquid equilibrium analogs of vapor-liquid equilib-

rium K-values. Therefore, the distribution coefficient of
component i would be defined as:
Equation (8-1):
K Di  xiI / xiII
where:
KDI = liquid-liquid distribution coefficient of component i
xi = liquid mole fraction of component i
I, II represent the first and second liquid phases, respectively

Also See:
Utilities 8-524
Hydrates
General Information
Theory
General Information
PRO/II contains calculation methods to predict the occurrence of
hydrates in mixtures of water and hydrocarbons or other small com-
pounds. PRO/II can identify the temperature/pressure conditions
under which the hydrate will form, as well as identify the type of
hydrate that will form (type I or type II). The effect of adding an
inhibitor (either methanol, sodium chloride, ethylene glycol, di-eth-
ylene glycol, or tri-ethylene glycol) on hydrate formation can also
be predicted by PRO/II.
Theory
Hydrates are formed when water acts as a “host” solid lattice to
“guest” molecules which occupy a certain portion of the lattice cav-
ity. Only molecules which are small in size, and of a certain geome-
try may occupy these guest cavities. These hydrates are a form of an
inclusion compound known as clathrates, and no chemical bonds
form between the water lattice and enclosed gas molecules. Two
different types of hydrates can be identified, as illustrated in Figure
8-3. Their characteristics are given in Table 8-4. Table 8-5 lists the
gas molecules which may occupy the cavities of these hydrates.
Note: Water does not have to be specifically defined by the user as

a component in the system for hydrate calculations to proceed.
PRO/II will assume the presence of free water when hydrate calcu-
lations are requested.
Table 8-4: Properties of Hydrate Types I and II

Property Type I Type II
Number of water molecules per  46 136
unit cell
Number of small cavities per cell 2 16
Number of large cavities per cell 6 8

Table 8-4: Properties of Hydrate Types I and II
 
Cavity diameter   
Small 7.95 7.82
Large 8.60 9.46
Table 8-5: Hydrate-forming Gases

Methane Ethane Propane
N-butane Isobutane Carbon dioxide
Hydrogen sulfide Nitrogen Ethylene
Propylene Argon Krypton
Xenon Cyclopropane Sulfur hexafluoride
The hydrates formed are stabilized by forces between the host water
and guest gas molecules.
Figure 8-3: Large Cavities of Type I and II Hydrates

Statistical thermodynamic techniques are used to represent the
properties of these hydrates. At equilibrium, the chemical potential
of the water in the hydrate phase is equal to the chemical potential
of water in any other phase present (e.g., gaseous, ice, or liquid). In
1958, van der Waals and Platteeuw derived the following equation
relating the chemical potential of water in the hydrates to the lattice
molecular parameters:
Utilities 8-526
Equation (8-2):
 
 wH  RT i h 1   Yki 
i  k 
i = 1, 2, ..., Ncav
k = 1, 2, ..., Ncomp
where:
Hw = difference in chemical potential between the filled

gas-hydrate lattice and the empty hydrate lattice
vi = number of cavities of type i in the hydrate
Yki = probability of cavity i being occupied by a hydrate-form-

ing molecule of type k
The probability, Yki, may be described by a Langmuir-type adsorp-
tion expression:
Equation (8-3):
Cki f k
Yki 
1   C ji f j
j
j = 1, 2, ..., Ncomp
k = 1, 2, ..., Ncomp
where:
fk = fugacity of hydrate-forming component k
Cki = adsorption constant
Using equation (8-3), equation (8-2) then becomes:

Equation (8-4):
 
 wH  RF i h  1   Cki f i 
i  k 
The adsorption constant Cki is related to the spherical-core cell
potential by:

Equation (8-5):
1   W r  
Cki   exp    4 r dr
2
kT 0
 kT 
where:
k = Boltmann's constant = 1.38 x 10-16 erg/K
T = temperature, K
W(r) = spherical cell potential, erg
r = radial coordinate,
The spherical cell potential, W, is a function of the radius of the unit
cell, the coordination number of the cavity containing the gas mole-
cule, and sum of the interactions between the enclosed gas molecule
and the water molecules in the lattice wall.
The Kihara potential between a single gas molecule and one water
molecule in the lattice wall is given by:
Equation (8-6):
  12   6 
  r   4      for r > 2
 r  2   r  2  
Equation (8-7):
 r    for r  2
where:
 = Kihara potential, ergs
 = characteristic energy, ergs
 = core radius,
 + 2 = collision diameter,
Summing the gas-water interactions over the entire lattice yields:
Utilities 8-528
Equation (8-8):
  12    6   
W  r   2 z  11   10   11   5   4   5  
 Rc r  Rc  Rc r  Rc  
and,
Equation (8-9):
 r  
N
 r   
N
 1      1    
 Rc Rc   Rc Rc  
N   N  4,5,10,11
N
where:
z = coordination number of cavity
Rc = cell radius
When liquid water is present with the hydrate, the chemical poten-
tial difference between water in the liquid phase and the empty
hydrate is given by:
Equation (8-10):
 
 wL  RT i h  1   Cki f k   RThxw
i  k 
where:
Hw = chemical potential difference between water in the liq-

uid phase and the empty hydrate
xw = mole fraction of water in the liquid phase
The method used for determining the temperature and pressure

conditions under which hydrates form is given in Figure 8-4

Figure 8-4: Method Used to Determine Hydrate-forming
Conditions
Gas mixtures may be accommodated by introducing a binary inter-
action parameter, aj, into equation (8-10), The purpose is to repre-
sent the interaction between the most volatile hydrate-forming gas
molecule and all other molecules. This results in equation (8-11).
Utilities 8-530
Equation (8-11):
 
 wL  RT  k 1  3  k  1 yk2  2  k  1 yk3 
   
 i h 1   Cki f k   RThxw 
 i  k  
where:
k = binary interaction parameter between the most volatile
component and component k
yk = mole fraction of component k in the vapor phase
Reference
1 Munck, J., Skjold-Jorgensen, S., and Rasmussen, P., 1988,
Computations of the Formation of Gas Hydrates, Chem.
Eng. Sci., 43(10), pp. 2661-2672.
2 Ng, H.-J., and Robinson, D.B., 1976, The Measurement
and Prediction of Hydrate Formation in Liquid Hydrocar-
bon-Water Systems, Ind. Eng. Chem. Fundam., 15(4), pp.
293-298.
3 Parrish, W. R., and Prausnitz, J.M., 1972, Dissociation
Pressures of Gas Hydrates Formed by Gas Mixtures, Ind.,
Eng., Chem. Proc., Des. Develop., 11(1), pp. 26-35.
4 Peng, D. Y., and Robinson, D.B., 1979, Calculation of
Three-Phase Solid-
Liquid-Vapor Equilibrium Using an Equation of State,
Equations of State in Engineering and Research, Advances
in Chemistry Series, No. 182, ACS, pp. 185-195.
Also See:
Hydrates

Check Solids
General Information
Calculation Considerations
Report Considerations
General Information
The Check Solids unit operation is a Simsci Add-on module that
tests specified streams for the formation of a solid phase for a lim-
ited list of components: CO2, H2S, and benzene. The unit checks for
conditions under which these components freeze and form solids.
No solids form when the stream temperature is above the melting
point of the potential solids former.
Feeds
Each feed stream must have a positive flow rate with 2 or more
components having positive (non-zero) compositions. Pure (single)
component streams are bypassed, and the unit issues an error.
The unit requires one feed stream and allows up to 10. Because the
PROVISION Graphical User Interface does not allow a single
stream to feed more than one unit operation, a typical strategy is to
lay down additional streams to feed the Check solids unit. These
streams should “reference” other process streams in the flow sheet
that are candidates for solids formation. Refer to section 9.3, “Ref-
erence Streams”, in the PRO/II Keyword Input Manual.
Products
There are no product streams from this unit operation. Since the
unit operation does not affect the thermodynamic state of the feed
streams, it does not participate in the material balance of the flow
sheet simulation in which it is embedded.
Components
The three components tested for formation of a solid phase are:
Table 8-6: Supported Solid-forming Components

Component Formula Library ID Number
carbon dioxide CO2 16020040
Utilities 8-532
hydrogen sulfide H2S 16020140
benzene C6H6 12010010
At least one of these components must be present in a feed stream

for this unit to detect the formation of solids.
Currently, no more than 50 components are supported.
Calculation Considerations
The algorithm in this unit uses correlations derived by D. Y. Peng of
Robinson and Associates to compute the properties of solids. It also
uses the Peng-Robinson form of the generalized cubic equation of
state to model the fluid properties during the analysis. The solid
property correlations are similar to the property correlations used by
the hydrates package in PRO/II. Unlike the hydrate calculations,
solids form by freezing, not by forming a complex with water. In
this model, solid formation calculations are performed on a dry
(water-free) basis.
The presence of certain other specific components (that may inter-
act with the solid-forming components) cause adjustments to the
data and coefficients of the Peng-Robinson equation of state:
Table 8-7: Components that Affect Solids-Forming

Presence of Causes adjustment of these data
hydrogen Tc, Pc, Kij’s, and terms “a” and “b” of the
Peng-Robinson equation of state.
helium Tc, Pc, and terms “a” and “b” of the Peng-
Robinson equation of state.
methanol  (acentric factor)

bitumen- Kij’s
CO2 binary
Additional adjustments are made to the alpha terms (ij’s) and the
overall temperature-dependent a(T) term in the equation of state to
account for the departure of the fluid from ideal behavior as the
operating temperature diverges from the critical temperature.
Algorithm
Each feed stream is processed individually. The phase state of the
stream is determined by a flash calculation at stream temperature

and pressure. Each phase that is present (vapor, liquid, L1, and L2)
is checked individually for solids formation. A separate analysis is
made for each solids-forming component in each phase.
The algorithm iterates by removing a fraction of the solid-forming
component from the fluid and placing it in the solid phase. The
solid properties (fugacity and volume) are computed from the solid
property correlations.
The composition of the fluid is normalized to accommodate the loss
of mass to the solid phase. The fluid is re-flashed to compute its
new fugacity and volume at the stream temperature.
Iterations converge when the fugacity of the solid matches the
fugacity of the solid-forming component in the fluid, indicating the
fluid and the solid phases are at equilibrium. Additionally, total
stream pressure, volume, and the mass balances are maintained.
When a solution is found that satisfies all these criteria, solids for-
mation is confirmed. When no such solution is found, solids are
reported to be absent.
Report Considerations
The output report consists of a single table that includes one line of
information for each feed stream. Reported data include the stream
temperature and pressure and the results for each of the three possi-
ble solids-forming components.
Example
Test stream T60 for solids formation at one degree temperature
increments between 40 K and 44 K.
TITLE PROJECT=CHKSOLID, PROBLEM=ST2
DESC CHECK SOLID FORMATION (AT 27.2 ATM)
PRINT INPUT=NONE, STREAM=NONE
DIMENSION ENGLISH, TEMP=K, PRES=ATM, LIQVOL=CUFT, VAPVOL=CUFT, &
XDENSITY=SPGR, CONDUCT=BTUH, SURFACE=DYNE
SEQUENCE ASENTERED
COMPONENT DATA
LIBID 1, C1/ 2, C2/ 3, C3/ 4, CO2/ 5, H2S, BANK=PROII_8.2:SIMSCI, PROCESS
ASSAY CONVERSION=API94, CURVEFIT=IMPROVED, KVRECONCILE=TAILS
THERMODYNAMIC DATA
METHOD SYSTEM=SRK, SET=SRK01
STREAM DATA
PROPERTY STREAM=T060, TEMPERATURE=60, PRESSURE=27.2, &
PHASE=M, COMPOSITION(M,LBM/H)=1, 66 / 2, 3 / 3, 1 / 4, 8 / 5, 22
Utilities 8-534
PROPERTY STREAM=T040, TEMPERATURE=40, REFSTREAM=T060
UNIT OPERATIONS
SOLCHK UID=UT04X, Name = Solids-Check Sample
FEED T040, T041, T042, T043, T044
END
The output report for this input is:
SIMULATION SCIENCES INC. R PAGE P-1
PROJECT CHKSOLID PRO/II VERSION 9 ELEC V6.6
PROBLEM ST2 OUTPUT
SOLIDS CHECKING SUMMARY MARCH 2007
========================================================================
UNIT 1, 'UT04X'
SOLID FORMATION PREDICTION UNIT OPERATION
SOLID FORMERS
------------------------------------
TEMP, PRES,
STREAM IDS K ATM CO2 - MOL% C6H6 - MOL% H2S - MOL%
----------- -------- --------- ----------- ----------- -----------
T040 40.0000 27.2000 YES 8.000 NSF N/A YES 21.995
T041 41.0000 27.2000 YES 8.000 NSF N/A YES 21.994
T042 42.0000 27.2000 YES 8.000 NSF N/A YES 21.993
T043 43.0000 27.2000 YES 8.000 NSF N/A YES 21.992
T044 44.0000 27.2000 YES 8.000 NSF N/A YES 21.990
KEY -- YES - SOLID FORMATION PREDICTED

NO - NO SOLID FORMATION PREDICTED
NO+ - TEMPERATURE TOO HIGH FOR SOLID CORRELATIONS -
NO SOLID FORMATION PREDICTED
NO- - TEMPERATURE TOO LOW FOR SOLID CORRELATIONS -
NO SOLID FORMATION PREDICTED
NSF - NO SOLID FORMERS - SOLID FORMATION NOT POSSIBLE
UTP - UNABLE TO PREDICT
N/A - NOT APPLICABLE OR DATA NOT AVAILABLE

Streams T040, T041, T042, T043, and T040 that feed the check solids
unit all obtain their data by referencing stream T060. None of the
streams that feed the check solids unit participate elsewhere in the
simulation.
Notice in the sample output that all the CO2 and most of the H2S
form solids. Since benzene is not present in any of the feed streams,
it always is reported as “no solid formers”.
Utilities 8-536
Exergy
General Information
Interpreting Exergy Reports
General Information
Exergy (or availability) calculations may be requested by the user
by supplying the EXERGY statement in the General Data Category
of input. All entries are optional. When requested, exergy calcula-
tions are performed in the final stages of writing the PRO/II output
report. As such, exergy calculations are not available during, and in
no way whatsoever affect, flow sheet convergence. Exergy results
appear after the Stream Summary reports in the PRO/II output
report.The availability function, B, is defined as:
Equation (8-12):
B  H  TS
where:
H = enthalpy
T = temperature
S = entropy
Interpreting Exergy Reports

In the exergy report, enthalpy and entropy are reported on a total
stream basis and reflect the actual state of the stream (i.e., at what-
ever phase conditions prevail at the actual stream temperature and
pressure).The availability functions shown in Table 8-8 are pro-
vided in the exergy report:
Table 8-8: Availability Functions

Availabilit Description
y Function
B(EXS) The exergy (availability) at the EXisting State (i.e.,
actual state) of the stream.
B(TES) The exergy (availability) at reference temperature Tzero
and actual stream pressure.

Table 8-8: Availability Functions
B(EVS) The exergy (availability) at the EnVironmental State
(i.e., the reference or “zero” state at Tzero and Pzero).
B(EVS) TOTAL is calculated rigorously assuming the
stream is actually at Tzero, Pzero conditions, and no
assumptions are made about the phase state.
B(EVS) VAPOR also is calculated at Tzero and Pzero,
but an a priori assumption is made that the stream is
exclusively in a vapor state. This is provided as a
convenience to users who make this simplifying
assumption when performing manual calculations.
B(MES) This represents stream exergy (availability) at Modified
Environmental State, computed as follows:
Equation (8-13):
B  MES   H  Tzero   Si  xi log  xi  
where:
H = total stream enthalpy
Si = entropy of component i
xi = mole fraction of component i in the stream
These calculations are carried out at the same conditions
used to compute B(EVS) VAPOR.
E(T) This function is equal to B(EXS) - B(TES)
E(P) This function is equal to B(TES) - B(EVS) VAPOR
E(M) This function is equal to B(EVS)VAPOR - B(MES)
For unit operations, the availability is calculated as follows:

Equation (8-14):
DELTA  B   B  EXS  feeds  B  EXS  product W  EXT 
The external work done by the unit operation (W-ext), and the heat
duty of the unit operation (Duty) are also given in the exergy report.
Reference
1 Venkatesh, C.K., Colbert, R.W., and Wang, Y.L., Exergy
Analysis Using a Process Simulation Program, presented at
National Convention of the Mexican institute of Chemical
Engineers, October 17, 1980.
2 de Nevers, Noel, and Seader, J.D., Mechanical Lost Work,
Thermodynamic Lost Work, and Thermodynamic Efficien-
Utilities 8-538
cies of Processes, presented at 86th AIChE National Meet-
ing, Houston, Texas, April 1979.
Also See:
Exergy

Utilities 8-540
Chapter 9: Stream Calculator
General Information
Feed Blending Considerations
Stream Splitting Considerations
Stream Synthesis Considerations
General Information
The Stream Calculator is a multi-purpose module intended to facili-
tate the manipulation of process streams in a PRO/II simulation
flowsheet. There are two distinctly different modes of operation
available: stream splitting and stream synthesis. A single Stream
Calculator module may operate in either of these two modes exclu-
sively, or may be configured to operate in both modes simultane-
ously. When configured to operate in both modes, a single set of
feed streams and feed blending factors is utilized by both the split-
ting and synthesis calculations. However, each mode uses the feed
streams and blending factors independently. In no way do the split-
ting calculations affect the synthesis calculations. In a completely
complementary manner, the synthesis calculations never in any way
affect the splitting calculations.
Also See:
Stream Calculator
Feed Blending Considerations

As stated in the PRO/II Keyword Input Manual, feed blending may
be considered a third mode of operation, but this viewpoint is
slightly misleading. In fact, feed blending is merely a preliminary
setup operation that prepares available feed stream data for use in
subsequent stream splitting and/or stream synthesis calculations.
Without the subsequent splitting or synthesis calculations (which
are required), feed blending performs no useful function.Feed
blending occurs whenever feed streams are present in the definition
of a Stream Calculator module. The result of this blending is a sin-
gle combined stream that is a composite of all the individually
declared feed streams. The resultant combined feed then serves as
the sole reference of feed stream data for all splitting and synthesis

factors that refer to feed data. For splitting calculations, the
FOVHD and FBTMS factors refer to the component compositions
stored in the combined feed. For synthesis calculations, the
FPROD factors refer to the component compositions stored in the
combined feed.
The FEED statement allows the user to supply a single feed blend-
ing factor for each feed stream. Each such factor is a relative scal-
ing factor that is used to multiply the total flow rate of its respective
feed stream. All the feed streams then are blended together to yield
the combined feed stream that has total rate dictated by the feed
blending factors. The proportion of each component in the com-
bined feed is the result of proportional blending based on the frac-
tion of each component in the original individual feed streams.
It is important to remember that feed blending always occurs when-
ever two or more streams feed the Stream Calculator. All streams
that do not have a feed blending factor supplied by the user assume
a blending factor of unity. This means each such stream is blended
at exactly 100% of its rate in the flowsheet.
The Stream Calculator allows the user to assign any value to each
feed blending factor. A positive blending factor indicates additive
blending of the stream while a negative factor causes subtracting a
stream to create the combined feed. In this way, the careful user can
create a combined feed of almost any desired composition.
Note that true mass balance between the Stream Calculator and the
rest of the flowsheet is achieved only when all feed streams have a
blending factor of unity. Blending factors greater than unity cause a
virtual creation of mass flow while factors less than unity cause a
virtual removal of mass. Note this “adjustment” represents a dis-
continuity between the mass contained in the individual feed
streams and the single combined feed that is created. There is no
accounting for this gain or loss, and any products of such a Stream
Calculator that feed back into the flowsheet cause the flowsheet to
be out of mass balance. However, whenever feed streams are pres-
ent, mass balance is preserved across the Stream Calculator (i.e., the
products and the combined feed are kept in mass balance).
Also See:
Stream Calculator
Stream Calculator 9-542

Stream Splitting Considerations
The stream splitting capability of the Stream Calculator allows
dividing the combined feed into two product streams of virtually
any desired composition. This is a brute-force “black box” opera-
tion, since equilibrium and thermodynamic constraints (such as
azeotrope formation) are not applied. This capability is useful when
fast, non-rigorous modeling is desired or expedient. For example,
assume a flowsheet under construction includes a rather compli-
cated reactor. Further assuming the feed and desired product condi-
tions are known, a Stream Calculator could be used as a quick,
simple preliminary reactor model that would produce the desired
reaction products without requiring the developer to worry about
kinetics, reaction rates, and other reaction complexities. Develop-
ment of the remainder of the flowsheet could proceed immediately
while the time-consuming development of a rigorous reactor model
could be deferred.Stream splitting always requires the presence of
at least one feed as well as both the OVHD (overhead) and BTMS
(bottoms) product streams. All of the combined feed is distributed
between these two products. If all feed streams have blending factor
values of unity (i.e., 1.0), overall flowsheet material balance is pre-
served.
The stream splitting operation also requires the user to supply a
splitting factor for every component in the flowsheet, even if that
component does not appear in any of the feeds to the Stream Calcu-
lator. The disposition of each component must be defined in one
and only one splitting factor specification. The most straightfor-
ward way to accomplish this is to define splitting factors for all
components in terms of only one product. For example, use only
FOVHD, ROVHD, and XOVHD splitting specifications to define
all component splitting in terms of only the overhead product. The
rate and composition of the bottoms stream then is calculated as the
difference between the combined feed and the overhead product.
Alternatively, use only FBTMS, RBTMS, and XBTMS splitting
specifications to define all component splitting in terms of only the
bottoms product. In the latter case, the rate and composition of the
overhead product is calculated as the difference between the com-
bined feed and the bottoms product. Splitting factors of zero
exclude the component (or group of components) from the specified
product stream. Negative splitting factor values are invalid.
Note: The XOVHD and XBTMS splitting factors specify only the
relative composition of components in the overhead and bottoms
products respectively. This means they do not and cannot be used

as a basis for calculating the rate of either product. Since mass
balance between the combined feed and the products is always
enforced, some splitting factor that establishes a basis for calculat-
ing product flow rates is required. For this reason, the distribution
of at least one component must be specified using an FOVHD,
FBTMS, ROVHD, or RBTMS separation factor.
Also See:
Stream Calculator
Stream Synthesis Considerations

