Manual de Modelos Termodinamicos

Component and Thermodynamic Data Keyword Input Manual Volume II: Thermodynamic Data PRO/II 8.
1 Edition
PRO/II 8.1 Component and Thermodynamic Data Keyword Input Manual Copyright Notice
Use of the PRO/II program, and its component parts and subsystems, is governed by the terms and conditions of a separate written agreement between your employer and Invensys Systems, Inc., its subsidiaries or affiliates. Copyright 2007 Invensys Systems, Inc. All rights reserved. No part of the material protected by this copyright may be reproduced or utilized in any form or by any means, electronic or mechanical, including photocopying, recording, broadcasting, or by any information storage and retrieval system, without permission in writing from Invensys Systems, Inc.Trademarks. PRO/II and Invensys SIMSCI-ESSCOR are trademarks of Invensys plc its subsidiaries and affiliates. AMSIM is a trademark of DBR Schlumberger Canada Limited. RATEFRAC is a registered trademark of KOCH - GLITSCH. BATCHFRAC is a registered trademark of KOCH GLITSCH. Visual Fortran is a trademark of Intel Corporation. Windows NT, Windows 2000, Windows XP, Windows 2003, and MS-DOS are trademarks of Microsoft Corporation. Adobe, Acrobat, Exchange and Reader are trademarks of Adobe Systems, Inc. All other products may be trademarks of their respective owners. U.S. GOVERNMENT RESTRICTED RIGHTS LEGEND The Software and accompanying written materials are provided with restricted rights. Use, duplication, or disclosure by the Government is subject to restrictions as set forth in subparagraph (c) (1) (ii) of the Rights in Technical Data And Computer Software clause at DFARS 252.227-7013 or in subparagraphs (c) (1) and (2) of the Commercial Computer Software-Restricted Rights clause at 48 C.F.R. 52.227-19, as applicable. The Contractor/Manufacturer is: Invensys Systems, Inc. (Invensys SIMSCI-ESSCOR) 26561 Rancho Parkway South, Suite 100, Lake Forest, CA 92630, USA. Printed in the United States of America, June 2006.
Table of Contents
Chapter 1 Thermodynamic Data Overview
General Information. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-1 Notes Statement (optional) . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-13 Minimum Required User Input . . . . . . . . . . . . . . . . . . . . . . . . . .1-13 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-13 Order of Input . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-16 Thermodynamic Sets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-17 Input Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-22 Predefined Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-26 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-26 Input Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-27 Multiple Thermodynamic Sets. . . . . . . . . . . . . . . . . . . . . . . . . . .1-29 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-29 Free-water Decant Considerations. . . . . . . . . . . . . . . . . . . . . . . .1-32 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-32 Input Description. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-33 Vapor-liquid-liquid Equilibrium Considerations . . . . . . . . . . . . .1-35 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-35 Input Description. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-41
Chapter 2 Application Guidelines

General Information. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-1 Refinery and Gas Processing Applications . . . . . . . . . . . . . . . . . .2-2 Water Handling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-2 Low Pressure Crude Systems . . . . . . . . . . . . . . . . . . . . . . . . .2-3 High Pressure Crude Systems, FCCU, and Main Coker Fractionators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-3 Reformers and Hydrofiners. . . . . . . . . . . . . . . . . . . . . . . . . . .2-4 Lube Oil and Solvent De-asphalting Units . . . . . . . . . . . . . . .2-4 Natural Gas Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-5 Glycol Dehydration Systems. . . . . . . . . . . . . . . . . . . . . . . . . .2-6 Sour Water Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-7 Amine Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-7 Petrochemical Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-8 PRO/II Component and Thermodynamic Data Keyword Input Manual 1
Light Hydrocarbon Systems . . . . . . . . . . . . . . . . . . . . . . . . . . 2-8 Aromatic Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-9 Aromatic/Non-aromatic Systems . . . . . . . . . . . . . . . . . . . . . . 2-9 Non-hydrocarbon Systems . . . . . . . . . . . . . . . . . . . . . . . . . . 2-10 Alcohol Dehydration Systems . . . . . . . . . . . . . . . . . . . . . . . 2-12 HF Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-12 Chemical and Environmental Applications. . . . . . . . . . . . . . . . . 2-13 Non-Ionic Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-13 Carboxylic Acid Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-14 Environmental Applications . . . . . . . . . . . . . . . . . . . . . . . . . 2-14 Solid Applications. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-15 Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-15
Chapter 3 Generalized Correlations

Ideal and Library Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-1 Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-1 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-1 Input Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-2 Grayson-Streed . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-4 Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-4 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-4 Input Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-5 Chao-Seader. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-8 Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-8 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-8 Input Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-9 Modifications to GS and CS . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-11 Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-11 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-11 Input Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-12 Curl-Pitzer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-15 Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-15 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-15 Input Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-15 Braun K10 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-18 Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-18 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-18 Input Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-19 Johnson-Grayson . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-21 2
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-21 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-21 Input Description. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-21 Lee-Kesler . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-23 Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-23 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-23 Input Description. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-24 API Liquid Density . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-26 Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-26 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-26 Input Description. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-26 Rackett Liquid Density . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-28 Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-28 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-28 Input Description. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-28 Costald Liquid Density . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-30 Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-30 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-30 Input Description. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-30 User-supplied K-value Data. . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-32 Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-32 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-32 Input Description. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-33
Chapter 4 Equations of State

Soave Modified Redlich-Kwong . . . . . . . . . . . . . . . . . . . . . . . . . .4-1 Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-1 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-1 Input Description. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-2 Peng-Robinson. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-7 Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-7 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-7 Input Description. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-8 Modified Soave-Redlich-Kwong and Peng-Robinson. . . . . . . . .4-13 Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-13 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-13 Input Description. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-14 UNIWAALS. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-23 Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-23 PRO/II Component and Thermodynamic Data Keyword Input Manual 3
General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-23 Input Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-24 Filling in Missing Parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-27 Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-27 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-27 Input Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-28 Cubic Equation Of State Alpha Formulations . . . . . . . . . . . . . . . 4-29 Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-29 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-29 K-value Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-30 Benedict-Webb-Rubin-Starling . . . . . . . . . . . . . . . . . . . . . . . . . . 4-33 Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-33 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-34 Associating Hexamer Equation Of State . . . . . . . . . . . . . . . . . . . 4-37 Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-37 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-37 Lee-Kesler-Plocker . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-41 Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-41 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-41 Input Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-42
Chapter 5 Special Packages

Alcohols. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5-1 Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5-1 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5-1 Input Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5-2 Glycols. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5-12 Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5-12 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5-12 Input Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5-13 Sour Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5-17 Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5-17 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5-17 Input Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5-18 GPA Sour Water. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5-21 Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5-21 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5-21 Input Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5-22 Amines. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5-24 4
Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5-24 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5-25 Input Description. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5-26 User-added Subroutines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5-29 Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5-29 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5-29 Input Description. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5-31 CAPE-OPEN . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5-32 Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5-32 Input Description. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5-33
Chapter 6 Liquid Activity Methods