Stream synthesis is useful for dynamically creating a stream or
modifying the composition and rate of a stream during flowsheet
convergence calculations. Stream synthesis does not require the
presence of any feeds to the Stream Calculator, but always creates
“something from nothing,” a virtual mass flow that introduces a dis-
continuity in the material balance of the flowsheet. Typically, the
synthesized stream is intended to serve as an “source” stream that
feeds the flowsheet. When used in this manner, the synthesized
stream does not compromise the mass balance of the overall flow-
sheet since it is considered to originate in an “infinite source” that is
external to the flowsheet.
Note: The XPROD splitting factors specify only the relative com-
position of components in the synthesized product. This means
they do not and cannot be used as a basis for calculating the
rate of the synthesized product; some splitting factor that estab-
lishes an absolute basis for calculating product flow rate is
required. For this reason, the rate of at least one component must
be specified using an FPROD or RPROD separation factor.
Also See:
Stream Calculator
Stream Calculator 9-544

Chapter 10: Flowsheet Solution Algo-
rithms
PRO/II is able to find all recycle streams of a flowsheet and gener-

ate a unit calculation sequence. For loop convergence, direct substi-
tution as well as Wegstein and Broyden acceleration are available.
Sequential Modular Solution Technique
Calculation Sequence and Convergence
Acceleration Techniques
Flowsheet Control
Feedback Controller
Multi-variable Feedback Controller
Flowsheet Optimization

General Information
Methodology
Process Unit Grouping
General Information
PRO/II solves process flow sheets using a Sequential Modular
Solution Technique. This technique solves each individual process
unit, applying the best solution algorithms available. Additionally,
PRO/II applies several advanced techniques known as Simultane-
ous Modular Techniques, to enhance simulation efficiency.
Methodology
Any given simulation is equivalent to a large system of nonlinear
simultaneous equations. This system of equations includes the eval-
uation of all necessary thermodynamic properties for all streams in
the flowsheet, as well as all rates and compositions using the
selected thermodynamic and unit models. In principle, it is possible
to solve all these equations simultaneously, but PRO/II utilizes a

different approach: Every unit in the flowsheet is solved using the
most efficient algorithms developed for each case. For example,
one can choose different methods for multiple distillation columns,
ranging from shortcut to a variety of rigorous models and, for each
case, PRO/II will use the corresponding specialized column algo-
rithms. Should an error occur in any unit, due, for example, to
incorrect column initialization or poorly chosen design parameters,
it can be easily identified, confined and corrected.To calculate a
flowsheet of interconnected units, a sequence of unit calculations is
determined automatically (or optionally provided by the user). If
recycles are present, an iterative scheme is set up where recycle
streams are “torn” and a succession of convergent “guesses” is cre-
ated. These guesses are obtained by directly substituting the values
calculated in the previous pass through the flowsheet (the Direct
Substitution technique) or by applying special recycle acceleration
techniques (see Section - Acceleration Techniques). For example,
consider the following schematic flowsheet:
Figure 10-1: Flowsheet with Recycle

One possible solution sequence for this flowsheet is U1,
U2,U3,U4,U5. In this sequence there are two recycle streams, R1
and R2. The subsequence U2,U3,U4 is a recycle loop and is solved
repeatedly until convergence of the recycle streams is achieved.
Note: The Sequential Modular Solution Technique provides physi-

cally meaningful solution strategies, therefore allowing a process
simulation to be easily constructed, debugged, analyzed, and inter-
preted.
Recently, the Simultaneous Modular Solution concept has been

coined for the art of flexibly solving simulation problems made up
of process modules, introducing some aspects of equation-oriented
Flowsheet Solution Algorithms 10-546

strategies. This new concept covers several techniques to improve
the performance of strictly sequential modular solvers, including:
 Optimal tear streams selection
 Controlled simulations
 Unit grouping
 Stream referencing
 Flowsheet specifications
 All stream/tear stream convergence
 Linear and nonlinear derived models
 Inside-out strategies
 Simple-rigorous iterative procedures (two-tier algorithms).
PRO/II applies several simultaneous modular techniques when
solving process flowsheets. Overviews of optimal tear stream tech-
niques can be found in section - Calculation Sequence and Conver-
gence, and the use of Controllers in simulations is reviewed in
section - Flowsheet Control. Several other strategies (inside-out, all
stream convergence, Simple-rigorous) are used to solve individual
models.
Also See:
Process Unit Grouping

PRO/II uses Unit Grouping to allow improved simulation effi-
ciency. Unit grouping is a special technique that simultaneously
solves groups of units that are closely associated. One example of
this is the integration of sidestrippers and pumparounds with col-
umn units. Consider the crude column shown in Figure 11-2:

Figure 10-2: Column with Sidestrippers
There are three pumparounds and three sidestrippers in the flow-
sheet. A strict application of the Sequential Modular Solution Tech-
nique requires six tear streams. Instead, by grouping the column and
sidestrippers and solving them simultaneously, the number of tear
streams is reduced to only three pump around recycles. Moreover, if
the attached heat exchangers corresponding to the pumparounds are
also grouped, a unique model is obtained that does not contain recy-
cles, further improving the simulation efficiency.
Also See:

General Information
Tearing Algorithms
Convergence Criteria
General Information
PRO/II performs an analysis of the flowsheet and determines the
recycle streams and the loops of units with which they are associ-
ated. Then, tear streams and a solving sequence are determined. The
user can override all these calculations and define his/her own cal-
culation sequence. Initial estimates for the tear streams are desirable
but not mandatory. If good estimates are provided, convergence will
be achieved faster.
Tearing Algorithms
Two calculation sequence methods are available:
Minimum Tear Streams (SimSci Method)
This default sequencing method uses improved algorithms devel-
oped by SimSci to determine the best sequence for calculation pur-
poses. This method provides a calculation sequence featuring a
minimum number of tear streams.
Alternate Method (Process Method)
This method determines the sequence based partially on the order in
which the unit operations were placed during the construction of the
flowsheet. The units which were placed first are likely to be solved
earlier than the units which were placed at a later time.
Both methods determine the independent calculation loops in the
flowsheet, moving all calculations not affected by the recycle
streams outside these independent loops. These units will not be
calculated until the loops are solved. Then, for each loop, a tear set
is determined. In the case of the SimSci Method, a minimum tear
set based on the algorithm developed by Motard and Westerberg
(1979) is used. If more than one choice is available for the tear set,
the Simsci Method will pick the stream that has been initialized by
the user. In the case of the Process Method, an algorithm that pre-
serves as much as possible the order in which the user placed the
units is used.

Single variable controllers which affect units within loops will be
included in the loops. In turn, multi variable controllers and opti-
mizers which affect units within loops will not be included in the
loops. If any of these options is not desired a user-defined calcula-
tion sequence should be used.
Recycle loops concern two primary effects: Composition and Ther-
mal changes for streams. The reference stream concept in PRO/II
may often be used to redefine the tearing process and eliminate
thermal recycles.
To illustrate how both algorithms find tear sets and calculation
sequences, consider the following simplified flowsheet shown in
Figure 11-3.
Figure 10-3: Flowsheet with Recycle

Given the way this flowsheet is drawn, it has two recycle streams
(R1,R2). The SimSci method will find the calculation sequence
U3,U1,U2,U4 as only one tear stream (S3) and is the minimum tear
set. The sequence U3,U1,U2, will be solved until convergence is
reached and only then, unit U4 will be solved. Depending of the
sequence entered by the user, the Process Method will identify the
calculation sequences shown in Table 10-1.
Table 10-1: Possible Calculation Sequences

Order of Units Calculation Tear Streams
Entered  Sequence
by the User
a) U1,U2,U3,U4 U1,U2,U3,U4 R1,R2
b) U1,U3,U2,U4 U1,U3,U2,U4 R1,S3
c) U2,U1,U3,U4 U2,U1,U3,U4 S2,R2,R1
d) U2,U3,U1,U4 U2,U3,U1,U4 S2,R2

Table 10-1: Possible Calculation Sequences
e) U3,U1,U2,U4 U3,U1,U2,U4 S3
f) U3,U2,U1,U4 U3,U2,U1,U4 S3,S2
g) U4,U3,U2,U1 U3,U2,U1,U4 S3,S2
h) U3,U4,U2,U1 U3,U2,U1,U4 S3,S2
Note: The Process Method always preserves the user input

sequence of units of a loop (U1,U2,U3 in this case), picking the tear
streams accordingly, and placing units not belonging to loops
before or after them as needed (see cases g and h in Table 10-1).
Reference
Motard, R.L. and Westerberg, A.W., 1979, DRC-06-7-79.
Also See:
Convergence Criteria
Convergence is defined as being met when the following three
requirements are achieved for two successive determinations of the
recycle streams: Component molar flow convergence test:
Equation (10-1):
 Error in flow  min 1  min  Component 

  n 1
 ec   
 of component i  mi  flowtolerance 
where:
m in 1 , m in = current and last values of the flow of component
i in the recycle streams
Only components with mole fractions greater than a threshold value
(default is 0.01) are considered for the above test. The component
tolerance and threshold value may be set by the user using the TOL-
ERANCE statement in the General Data category of input. Values
of these tolerances may also be provided on the LOOP statements.
Care should be exercised that inside loop tolerances are set always
as tight or tighter than those for outside loops.
Temperature convergence test:

Equation (10-2):
 Error in   Temperature 
   Tn  Tn 1  eT   
 temperature   tolerance 
Pressure convergence test:
Equation (10-3):
 Error in  Pn  Pn 1  Temperature 
   eP   
 pressure  Pn  tolerance 
Default component molar flow, temperature and pressure tolerances
of c = 0.01, eT = 1.0 F (0.55 C) and ep = 0.01 will be assigned by
PRO/II. These tolerances may also be redefined in the General Data
category of input or on the LOOP statement.
These convergence tests are applied to all streams, but the user has
the option to apply them to the tear streams only.
Also See:
Flowsheet Solution Algorithms
General Information
Wegstein Acceleration
Broyden Acceleration
General Information
Unless acceleration techniques are requested by the user, PRO/II
will use direct substitution for closure of all recycle streams. This
method usually works well; however, for loops in which closure is
asymptotic an acceleration technique becomes desirable to reduce
the number of trials required.
Wegstein Acceleration
The Wegstein acceleration technique takes advantage of the result
of the previous trials, but ignores the interaction between different
components. To use this technique, at least one trial must be made
with direct replacement. Let xk represent the estimated rate of a

component or a temperature of a recycle stream at the beginning of
trial k and xk 1 the calculated rate or temperature after trial k. The
estimated rate for trial k + 1, xk 1 , will be computed using these val-
ues as follows:
Equation (10-4):
xk 1  qxk  1  q  xk 1
In equation (1), q is the so-called acceleration factor and is deter-

mined by the following formula
Equation (10-5):
w
q
w 1
where:
xk 1  xk
w
xk  xk 1
Table (10-1) shows how values of q affect convergence.
Table 10-1: Significance of Values of the

Acceleration Factor, q
q Convergence Region
q<0 Acceleration
q=0 Direct Substitution
0<q<1 Damping
q=1 Total damping (no convergence)
The more negative the value of q, the faster the acceleration. How-
ever, if the value of q thus determined is used without restraint,
oscillation or divergence often results. It is therefore always neces-
sary to set upper and lower limits on the value of q. These limits
should be set based on the stability of the recycle stream. Normally,
the upper limit should be at 0.0. A conservative value for the lower
limit may be set at, -20.0 or -50.0 to speed up the convergence.
The Wegstein acceleration can be applied only after one or more tri-
als with direct replacement have been made. If the initial estimate
of the recycle stream composition is far different from the expected
solution, e.g., zero total rate, a number of trials should first be made
with direct replacement. Once started, Wegstein acceleration may
be applied every trial or at frequencies specified by the user.

Recommended Uses for Wegstein
The Wegstein method works best for situations in which conver-
gence is unidirectional; that is when a key component (or compo-
nents) either builds up or decreases in a recycle stream. Because the
Wegstein method does not consider the interaction effects of com-
ponents, it may not be suitable for cases involving multiple recycle
steams which are interdependent. Under these conditions the
method may cause oscillation and hinder convergence. If oscillation
occurs with direct replacement, upper and lower q values at 0.5 may
be used in the Wegstein equation, forcing averaging to take place.
Reference
Wegstein, J. H., 1958, Comm. ACM, 1, No. 6, 9.
Also See:
Broyden Acceleration
Broyden's method is a Quasi-Newton method. It consists of updat-
ing the inverse of the Jacobian at each iteration instead of calculat-
ing it or approximating it numerically. This method takes
specifically into account all interactions between component rates
and temperature of all streams included in the recycle loop. Let
represent the estimated rate of all components in a recycle stream at
the beginning of trial k and the calculated rate after trial k.
Broyden uses an approximation to the inverse of the Jacobian
which is being updated at every iteration. Broyden's procedure pro-
vides as follows:
Equation (10-6):
xk 1  xk  d k xk
where:
dk=a damping factor
In equation (4), is given by:

Equation (10-7):

xk  H k xk 1  xk 
The update of Hk is performed using the following formula:

Equation (10-8):
H k  H k 1 
 H k 1 yk  d k xk 1  xkT1 H k 1
xkT1 H k 1 yk
where:
Equation (10-9):
  
yk  xk 1  xk  xk  xk 1 
The algorithm starts with Ho=I, avoiding thus expensive numerical
calculations and inversion of the Jacobian. The damping factor has
a default value dk=1 at every iteration, and it is reset to a smaller
value automatically to prevent the new estimates xk 1 from becom-
ing negative.
Recommended Uses for Broyden

It is recommended that the Broyden acceleration be applied only
after sufficient direct substitution trials have been made. If the ini-
tial estimate of the recycle stream composition is far different from
the expected solution, e.g., zero total rate, a number of trials should
first be made with direct substitution. Once started, Broyden accel-
eration will be applied every trial, without exception.
The Broyden method works best for cases involving multiple recy-
cle steams, which are interdependent. PRO/II will apply Broyden
acceleration to all recycle streams corresponding to each loop. Cau-
tion must be taken when using Broyden acceleration with a user-
supplied set of streams to accelerate: if this set does not contain all
the tear streams of the loop or loops it belongs to, the inter-depen-
dence may not be well represented by Hk, and therefore, the algo-
rithm may behave poorly.
Reference
Broyden, C.G., 1965, Math Comp., 19, pp 577-593.
Also See:

Flowsheet Control
General Information
General Information
PRO/II allows both feedback controllers and multi variable control-
lers to be included within a flowsheet. These units, which are
described in more detail below, allow specifications on process
units or streams to be met by adjusting upstream flowsheet parame-
ters. If there is a one-to-one relation between a control variable and
a specification, it is best to use a feedback controller. If, on the other
hand, several specifications and constraints are to be handled simul-
taneously, the multi variable controller should be used.Both the
feedback and multi variable controllers terminate when the error in
the specifications is within tolerance. By default, the general flow-
sheet tolerances are used as shown in Table 10-2.
Table 10-2: General Flowsheet Tolerances

Temperature Absolute tolerance of 0.1F or
equivalent
Pressure Relative tolerance of 0.005
Duty Relative tolerance of 0.005
Miscellaneous Relative tolerance of 0.01
If the specification does not set a temperature, pressure or duty the

“miscellaneous” relative tolerance is used. The tolerances on the
controller specifications can be modified either by changing the tol-
erances at the flowsheet level or directly within the controller unit
as part of each SPEC definition.
Feedback Controller
General Information
Recommendations
General Information
The PRO/II CONTROLLER is analogous to a feedback process
controller; it varies a particular parameter (control variable) in order

to meet a downstream specification on a process unit or stream
property or rate. Each CONTROLLER involves exactly one speci-
fication and control variable. The specification may be made on a
stream property or rate, a unit operating condition or a CALCULA-
TOR result. The control variable can be a stream or unit operating
condition, a thermodynamic property or a CALCULATOR
result.Figure 11-5 illustrates a typical controller application. Here,
the controller varies the cooler duty in order to achieve a desired
flow rate of stream 6.
Figure 10-4: Feedback Controller Example

The CONTROLLER uses an iterative search technique to vary the
value of the control variable until the specification is satisfied
within tolerance. PRO/II automatically creates the computational
loop for the CONTROLLER; the units inside this loop are solved
repeatedly until the CONTROLLER has converged. For the exam-
ple in Figure 11-5 units C1, D1, V1 and D2 are solved each time the
CONTROLLER varies the cooler duty. The calculations terminate

successfully when the flow rate of stream 6 has reached the desired
value.
Recommendations
When defining control variables and specifications, it is important
to note that the value of a control variable must remain fixed unless
it is changed by the CONTROLLER. Typical control variables
include inlet feed rates, specified heat duties of heat exchangers and
adiabatic flash drums as well as specified reflux ratios of distillation
columns. Conversely, the CONTROLLER specifications must be
defined as calculated results of the flowsheet simulation e.g. outlet
flow rates, column heat duties or temperatures of intermediate
streams. However, it is meaningless for the CONTROLLER to
specify the temperature of an isothermal flash.
For best performance, the functional relationship between the con-
trol variable and the controller specification should be continuous
and monotonically increasing or decreasing as illustrated in region
III of Figure 11-6. Functions that are discontinuous (region I),
exhibit local maxima or minima (region II), or are invariant (region
IV) may cause convergence problems. Frequently, these difficulties
can be overcome by including upper and/or lower bounds on the
control variable to restrict its range (for example VMIN1 and
VMAX1 in Figure 11-6).

Figure 10-5: Functional Relationship Between Control Variable
and Specification
The PRO/II sequencer automatically determines an appropriate cal-
culation sequence for the CONTROLLER loop. When recycle
loops are also present, PRO/II determines the loop ordering which
allows for most effective flowsheet convergence. To override the
default ordering, the desired sequence must be specified explicitly
using a SEQUENCE statement. The user should be aware that con-
trol loops can significantly increase computational time.
When controllers are placed within recycle loops, careful selection
of the controller variable and specification can greatly reduce inter-
ference caused by the simultaneous convergence of the two loops.
Consider for example the flowsheet shown in Figure 11-7 where
stream 2 contains pure reactant A. The rate of stream 2 is to be var-
ied by a CONTROLLER in order to achieve a certain concentration
of A in the feed to the reactor.

Figure 10-6: Feedback Controller in Recycle Loop
In this example, the controller would normally be placed inside the
recycle loop, after unit 1. Here, the CONTROLLER adjusts the
flow rate of stream 2 to achieve the desired concentration in stream
3. The recycle loop is then solved to obtain a new value for the
recycle flowrate. This configuration is effective when a good initial
estimate for stream 4 is available. If the initial estimate of the flow
rate of stream 4 is unavailable, positioning the controller inside the
recycle loop may cause the flow rates of stream 2 calculated by the
controller to change significantly from one controller solution to the
next. This, in turn, causes the recycle loop to experience difficulties.
In this situation, it would be more appropriate for the controller to
be the outermost loop, allowing the recycle loop to solve and gener-
ate an estimate for the flow rate of stream 4 prior to any controller
action.
By default, PRO/II prints convergence information at each control-
ler iteration. The controller may fail to converge under the follow-
ing conditions:
 The specification is not affected by the control variable
 The control variable is at the user-specified maximum or mini-
mum value and the specification is not satisfied

 The maximum number of iterations have been performed
 Three consecutive controller iterations fail to reduce the speci-
fication error
For controllers that are not inside other loops, the above conditions
cause an error message and all calculations are terminated. For con-
trollers inside recycle or other loops, the calculations are continued
until the maximum number of iterations allowed for these outer
loops has been performed. If the controller specification is still not
met, flowsheet solution then terminates.
Also See:
Feedback Controller

General Information
The Algorithm
General Information
The Multi-variable feedback controller (MVC) in PRO/II allows
control variables to be varied to satisfy an unlimited number of
flowsheet specifications. The specifications can include stream and
unit operating conditions as well as CALCULATOR results. The
control variables can be defined as stream or unit operating condi-
tions, thermodynamic properties and CALCULATOR results. The
number of variables must equal the number of specifications. If
desired, upper and lower bounds as well as maximum step sizes can
also be included for each control variable.Figure 11-8 shows an
example of a simple MVC application. There are three input
streams, S1, S2 and S3, all of which contain the three gaseous com-
ponents C1, C2 and C3 as well as inert gas C4. The flow rates and
compositions of the three streams are known. They are mixed to
form stream S4 and the MVC is used to specify the total flow rate
of S4 as well as the final ratio of C1 to C2 and of C2 to C3. The
MVC specifications are to be met by varying the flow rates of the 3
input streams.

Figure 10-7: Multi-variable Controller Example
The MVC is essentially an expanded form of the feedback control-
ler. Its main advantage is that it accounts for the interdependence of
control variables that are inherently coupled (several control vari-
ables affect the same specification). In the above application, for
example, each MVC specification is directly affected by all the
MVC variables to a greater or lesser extent. Trying to solve the
problem using a series of simple feedback controllers will be ineffi-
cient and may even result in failure if the changes in the individual
controller variables have opposing effects on the specifications.
Note though that if the variables are not coupled, it is generally
more efficient to use separate feedback controllers for each variable
and specification pair.
PRO/II automatically creates a loop for the MVC which incorpo-
rates all the units that are affected by changes in the MVC variables.
The units inside this loop will be solved repeatedly until all the
MVC specifications are met within tolerance. If the MVC affects
units in a recycle loop, either the MVC loop or the recycle loop may
be the outermost one. If the units affected by MVC variables and
specs are all inside the recycle loop, the MVC will be solved repeat-
edly every time changes are made to converge the recycle loop. If,
on the other hand, MVC specifications or variables affect any unit
outside the recycle loop, the latter is converged each time the MVC
varies a control variable. This choice of sequencing usually results
in the lowest solution times. To override the default, the desired

sequence must be specified explicitly using a SEQUENCE state-
ment.
The Algorithm
The MVC uses a first-order unconstrained optimization method to
simultaneously converge all the specifications. The objective func-
tion to be minimized consists of the sum of the squared errors in the
specifications. If bounds on the control variables are defined, these
are included in the objective function as penalty terms. Figure 11-9
illustrates the solution procedure for an MVC with 2 variables and
specifications.
Figure 10-8: MVC SolutionTechnique

For two variables, the algorithm involves the following steps:
3. Solve the flowsheet at the base case values of control vari-
ables V1 and V2.
4. Increase V1 by 10% (or set V1 equal to EST2, if supplied
by the user) and resolve the flowsheet. Compare the value
of the objective function at the base case and at the new
point. Move to the new point if the objective function is
lower here (point 2 in Figure 11-9).

5. Repeat step 2 for control variable V2.
6. Using the base case flowsheet solution and those from steps
1 and 2, estimate the derivatives of the objective function
with respect to variables V1 and V2 using finite differ-
ences.
7. Determine a new search direction using the derivative
information at the current point. Here, a hybrid method is
used which combines features from Newton-Raphson,
Steepest descent and Marquardt methods. Resolve the flow-
sheet at the new point.
8. If the MVC specifications are not met within tolerance
update the matrix of first derivatives using Broyden's
method and return to step 5.
The search step determined by the optimizer (step 5 of the above
algorithm) is adjusted if it exceeds the user defined STEPSIZES on
the variables or if it fails to improve the objective function suffi-
ciently.
For the example in Figure 11-9, a total of 5 MVC cycles is required
to reach the solution.
If requested, the MVC prints a detailed convergence history and a
series of diagnostic plots. These are intended to help the user deter-
mine what corrective action to take when the MVC fails to reach the
solution.Also See:
General Information
Solution Algorithm
General Information
The optimization algorithm within PRO/II is a powerful tool which
allows the operating conditions of a single unit or an entire process
flowsheet to be optimized. Typical applications are the minimiza-

tion of heat duty or the maximization of profit.Most generally, the
optimization problem can be formulated as:
Equation (10-10):
minimize f  x1, x2 ,..., xn  objective function

suchthat hi  x1, x2 ,..., xn   0 i  1,2,..., m1 specifications
gi  x1, x2 ,..., xn   0 i  1,2,..., m2 constraints
xi,min i  xi  xi,max i i  1,2,..., m1 bounds
where n is the number of variables, m1 is the number of specifica-

tions and m2 is the number of constraints.
Note: Maximizing f is equivalent to minimizing -f.
PRO/II requires an objective function and at least one variable to be

defined in the OPTIMIZER unit. In addition, upper and lower
bounds must be specified for each variable. If specifications are
included, m1 can be at most equal to the number of variables. The
number of constraints which can be defined is independent of the
number of variables. There is no hard upper limit on the size of the
optimization problem which can be solved.
Typical Application
depicts a typical optimization application:

Figure 10-9: Optimization of Feed Tray Location
In this example, the OPTIMIZER determines the feed tray location
which maximizes a profit function computed by the CALCULA-
TOR. This profit function includes the value of the overhead prod-
uct less the operating costs of the column. Hence:
Equation (10-11):
maximize Total profit comuted byCALCULATOR objective

function
suchthat Lowerlimit  Feed traylocation  UpperLimit bounds
The feed tray location is the optimization variable. The flowsheet
has two additional degrees of freedom, the heat duties of the
reboiler and the condenser. These are used as flowsheet variables

inside the column in order to meet the COLUMN specifications on
the purity of the overhead and bottoms products.
Objective Function
Exactly one objective function is required in the OPTIMIZER; it
must be defined so that it is the result of a calculation within PRO/II
and not a value which is fixed by the user.
The OPTIMIZER objective may be either a design or performance
objective. It may be expressed as an operational criterion (e.g.,
maximum recovery or minimum loss) or an economic criterion
(e.g., minimum cost or maximum profit). The CALCULATOR can
be used to develop more complex objective functions which
account for a variety of design and economic factors.
Finally, the objective function may also be defined via a user-writ-
ten subroutine.
Note that the objective function should be continuous in the region
of interest. The OPTIMIZER will perform best if the objective
function shows a good response surface to the variable; it should
neither be too flat nor too highly curved. Unfortunately, in practice,
many objective functions tend to be quite flat which may cause the
optimizer to terminate at different solutions when different starting
points are used. These solutions, which are all valid within toler-
ance will have similar objective function values but the values of
the variables may be quite different.
Optimizer Variables
Any flowsheet value which is defined as a fixed input parameter
can be used as a variable for the PRO/II optimizer. This includes
stream rates or properties, unit operating conditions, thermody-
namic properties and CALCULATOR results.
Certain restrictions apply; for example, if the location of COLUMN
feeds, draws, heaters or coolers are used as variables within the
OPTIMIZER, the rate and/or heat duty cannot also be used.
If the variables to be manipulated by the optimizer are specifica-
tions made on the flowsheet base case, the simplest specifications
should be chosen if possible since this speeds up the solution time.
For example, suppose a splitter specification is an optimization
variable. The base case specification on the splitter should be a
molar rate or ratio, this being the simplest specification possible.
The optimizer varies the value of this specification and resolves the
flowsheet. Making a more complex specification on the splitter

such as the weight rate of a given component in a given product
from the splitter and varying this in no way alters the solution to the
optimization problem but may increase the computational effort.
The problem may be more acute when column specifications are
optimization variables. Here, the simplest specifications, i.e., rate of
recovery or reflux should always be chosen since these specifica-
tions will make the column easier and faster to solve.
It is important to note that only those flowsheet parameters which
are fixed in the base case can be optimization variables. Thus for an
isothermal flash where both temperature and pressure are fixed,
both the temperature and pressure may be optimization variables.
For an adiabatic flash, on the other hand, the pressure is fixed and
the temperature is calculated. Here, it is incorrect to make the tem-
perature an optimization variable. Only the pressure is available for
this purpose. In addition, care must be taken that optimization vari-
ables are not varied by any other unit. This mistake is especially
common when the parameter defined as an optimization variable is
already fixed by the remainder of the flowsheet. Consider, for
example, the flowsheet in Figure 11-11.
Figure 10-10: Choice of Optimization Variables

If the rate of stream 3 is declared as an optimization variable and the
splitter S1 is specified with a fixed rate going to stream 2 then, how-

ever much the optimizer changes the rate of stream 3, the flowsheet
solution does not change. The solution stops in the OPTIMIZER
with an error message that another unit is also varying the rate of
stream 3. One way to model this particular case would be to specify
a splitter fraction on S1 and vary the rate of stream 3. Alternatively,
depending on the problem to be solved, the splitter specification can
also be varied directly.
PRO/II requires upper and lower bounds to be provided for all vari-
ables. For best OPTIMIZER performance, these bounds should be
chosen to reflect the actual range within which the flowsheet values
are expected to lie. For example, while 0 and 100 degrees Celsius
may be a physically valid temperature range for water, 15 and 25
degrees Celsius provide a more meaningful range for the expected
temperatures of a cooling water stream.
Specifications and Constraints

Constraints define the domain of acceptable solutions to the optimi-
zation problem; that is, they define ranges into which certain flow-
sheet values must fall (within tolerance) to represent an acceptable
solution to the optimization problem. Specifications define specific
values within the flowsheet which must be met (within tolerance) to
obtain an acceptable solution to the optimization problem.
Constraints and specifications may be made on design or perfor-
mance values, including values defined by a CALCULATOR unit
operation.
Cycles, Trials and Iterations

The optimizer introduces an outer iterative loop in the flowsheet
calculation. For the flowsheet in Figure 11-11, for example, the
COLUMN is solved repeatedly until the OPTIMIZER has deter-
mined the optimal feed tray location. These iterative loops are
referred to as “cycles”. Frequently, flow sheets to be optimized also
contain recycle streams. Therefore each optimization cycle may
involve a number of recycle “trials”. Likewise, any column must be
converged in a number of “iterations” at every flowsheet pass. This
terminology is maintained throughout the PRO/II program and all
supporting documentation.
Cycles:Number of optimizer steps (see section on 
Solution Algorithm below).
Trials:Number of recycle trials in each flowsheet solution. 
Reset to zero after each flowsheet solution.

Iterations:Number of column iterations per column solution.
For both columns and recycle loops, the maximum number of trials
and iterations allowed should be increased to prevent flowsheet fail-
ure. While the defaults may be adequate when solving the base
case, the OPTIMIZER may cause the flowsheet to move to a new
state where the columns and recycle loops are more difficult to con-
verge.
Recommendations
When solving an optimization problem, the following points should
be noted:
 Always solve the base case separately. Check the results care-
fully to ensure that the problem setup and solution are exactly
what is required.
 Carefully select the bounds and constraints to ensure that the
flowsheet is physically well-defined over the entire solution
space. The flowsheet will not solve if, for example, flow rates
or absolute temperatures are allowed to go negative.
 Flowsheet tolerances should be tightened for improved accu-
racy. This is necessary in order to obtain good first order deriv-
atives and is particularly important when the flowsheet
contains columns or recycle loops.
Solution Algorithm
Introduction
PRO/II uses Successive Quadratic Programming (SQP) to solve the
nonlinear optimization problem. The algorithm consists of the fol-
lowing steps. To simplify the notation, define xk=(x1,k,x2,k,...xn,k)
as the vector of the optimization variables which define the state of
the system.
1. Set the cycle counter k=1 and solve the flowsheet at x1.
2. < >Perturb each optimizer variable by some amount hi and
resolve the flowsheet. Use the base case flowsheet solution and
the n additional flowsheet solutions to approximate the first
derivatives of the objective function, specifications and con-
straints via finite differences.
3. If  the
kuse 2 first order derivatives at the previous and current
cycles to approximate the second order derivatives.

4. Solve a quadratic approximation to the nonlinear optimization
problem (QP subproblem). This yields a search direction dk.
Set the search step .
5. Solve the flowsheet at xk+1 = xk + dk.
6. If the flowsheet solution at xk+1 is not a sufficient improvement
as compared to the flowsheet solution at xk reduce the search
step  and return to step 4.
7. Let xk+1 be the new base case. Set k=k+1 and return to step 2.
Various tests are included after the solution of the quadratic approx-
imation (step 3) and after each “non derivative” flowsheet solution
(step 4) to determine whether the convergence tolerances are satis-
fied.
The quadratic programming algorithm used in step 3 automatically
determines which of the constraints are binding or active i.e. which
of the inequality constraints gi ( x)  0 are satisfied as equality con-
straints g A ( x)  0 at the current value of the optimizer variables. In
addition, the quadratic programming algorithm ensures that the
optimizer variables do not exceed their bounds and determines
which variables are exactly at a bound (e.g., x1=x1,maxi)
Note that each optimizer cycle includes steps 2 through 6. If the
algorithm has to return to step 4, this is referred to as a line search
iteration. Line search iterations are common initially; if line search
iterations are necessary close to the solution this frequently indi-
cates that the error in the first order derivatives is too large and the
algorithm is having difficulties meeting the convergence tolerances.
Calculation of First-order Derivatives

PRO/II calculates the derivatives of the objective function, specifi-
cation and constraints with respect to the OPTIMIZER variables
using finite differences. A small perturbation is made to each vari-
able separately and the flowsheet is resolved. Each derivative is
then calculated by:
Equation (10-12):
f f  xi  hi   f  xi 

xi hi
To obtain the best derivative information, the step size hi for each
variable xi should be small enough so that the higher order terms
which are neglected in the above formula are minimized. However,

if hi is too small, the derivatives will be dominated by flowsheet
noise. The accuracy of the derivatives can be improved by tighten-
ing the flowsheet tolerances and by using the appropriate perturba-
tion steps.
By default, the perturbation steps are calculated as 2% of the range

of each of the variables (this is increased to 5% if NOSCALE is
entered on the OPTPARAMETER statement). The user can over-
ride this default by entering values for APERT or RPERT. If the
functions and derivatives are well-behaved, the “ideal” perturbation
size is given by:
Equation (10-13):
hi   R xi ,typical
where:
R = the relative accuracy with which the functions are evalu-
ated.
For simple functions this is on the order of machine precision (~
10E-6); for complex flow sheets with sufficiently tight tolerances
the relative accuracy is on the order of 10E-3 to 10E-4.
To aid the user in selecting appropriate step sizes, a full diagnosis is
printed when the keyword DERIV is included on the OPTPARAM
statement of keyword input. To activate this through PROVISION,
on the main Data Entry Window for the Optimizer, press the
Options button. From the Options DEW, press the Advanced
Options button. From the Advanced Options DEW, turn Deriva-
tive Analysis: to ON. This is independent of the number of opti-
mizer cycles. In addition to the forward difference formula given
above, the derivatives are also calculated using backward differ-
ences and central differences.
The information shown in Table 10-3 is then displayed for each
variable for the objective function and each specification and con-
straint.
Table 10-3: Diagnostic Printout

Sign (backward, central, forward) - or 0 or +
Effect none or low or high
Maximum deviation percentage
Current perturbation size value

Table 10-3: Diagnostic Printout
Suggested perturbation size value

Unless a variable has no effect, the first line displays the sign of the
backward, central and forward derivatives. If the maximum differ-
ence between the central derivative and forward or backward deriv-
atives is greater than 1%, it is reported on line 3. The perturbation
size should be chosen so as to minimize this difference. The current
value of the absolute perturbation is reported on line 4 and a sug-
gested perturbation, calculated assuming that the accuracy of the
flowsheet solution is 10-4, is printed on the last line. Note that this
value is only intended as a guideline; the change in the maximum
deviation should be monitored when the perturbation size is modi-
fied. Note also that if the magnitude of a variable changes by sev-
eral orders of magnitude, the perturbation size determined at the
initial point will no longer be appropriate.
To ensure consistent flowsheet solutions it may also be necessary to
invoke the COPY option (an OPTPARAMETER keyword). Here,
the entire PRO/II database is stored which allows the flowsheet
variables to be initialized identically for each perturbation evalua-
tion rather than at the final value from the previous perturbation.
Bounds on the Variables

For best optimizer performance it is very important to supply appro-
priate upper and lower bounds for each variable. The bounds are
used for the automatic scaling of the variables. As discussed previ-
ously, they are also used to determine the default perturbation size
and, finally, they may also affect the magnitude of the optimizer
steps during the first three cycles (see the section following).
STEP Sizes
By default, the OPTIMIZER variables are not allowed to move
more than 30, 60 and 90 percent to their upper or lower bound dur-
ing optimization cycles 1, 2 and 3, respectively. This is intended as
a “safety feature”; it prevents the optimizer from moving too far,
particularly when the derivatives are inaccurate. The STEP key-
word is used to override this default by providing an absolute limit
for the maximum change in a variable during one optimization
cycle. Providing a value for STEP which is larger than MAXI-MINI
for a particular variable allows that variable to move through its full
range at every optimization cycle.

If the OPTIMIZER contains more than one VARY statement, the
changes in the variables determined in step 3 of the above algorithm
will all be reduced by the same factor until all the variables are
within the limits imposed by the individual STEPSIZEs. Hence, the
relative change in the variables is not affected by the STEPSIZE on
each variable.
Termination Criteria
The following conditions are tested at every optimizer cycle:
1. Is the relative change in the objective function at consecutive
cycles less than 0.005 (or the user defined value RTOL for the
objective function)?
2. Is the relative change in each variable at consecutive cycles less
than 0.0001 (or the user defined values RTOL for each vari-
able)?
3. Has the maximum number of cycles been reached?
4. Does the scaled accuracy of the solution fall below 10-7 (or the
user defined value SVERROR)? The scaled accuracy, which is
also known as the Kuhn-Tucker error, is calculated from:
Equation (10-14):
KTE  f T d   i hi   i gi
i i

where:
f = a vector which contains the first derivatives of the objec-
tive function
d = the search direction from the QP subproblem
h and g = specifications and constraints, respectively.
The weights on the specifications and constraints, and  are deter-
mined automatically when the QP subproblem is solved (step 3 in
the algorithm previously described). These weights are referred to
as multipliers or shadow prices (see the following section).
If none of the above conditions are satisfied, the optimizer contin-
ues to the next cycle. If at least one of conditions 1 to 4 is satisfied,
the following conditions are also tested.
5. Is the relative error for each specification less than 0.001 (or the
user defined value RTOL or ATOL for each specification)?

6. Is the relative error for each constraint less than 0.001 (or the
user defined value RTOL or ATOL for each constraint)?
If both 5 and 6 are satisfied, the OPTIMIZER terminates with the
message SOLUTION REACHED. If the relative error for any spec-
ification or constraint is greater than the required tolerance, the
OPTIMIZER will terminate with SOLUTION NOT REACHED.
The optimization problem may also fail for one of the following
reasons:
 Another unit in the flowsheet may fail to converge.
 The number of column, controller or recycle loops which is
allowed is insufficient.
 The optimization problem is infeasible.
Post-Optimality Analysis (Shadow Prices)

Once the flowsheet optimization has converged and the appropriate
operating conditions have been determined, the shadow prices or
Lagrange multipliers can be used to assess the sensitivity of the
objective function to the specifications, constraints and bounds.
These values, which are calculated automatically by the optimiza-
tion algorithm are reported in the output report if OPRINT=ALL is
selected on the OPTPARAMETER statement. The signs of the mul-
tipliers follow the following convention:
 If the multiplier of a specification or constraint is positive, then
increasing the corresponding MINI, MAXI or VALUE will
increase the value of the objective function.
 If the multiplier of a specification or constraint is negative, then
increasing the corresponding MINI, MAXI or VALUE will
decrease the value of the objective function.
In addition, the magnitude of the shadow prices indicates which
specifications and constraints have the greatest effect on the optimal
solution.
Reference
1 Fletcher, R., 1987, Practical Methods of Optimization,
Wiley.
2 Gill, P.E., Murray, W., and Wright, M.H., 1981, Practical
Optimization, Academic Press.

Also See:

Chapter 11: Depressuring
General Information
Theory
Calculating the Vessel Volume
Valve Rate Equations
Orifice Rate Equations
Heat Input Equations
Isentropic Efficiency Considerations
General Information
All unit operation calculation methods described in previous chap-
ters of this manual relate to process units operating under steady-
state conditions. PRO/II also provides a model for one unsteady-
state process unit -- the depressuring unit. This unit operation may
be used to determine the time-pressure-temperature relationship
when a vessel containing liquid, vapor, or a vapor-liquid mixture is
depressured through a relief or control valve. The user may input
the valve flow characteristics. This unit operation also finds appli-
cation for problems relating to refrigeration requirements in storage
vessels. Product streams may be generated as a user option, but the
calculations are not performed until output time. A heat input may
also be described by the user to simulate the pressuring of the vessel
by a fire or other means.
Theory
The depressuring calculations begin by mixing the feed streams adi-
abatically to give the composition, xi,0, temperature, T0, and pres-
sure P0 of the vessel at time t=0. The initial composition of the
liquid and vapor inside the vessel is calculated following the guide-
lines below.If a liquid holdup is specified:
 For a mixed-phase feed, the composition of the liquid phase,
will be set equal to the composition of the liquid portion of the
feed, and the vapor-phase composition set equal to the feed
vapor composition.