NRTL . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6-1 Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6-1 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6-1 Input Description. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6-2 UNIQUAC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6-7 Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6-7 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6-7 Input Description. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6-8 UNIFAC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6-14 Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6-14 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6-15 Input Description. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6-16 Modifications to UNIFAC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6-22 Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6-22 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6-22 Input Description. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6-23 Wilson . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6-30 Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6-30 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6-31 Input Description. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6-31 Van Laar . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6-35 Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6-35 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6-36 Input Description. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6-36 Margules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6-41 Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6-41 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6-41 PRO/II Component and Thermodynamic Data Keyword Input Manual 5
Input Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-42 Regular Solution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-46 Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-46 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-46 Input Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-47 Flory-Huggins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-50 Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-50 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-50 Input Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-51 Filling in Missing Parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-57 Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-57 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-57 Input Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-58 Henrys Law for Non-condensible Components . . . . . . . . . . . . . 6-62 Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-62 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-62 Input Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-63 Henrys Law Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-66 Hayden-OConnell Vapor Fugacity . . . . . . . . . . . . . . . . . . . . . . . 6-68 Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-68 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-69 Input Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-69 Truncated Virial Vapor Fugacity . . . . . . . . . . . . . . . . . . . . . . . . . 6-72 Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-72 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-73 Input Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-73 IDIMER Vapor Fugacity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-76 Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-76 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-76 Input Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-77 Redlich-Kister, Gamma Heat of Mixing . . . . . . . . . . . . . . . . . . . 6-80 Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-80 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-80 Input Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-80
Chapter 7 Solid Solubility Methods

Van't Hoff Solubility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7-1 Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7-1 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7-1 6
Input Description. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7-2 Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7-3 User-supplied Solubility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7-3 Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7-3 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7-3 Input Description. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7-4 Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7-5
Chapter 8 Transport and Special Properties

Transport Properties. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8-1 Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8-1 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8-1 Input Description. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8-2 Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8-8 Special Properties. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8-10 Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8-10 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8-10 Input Description. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8-12 Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8-25
Chapter 9 Method-specific Pure Component Data

Method-specific Pure Component Data. . . . . . . . . . . . . . . . . . . . .9-1 Typical Usage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .9-1 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .9-1 Input Description. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .9-2 Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .9-6
Index
PRO/II Component and Thermodynamic Data Keyword Input Manual
Chapter 1 Thermodynamic Data Overview

This section provides an overview of the Thermodynamic Data Category. Detailed documentation, along with examples of common usage of all the thermodynamic features, follows in Chapters 2 through 9.
General Information
The program offers many thermodynamic methods and options ranging from the simple to the very complex. However, the thermodynamic data input requirements for most simulations are simple, requiring only a few input statements. For example, to use the Soave-modification to the Redlich-Kwong equation of state in a flowsheet requires only two lines of code in the keyword file:
Note: THERMODYAMIC DATA
METHOD SYSTEM=SRK The first statement THERMODYNAMIC DATA declares the beginning of the Thermodynamic Data Category. The second statement states that the predefined SRK system of thermodynamic generators be employed. The usage of each thermodynamic generator is fully documented in individual sections. Thermodynamic methods are packed into sets or systems, each containing a group of methods for performing all necessary thermodynamic calculations. Most applications require only one set, but complex flowsheets may be modeled best with several. The program allows a maximum of 100 different sets of thermodynamic methods in each input file. When an input file includes only one set of methods, all unit operations use that set for all calculations. When an input file contains
PRO/II Thermodynamic Data Keyword Input Manual II-1-1
two or more of these, one set serves as the default. If one set is not explicitly specified as the default, then the program chooses the first thermodynamic set in the input file as the default. Unit operations that do not explicitly specify a set of methods use the default. The SIMSCI databanks contain an extensive collection of pure component data and binary interaction data for equations of state and liquid activity methods. Additional special databanks for alcohol and glycol components are available. Vapor-liquid, rigorous vapor-liquid-liquid, solid-liquid equilibria, and electrolyte calculations can all be handled by the program using suitable thermodynamic methods. In addition, the program can compute enthalpies, entropies, flowing densities, and transport properties. Special water handling options may be declared locally within each set of methods. Method-specific options apply only to calculations controlled by the set of methods that contains the options. Usually, all component data are retrieved from the component libraries or are estimated for stream assay cuts and PETRO components (petroleum pseudocomponents). Other component data, such as for NONLIB components (those components missing from the component databank), are usually supplied in the Component Data Category of input. These data are global, applying to all calculations in the problem. Each set of methods optionally may include additional method-specific data that override the data obtained from other sources such as the SIMSCI databank, but which apply only to calculations controlled by the methods set containing the data. Method-specific data include selected pure component properties (e.g., critical temperature and pressure) and multi-component data such as binary interaction parameters.
II-1-2
Thermodynamic Data Overview
Table 1-1: THERMODYNAMIC DATA Category of Input Statement Category Heading Statement, Required
THERMODYNAMIC DATA
Keywords None
For details see Chapter 1 Notes Statement (optional) on page 1-13
Notes Statement, Optional