 For a liquid-phase feed, then the initial vapor composition in
the vessel will be set equal to the vapor in equilibrium with the
feed liquid at its bubble point temperature.
Note: For a vapor only feed, PRO/II will give an error message if a
liquid holdup is specified.
After the initial composition of the vapor and liquid portion of the
vessel contents is determined, the initial total number of moles for
each component, Fi,0, in the vessel is calculated using:
Equation (11-1):
Fi ,0  xiL,0V0L 0L  xiV,0V0V  0V
where:
Fi,0 = moles of component i at time t=0
xLi,0 = mole fraction of component i in liquid
xVi,0 = mole fraction of component i in vapor
VL0 = initial liquid volume in vessel
VV0 = initial vapor volume in vessel
If no liquid holdup is specified:
 The composition of the vessel contents is set equal to the com-
position of the feed, and the temperature and pressure of the
vessel are set equal to that of the feed stream. The total number
of moles of each component in the vessel at time t=0, Fi,0, is
calculated using:
Equation (11-2):
Fi ,0  xifeedV0  f ,mix

where:
Fi,0 = moles of component i at time t=0
xifeed = mole fraction of component i in feed
V0 = volume of vessel
f,mix = mixture density of feed stream
Depressuring 11-578
Also See:
Depressuring
Calculating the Vessel Volume

The volume of the vessel holdup liquid is calculated for spherical,
vertical cylindrical, or horizontal cylindrical vessels, using the fol-
lowing relationships:
Horizontal Cylinder Vessel

Equation (11-3):
 
Vv   r 2 L  2Vend V fac
where:
r = radius of vessel
L = tangent to tangent vessel length
Vfac = volume factor which corrects for pipes and fittings
Vend = end cap volume, which is given by:
Equation (11-4):
1
Vend    0.5r  *  3*1.25r  0.5r 
2
3
The optional user-supplied volume correction factor, Vfac, defaults
to a value of 1.0, if not supplied.
Vertical Cylinder Vessel

Equation (11-5):
 
Vv   r 2 h  2Vend V fac
where:
r = radius of vessel
h = tangent to tangent vessel height
The end cap volume, Vend, is again given by equation (4) above.

Spherical Vessel
Equation (11-6):
4
Vv   r 3V fac
3
Also See:
Depressuring
Valve Rate Equations

All the valve equations are based on vapor flow only through the
valve. The valve upstream pressure is assumed to be the same as the
vessel pressure.
Sonic Flow:
For sonic flow, the pressure drop across the discharge valve, ΔP
should satisfy the relationship:
Equation (11-7):
P  0.5C 2f P1
where:
Cf = critical flow factor, dimensionless
ΔP = actual pressure drop = P1 - P2, psia
P1 = upstream pressure, psia
P2 = downstream pressure, psia
The valve rate for sonic flow is given by:
Equation (11-8):
W  2.8Cv C f P1 G f
where:
W = vapor flow rate through valve, lbs/hr
Cv = valve flow coefficient, dimensionless
Gf = specific gravity at temperature T(oR)
The gas specific gravity can be written as:
Depressuring 11-580
Equation (11-9):
520 MW
Gf 
MWairT
where:
MW = molecular weight of discharge stream
MWair = molecular weight of air
T = temperature of stream, oR
The stream molecular weight is given by:
Equation (11-10):
v
MW  zRT
Pi
where:
z = gas compressibility factor
R = gas constant = 1.98719 BTU/lb-molR
v = vapor density, lb/ft3
Substituting equations (9) and (10) in equation (8) gives the follow-
ing expression for the vapor rate through a valve under sonic flow
conditions:
Equation (11-11):
W  C1 P1 v
where:
Equation (11-12):
520 zR
C1  2.8Cv C f
MWair
Subsonic Flow:
For subsonic flow, the pressure drop across the valve must satisfy:
Equation (11-13):
P  0.5C 2f P1
The valve rate for subsonic flow is given by:

Equation (11-14):
W  3.22Cv PPG
1 f
Again, substituting equations (9) and (10) into (13), the valve rate
for subsonic flow becomes:
Equation (11-15):
W  C1 P v
where:
Equation (11-16):
520 zR
C1  3.22Cv
MWair
The constant C1 has units of:

(weight/time) / (pressure.weight / volume)0.5.
Constant Flow:
Alternatively, the user can specify a constant discharge rate:
Equation (11-17):
W  Constant
Masolenian Model:
The user may also specify a more general valve rate formula:
Equation (11-18):
W  AC f CvY f P1 v
where:
A = a constant with units of (weight.volume/pressure.time2)1/2.
Values for the constant A in equation (16) in English, SI, or Metric
units are given in Table 11-2.
Table 11-2: Value of Constant A

Dimensional Units System Value of A
English 38.84
SI 1.6752
Depressuring 11-582
Table 11-2: Value of Constant A
Metric 16.601
Yf is given by:
Equation (11-19):
Y f  Y  0.148Y 3
and,
Y is given by:
Equation (11-20):
0.5
 P 
1.63  
 P1 
Y
Cf
If Y > 1.5, Yf is not calculated by equation (19), but is instead set

equal to 1.0.
The control valve coefficient, Cv, is defined as “the number of gal-
lons per minute of water which will pass through a given flow
restriction with a pressure drop of 1 psi.”. This means that the value
of Cv is independent of the problem input units.
Orifice Rate Equations

Equation will be selected based on the flow conditions.
If Pcf > Pb - Sonic Flow.
If Pcf <= Pb - Subsonic flow.
Once the flow changes from Sonic to Subsonic, it always remains
subsonic.
Equation (11-21):
 -
----------
P cf 2 –1
------- = -----------
P1 +1
Where
Pcf = Critical flow nozzle pressure
P1 = Upstream relieving pressure

Orifice Subsonic flow:
2
D2 
The valve rate (weight/time) = C    ---------  -----------------  2     P – Pb 
4 4
1–
  ---------
– 1

  
 2
 ---  Pb  2  
   1–  ------  --
-
  
Pb   P Pb 
 =   ------   ---------  -------------------------------   1 –     1 –    ------  
4 4
where      – 1   P  
Pb
  1 –  ------  
  P  
 
Pb = Value down stream pressure
β = Ratio of Orifice diameter to Pipe diameter
Orifice Sonic Model:   + 1
----------
   
  2 -  – 1
The valve rate (weight/time) = CA  ---------  p  
   + 1 
 
where γ is specific heat ratio.
Also see:
Depressuring
Heat Input Equations

The heat flow between the depressuring vessel and a heat source or
sink may be defined using one of four types of heat input models.
User-defined Model
This heat model is given by:
Equation (11-22):
v Vt 4
Q = C 1 + C 2 t + C 3  C 4 – T t  + C 5 ----- + C 6  T v 
Vi
where:
Q = heat duty in millions of heat units/time
C1, C2, C3, C4, C5 , C6 = constants in units of millions of heat
units/time
t = time (elapsed since start of depressuring)
TV = vessel temperature at time t
Vt = volume of depressuring vessel at time t
Vi = volume of depressuring vessel at initial conditions
Depressuring 11-584
If values for the constants are not provided, the general heat model
defaults to Q = 0.0, i.e., to adiabatic operation.
The User-Defined model allows up to six coefficients while the
Blowdown model allows five coefficients. In these two models,
each coefficient ‘Ci’ is used as a separate term. By omitting or pro-
viding zero as the value of coefficient effectively removes it from
the equation (i.e. the contribution of the term is zero). Therefore, by
selecting non-zero values for different combinations of coefficients,
these two equations will support wider variety of equation forms.
For example, the sixth coefficient in the User-Defined model allows
a modelling called NORSOK correlation.
API 2000 Model

This heat model is recommended for low pressure vessels and is
given by:
Equation (11-23):
Q  C1  At 
C2
where:
C1, C2 = constants whose values are given in Table 11-3
At = current vessel wetted area = Ai
Ai = initial wetted area, ft2
Table 11-3: Value of Constants C1 & C2
For AT C1 C2
20 - 200 20000 1.000

201 - 1000 199300 0.566
1001 - 2800 963400 0.338
> 2800 21000 0.820
A dimensionless area scaling factor may also be used with the
API 2000 heat model. If a scaling factor, Afac, is specified, the
current vessel wetted area is not equal to the initial wetted area,
but is instead calculated using:
Equation (11-24):
Vt
At  Ai Afac
Vi

APISCALE Model
This heat model is similar to the API 2000 heat model, except the
heat duty is scaled and is given by:
Equation (11-25):
Vt
Q  C1  At 
C2
Vi
Again, an area scaling factor may or may not be specified. If Afac is

used, At is given by equation (12-23). If Afac isn't specified, At is
set equal to the initial wetted area.
ANSI/API 521
This heat model applies to uninsulated vessels above ground level
and is the recommended model for pressure vessels. The heat model
is given by:
Equation (11-26):
Q  21000  At 
0.82

ANSI/API 521 with Scaling

This heat model is similar to the ANSI/API 521 model, but with
scaling applied. It is given by:
Equation (11-27):
Vt
Q  21000  At 
0.82
Vi

Fire Relief Model

The fire relief model is given by:
Equation (11-28):
Q  C1C2  At 
C3
Depressuring 11-586
where:
C1, C2, C3 = user-supplied constants
Gas Blowdown Model

The gas blowdown mode assumes an external heat input to the ves-
sel metal followed by transfer of heat from the vessel metal to the
gas. Initially, the vessel temperature is taken to be the same as the
gas temperature. The external heat input is then calculated from:
Equation (11-29):
Vt
Q  C1  C2t  C3  C4  Twall   C5
Vi
The heat transfer to the fluid inside the vessel is computed using:
Equation (11-30):
Qint  hv Avap T  hl Aliq T

Equation (11-31):
T  Twall  T fluid
where:
hv = heat transfer coefficient between the vessel and the vapor
phase of the fluid
Avap = area of vapor phase in vessel
Tfluid = temperature of fluid in the vessel at time t
hl = heat transfer coefficient between the vessel and the liquid
phase of the fluid
Aliq = area of liquid phase in vessel
The gas is depressured isentropically using either a user-defined
isentropic efficiency value or the default value is 0.0. For each time
interval, the heat transfer from the vessel is calculated by using the
Nusselt heat transfer correlations. The heat transfer coefficient
between the vessel and the vapor phase of the fluid, hv, is deter-
mined using:
Equation (11-32):
0.13kv  N Gr N Pr  h fac
1/3
hv 
r

where:
kv = thermal conductivity of vapor phase
NGr = dimensionless Grashof number
NPr = dimensionless Prandtl number
hfac = heat transfer coefficient factor (=1.0 by default)
The Grashof and Prandtl numbers are given by the following rela-
tionships:
Equation (11-33):
r 3 v2  g c T
N Gr 
v2
Equation (11-34):
cpv v
N Pr 
kv
where:
 = volumetric coefficient of thermal expansion, 1/oF
v = viscosity of vapor
T = Twall - Tfluid
cpv = heat capacity of vapor
The heat transfer coefficient between the vessel and the liquid phase
of the fluid, hl, is determined in a similar manner using the follow-
ing relationships.
Equation (11-35):
0.13kl  N Gr N Pr  h fac
1/3
hl 
r
where:
kl = thermal conductivity of liquid phase
The Grashof and Prandtl numbers are given by the following rela-
tionships:
Depressuring 11-588
Equation (11-36):
r 3 l2  g c T
N Gr 
l2
Equation (11-37):
cpl l
N Pr 
kl
where:
l = viscosity of liquid
cpl = heat capacity of liquid
The change in the wall temperature, Twall, is determined from the

isentropic enthalpy change and the heat transferred to the gas from
the wall, i.e.,
Equation (11-38):
Qext t   q fluid  qisen  M t

Twall 
Wvess cpvess
where:
qfluid = change in specific enthalpy of the fluid, BTU/lb-mole
qisen = isentropic specific enthalpy change as the gas expands
Mt = moles of gas depressured in time period t, lb-mole
Wvess = weight of depressuring vessel, lb
cpvess = heat capacity of depressuring vessel, BTU/lb-F
Isentropic Efficiency Considerations

Isentropic efficiency is the percentage of isentropic fluid expansion
consumed as work. The application of external heat is not a source
of isentropic work. Specifying a positive value for isentropic effi-
ciency activates isentropic calculations in the depressuring unit.
At each depressuring step, a pressure change is applied and used in
iterative calculations to compute new values for the enthalpy and
temperature of the vessel fluid. At convergence of each step, the
energy and material balances are satisfied using these new values.

With isentropic efficiency specified, additional calculations apply
to the energy balance.
An isentropic flash computes the enthalpy change of the fluid due
only to isentropic fluid expansion (positive or negative). Isentropic
efficiency is applied to the isentropic enthalpy change of the fluid.
Equation (11-39) computes the energy consumed as isentropic
work.
Equation (11-39):
Workisen   H isen  H init  * Eisen
The new fluid enthalpy is adjusted by subtracting the energy con-

sumed as isentropic work, as shown in equation (11-40).
Equation (11-40):
H fluid   H final  H init   Workisen
where:
E isen is the specified isentropic efficiency.
H init is the initial enthalpy of the fluid at the start of the step.
H isen is the fluid enthalpy computed by the isentropic flash.
Work isen is the energy consumed as isentropic work.
H fluid is the final adjusted enthalpy change of the fluid.
Removing work in this manner eliminates the energy lost to isentro-
pic expansion from the overall energy balance. This means subse-
quent heat transfer calculations do not need to consider losses due
to isentropic work.
Reference
2 Masoneilan Handbook, 1977, 6th Ed., Masoneilan Ltd.,
London, GB.
3 Perry, R.H., and Green, D.W., 1984, Chemical Engineering
Handbook, 6th Ed., McGraw-Hill, N.Y., pg. 10-13.
Also See:
Depressuring
Depressuring 11-590
Chapter 12: Batch Distillation Model-
ing Using BATCHFRAC®
BATCHFRAC® is a batch distillation model that resolves unsteady-

state heat and material balance equations. These equations
outline the behavior of a multi-stage batch distillation column.
BATCHFRAC® utilizes rigorous heat balances, material balances,
and equilibrium relationships at each stage. BATCHFRAC® com-
putes the profiles of column composition, temperature, pressure,
and vapor and liquid flows as a function of time.
Model Column Schematic
Total Mass Balance Equations
Component Mass Balance Equations
Enthalpy Balance Equations
Other Equations
Product Accumulator Equations
Model Column Schematic

A typical schematic using BATCHFRAC® is illustrated below.
BATCHFRAC® numbers stages from the top down, starting with
the condenser. The distillation operation is presented by a series of
sequential operation steps. BATCHFRAC® executes a total reflux
calculation at the beginning of the first operation step.

Figure 12-1: Model Column Schematic
The algorithm is partitioned into an inner and outer loop. IN the

inner loop, the heat, material, and design specifications are solved.
Simple thermodynamic models for enthalpy and vapor liquid equi-
librium K-values are used in the inner loop. In the outer loop, the
simple thermodynamic model parameters are updated based on the
new composition and the results of rigorous thermodynamic calcu-
lations. The inner loop equations are solved using Newton-Raphson
method. The algorithm is similar to I/O column.
The equilibrium K-value simple model is given by Kij = áijKb
where áij = relative volatility of component I on tray j, and
Kb = base component K value, where
Equation (12-1):
1 1 
K b  A  B   ref 
T T 
Total Mass Balance Equations

The total mass balance equations are as follows.
Batch Distillation Modeling Using BATCHFRAC® 12-592

Condenser
Equation (12-2):
dH1
V2  1  R  D   F1
dt
Typical Internal Stage

Equation (12-3):
n dH j n n n
Vn 1  Ln  D     Fj   WL j   Wv j
j 1 dt j 1 j 2 j 2
Reboiler
Equation (12-4):
dH n
LN 1  VN   Fn  B  Wvn
dt
Overall
Equation (12-5):
n N 1
dH n N N
D     Fj   WL j   Wv j
n 1 dt j 1 j 2 j 2
Component Mass Balance Equations

The component mass balance equations are furnished below.
Condenser
Equation (12-6):
dH1 X i1
 1  R  DX i1  K i 2V2 X i 2   f i1
dt
where i = 1, …, n (n – no. of components)

Equation (12-7):
 
dH n X in
Ln 1 X in 1  ( L  K in v ) X in  K in 1Vn 1 X in 1   f i1
n n dt

Reboiler
Equation (12-8):
dH n X iN
Ln 1 X in 1  ( K in vn  B) X iN   f i1
dt
Equation (12-9):
Ln  Ln  WLn
Equation (12-10):
Vn  Vn  Wvn
where
B Bottom residual
D Distillate
fij Feed of component i to stage j
Hi Holdup of tray i
Kij K-value for component i on tray j
Li Net liquid entering tray i
L̃ i Total liquid flow rate from tray i-1
R Reflux ratio
Wvi Net vapor draw from tray i
WLi Liquid draw from tray i-1
Vi Vapor leaving tray i
Xij Mole fraction of component i on tray j

Enthalpy Balance Equations
The enthalpy balance equations are as follows.
Condenser
Equation (12-11):
dH1hL1
V2 hv 2  (1  R) DhL1  Qc   F1hF 1
dt

Equation (12-12):
n
dHJ hLJ n n n
Vn1hvn1  LnhLN  DhL1 Qc    Fj hFj  WLj hLj  Wvj hvj
j 1 dt j 1 j 2 j 2
Reboiler
Equation (12-13):
dH n hL N
QR  LN 1hLN 1  VN hVN   FN hFN  BhLN  Wvn H vn
dt
Overall
Equation (12-14):
N N 1
dH n hL N N N
QR  Qc  DhL1     Fj H Fj  WLJ H LJ  WVJ hVJ
n 1 dt j 1 j 2 j 2
Where
hvi Enthalpy of vapor from tray i
hLj Enthalpy of liquid to tray j
hFi Enthalpy of feed to stage i
Qc Condenser duty
QR Reboiler duty

Other Equations
The other related equations taken into consideration are as follows:
Equilibrium relation
Equation (12-15):
 (K
i
in  1) X in  0
 Yij 
 K ij  
 X ij 
comp
Y
i 1
ij 1
VLE
Equation (12-17):
yin  K in X in
State
Equation (12-18):
Gn  n
Hn 
Mn
where
Gn Liquid volume on tray n
ñn Density
Mn Molecular weight

Mixture density
Equation (12-19):
Mn
n 
XM
i  i(T i)
i n
Mixture molecular wt.