NOTES TEXT = notes line (up to 256 characters)
The METHOD Statement, Required Selecting a Pre-defined System of Methods

METHOD SYSTEM(VLE or VLLE)= option, {KVALUE (SLE)= option}, {L1KEY= i and L2KEY = j}, {KVALUE(VLE or LLE or VLLE)=option, ENTHALPY = option, DENSITY=option, ENTROPY=option}, { RVPMETHOD}, (TVPMETHOD} {PHI=option}, {HENRY}, {PROPERTY = method}, {SET = setid, DEFAULT} TRANSPORT = NONE or TRANSPORT = PURE or PETRO or TRAPP or TACITE or U1 or U2 or U3 or U4 or U5
Predefined Systems on page 1-28
Selecting Individual Methods

METHOD SET= setid, {DEFAULT} KVALUE (VLE) = option, {KVALUE (SLE)= option} {KVALUE (LLE) = option}, {L1KEY = i and L2KEY = j}, {PHI=option}, {HENRY}, or KVALUE(VLLE) =option, {L1KEY = i and L2KEY = j}, {KVALUE (SLE) = option}, {PHI = option}, {HENRY}, ENTHALPY(VL) = option, or ENTHALPY(V) = option and ENTHALPY(L) = option, {RVPMETHOD}, {TVPMETHOD}, {PROPERTY=method} DENSITY(VL) = option, or DENSITY(V) = option and DENSITY(L) = option ENTROPY(VL)=NONE or ENTROPY(V)=option, ENTROPY(L)=option, TRANSPORT = NONE or TRANSPORT = PURE or PETRO or TRAPP or TACITE or U1 or U2 or U3 or U4 or U5 or
( ) = Keyword qualifiers; { } = Optional entries; Values given are defaults; Underlined keywords are defaults.
Thermodynamic Sets on page 117
PRO/II Thermodynamic Data Keyword Input Manual
II-1-3
Table 1-1: THERMODYNAMIC DATA Category of Input Statement Keywords

VISCOSITY(VL) = NONE or VISCOSITY(VL) = PURE or PETRO or TRAPP or U1 or U2 or U3 or U4 or U5 or VISCOSITY(V) = option, VISCOSITY(L) = option and/or CONDUCTIVITY(VL) = NONE or CONDUCTIVITY(VL) = PURE or PETRO or TRAPP or U1 or U2 or U3 or U4 or U5 or CONDUCTIVITY(V) = option, CONDUCTIVITY(L) = option and/or SURFACE = NONE or SURFACE = PURE or PETRO or PARACHOR or U1or U2 or U3 or U4 or U5 DIFFUSIVITY(L) = NONE or DIFFUSIVITY(L) = WILKE or DIFDATA
For details see
Method-specific Water Handling Options, Optional

WATER DECANT = ON or OFF, {GPSA}, SOLUBILITY = SIMSCI or KEROSENE or EOS, PROPERTY = SATURATED or STEAM
Free-water Decant Considerations on page 1-34
Property Statements, Optional Vapor-Liquid Equilibrium Options, Optional