Equation (12-20):
M n   X in M i
i
Equation (12-21):
 
hLn  hLn  Tn ,  n , xn 
  
Equation (12-22):
 
hvn  hvn  Tn ,  n , yn 
  
Equation (12-23):
 
kin  kin  Tn ,  n , xn yn 
   
Product Accumulator Equations

The product accumulator equations taken into consideration are as
follows:
Equation (12-24):
dH 
 D  W
dt
or
Equation (12-25):
dH  X i
 DX i1  W X i 
dt

Appendix A: HXRIG Heat Transfer
Correlations
Shell side
Tubeside
Shell side
Modified Chen Vaporization Method
A1) Shellside Vaporization (Except Kettle Reboiler):
Equation (A-1):
HF 
(HLIQ  H NB)  (QREB  QLIQ  QWAT)  HVAP  (QVAP  QSTE )
QR
QCHF
 if (TSAT  H F )  QCHF
TSAT
Equation (A-2):
H LIQ  H LIQ  FF
HLIQ and HVAP are calculated using the Shell side heat transfer cor-
relations listed in equations from (5-11) to (5-15) in Chapter 5.
Equation (A-3):
FF  1 if XTT  10
0.7
 1 
 2.25    0.113 if XTT  10
 XTT 
Equation (A-4):
0.9 0.5 0.1
 (1  X V )     
XTT      V    L 
 X V   L   V 
Equation (A-5):
(WAV  WAS )
XV 
WTOT

Equation (A-6):
(WVi  WVo )
WAV 
2
Equation (A-7):
(WLi  WLo )
WAL 
2
Equation (A-8):
(WWi  WWo )
WAW 
2
Equation (A-9):
(WSi  WSo )
WAS 
2
Equation (A-10):
QCHF  176.0  C1  C2 if C1  0.1

 176.0  0.1 C2 if C1  0.1
Equation (A-11):
 DOTL  TL 
 
 12 
C1 
 A 
 
 Np 
 
Equation (A-12):
C2  L   V0.5  (4.173 108  TS  (  L   V ))0.25

Equation (A-13):
TSAT  TW  TC if (WAV  WAS )  1.0

 TW  TB if (WAV  WAS )  1.0
Equation (A-14):
 0.09592  K L0.79  Cp0.45   L0.49  TSAT

0.25 0.75
 PSAT  Fbs 
H NB   L  F F
 T 0.5
  0.29
  0.24
  0.24  ONB
 s L L V 
Appendix Appendix A:-600

Equation (A-15):
TSAT 144
PSAT 
TTP
Equation (A-16):
 1 1 
TC     144
  V  L 
TTP 
778  L
Equation (A-17):
1
Fbs 
(1  1.17
N Re tp
10 5 )
Equation (A-18):
2.5
 TSAT 
FONB   
T 
 W CT
Equation (A-19):
FWBT  e ( 0.009(TD TB ))

 1 if FWBT  1
 0.2 if FWBT  0.2
Equation (A-20):
N Re tp  N Re L  FF1.25
Equation (A-21):
DW  GT
N Re L 
12  L
Equation (A-22):
(WAL  WAW )
GT 
N p  AF
Equation (A-23):
AC
AF 
144

Equation (A-24):
QREB  QR  QTOT
Equation (A-25):
QTOT  QLIQ  QVAP  QWAT  QSTE

Equation (A-26):
QLIQ  Cp L  T  WAL
Equation (A-27):
QVAP  Cp V  T  WAV
Equation (A-28):
QWAT  Cp W  T  WAW
Equation (A-29):
QSTE  CpS  T  WAS
A2) Shellside Vaporization for Kettle Reboiler:

Equation (A-30):
H1  ( H1a  H1b )  FWBT

Equation (A-31):
0 . 69 0 . 31
 Q TOT  C p L   144  PAV  K L   
H 1 a  0 . 225         L 
 A  L   TS   V
0 .7 0 . 17
Q   PAV 
 2 . 99   TOT    
 A   3208 . 0 
if (W HCL  H HCV )  1 and (W S  W W )  1
Equation (A-32):
0.25
140.963  K L  d o   L    TB  Cp L 
3 2
H1b   
d o   L  K L 
 
Equation (A-33):
d o  d o  (tf  2)

Equation (A-34):


  L2
2
L 
TB   L   L 
Equation (A-35):
TB  TW  TC if (WAV  WAS )  1.0

 TW  TB if (WAV  WAS )  1.0
Equation (A-36):
0.25
 TB 
FONB    if (WAV  WAS )  1.0
 (TW  TC ) 
 1.0 if (WAV  WAS )  1.0
Equation (A-37):
FWBT  e ( 0.009(TD TB ))

 1.0 if FWBT  1
 0.2 if FWBT  0.2
 1.0 if (WHCL  H HCV  1 and WS  WW  1)
B) Shellside Condensation:
Equation (A-38):
1
H F
 1   QF 
    
H
 F   1
 C  H VAP 
Equation (A-39):
QVAP  QSTE
QF
QR
Assume C1= 1 and calculate

Equation (A-40):
 A 
C2  0.5   C1  ( A )1 
 
e 1 1  

Equation (A-41):
WTOT  A2 Cp VS
A1 
H VAP
Equation (A-42):
H F  T BWFd
A2 
WTOT  L
Equation (A-43):
T BW 0.5  (Ti  To )  TW

Equation (A-44):
QCOND
Fd 
QR
Equation (A-45):
Cp VS 
WAV  Cp  WAS  Cp 
V S
WAV  WAS 
Assign C2 value to C1 and repeat calculation of HF till
 C2  C1 
   10 6
 C1 
Equation (A-46):

2
H F  H LI 2
Q  H SHL  0.5
Equation (A-47):
0.78
 1 
H LIQ  1.26  H LIQ   
 XTT 
HLIQ and HVAP are calculated using the shell side heat transfer cor-
Equation (A-48):
0.9 0.5 0.1
 (1  X V )     
XTT      V    L 
 XV   L   V 

Equation (A-49):
(WAV  WAS )
XV 
WTOT
Equation (A-50):
a2
H SHL  1.51 
a1
Equation (A-51):
 L2 1  3
 --------------------------------------------------------------------
  L   L –  v   4.17312  10 8 
a 1 = ---------------------------------------------------------------------------------
KL
Equation (A-52):
( 1 / 3)
 4  Wx 
a2   
 L 
Equation (A-53):
Equation (A-54):
WTOT  (1  X V )
Wx 
N pN pp
HEX5 Method
C1) Shellside Vaporization (except Kettle Reboiler):
Equation (A-55):
( H F  Q REB )  H LIQ  (Q LIQ  Q WAT )  H VAP  (Q VAP  QSTE )

HF  if Q
QR
H F  H LIQ  H VAP 
 if Q R  0
3
HLIQ and HVAP are calculated using the Shell side heat transfer cor-

Equation (A-56):
0.6667
 
H F  749.0  RJ  KL   L 
 L 
 H F  F if shell type is ' X' and orientation is vertical
Equation (A-57):
RJ  10( 0.25545 X 1 ( 0.0022358) X 2 ( 0.32638) X 1  X 2 (0.0067075)) if N Re  100

 1.1258  X 1  (0.27941  X 1  0.079434)
 X 2  ((0.50141  X 1  (0.21098  X 1  0.051097)
 X 2  (0.067757  X 1  (0.043285  X 1  0.006845)) if N Re 
Equation (A-58):
X 1  ln  N Pr 
Equation (A-59):
X 2  Log10  N Re 
Equation (A-60):
Cp L   L
N Pr 
KL
Equation (A-61):
3.993  Cr
N Re 
L
Equation (A-62):
F  1.0009929  C1  (0.1649254  C1  (0.09907  C1  0.0213

Equation (A-63):
C1  Log10 (C2 )
Equation (A-64):
(Hot temp (current zone)-Cold temp (current zone))

C2 
(Hot temp (next zone)-Cold temp (next zone))
Equation (A-65):
(WAL  WAW )  Nsp

Cr  if orientation is Horizontal
AN TL  N p  N pp

Equation (A-66):
3.8197 (WAL  WAW )  Nsp

Cr  if orientation is Vertical
NT  do  Np  Npp
A N = 0.87  N T
AN = 1.38 AN if layout is triangular (30º)

AN = 1.38 AN if layout is rotated square (45º)
Equation (A-67):
d o  d o  (tf  2)
Equation (A-68):
Equation (A-69):

Equation (A-70):
QLIQ C p L T WAL

Equation (A-71):
QVAP C p V T  WAV

Equation (A-72):
QWAT C p W T  WAW
C2) Shellside Vaporization for Kettle Reboiler:

Equation (A-73):
H F  H1  FC
Equation (A-74):
H1  ( H1a  H1b )

Equation (A-75):
0.69 0.31 0
 QTOT  Cp L   144  PAV  K L   
H1a  0.225   
      L  1
 A  L   TS   V 
0.7 0.17
Q   P 
 2.99   TOT    AV 
 Area   3208.0 
if (WHCL  H HCV )  1 and (WS  WW )  1
Equation (A-76):
0.25

140.963  K L  d o   L    TB  Cp L
3 2
H1b   
d o  
 L  K L
 
 0 if (WHCL  H HCV )  1 and (WS  WW )  1
Equation (A-77):

   L2
2
L 
TB   L   L 
Equation (A-78):
TB  TW  TC
Equation (A-79):
Fc  e ( 0.015(To Ti ))
 1 if (WHCL  H HCV  1 and WS  WW  1)
D) Shellside Condensation:
Equation (A-80):
QR
H F
 QCOND   QLIQ  QWAT   QVAP  QSTE 
     
  
 H F   H LIQ   H VAP 
HLIQ and HVAP are calculated using the shell side heat transfer cor-
relations listed in equations from(5-11) to (5-15) in Chapter 5.

Equation (A-81):
0.6667
 
1737.3  b11.33  K L   L 
 L 
H F 0.3333
if N Re  100.0
N Re
0.6667
 
 749.0 R J K L   L  if N Re  100.0
 L 
 H F  F if shell type is ' X' and orientation is vertical
Equation (A-82):
b1  0.728  b20.75 if X V  0.0

 10-10 if X V  0.0
Equation (A-83):
1
b2 
  X     0.6667 
1   L    V  
  X V    L  
 
Equation (A-84):
X V  1 X L
Equation (A-85):
1
XL 
 (WAV  WAS )  WF 
  1
 (WAL  WAW ) 
Equation (A-86):
0.1111 0.5556
   
WF   V    L 
 L   V 
Equation (A-87):
RJ  1.1258  X 1  (0.27941  X 1  0.079434)

 X 2  ((0.50141  X 1  (0.21098  X 1  0.051097)
 X 2  (0.067757  X 1  (0.043285  X 1  0.006845))

Equation (A-88):
X 1  ln  N Pr 
Equation (A-89):
X 2  Log10  N Re 
Equation (A-90):
Cp L   L
N Pr 
KL
Equation (A-91):
3.993  Cr
N Re 
L
Equation (A-92):
F  1.0009929 C1  (0.1649254 C1  (0.09907  C1  0.021335))

Equation (A-93):
C1  Log10 (C2 )
Equation (A-94):

C2 
Equation (A-95):
(WAL  WAW )  Nsp

AN TL  Np  Npp
3.8197 (WAL  WAW )  Nsp
 if orientation is Vertical
NT  do  Np  Npp
Equation (A-96):
AN  0.87  N T
 1.38 AN if layoutis Triangular(30 ) or Rotated square(4
Equation (A-97):
QCOND  QR  QTOT
Equation (A-98):

Equation (A-99):
QLIQ C p L T  WAL

Equation (A-100):

Equation (A-101):

Equation (A-102):
Tubeside
Modified Chen Vaporization Method
A) Tubeside Vaporization:
Equation (A-103):
HF 
( H LIQ  H NB )  (QREB  QLIQ  QWAT )  H VAP  (QVAP  QSTE
QR
 GR  Cp V   V 
0.2
 0.056  K V  N Re    if (TSAT  H F )  QCHF

V
 KV 
Equation (A-104):
H LIQ  H LIQ  FF
HLIQ and HVAP are calculated using the Tube side heat transfer cor-
Equation (A-105):
FF  1 if XTT  10
 ( FF  1)  FWBT  1 if XTT  10
Equation (A-106):
0.7
 1  
FF  2.25      0.113 
  XTT  

Equation (A-107):
0.9 0.5 0.1
 (1  X V )     
XTT      V    L 
 X V   L   V 
Equation (A-108):
(WAV  WAS )
XV 
WTOT
Equation (A-109):
(WVi  WVo )
WAV 
2
Equation (A-110):
(WLi  WLo )
WAL 
2
Equation (A-111):
(WWi  WWo )
WAW 
2
Equation (A-112):
(WSi  WSo )
WAS 
2
Equation (A-113):
    L –  V   4.17312 10
F CHF  F CHF 1   B   V   ----------------------------------------------------------
 L
Q CHF = -----------------------------------------------------------------------------------------------------------------------------
41.5
Equation (A-114):
86.4 0.5658
FCHF  5.622  
Pcp Pcp2
Equation (A-115):
FCHF1  1  N Re L 10 6

Equation (A-116):
Pav
Pcp 
Pcrit
 0.001 if Pcp  0.001
 1.0 if Pcp  1.0
Equation (A-117):
B  (1  X V )  L
Equation (A-118):
 0.09592 K L0.79  Cp0.45  L0.49  TSAT

0.25 0.75
 PSAT  Fbs 
H NB   L  F  F
 T 0.5
  0.29
 0.24
  0.24  ONB
 s L L V 
Equation (A-119):
TSAT 144
PSAT 
TTP
Equation (A-120):
 1 1 
TC     144
  V  L 
TTP 
778  L
Equation (A-121):
1
Fbs 
(1  1.17
N Re tp
 2.53  10 6 )
Equation (A-122):
2.5
 TSAT 
FONB   
T 
 W CT
Equation (A-123):
FWBT  e ( 0.009(TD TB ))

 1 if FWBT  1
 0.2 if FWBT  0.2
Equation (A-124):
N Re tp  N Re L  FF1.25

Equation (A-125):
d i  GT
N Re L 
12  L
Equation (A-126):
(WAL  WAW )
GT 
AT
Equation (A-127):
5.45 10 3  d i2  N T
AT 
N tp
Equation (A-128):
Equation (A-129):

Equation (A-130):
QLIQ  Cp L  T WAL
Equation (A-131):
QVAP  Cp V  T  WAV
Equation (A-132):
QWAT  Cp W  T  WAW
Equation (A-133):

Equation (A-134):
d i  GT
N Re V 
12 V
Equation (A-135):
 W  WAS 
GT   AV 
 AT 

Equation (A-136):
8
4.17312 10   V    L –  V 
G R = ------------------------------------------------------------------------
-
2
V
B1) Tubeside Condensation on Horizontal Tubes:
Equation (A-137):
HF  HSTR if VSG  0.5

 HSTR  (VSG  0.5)  (HCAL  HSTR ) if VSG  0.5 andVSG 
 HCAL if VSG  1.5
Equation (A-138):
GTOT  C2
VSG 
C1
Equation (A-139):
8 0.5
  V    L –  V   4.17312 10  d o
C 1 =  -------------------------------------------------------------------------------------
 12 
Equation (A-140):
C3
C2 
(C3  XTT1.111 )
Equation (A-141):
0.555 0.111
   
C3   V    L 
 L   V 
Equation (A-142):
0.9 0.5 0.1
 (1  X V )     
XTT      V    L 
 X V   L   V 
Equation (A-143):
WTOT  N tp
GTOT 
5.454 10 3  d i2  N t  N p
Equation (A-144):
0.25
a 
H STR  b1   1 
 a2 

Equation (A-145):
0.75
b1  0.728  b2
Equation (A-146):
1
b2 
  1  X     0.6667 
1   V 
 V  
  X V    L  
 
Equation (A-147):
WAV  WAS
XV 
WTOT
Equation (A-148):
3 8
a1 = KL  L  L –  V   4.17312 10   L
Equation (A-149):
 L  d o  TBW
a2 
12
Equation (A-150):
H CAL  H CAL1 if Si  0
 H CAL2 if Si  0
Equation (A-151):
Si  0.5  ff 1  V VG2 if VSG  0.5

 0 .0 if VSG  0.5
Equation (A-152):
ff 1  (1  850.0  ff 2)  ff 3
Equation (A-153):
    ff 4 
0.5
 
ff 2   V    L    0.9 
 L    V   Re g 

Equation (A-154):
(-0.2)
ff 3  0.046  Re g

Equation (A-155):
   0.0379  N 
0.4
ff 4   0.707  N Re 0.9 2.5 
0.5 2.5
Re 
 
Equation (A-156):
G tot   1 – X V   d inside
N Re = ---------------------------------------------------------
-
12   L
Equation (A-157):
 V  VG  d o
Re g 
12   V
Equation (A-158):
GTOT  X V
VG 
V
Equation (A-159):
0.5
H CAL2  1.41  N Re if N Re  50.0
 ( Z1  Z 2 ) (1 / Z 3 ) if N Re  50.0
Equation (A-160):
Z3
 1.41 
Z1   0.5 
 N Re 
Equation (A-161):
Z3
 0.071  N Pr
0.5 
Z 2   0.04167


 N Re 
Equation (A-162):
N Pr  3
Z3 
2
Equation (A-163):
Cp L   L
N Pr 
KL

Equation (A-164):
0.5
 S 
H CAL1  H CAL2  m1   i 
 m2 
Equation (A-165):
8 L
2 13
m 1 = K L  4.17312 10  ------ 
   L 
Equation (A-166):
2 8 23
  L   L  4.17312 10 
m 2 = -----------------------------------------------------------------------
L
Assume Y1  Si and calculate
Equation (A-167):
0.5
Y 
Y2  H CAL2  m1   1 
 m2 
Equation (A-168):
Y2  TBW  VG  Fd
Y3 
 L S i
Equation (A-169):
Si  Y3
Y4 
1  e ( Y3 )
Equation (A-170):
QCOND
Fd 
QR
Assign Y4 value to Y1 and repeat calculation of HCAL1 till
 Y4  Y1 
   10 6
Y
 1 
B2) Tubeside Condensation on Vertical Tubes:

Equation (A-171):
H F  Maximum of H VGR and H CAL

Equation (A-172):
H VGR  H LAM1 if N Re  30.0

 H LAM2 if N Re  1600.0
 H turb if N Re  1600.0
Equation (A-173):
( 1 / 3)
1.1  N Re
H LAM1 
a1
Equation (A-174):
 4  Wx 
N Re   
 L 
Equation (A-175):
W tot   1 – X V   N TP  12
W x  = ----------------------------------------------------------------
-
  N T  d inside
Equation (A-176):
(WAV  WAS )
XV 
WTOT
Equation (A-177):
2 13
 L 
 -------------------------------------------------------------------8-
  L *   L –  V *4.17312 10 
a 1 = --------------------------------------------------------------------------------
-
KL
Equation (A-178):
0.22
0.756  N Re
H LAM2 
a1
Equation (A-179):
0.25 0.5
0.023  N Re  N Pr
H turb 
a1
Equation (A-180):
Cp L  L
N Pr 
KL

Equation (A-181):
H CAL  H CAL1 if Si  0.0

 H CAL2 if Si  0.0
Equation (A-182):
0.5
H CAL2  1.41  N Re if N Re  N Recrit
 Z1  Z 2 
(1/Z3 )
if N Re  N Recrit
Equation (A-183):
Z3
 1.41 
Z1   0.5 
 N Re 
Equation (A-184):
Z3
 0.071  N Pr
0.5 
Z 2   0.04167


 N Re 
Equation (A-185):
N Pr  3
Z3 
2
Equation (A-186):
N Recrit  1600.0  226.0  b1  0.667  b13 if b1  9.04

 50.0 if b1  9.04
Equation (A-187):
Si
b1 
b2
Equation (A-188):
Si  0.5  ff 1   V  VG2
Equation (A-189):
8 23
  L *   L –  V *  L * 4.17312 10 
b 2 = -----------------------------------------------------------------------------------------------
-
L
Equation (A-190):
ff 1  (1  1400.0  ff 2  (1  e J1 ))  ff 3

Equation (A-191):
0.5
      ff 4 
ff 2   V    L    0.9 
 L    V   Re g 
Equation (A-192):
ff 3  0.046  Re (-0.2)
g
Equation (A-193):
   0.0379  N 
0.4
ff 4   0.707  N Re 0.9 2.5 
0.5 2.5
Re 
 
Equation (A-194):
 V  VG  d o
Re g 
12   V
Equation (A-195):
 (1  1400.0  ff 2)1.5
J1 
(13.2  ff 5  ff 2)
Equation (A-196):
8
 L  4.17312 10  d o
ff5 = ------------------------------------------------------
-
2
12   V  ff3  V G
Equation (A-197):
0.5
S 
H CAL1  H CAL2  m1   i 
 b2 
Equation (A-198):
1
m1 
a1
Assume Y1  Si and calculate

Equation (A-199):
0.5
Y 
Y2  H CAL2  m1   1 
 m2 

Equation (A-200):
Y2  TBW  VG  Fd
Y3 
 L S i
Equation (A-201):
Si  Y3
Y4 
1  e ( Y3 )
Equation (A-202):
QCOND
Fd 
QR
Assign Y4 value to Y1 and repeat calculation of HCAL1 till
 Y4  Y1 
   10 6
 Y1 
HEX5 Method
C) Tubeside Vaporization:
Equation (A-203):
HF 
(H F  QREB )  H LIQ  (QLIQ  QWAT )  H VAP  (QVAP  QSTE ) if Q
QR

H F  H LIQ  H VAP  if QR  0
3
H F d i
 if orientation is Horizontal
do
HLIQ and HVAP are calculated using the Tube side heat transfer cor-
Equation (A-204):
0.6667
 
HF  749.0  RJ  KL   L 
 L 
 HF  F if shell type is ' X' and orientation is vertical

Equation (A-205):
RJ  10 ( 0.25545  X 1 ( 0.0022358 )  X 2 ( 0.32638 )  X 1  X 2 ( 0.0067075 )) if N Re  100

 1.1258  X 1  (0.27941  X 1  0.079434 )
 X 2  (( 0.50141  X 1  ( 0.21098  X 1  0.051097 )
 X 2  (0.067757  X 1  (0.043285  X 1  0.006845 )) if N Re 
Equation (A-206):
X 1  ln  N Pr 
Equation (A-207):
X 2  Log10  N Re 
Equation (A-208):
Cp L   L
N Pr 
KL
Equation (A-209):
3.993  Cr
N Re 
L
Equation (A-210):
F  1.0009929  C1  (0.1649254  C1  (0.09907  C1  0.0213

Equation (A-211):
C1  Log10 (C2 )
Equation (A-212):

C2 
Equation (A-213):
(WAL  WAW )
N TTL  X V  Np
Equation (A-214):
(WAL  WAW )  3.8197

Cr  if orientation is Vertical
N T  di  N p
Equation (A-215):
X V  1 X L

Equation (A-216):
1
XL 
 (WAV  WAS )  WF 
  1
 (WAL  WAW ) 
Equation (A-217):
0.1111 0.5556
   
WF   V    L 
 L   V 
Equation (A-218):
Equation (A-219):

Equation (A-220):

Equation (A-221):

Equation (A-222):

Equation (A-223):
D) Tubeside Condensation:
Equation (A-224):
QR
H F
 QCOND   QLIQ  QWAT   QVAP  QSTE 
     
H  Q   QVAP
 F   LIQ   
HLIQ and HVAP are calculated using the tube side heat transfer cor-

Equation (A-225):
0.6667
 L 
1737.3  b11.33  KL   

 L
H F 0.3333
if NRe  100.0
NRe
0.6667
 
 749.0RJ KL   L  if NRe  100.0
 L 
H FF if shell type is ' X' and orientation is vertical
Equation (A-226):
b1  0.728  b20.75 if X V  0.0

 10-10 if X V  0.0
Equation (A-227):
1
b2 
  X    0.6667 
1   L    V  
  X V    L  
 
Equation (A-228):
X V  1 X L
Equation (A-229):
1
XL 
 (WAV  WAS )  WF 
  1
 (WAL  WAW ) 
Equation (A-230):
0.1111 0.5556
   
WF   V    L 
 L   V 
Equation (A-231):
RJ  1.1258  X 1  (0.27941  X 1  0.079434)

 X 2  ((0.50141  X 1  (0.21098  X 1  0.051097)
 X 2  (0.067757  X 1  (0.043285  X 1  0.006845))

Equation (A-232):
X 1  ln  N Pr 
Equation (A-233):
X 2  Log10  N Re 
Equation (A-234):
Cp L   L
N Pr 
KL
Equation (A-235):
3.993  Cr
N Re 
L
Equation (A-236):
F  1.0009929 C1  (0.1649254 C1  (0.09907  C1  0.021335

Equation (A-237):
C1  Log10 (C2 )
Equation (A-238):

C2 
Equation (A-239):
WCOND  QTOT  N tp
Cr 
QCOND  N T F VTL  N p
Equation (A-240):
WCOND  WWo  WLo  WWi  WLi

Equation (A-241):
QCOND  QR  QTOT
Equation (A-242):

Equation (A-243):

Equation (A-244):

Equation (A-245):

Equation (A-246):
where
Table A-12: Definition of Equation Terms

Parameter Description
HF Film coefficient, Shell side (or) tube side
HLIQ Film coefficient, liquid
HVAP Film coefficient, vapor
HNB Film coefficient, Nucleate boiling
QREB Vaporization duty (Region duty-sensible

duty)
QCOND Condensing duty (Region duty-sensible
duty)
QTOT Duty, total
QLIQ Duty, liquid
QWAT Duty, water
QVAP Duty, vapor
QSTE Duty, steam
QR Duty, region
QCHF Critical heat flux
Tsat Saturation temperature

FF F factor
XTT Martennelli factor

XV Vapor flow fraction
XL Liquid flow fraction
V Vapor density
L Liquid density
L Liquid viscosity
V Vapor viscosity
WAV Average vapor flowrate
WAL Average liquid flowrate
WAW Average water flowrate
WAS Average steam flowrate
WTOT Total flowrate, shell side or tube side
WVi Vapor flowrate, inlet
WVo Vapor flowrate, outlet
WLi Liquid flowrate, inlet
WLo Liquid flowrate, inlet
WWi Water flowrate, inlet
Wwo Water flowrate, outlet
WSi Steam flowrate, inlet
WSo Steam flowrate, outlet
DOTL outer tube limit diameter

A Area per shell
Np No. of shells in parallel
TL Tube length
ëL Latent heat
ST Surface tension
CpL Specific heat, liquid
CpV Specific heat, vapor
CpW Specific heat, water
C pS Specific heat, steam
TW Temperature, wall
TC Temperature, average
TB Temperature, bubble point
TD Temperature, dew point
KL Thermal conductivity, liquid
KV Thermal conductivity, vapor
Psat Saturation pressure
Fbs Boiling suppression factor
FONB Correction factor for onset of nucleate boil-

ing
FWBT Wide boiling temperature range correction
factor

N Re Reynolds number
N Re tp Reynolds number, two phase
N Re L Reynolds number, liquid
N ReV Reynolds number, vapor
DW Cross flow equivalent diameter
AF Flow area
AC Cross flow area
GT Mass velocity
Pav Pressure, average
K L Thermal conductivity of liquid at tf
 T  TB 
 tf  C 
 2 
 L Density of liquid at tf
Specific heat of liquid at tf

Cp L
 L Viscosity of liquid at tf
do tube outside diameter
di tube inside diameter
tf fouling layer thickness, shell side
WHCL Flowrate, hydrocarbon liquid flowrate

WHCV Flowrate, hydrocarbon vapor flowrate
WS Flowrate, steam
WW Flowrate, water
ëB Saturation enthalpy-bulk enthalpy
Pcrit Critical pressure
AT Tube cross sectional area per tube pass
Specific heat, average of vapor and steam

Cp VS
Ti Inlet temperature
To Outlet temperature
Nt Number of tubes per shell
NTP Number of tube passes per shell
Npp Number of parallel passes per shell
HSTR Heat transfer coefficient, stratifying
VSG Superficial gas velocity dimensionless
Si Interfacial Shear
Reg Reynolds number, gas
Vg Velocity, gas
NPr Prandtl number
HVGR Heat transfer coefficient, vertical tube side

(gravity contribution)
HLAM1 Heat transfer coefficient, laminar wave free
H LAM2 Heat transfer coefficient, laminar wavy

H turb Heat transfer coefficient, turbulent
N Recrit Reynolds number, critical

Index
Numerics AIME , 3-44

AJ , 4-125, 8-291
1 , 5-150 Ak , 8-286
1990 AICHE Annual Meeting , 4-67 ALCOHOL , 1-14
86th AIChE National Meeting , 8-300 Alcohol Synthesis Absorber , 4-109
Algorithm Schematic , 4-77
Algorithm/ IEG Method , 4-75
A Algorithms , 6-218, 10-310, 10-311, 10-324
Tearing , 10-311
Absorbing Type Demethanizer/Deethanizer , 4-109
Top Section , 4-108 Aliq , 11-345
Absorption/ d , 4-117 Alk , 4-125
Academic Press , 10-336 All , 4-60, 4-62, 10-335
Acceleration Factor , 10-314 All stream/tear , 10-308
Acceleration Techniques , 10-313, 10-315 Allowing , 4-134, 10-331
Accurate Hand , 5-173 flowsheet , 10-331
PRO/II , 4-130, 4-133, 4-134, 4-135
ACFS , 4-109
Alternate Method , 10-310
ACM , 10-315
Alternitively , 8-282
ACS , 8-286
Aluminum , 7-253
Addition/removal , 6-232
Extractive Metallurgy , 7-251
ADIABATIC , 1-15, 6-210
American Society , 2-25
Adiabatic , 1-15, 6-210 Mechanical Engineers , 2-25
flash calculations , 1-2
AMINE , 1-14
temperature , 7-237
two-phase flash calculations , 1-11 Amine Contactor , 4-108
AMINE GPSWATER , 1-14
adiabatic , 1-17
Amine Regenerator , 4-108
Adiabatic flash calculations , 1-17
Adiabatic Head , 2-22, 2-30 Amine Stills , 4-109
An Experimental Study
Adiabatically , 6-211, 6-212, 11-338
Inclined Two-Phase , 3-44
Adk , 10-331 Two-Phase Flow , 3-35
Afac , 11-346, 11-347
And/or , 3-32, 4-50, 4-73, 6-217, 7-261, 7-271, 9-302, 10-
Affect , 8-274 319, 10-325
flowsheet , 8-274 splitting , 9-302, 9-303
Ahk , 4-125 And/or pumparound , 7-262
Ai , 6-226, 11-346 Ao , 5-151
AIChE , 4-81 Ap , 7-254
AIChE 1990 Annual Meeting , 4-67, 4-146 APERT , 10-333
AIChE Annual , 4-67, 4-72 API , 3-32, 3-44, 11-346
AIChE J , 6-223 API2000 Model , 11-347
AIChE Spring , 4-146 APISCALE Model , 11-347
Depressuring unit , 11-347
Aij , 6-225
PRO/II Unit Operations Reference Manual Index-633

API 14B , 3-44 Berl Saddles , 4-112, 4-113
API 2000 Heat Model Bij , 4-58
Depressuring unit , 11-346 Binary VLE/VLLE Data , 8-283, 8-284
API RP520 Model , 11-347 Binary VLE/VLLE Data-XVALUE entry , 8-284
API scale heat model , 11-347 Blowdown
Applied Mathematics , 4-72 depressuring heat model , 11-348
Applying , 11-345 Bluck , 4-146
uninsulated , 11-347 Boiling Pot Model , 6-228
Arrhenius , 4-69, 6-214, 6-226 Bolles , 4-52, 4-108, 4-123
ASME , 2-23, 2-24, 3-44, 5-157 Boltmann s , 8-286
method , 2-23, 2-25
Bondy , 4-67, 4-72, 4-146
Power Test Code 10 , 2-23
Bowman , 5-153
ASME method , 2-25
Braun K10 , 1-11
ASTM , 4-74
Brill , 3-44
95 Distillation , 4-131
TBP , 4-133, 4-134, 4-141 Brown , 3-45
TMP Distillations , 4-134 Brownell , 7-241, 7-247
Availability Functions , 8-298 Broyden , 10-315
Availability ofResults , 8-280 Recommended Uses , 10-315
average relative volatility , 4-124 Broyden Acceleration , 10-306, 10-316
Azeotrope , 9-304 Broyden s , 4-54, 10-315, 10-324
Azeotropic , 4-53 Bubble , 3-40
Bubble point
flash , 1-15
B flash calculations , 1-9
Built-in Packing Factors , 4-112
Back-calculates , 2-23 Bundle weight , 5-170, 5-171
Balance , 4-77, 6-229, 9-305 BVLE , 8-283
flowsheet , 9-305
one-dimensional PFR , 6-229
Balance Equations , 7-263 C
Base , 4-141
C.A. Hsieh , 1-11
Base Case , 4-139
C3 , 10-322, 11-345
Basecase , 10-324, 10-325
C2 , 10-322
solving , 10-331
C4 , 4-117, 10-322, 11-345
Basecase flowsheet , 10-324
Basic Algorithm , 4-63, 4-66, 4-67, 4-68, 4-77 C5 , 11-345
Calculate , 11-340
Basic Calculations , 2-19, 2-28, 3-33, 3-45
distillation models , 4-131
Basic Principles , 1-2
Fenske , 4-131
Bbls/Day , 4-141 Vessel Volume , 11-340
BBM , 3-36, 3-37 Calculating Recovery , 7-251
BBMHV , 3-36 H.E. Equations , 7-251
BBP , 3-35 Calculating theVessel Volume , 11-340
Beggs-Brill-Moody-Palmer , 3-37 Calculation Methods , 2-25, 5-151, 5-154, 5-173, 5-174,
Bell-Delaware , 5-165 7-237, 7-238, 7-242, 7-248, 7-271
Benedict-Webb , 1-11 Calculation of Bundle weight, Shell weight (dry) and
Shell weight (with water) , 5-170
Benedict-Webb-Rubin-Starling , 2-18
Index-634
Calculation Options , 8-277 column specifications , 4-131
Calculation Procedure , 6-217 Columns
Equilibrium , 6-217 simple , 4-132
Calculation Scheme , 7-251, 7-272, 7-273 Complex Columns , 4-133, 4-140
Calculation Sequence , 10-310, 10-311 Complex Distillation Column , 4-50, 4-51
Calculation Sequence and Convergence , 10-310, 10- Component Balance , 4-77, 7-248
312 COMPONENT ERROR , 4-54
CalculationOptions , 8-277 Component Libraries , 6-212
CalculationProcedure forEquilibrium , 6-217 Component library databank , 6-211, 6-212
CALCULATOR , 10-318, 10-322, 10-327, 10-328, 10-330 Component Mass Balance , 1-3, 4-62
Carbon Balance , 4-77 Composition Convergence , 1-8, 1-9
CASESTUDY , 8-276, 8-283 Compostion sensititve K-values , 4-54
Cat Fractionators , 4-135, 4-138 Compressibility , 2-23, 2-25, 2-28, 7-238, 11-341
Caustic Regenerator , 4-109 Compression , 2-19, 2-20, 2-21
Caustic Wash , 4-109 Compressor , 2-19, 2-22, 2-23, 2-27, 3-46
CCD , 7-248, 7-249 Compressor work , 2-23
Ceram , 4-112 CONREACTOR , 6-210
CG , 4-119 Constraints , 10-326, 10-330, 10-331
Chao-Seader , 1-11 Contents , 1-1, 1-14, 7-236, 7-237, 7-242, 7-253, 7-262, 8-
Chao-Seader-Erbar , 1-11 276, 11-339
Characteristics , 4-54, 7-238, 7-240, 11-338 Table , 1-1
function , 7-238, 7-240 Continuation Method , 4-72
Chemdist , 1-1, 4-48, 4-50, 4-62, 4-67, 4-73, 4-77 Functional Equations , 4-67
Simple Stage , 4-62 Continuous Stirred Tank Crystallizer , 7-262
Chemical Engineer s Handbook , 4-117 Continuous Stirred Tank Dissolver , 7-254
Chemical Engineering Handbook , 1-12, 5-173, 11-351 Continuous stirred tank reactor , 6-224
Chemical Engineering Kinetics , 6-232 Continuous Stirred Tank Reactor (CSTR) , 6-224, 6-
Chemical Engineers , 7-260, 8-299 225, 6-227, 6-228
Chemical Reaction Equilibrium Analysis , 6-218 CONTROLLER , 4-49, 8-276, 8-280, 8-283, 10-317, 10-
318, 10-319, 10-320, 10-321, 10-322
Chilton , 4-123, 5-173
sequence , 10-319
Chlorine Balance , 4-77
Controllers , 10-306
Clarified Oil , 4-138
CONVENTIONAL , 4-75, 4-76, 4-133
Clathrates , 8-286
Convergence Criteria , 1-5, 10-312
CO , 6-212, 6-216
Convergence Region , 10-314
CO2 , 4-78
Conversion Reaction , 4-52
CO2 Absorber , 4-109
Conversion Reactor , 6-210, 6-211
CO2 Regenerator , 4-109
Cooler/heater , 4-76
Cocurrent , 5-152, 5-153, 5-155, 6-229, 6-232
Cooling Curves , 8-276
Cold Box , 5-174
Correlations , 4-118, 4-120, 4-121, 4-122, 4-123
COLUMN , 10-327, 10-328, 10-329, 10-330, 10-331
Countercurrent Decantation Washing System , 7-253
Column
Countercurrent Decanter , 7-247, 7-248, 7-251
Equilibrium Efficiency , 4-148
Murphree Efficiency , 4-147 Cpv , 11-345
Tray Efficiency , 4-146 Cpvess , 11-350
Vaporization Efficiency , 4-148 Cricondenbar , 8-275
Column Hydraulics , 4-107, 4-108, 4-112, 4-117 Cricondentherm , 8-275

Critical Point and Retrograde Region Calculations , 8- Decantation , 7-247, 7-248
277 Decanter Stage , 7-248
Critical Points , 8-277
Decanting , 8-279
Multicomponent Mixtures , 8-275
K-value , 8-279
Critical pressure , 8-278 DEFINE , 4-70
Crossflow , 5-162, 5-165
Defined.Note , 4-139
number , 5-165
Density , 3-32, 3-33, 3-35, 4-108, 4-112, 4-117, 5-165, 7-
Cross-references , 1-1 238, 7-242, 7-254, 7-263, 11-338, 11-341
Crude Unit Yields Incremental Yields , 4-141 Depressuring unit , 11-338
Crude-distillation , 4-62 calculations , 11-338
Crude-preflash , 4-137 equations
Crystal Particle , 7-265 heat input, 11-345
Crystallization , 5-173, 7-261, 7-262, 7-269 isentropic efficiency, 11-351
Crystallization Kinetics , 7-263 valve rate, 11-341
Crystallization Kinetics and Population Balance fire relief model , 11-347
Equations , 7-263 gas blowdown model , 11-348
Crystallizer , 7-261, 7-262, 7-264, 7-268, 7-269 heat input , 11-345
Crystallizer-crystal growth rate , 7-263 isentropic efficiency , 11-350
valve rate , 11-341
Crystallizer-crystal nucleation rate , 7-263
vessel
Crystallizer-crystal nucleii number density , 7-263
cylinder, 11-340
Crystallizer-heat balance , 7-267
Crystallizer-magma density , 7-263
horizontal, 11-340
Crystallizer-mass balance , 7-267
spherical, 11-341
Crystallizer-population balance equations , 7-263 vertical, 11-340
vessel volume , 11-340
Crystallizer-solid-liquid equilibrium , 7-267
Des , 8-292
Crystallizer-vapor-liquid equilibrium , 7-267
CSTR , 4-67, 6-224, 6-225, 6-227, 6-228 Design , 3-35, 7-260
Stirred Tank Dissolver , 7-260
Thermal Behavior , 6-227
Two-Phase Gathering Systems , 3-44
CSTR Operation Modes , 6-228
DESIGN DP GENERAL DESIGN , 7-237
CSTR OperationModes , 6-228
DESIGN PRESSURE GENERAL DESIGN , 7-237
CSTR reactor , 6-229
DESIGN TEMPERATURE GENERAL DESIGN , 7-
Curl-Pitzer , 2-18, 2-19 237
Cut Ranges , 4-141 Diesel , 4-138
Cuts , 4-142 Diesel - Gas Oil , 4-131
Cyclohexanone , 4-117 Di-ethylene , 8-286
Cyclopropane , 8-286 Diffusivity , 7-256
Dimensional Units , 11-343
D Direct Substitution , 10-307, 10-314

Dissociation Pressures , 8-286
Dahlstrom , 7-241 Gas Hydrates Formed , 8-292
Data For , 8-281, 8-282 Dissolver , 7-253, 7-254, 7-255, 7-256, 7-257, 7-258, 7-
260
Databank , 6-210
Dissolver follows , 7-255
DBASE , 8-281
Dissolver model , 7-257
DECANT , 8-278, 8-279
Dissolver-heat balance , 7-258
Decant Considerations , 8-278
Index-636
Dissolver-mass balance , 7-258 EnVironmental State , 8-298
Dissolver-mass transfer coefficient correlations , 7-254 Equations
Dissolver-mass transfer rate , 7-254 Depressuring unit
Dissolver-model assumptions , 7-254

heat input, 11-345
Dissolver-residence time , 7-258 equations
isentropic efficiency , 11-350
Dissolver-solid-liquid equilibrium , 7-258
Equations of State , 1-4, 8-274, 8-277, 8-283, 8-286
Dissolver-vapor-liquid equilibrium , 7-258
Equilibrium , 6-217
Distillation , 4-48
Equilibrium Constants , 6-212, 6-217, 6-218
Distillation and Liquid-Liquid Extraction Columns , 4-
48 Equilibrium Efficiency , 4-148
Distillation Models , 4-130 Equilibrium Flash , 1-2
Distillation Problems , 4-72 equilibrium reactions , 4-50
Distillation-rigorous-ELDIST algorithm , 4-77 Equilibrium Reactor , 6-212, 6-215, 6-216, 6-217
Distribution Coefficient , 8-285 Equilibrium Stage , 4-68
Dombrowski , 7-241, 7-247 Equilibrium Unit Operations-flash drum , 1-14
Downcomer , 4-69 Equilibrium Unit Operations-mixer , 1-16
DRY BASIS , 8-279 Equilibrium Unit Operations-splitter , 1-17
Dry Basis Properties , 8-279 Equilibrium Unit Operations-valve , 1-15
Dryer , 7-236, 7-237 Equlibrium , 4-143
DRYER SPECIFICATION , 7-236 EQUREACTOR , 6-212
Dukler-Eaton-Flanigan correlation , 3-35 ERRINC , 4-146
Estimate Generator , 4-73, 4-75, 4-76
Estimates , 4-54
E distillation models , 4-131
Fenske , 4-131
E.A. Eckert , 1-11
Estimating Separation Efficiency , 4-123
Eaton , 3-35
Ethylbenzene , 4-117
Efficiency
EVAL , 8-284
Column tray , 4-146
Equilibrium , 4-148 EVALUATE , 8-284
Murphree , 4-147 EVS , 8-298
Vaporization , 4-148 Exergy , 8-293, 8-298, 8-299
efficiency , 2-18, 2-19, 2-23, 2-25, 2-28, 3-45, 4-50, 4-112, EXisting State , 8-298
7-248, 8-298, 10-306, 10-308, 11-345 Expander , 2-27, 2-28, 2-29
isentropic
EXS , 8-298
Depressuring unit, 11-350
Extractive Metallurgy , 7-253
Eldist , 4-49, 4-50, 4-52, 4-53, 4-75, 4-77
Electroneutrality Equation , 4-78
Elsevier , 7-261 F
Energy Balance , 4-65, 4-77
Factors , 5-173
Englewood Cliffs , 1-12
Fouling , 5-173
Enthalpy , 1-2, 2-19, 2-23, 2-28, 3-45, 4-54, 4-67, 4-125,
Features Overview , 4-52
5-151, 5-174, 6-208, 6-217, 6-225, 7-261, 8-276, 8-
280, 8-293, 8-298, 11-345 Each Algorithm , 4-51
Enthalpy-temperature characteristics , 5-154 FEED , 6-211, 9-302, 9-303
Entropy , 1-14, 2-18, 2-19, 2-23, 2-28, 8-293, 8-298 Feed Blending Considerations , 9-302
Thermodynamic Generators , 2-18 Feed BlendingConsiderations , 9-302

Feed Tray Location , 10-327, 10-330 Flowsheet , 4-67, 8-280, 8-283, 8-293, 8-298, 9-302, 9-
Feedback Controller , 5-175, 10-317, 10-321, 10-322, 10- 304, 9-305, 10-306, 10-308, 10-310, 10-317, 10-319,
323 10-322, 10-324, 10-325, 10-331
balance , 9-305
Feedback controller-typical application , 10-319
feeds , 9-305
Feeds , 4-125, 9-305
number , 10-322
flowsheet , 9-305
results , 10-319
thermal condition , 4-127
Solve , 10-324, 10-331, 10-332
Fenske , 4-73, 4-124, 4-139 streams , 10-306
calculate , 4-134
Flowsheet basecase , 10-325
estimates , 4-133
Model , 4-131 Flowsheet Control , 10-317
number , 4-131 Flowsheet Optimization , 10-325, 10-331
violate , 4-132 Flowsheet optimization-Optimizer , 10-324
F-factors , 5-153 Flowsheet Solution Algorithms , 10-306
Fibonacci , 6-222 Flowsheeting , 4-49
Ficken , 4-72 Flowsheets , 10-306, 10-308, 10-330, 10-333
Filtering Centrifuge , 7-242, 7-244 Foaming Applications , 4-108
FINDEX , 4-138, 4-139 System Factors , 4-108
Fire Relief Model , 11-345 Formation , 6-208, 6-210, 6-211, 6-212, 8-292
Gas Hydrates , 8-286
First-order Derivatives , 10-332
Heat , 6-208, 6-210, 6-212
Fixed Duty , 1-15
Foul Water , 4-109
fixed duty , 7-237
Fouling , 5-173
Flanigan , 3-38, 3-44
Factors , 5-173
FLASH , 6-209, 6-210
FOVHD , 9-302, 9-305
Flash Calculations , 1-2, 1-8, 1-9, 1-10, 1-11, 1-13, 1-14,
FPROD , 9-302, 9-305
1-15, 1-16, 1-17
two-phase isothermal , 1-4 fractionation index , 4-76, 4-138, 4-140
Flash calculations Fractionator , 4-73, 4-140
Bubble point , 1-2 Fractionators , 4-49, 4-74, 4-131
Isothermal, Newton-Raphson technique , 1-2 Frank , 4-115
MESH equations , 1-2
Free Energy Minimization , 6-218, 6-221
splitter , 1-17
Mathematics , 6-218
two-phase , 1-2
Free Water Decant , 4-52
Flash calculations-MESH equations , 1-3
Friction Factors , 3-44
Flash Drum , 1-14, 1-15
Pipe Flow , 3-44
Flash Unit Operation , 1-15 Froude , 3-36
Flash valculations
Fugacities , 4-78
two-phase adiabatic , 1-11
Fugacity , 4-48, 4-54, 8-279, 8-283, 8-284, 8-286
Fletcher , 10-336
Function.Feed , 9-302
Flow Distribution , 5-173
Functional Equations , 4-72
Flowrate , 3-42, 5-151, 5-166, 6-219, 6-223, 7-239, 9-303,
Continuation Method , 4-67
10-318, 10-319, 10-321, 10-322
utility , 5-151, 5-153 Functional Relationship , 10-319, 10-320
Flowrate/cross , 3-34 Fundam , 8-286
Flowrates , 4-56, 4-73, 7-257, 9-305, 10-319, 10-321, 10- Furfural Fractionator , 4-109
322, 10-331 Fusion , 7-261
varying , 10-322 heat , 7-262
Index-638
G GPSA method , 2-23, 2-24, 2-25
GPSA pump , 3-45
GAMMA , 8-277, 8-279, 8-280 Graetz , 5-163
GAMMA and KPRINT Options , 8-279 Grashof , 11-349
Gas Blowdown Gray correlation , 3-35
depressuring model , 11-348 Grayson-Streed , 1-11
Gas Hydrates , 8-292
Grayson-Streed-Erbar , 1-11
Formation , 8-286
Green , 1-12, 11-351
Gas Hydrates Formed , 8-286
Grossell , 4-123
Dissociation Pressures , 8-292
Growth Rate , 7-263
Gas Mixtures , 8-286
GSE , 1-14
Gas Oil , 4-138, 4-139, 4-141
Gas Wells , 3-44
Gases , 8-286 H
Hydrate-forming , 8-287, 8-288, 8-291
Gas-Liquid Flow , 3-45 H.E. Equations , 7-251
Gasoline Calculating Recovery , 7-253
Light Cycle , 4-131 H2O , 4-78
Gaussian , 7-251 H2S Stripper , 4-109
Gautam , 6-223 Hagedorn , 3-45
Gear , 6-232 Hagedorn-Brown , 3-44
General Column Model , 4-50 Hagedorn-Brown correlation , 3-35
General Data , 10-312, 10-313 Hausen , 5-163
General Flowsheet Tolerances , 10-317 HCURVE , 8-276, 8-277, 8-278, 8-279, 8-280, 8-283
General Stream , 1-15 HCURVE Point , 8-280
GeneralInformation , 1-1, 2-27, 4-48, 4-107, 4-124, 4- Data For , 8-280
143, 5-150, 5-154, 5-158, 5-174, 6-217, 7-236, 7-237, HCURVE-DBASE option , 8-280
7-242, 7-247, 8-274, 8-276, 8-283, 8-286, 8-293, 8-
HCURVE-GAMMA option , 8-277
298, 10-306, 10-310, 10-313, 10-317, 10-322, 10-325,
11-338 HCURVE-output , 8-280
Gibbs , 6-218 HCURVE-Using PDTS with , 8-280
change , 6-219, 6-222, 6-223 Heat , 1-3, 4-67, 6-208, 6-210, 6-212, 6-225, 6-229, 7-261
Gibbs Free Energy Minimization , 6-218 fire relief model , 11-347
Objective Function , 6-218, 6-219, 6-220 Formation , 6-208, 6-210, 6-212
Gibbs Reactor , 6-217, 6-218 fusion , 7-261
gas blowdown model , 11-348
Gilliland , 4-124, 4-142
reaction , 4-68, 4-69, 4-70, 4-71, 4-72, 6-208, 6-209,
Gilliland Correlation , 4-129 6-210, 6-211, 6-213, 6-214, 6-225, 6-226, 6-230, 6-
Glitsch , 4-52, 4-108 231
Glitsch Bulletin No , 4-123 Heat Balance , 1-3, 7-260, 7-268
GLYCOL , 1-14 Heat Exchanger Temperature Profiles , 5-152
Glycol Contactors , 4-109 Heat Exchanger Types , 5-159
Glycol Stills , 4-109 Heat exchangers , 4-53, 5-150, 5-153, 5-154, 5-158, 5-
174, 7-261, 8-277
Glycol Synthesis Gas , 4-109
Heat Input Equations , 11-345
Gnielinski , 5-161, 5-173
Heat of formation , 6-208, 6-210, 6-212
GPSA , 2-25, 2-27
GPSA Engineering Data Book , 2-23, 3-46 Heat of fusion , 7-262

Heat of Reaction , 4-68, 6-208, 6-209, 6-210, 6-211, 6- In-Line Procedures , 4-50
212, 6-225, 6-231 INNER , 4-54, 4-58, 4-59, 4-61, 4-62
Heat Transfer Correlations , 5-160 Inner Speciation Loop , 4-77
Heater/cooler , 4-53, 7-262 Input Considerations , 8-284
Heating / Cooling Curves , 8-276, 8-277, 8-278, 8-279, 8-Inside Out Algorithm , 4-54
280
Inside/Out , 1-1, 4-49, 4-54, 4-58
Heating/cooling , 7-261, 8-276, 8-279, 8-280
Intalox , 4-112
Heats of reaction occurring , 6-209
Intalox High-performance Separation Systems , 4-123
Heavy Cycle , 4-138
Intalox Saddles , 4-112
Heavy Ends Column , 4-131
Interconversion , 7-256
Heavy Gas Oil , 4-131
Inter-dependence , 10-316
Height Equivalent , 4-115
Interdependence , 10-323
Theoretical Plate , 4-112
Interpreting Exergy Reports , 8-298
HETP , 4-116, 4-117
compute , 4-116 Introduction , 1-1, 10-331
HEXAMER , 1-14, 2-19 Invalidate , 4-133
HF , 4-125 Underwood , 4-132, 4-133
Ions , 4-78, 4-79
Hfac , 11-345
Isentropic , 1-14, 2-19, 2-23, 2-25, 2-28, 11-345
Hideal , 5-161
value , 2-24, 2-25
Homotopy , 4-70, 4-71, 4-72
Isentropic efficiency , 2-25, 11-348
tracking , 4-67
isentropic efficiency
Horizontal Cylinder Vessel , 11-340
Depressuring unit , 11-350
Hot Carbonate Contactor , 4-109
Isentropic enthalpy , 11-350
Hot Carbonate Regenerator , 4-109
Isentropic expander , 2-28
Hydrate Formation , 8-286
ISO , 8-281
Prediction , 8-286
Isobutane , 8-286
Hydrate Types , 8-286
Unit Cell , 8-289 ISOTHERMAL , 1-15
Hydrate-forming , 8-286 Isothermal
flash , 1-14
Hydrates , 8-286, 8-287, 8-290, 8-292
Isothermal flash calculations , 1-2, 1-4
Hydrocarbon Processing , 4-123
Isothermal flash calculations-Newton-Raphson
Hydrocarbon-rich , 1-12 technique , 1-4
Hydrocarbon-water , 5-156 Isothermal flash calculations-solution algorithm
Hy-Pak TM , 4-112 flowsheet , 1-2, 1-4
ISOTHERMAL TEMPERATURE DP , 7-237
ISOTHERMAL TEMPERATURE PRESSURE , 7-237
I
IEG , 4-75 J
IGS , 1-14
IGS FLORY , 1-14 J.D. Mechanical Lost Work , 8-298
IMPORT , 8-282 J.M. Anderson , 1-11
Improved Grayson-Streed , 1-11 Jacobian , 4-55, 4-61, 4-65, 4-66, 4-67, 4-146, 10-315, 10-
316
Inclined Pipes , 3-44
Johnson , 5-166
Inclined Two-Phase , 3-35
Johnston , 5-173
Initial Estimates , 4-62, 4-73, 6-227, 10-313, 10-315, 10-
319
Index-640
K Liquid-Liquid Equilibria , 1-12
Liquid-Liquid Equilibrium Equations , 4-146
Katz , 7-241 Liquid-Liquid Extraction Columns , 4-48
KERAPAK , 4-119 Liquid-Liquid Extractor , 4-53, 4-143
Kern , 5-173 Liquids , 4-50
Kero , 4-138 Liquid-Vapor Equilibrium Using , 8-292
key component identification , 4-125 Liquified Natural Gas , 5-174
Kihara , 8-289 LKP , 1-14
Kinematic , 4-115 LLE , 1-13, 4-62
Kinetic Reaction , 4-52 performing , 4-62
Kinetic Reaction Homotopy , 4-67 LLEX , 4-49, 4-52, 4-54, 4-67, 4-70, 4-75, 4-143
Kirkbride , 4-129, 4-142 Simple Stage , 4-143
Kirkbride Method , 4-124, 4-129 LMTD , 5-152, 5-154, 5-155, 5-156, 5-157, 5-176
Kovach , 4-146 LNG , 5-174, 5-176
model , 5-174
KPRINT Options , 8-279
set , 5-175
Kuhn-Tucker , 10-335
solve , 5-174
Kv , 7-266, 11-345
LNG Heat Exchanger , 5-174, 5-176
KVALUE , 8-279 LOOP , 10-312, 10-313
superset , 8-279
LS , 6-217
K-value , 1-4, 2-19, 2-28, 4-54, 4-62, 4-77, 8-277, 8-279
LS Components , 4-52
decanting , 8-279
needed , 4-77 LTMD , 5-156, 5-157
K-VALUE ERROR , 4-54 Ludwig , 4-142
K-value generator , 1-2, 1-13, 8-278
K-value Method , 1-14
M
K-values , 1-5, 1-9, 1-10, 4-50, 4-54, 4-59, 4-61, 4-66, 4-
67, 4-77, 4-124, 4-132, 8-283, 8-285 Malabar , 6-223
Kwong , 1-11 Marks , 4-113
Norton Company , 4-113
Marquardt , 10-325
L Masoneilan Handbook , 11-351
Lagrange , 6-221, 10-336 Masoneilan Ltd , 11-351
Lagrange multipliers-Shadow prices , 10-331 Mass , 1-3, 4-68, 4-70
Langmuir-type , 8-288 Mass Transfer , 7-256, 7-257
Latent heat of vaporization , 4-125 Mass Transfer Coefficient Correlations , 7-256
Lee-Kesler , 2-18 Mass Transfer Operations , 4-142, 7-261, 7-270
Li , 4-64, 4-66 Mass-Transfer Operations , 7-241, 7-247
LIBID , 6-208 Material and Heat Balances and Phase Equilibria , 7-
258, 7-267
Light Cycle , 4-138
Material Balance , 6-228
Light Gas Oil , 4-138, 4-139
Math Comp , 10-316
Liquid fugacity , 8-283
Mathematical Models , 4-53, 6-217
Liquid Holdup , 3-36, 3-37, 3-38, 3-41, 3-43, 3-44, 3-45
Mathematics , 6-218
Liquid Hydrocarbon-Water Systems , 8-292
Free Energy Minimization , 6-218
Liquid/vapor , 4-126, 8-284
Mathematics of Free EnergyMinimization , 6-218
Liquid-extraction , 4-49

MAXI , 10-336 Mueller , 5-157
MAXI-MINI , 10-334 Mukherjee , 3-44
MDt , 11-345 Mukherjee-Brill , 3-38
Meier , 4-123 Mukherjee-Brill correlation , 3-35
Melter/Freezer , 7-271, 7-273 Multicomponent Mixtures
Melting temperature , 7-271 Critical Points , 8-275
MES , 8-298 Multicomponent Vapor-Liquid , 1-12
Computer Calculations , 1-12
MESH , 1-3, 1-13, 4-77
Multipass , 5-153
MESH Equations , 1-3
Multiple Steady States , 6-227
Methanation , 6-211, 6-212, 6-215, 6-216
Multivariable , 10-311, 10-317
Methanation Reactor Model , 6-212, 6-216
Multivariable Controller , 10-323
Methanation reactors , 6-211
Multivariable controller-algorithm , 10-324
MethanationReactorModel , 6-216
Multivariable Feedback Controller , 10-322
Methanator , 6-213
Munck , 8-292
Methanators , 6-212, 6-216
Murphree Efficiency , 4-147
Michelsen , 8-275
MVC , 8-276, 8-283, 10-322, 10-323, 10-324, 10-325
MINI , 10-336
MVC application , 10-322
minimum number of trays , 4-124
MVC Solution , 10-324
minimum reflux ratio , 4-124, 4-127
Minimum Tear Streams , 10-310
Missen , 6-223 N
MITA , 5-174
Mixer , 1-16 NaCl , 4-78
Mixer Unit , 1-16 Nagle , 5-157
Model , 5-174, 11-345, 11-346 Naphtha , 4-138
API RP520 Heat , 11-347 Naphtha - Kero , 4-131
API RP520 Model , 11-347 NBS , 6-216
APIScale , 11-347
N-butane , 8-286
Fire Relief , 11-347
New Approach , 4-62, 4-81
LNG , 5-174
R.W. , 4-81
Modified Environmental State , 8-298
Solving Electrolyte Distillation Problems , 4-67
Modifiy , 4-70
New Distillation Algorithm , 4-62, 4-146
Molal , 4-132 Non-Ideal System , 4-67
Molality , 4-78 R.W. , 4-146
Molarities , 4-78 Newton , 4-62, 4-65, 4-143, 4-145, 4-146
Mole Fractions , 4-64, 4-66, 4-144, 4-146, 8-280 Newton-based , 4-77
Molecular weight , 7-258, 7-267, 11-341 Newton-Raphson , 1-5, 1-11, 1-13, 4-49, 4-55, 4-65, 4-66,
Mollier chart , 2-20, 2-21, 2-22, 2-28, 2-29 4-67, 4-77, 4-79, 4-80, 4-145, 10-325
Monograph NX-28 , 3-45 Nomographs , 4-108, 4-110
Moody , 3-36, 3-41, 3-43, 3-44 Non-electrolyte , 4-48
Moody friction factor , 3-35 Non-Ideal System , 4-62, 4-146
New Distillation Algorithm , 4-67
Morris Plains , 4-81
NONLIB , 6-208
Motard , 10-310, 10-312
NONLIBRARY , 6-210
MSMPR , 7-261
Norton , 4-113, 4-115, 4-116
MSMPR Crystallizer , 7-270
Index-642
Norton Bulletin IHP-1 , 4-123 Overhead - Light Gas Oil , 4-131
NOSCALE , 10-333
NOTSEPARATE , 4-53
NRTL , 1-13
P
Nucleation Rate , 7-263 Packed Column , 4-52
Nucleii Number Density , 7-264 Packing , 4-112
Number , 4-133, 4-138, 5-165, 5-166, 5-169, 10-322, 10- Type , 4-112
326, 10-330, 10-331, 10-333, 10-335, 10-336 Pall Rings , 4-112
crossflow , 5-165, 5-166, 5-167
Palmer corection , 3-37
Fenske , 4-132, 4-133, 4-134, 4-138
flowsheet , 10-322 Pang , 7-261
optimizer , 10-326, 10-327, 10-328, 10-330, 10-331, Parikh , 7-261
10-332, 10-333, 10-334, 10-335, 10-336 Parrish , 8-292
Nusselt , 5-161, 5-163, 11-348 Particle Size , 7-257
Particle Size Distribution , 7-257, 7-264, 7-265, 7-266
Patterns , 3-39, 3-45
O
PDTS , 8-280
Objective Function , 6-218, 10-326, 10-328 Peng , 8-292
Gibbs Free Energy Minimization , 6-218 Peng-Robinson , 1-11, 2-18, 8-274, 8-278
Oil Reclaimer , 4-109 Performance Characteristics
OLI Systems , 4-50 Correlations , 4-117
Oliemens correlation , 3-35 Performing , 4-66, 4-67
LLE , 4-66
Olsen , 4-123
Perry R , 1-12
Optimization , 10-331
Practical Methods , 10-336 Petro , 3-32, 4-107, 6-208
Optimization Variables , 10-329 Petrochemical Plants , 4-142
Optimizer , 4-48, 4-50, 10-324, 10-325, 10-331 PFR Operation Modes , 6-232
cause , 10-328, 10-331 Phase , 6-223
Number , 10-325 Phase Envelope , 8-274, 8-275
prevents , 10-334
Phase Equilibria , 7-258
value , 10-332, 10-333, 10-334, 10-335, 10-336
Phase Split , 6-223
Optimizer Variables , 10-328
Physical Continuation Approaches , 4-67
Optimizer-objective function , 10-325
Solving Reactive Distillation Problems , 4-62
Optimizer-recommendations , 10-325 Pipe , 3-32, 3-33, 3-34, 3-36, 3-41, 3-43, 3-44
OPTIMIZERs , 8-280, 10-311, 10-325, 10-331
Pipe Flow , 3-35
number , 10-331 Friction Factors , 3-35
respect , 10-332
Pipelines , 3-44, 3-45
Optimizer-shadow prices , 10-331
Pipes , 3-32, 3-33, 11-340
OPTPARAMETER , 10-333, 10-334, 10-336
Platteeuw , 8-287
OR , 11-342, 11-343
Plug flow reactor , 6-229, 6-232
Order , 10-310, 10-311, 10-331, 10-332, 10-333
Plug Flow Reactor (PFR) , 6-229, 6-232
OSCIL , 7-242
Polytropic , 2-23, 2-24, 2-25, 2-26, 2-27
Outer Loop , 4-54, 4-58
Polytropic compressor , 2-26
Outer Newton-Raphson Loop , 4-79
Polytropic efficiency , 2-18, 2-19, 2-23, 2-24, 2-25, 2-27
Output Considerations , 8-284
Polytropic Efficiency Given , 2-24, 2-27
OutputConsiderations , 8-284
Polytropic efficiency gp , 2-25, 2-28

Polytropic expander , 2-28 PRO/II optimizer , 10-328
Population Balance Equations , 7-263 PRO/II sequencer , 10-320
Possible Calculation Sequences , 10-311 PRO/II User-added Subroutines User s Manual , 6-225
Postoptimality Analysis , 10-336 PRO/II utility , 8-282
Poynting correction , 8-279, 8-283 Problems , 4-62
PR , 2-18, 8-277 Process Heat Transfer , 5-173
PR Huron-Vidal , 2-18 Process Method , 10-310, 10-311, 10-312
PR Modified , 2-18 Process Simulation Program , 8-299
PR Panagiotopoulos-Reid , 2-18 Process Unit Grouping , 10-308
PR1 UFT3 , 1-14 Processes , 8-300
PR1 UNFV , 1-14 PROCHEM User s Manuals , 4-77
Practical Methods , 10-331 PROPERTY , 8-279
Optimization , 10-331, 10-332, 10-334, 10-336 Propylene-propane , 4-132
Practical Optimization , 10-331 PROVISION Graphical User , 1-1
Prandlt , 5-161, 5-163 PROVISION User s Guide , 8-277
Prandtl , 11-349 PRP , 1-14
Prausnitz , 1-12, 8-292 PRP MARGULES , 1-14
Prediction , 8-292 PRP REGULAR , 1-14
Hydrate Formation , 8-286
Pump , 3-45, 3-46
Pressure , 6-208
Pumparound , 4-53, 10-308
Pressure Drop , 3-35, 3-36, 3-37, 3-38, 3-40, 3-41, 3-43, 3-Pumparounds , 4-49, 4-50, 4-51, 4-52, 10-308, 10-309
44, 4-108, 4-109, 4-110, 4-111, 4-114, 4-115
corresponding , 10-309
Pressure Drop Correlations , 3-35, 5-165
Pumps , 3-45
PRESSURE FIXED DUTY , 7-237
Pure , 3-32, 4-67, 4-107
Pressure Gradients Occuring During Continuous Two- include , 3-32
Phase Flow , 3-35
Purities , 4-134
Pressure Losses Occurring During Continuous Two-
Phase Flow , 3-35
PRH , 1-14
Q
PRH MARGULES , 1-14
PRH VANLAAR , 1-14 Quadrature , 7-257
PRINT , 4-139 Quadratures , 6-231
PRINT PATH , 6-210 Quasi-Newton , 10-315
PRM , 1-14
PRM UNFV , 1-14
PRM VANLAAR , 1-14
R
PRO/II Application Briefs Manual , 1-1
Rachford , 1-4, 1-12
PRO/II Casebooks , 1-1 Rachford-Rice , 1-8, 1-9, 1-11
PRO/II CONTROLLER , 10-317 solve , 1-11
PRO/II CSTR , 6-227 Random packed column hydraulics-capacity , 4-112
PRO/II Data Transfer System , 8-280, 8-281 Random packed column hydraulics-Eckart flood point
PRO/II databanks , 1-13 correlation , 4-112
PRO/II dissolver , 7-253 Random packed column hydraulics-efficiency , 4-112
HETP , 4-112
PRO/II Help , 1-1
Random packed column hydraulics-flood point , 4-112
PRO/II Keyword Input Manual , 8-277, 9-302
Index-644
Random packed column hydraulics-Norton pressure Reports , 8-298
drop correlation , 4-112 Research , 8-292
Random packed column hydraulics-packing factors , 4-
Resid , 4-139
112
Residence Time , 7-260
Random packed column hydraulics-Tsai pressure drop
correlation , 4-112 Resolve , 10-324, 10-325, 10-331
Random Packed Columns , 4-112 flowsheet , 10-324, 10-325, 10-327, 10-328, 10-329,
10-330, 10-331, 10-332, 10-333, 10-334, 10-336
Random Packing Types , 4-112, 4-117
Retrograde Condensation , 8-278
Rankine , 8-282
Retrograde Region Calculations , 8-277
Raschig , 4-112
Revolutions/min , 7-239, 7-243, 7-263
Raschig Rings , 4-112
Reynolds , 3-38, 5-161, 5-162, 5-163, 7-256
Rasmussen , 8-292
Rice , 1-4, 1-12
Reaction , 4-67, 6-208, 6-210, 6-212, 6-225, 6-229
heat , 4-68, 6-208, 6-209, 6-210, 6-211, 6-212, 6-225, Rif , 7-257
6-230, 6-231 Rigorous Distillation Algorithms , 4-48, 4-50, 4-53, 4-
54, 4-62, 4-67, 4-73
Reaction Data , 4-70, 6-208, 6-209
Reactive Distillation , 4-67, 4-68, 4-70, 4-71 Rmin , 4-126, 4-127
solve , 4-125
Reactive Distillation Algorithm , 4-71
value , 4-126, 4-127
Reactive distillation algorithm uses , 4-71
Robinson , 8-292
Reactor Heat Balances , 6-208, 6-210
Rotary Drum Filter , 7-237, 7-238, 7-242
Reactor models , 6-215, 6-218
Rubin-Starling , 1-11
Reactor sizing , 6-210, 6-212
Rules-of-thumb , 4-112
Reactors , 4-67, 6-208, 6-211, 6-212, 6-215, 6-216, 6-217,
Runge-Kutta , 6-232
6-218, 6-224, 6-225, 6-227, 6-228, 6-229, 6-232, 9-
304, 10-319 Russell , 4-54, 4-62
Reactors-CSTR , 6-224
Reactors-equilibrium , 6-212
S
Reactors-heat balances , 6-208
Reactors-PFR , 6-229 Sample HCURVE , 8-281
Reboiler , 4-50, 4-51, 4-73, 4-74, 4-124, 4-129, 4-132, 10- Scandrett , 7-253
327
ScG , 4-116
Reboilers , 4-139
Schmidt , 4-116, 4-117, 7-256
Recommendations , 4-76, 10-319, 10-331
Seader , 8-299
Recommended Uses , 10-315, 10-316
Seider , 6-223
Broyden , 10-315, 10-316
Separation Columns
Wegstein , 10-313, 10-314, 10-315
Distillation , 4-123
Reconstituted Components , 4-79
Sequence , 10-319, 10-324
Recycle , 10-307, 10-310, 10-311
CONTROLLER , 10-319
Recycle acceleration-acceleration factor , 10-313 Sequencing-PROCESS , 10-310
Recycle acceleration-recommendations , 10-313, 10-315
Sequential Modular Solution Technique , 10-306, 10-
Recycle Loop , 10-321 307, 10-309
REFINE , 4-133 Series-parallel , 6-211
Refinery Heavy Ends Columns , 4-135 Shadow Prices , 10-335, 10-336
Refining , 4-75, 4-76 Shadow prices-Optimizer , 10-331
Refluxes , 4-138 Shell weight (dry) , 5-170, 5-171
relative volatility , 4-58, 4-124, 4-125, 4-126, 4-131 Shell weight (with water) , 5-171
Report Information , 8-280

Shellside , 5-161, 5-165, 5-166, 5-168, 5-173 Solubility Data , 7-261
Shellside Pressure Drop , 5-173 Soluble Values , 7-253
Shellside Reynolds , 5-165 Solute component kg/kgmol , 7-259
Shell-to-baffle , 5-162 solute components , 7-258, 7-261, 7-267
Sherwood , 4-122, 7-256 Solute Vapor Balance , 7-259, 7-268
Shift Reactor Model , 6-212, 6-215 Solute/kg , 7-254
ShiftReactorModel , 6-215 Solutility , 7-258
Shiras , 4-126 Solution Algorithm , 1-5, 1-13, 10-330, 10-331
SHORTCUT , 4-140, 4-142 Solution Procedure , 4-65, 4-145, 7-260, 7-269, 10-324
Shortcut Distillation , 4-48, 4-124, 4-125, 4-130, 4-131
Solve , 1-11, 4-127, 5-175, 7-251, 10-324, 10-329, 10-331
Column Models , 4-131 basecase , 10-328, 10-329, 10-331
Shortcut Distillation Column Condenser Types , 4-130 flowsheet , 10-324, 10-331
LNG , 5-174, 5-175
Si , 8-298, 11-343
Rachford-Rice , 1-11
Sidestream , 4-54, 4-57, 4-58, 4-61
Rmin , 4-125
Sidestream withdrawl , 4-61 triagonal , 7-251
Sidestrippers , 10-308, 10-309 Solved.All , 4-48
Sieder-Tate , 5-162, 5-163 Solving Electrolyte Distillation Problems , 4-62, 4-81
Silverblatt , 7-241 New Approach , 4-67
Simple Columns , 4-132, 4-139 Solving Reactive , 4-67
Simple Heat Exchangers , 5-151, 5-154 R.W. Physical Continuation Approaches , 4-67
Simple Stage , 4-56 Solving Reactive Distillation Problems , 4-67
Chemdist , 4-62, 4-65, 4-66 Physical Continuation Approaches , 4-62
I/O , 4-54, 4-56, 4-60 Souder , 4-120
LLEX , 4-143, 4-145, 4-146 SOUR , 1-14
Simple-rigorous , 10-308 Sour Water Stripper , 4-108
Simplicial , 4-67 SPEC , 4-62, 10-317
SimSci Method , 10-310, 10-311 SPEC ERROR , 4-62
Simultaneous Modular Solution , 10-307 Special Features , 4-123
Simultaneous Modular Solution Technique , 10-306 Speciation , 4-77, 4-78, 4-79
Simultaneous Modular Techniques , 10-306 needed , 4-77, 4-78
Size Distribution , 7-263 Specific gravity , 5-170, 11-341
Sizing , 4-107, 4-109 SPECIFICATION , 7-236, 7-237, 8-280, 10-319, 10-320,
trayed , 4-107 10-321, 10-322
Skjold-Jorgensen , 8-292 Specifications.Since , 4-139
Smith , 6-223 Spherical Vessel , 11-341
Soave Redlich-Kwong , 2-18 Spiegel , 4-123
Soave-Redlich , 1-11 Splitter , 1-17
Soave-Redlich-Kwong , 1-11, 2-18, 8-274, 8-278 implies , 1-17
Sodium Balance , 4-77 Splitter Unit , 1-17
Solid Phase , 7-261 SQP , 10-331
Solid/Liquid Separation Equipment Scale Up , 7-241 SRK , 2-18, 8-283
Solid-liquid Equilibrium , 7-260, 7-268 SRK Kabadi-Danner , 2-18
Solid-liquid Solute Balance , 7-259, 7-267 SRK SimSci , 2-18
Solids Handling , 7-236 SRK1 AMINE , 1-14
Solids Handling Unit Operations , 7-236 SRK1 NRTL , 1-14
Index-646
SRKH , 1-14 Subcooled , 4-76, 4-132, 5-157
SRKH UFT1 , 1-14 containing , 5-156, 5-157
guesses , 4-76
SRKKD , 1-14
Subsurface Controlled Safety Valve Sizing Computer
SRKM , 1-14, 2-19
Program , 3-44
SRKP , 1-14
Successive Quadratic Programming , 10-331
SRKP UFT1 , 1-14
Sulfur hexafluoride , 8-286
SRKP UFT2 , 1-14
Sulzer , 4-117
SRKS , 1-14
Sulzer Brothers , 4-51, 4-117
SRKS UFT2 , 1-14
Sulzer Packings Available
SRKS UFT3 , 1-14 Types , 4-118, 4-119, 4-121, 4-122, 4-123
State , 2-18, 8-274, 8-278, 8-283, 8-292 SUM , 4-61, 4-62
equation , 1-4, 1-5, 1-6, 2-18, 8-274, 8-278, 8-283, 8-
Super Intalox , 4-112
287, 8-288, 8-291, 8-292
Super Intalox R , 4-112
STEPSIZES , 10-325, 10-333, 10-335
Supersaturation , 7-261, 7-262, 7-263
Stirred Tank Dissolver , 7-261
Design , 7-261 Superset , 8-279
KVALUE , 8-280
Stirred Tank Reactor , 6-224
Supplying , 8-298
Stoichiometric , 4-67, 6-208, 6-212, 6-218, 6-225
EXERGY , 8-298
corresponding , 6-211
Sure , 4-49, 4-52, 4-75
Stoichiometric Reactor , 6-215
Sure Algorithm , 4-62
Stoichiometry , 6-218
Surface Tension , 3-32
Straightforward , 4-67, 9-304
Switzerland , 4-117
Stream Calculator , 9-302, 9-303, 9-304, 9-305
Sulzer Brothers , 4-117
Stream Calculator allows , 9-303
System Factors , 4-108
Stream Splitting Considerations , 9-304
Stream Summary , 8-298
Stream Synthesis Considerations , 9-305 T
Streams , 10-306
flowsheet , 10-306 Tablular , 8-274
Stripping Factor , 4-54 Tc , 5-156, 6-231, 6-232
Structural Approach , 4-146 Tear Streams , 10-310, 10-311, 10-312
Solving Multistage Separations , 4-146 Tearing , 10-310
Structured packed column hydraulics-applications , 4- Algorithms , 10-310
117 Tearing Algorithms , 10-310
Structured packed column hydraulics-efficiency Technol , 1-12
NTSM , 4-122
TEMA , 5-159
Structured packed column hydraulics-flood point , 4- Temperature.Only , 6-217
117
Temperature/pressure , 8-286
Structured packed column hydraulics-limit of
capacity , 4-117 identify , 8-286
Structured packed column hydraulics-pressure drop Temperature-gradient , 5-162
correlations , 4-117 Termination Criteria , 10-335
Structured packed column hydraulics-Souder Termperatures , 4-61
diagram , 4-117
TES , 8-298
Structured packed column hydraulics-Sulzer packing
Theoretical Plate , 4-115
types , 4-117
Height Equivalent , 4-112
Structured Packed Columns , 4-117
Theory , 1-1, 6-223, 8-286, 11-338

Depressuring unit , 11-338 Troubleshooting , 4-139
Thermal , 10-311 troubleshooting complex columns , 4-139
Thermal Behavior , 6-227 troubleshooting simple columns , 4-139
CSTR , 6-227 Tubepass , 5-153
Thermal condition , 4-125 Tubepasses , 5-153
feed , 4-127 Tubeside , 5-151, 5-158, 5-162, 5-163, 5-164, 5-169, 5-173
thermal condition of feed , 4-125
Twall , 11-349, 11-350
Thermodynamic , 8-298 Two-Phase
thermodynamic generators , 3-32, 3-33, 4-107 flash calculations , 1-2
Entropy , 2-18, 2-19 Two-phase Adiabatic Flash Calculations , 1-11
Viscosity , 4-107
Two-phase flash calculations , 1-4
Thermodynamic Lost Work , 8-299
Two-Phase Flow , 3-39, 3-44, 3-45
Thermodynamic Methods , 1-9, 4-107, 8-277, 8-278
Two-phase Isothermal Flash Calculations , 1-4
Thermophysical , 6-222
Type , 4-112, 4-117, 7-242, 8-280
Thomas , 7-251 Filtering Centrifuges , 7-242
Three-phase Flash Calculations , 1-13 heating/cooling , 8-280, 8-281, 8-282
Three-Phase Solid , 8-286 Packing , 4-112, 4-114, 4-115, 4-116, 4-117
Time-pressure-temperature , 11-338 Sulzer , 4-117, 4-118, 4-119, 4-121, 4-122, 4-123
determine , 11-338 Sulzer Packings Available , 4-117
TOLERANCE , 10-312 Typical Application , 10-326
Top Section , 4-109 Typical FINDEX , 4-138
Absorbing Type Demethanizer/Deethanizer , 4-108 Typical Values , 4-138
Topped Crude , 4-138, 4-139, 4-142 FINDEX , 4-131
TORSION , 7-242
Total Mass Balance , 1-3, 7-248
U
TPSPEC , 1-15
Tracking , 4-71 Underpinings , 4-70
homotopy , 4-67 Underwood , 4-124, 4-125, 4-131
Transport Properties , 3-32 invalidate , 4-131
TRAPP , 3-32 Underwood Method , 4-126
TRAY , 4-54 UnderwoodMethod , 4-125
Tray UNIFAC , 1-13
efficiency , 4-146 UNIQUAC , 1-13, 1-14
Tray Rating , 4-108 Unit Cell , 8-286
Tray Rating and Sizing , 4-108 Hydrate Types , 8-286
Tray Rating/Sizing , 4-52 Unit grouping , 10-308
Trayed , 4-48, 4-107, 4-108, 4-109, 4-143 UNIWAALS , 1-14, 2-18
sizing , 4-107 UNIWAALS FLORY , 1-14
Treaction , 6-214 UNIWAALS REGULAR , 1-14
Treybal , 4-142, 7-241, 7-247, 7-256, 7-261, 7-270 Uom , 5-151
Triagonal , 7-251 Uphill Flow , 3-44
solving , 7-251 Effect , 3-44
Trial-and-error Newton-Raphson , 1-9, 1-11 Use , 3-35, 10-307, 10-308
Tridiagonal , 4-57, 4-58 Controllers , 10-308
form , 4-54, 4-57, 4-58 Dukler , 3-37, 3-45
Tri-ethylene , 8-286 Eaton , 3-38, 3-43, 3-45
Index-648
USER , 1-1 Fenske , 4-131
User Manual , 3-35 Viscosity , 4-107
User-defined Model , 11-345 Thermodynamic Generators , 4-107
User-provided Estimates , 4-73 VL , 2-18, 2-19, 4-120, 6-217, 7-237
Utilities , 5-150, 5-153, 8-280 VLE , 1-4, 1-8, 1-13, 1-15, 4-54, 4-62, 7-269, 8-278, 8-279,
flowrate , 5-153 8-283, 8-284
VLLE
and DecantConsiderations, 8-278
V VLE Convergence , 1-9
VLE K-value , 8-279
V & L , 3-32
VLLE , 1-13, 1-15, 4-62, 8-278, 8-283, 8-284
V Total , 6-228
describing , 4-66
Vacuum Towers , 4-108
VLLE Data , 8-283
Vacuum Units , 4-135, 4-138 VLLE K-value , 8-279, 8-283
Valve , 1-16
VLLE Predefined Systems , 1-14
Valve Rate Equations , 11-341
Vload , 4-109
Valve RateEquations , 11-341 VLS , 6-217
Valve Unit , 1-16
VMAX1 , 10-319
van der Waals , 8-287
VMIN1 , 10-319
van't HoffEquation , 7-261 Volume Based , 4-67
VAPOR , 8-299
Vapor fugacity , 8-283
Vapor Mole Fractions , 4-74 W
Vapor pressure , 8-279
Wang , 8-299
Vapor Profiles , 4-74
WATER , 8-279
Vapor/heat , 4-127
Water and DryBasis Properties , 8-279
Vapor/liquid , 4-50
Water decant , 1-11, 4-49
Vaporization , 4-127
from flash , 1-2
latent heat , 4-127
water partial pressure , 1-12
Vaporization Efficiency , 4-148
Water/hydrocarbon , 4-49
Vapor-Liquid Equilibrium , 4-65, 4-79, 7-258, 7-260, 7-
268 Wegstein , 10-306, 10-313
Vapor-liquid-liquid , 4-62, 6-218, 8-283 Recommended Uses , 10-313
Wegstein Acceleration , 10-313, 10-314
Vapor-Liquid-Liquid Algorithm , 4-66
Weight.volume/pressure.time2 , 11-341
Vapor-liquid-liquid equilibrium (VLLE) , 1-2, 1-13
Variables , 10-331, 10-332, 10-333, 10-334, 10-335 Weight/time , 11-341
Westerberg , 10-310, 10-312
Various Two-Phase Flow Regimes , 3-39
White , 6-223
VARY , 10-335
Varying , 10-322 WIDE , 7-242
flowrates , 10-322 Wiley , 10-336
Venkatesh , 8-299 Willis , 5-166, 5-173
Vertical Cylinder Vessel , 11-340 Wright , 10-336
Vertical Flow Correlation , 3-44
Vessel Volume , 11-340
Calculating , 11-340
X
Violate , 4-131 XOVHD , 9-304

XPROD , 9-305
Y
Yadav , 7-261
Ysolute , 7-268
Z
Zones Analysis , 5-154, 5-156, 5-176
Zp , 4-116
Index-650
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P2 Ref Man

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Chapter 1: Component Data

Chapter 2: Thermodynamic Methods

PRO/II Reference Manual 3

Chapter 3: Flash Calculations

PRO/II Reference Manual 5

Chapter 2: Isentropic Calculations

Chapter 3: Pressure Calculations

Chapter 4: Distillation and Liquid-Liquid Extraction

Chapter 5: Heat Exchangers

PRO/II Reference Manual 7

Chapter 7: Solids Handling Unit Operations

PRO/II Reference Manual 9

Chapter 9: Stream Calculator

Chapter 10: Flowsheet Solution Algorithms

Chapter 11: Depressuring

Appendix A: HXRIG Heat Transfer Correlations

PRO/II Reference Manual 11

What is in This Manual?

Who Should Use This Manual?

Finding What you Need

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

PRO/II Comp & Thermo Reference Manual 1-2

Component Data 1-3

1 PPDS, Physical Property Data Service, jointly sponsored

PRO/II Comp & Thermo Reference Manual 1-4

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

Component Data 1-5

Properties From Structure

PRO/II Comp & Thermo Reference Manual 1-6

Property Generation– SIMSCI Method

Component Data 1-7

Tc  Tco [(1  2 fT ) / (1  2 fT )]2

fT  SGT 0.362456 / Tb1/2   0.0398285  0.948125 / Tb1/2  SGT 

SGT  exp 5  SG o  SG    1

SG o  0.843593  0.128624  3.36159 3  13749.5 12

PRO/II Comp & Thermo Reference Manual 1-8

fV  SGV 0.466590 / Tb1/2   0.182421  3.01721/ Tb1/2  SGV 

Pc  Pco Tc / Tco Vco / Vc  1  2 f P  / 1  2 f P  

 2.53262  46.1955 / Tb1/2  0.00127885Tb  

SGP  exp 0.5  SG o  SG    1

V = molar volume, ft3/lb-mole

Component Data 1-9

PR = reduced pressure (P/Pc)

TR = reduced temperature (T/Tc),

 = a parameter evaluated at the NBP and given by:

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

To compute the acentric factor, the parameter  is determined using

PRO/II Comp & Thermo Reference Manual 1-10

   log10  PR ,TR  0.7

Component Data 1-11

C2    0.9291  1.1543K  0.0368K 2  *104

C6    0.536  0.6828K  *107

C7  12.8  K 10  K  /10 K 

The Watson characterization factor, K, is defined as:

PRO/II Comp & Thermo Reference Manual 1-12

Property Generation– CAVETT Method

Tc  768.07121  1.7133693Tb  0.0010834003Tb2

Pc = critical pressure in psia

Tb = normal boiling point in degrees Fahrenheit

API = API gravity

D  a1  (9.1751011 API  5.633108 ) MW

a2  (3.107 104  5.832108 API ) MW

1.7025106 1.489106 API  API  2.857*105  API 