KVALUE(VLE) POYNTING = OFF or ON, MOLVOL = STANDARD or RACKETT or RCK2 or LIBRARY, {BANK = SIMSCI or ALCOHOL or GLYCOL or NONE} or { BANK=PROII_8.0:SIMSCI, PROII_8.0:ALCOHOL, PROII_8.0:GLYCOL LIBRARY1:USER1, LIBRARY1:USER2, LIBRARY1:bankid...} FILL = NONE or UNIFAC or UFT1 or REGULAR or FLORY, AZEOTROPE = SIMSCI or NONE or bankid, {WRITE = fileid}, ALPHA = ACENTRIC or SIMSCI or bankid (default depends on method) <optional data statements> ...
Chapter 5
Note: Only the STANDARD option is available for molar liquid volume (MOLVOL)
calculations when the WILSON K-value method is selected.

II-1-4
Table 1-1: THERMODYNAMIC DATA Category of Input Statement Keywords For details see Chapter 5
Liquid-Liquid Equilibrium Options, Optional

KVALUE(LLE) {BANK = SIMSCI or ALCOHOL or GLYCOL or NONE} or { BANK=PROII_8.0:SIMSCI, PROII_8.0:ALCOHOL, PROII_8.0:GLYCOL LIBRARY1:USER1, LIBRARY1:USER2, LIBRARY1:bankid...}, FILL = NONE or UNIFAC or UFT1 or REGULAR or FLORY, AZEOTROPE = SIMSCI or NONE or bankid, {WRITE = field}, {ALPHA = ACENTRIC or SIMSCI or bankid} or { BANK=PROII_8.0:SIMSCI, LIBRARY1:USER1, LIBRARY1:USER2, LIBRARY1:bankid...} (default depends on method) <optional data statements> ...
Solid-Liquid Equilibrium Options, Optional

KVALUE(SLE) SOLUTE SOLDATA(tunit) FILL = VANTHOFF or ONE or FREE i, j, .... i, j, c1, c2, c3/ ...
Chapter 7
Diffusivity Options, Optional

DIFFUSIVITY(L) DIFDATA(tunit) i, l, c1, c2, c3/ ...
Chapter 7
Vapor Fugacity Options, Optional

PHI {BANK= SIMSCI or NONE } or { BANK=PROII_8.0:SIMSCI, LIBRARY1:USER1, LIBRARY1:USER2, DIPPR, bankid...} {ALPHA= ACENTRIC or SIMSCI or bankid} or { {BANK=PROII_8.0:SIMSCI, LIBRARY1:USER1, LIBRARY1:USER2, LIBRARY1:bankid..} <optional data statements> ...
Chapter 5
Henrys Law Options, Optional

HENRY {BANK= SIMSCI or NONE} or { BANK=PROII_8.0:SIMSCI, LIBRARY1:USER1, LIBRARY1:USER2, LIBRARY1:bankid...} SOLUTE i, j, ... HENDATA(punit, tunit) i, l, c1, c2, c3, c4 / ...
Chapter 5
Density Options, Optional

Chapters 4 & 5
II-1-5
Table 1-1: THERMODYNAMIC DATA Category of Input Statement

DENSITY(VL)
Keywords
{BANK = SIMSCI or NONE } or { BANK=PROII_8.0:SIMSCI, LIBRARY1:USER1, LIBRARY1:USER2, LIBRARY1:bankid...} ALPHA = ACENTRIC or SIMSCI or bankid {BANK = SIMSCI or NONE} or { BANK=PROII_8.0:SIMSCI, LIBRARY1:USER1, LIBRARY1:USER2, LIBRARY1:bankid...} {ALPHA = ACENTRIC or SIMSCI or bankid} or { BANK=PROII_8.0:SIMSCI, LIBRARY1:USER1, LIBRARY1:USER2, LIBRARY1:bankid...} {BANK = SIMSCI or NONE } or { BANK=PROII_8.0:SIMSCI, LIBRARY1:USER1, LIBRARY1:USER2, DIPPR, bankid...} {ALPHA = ACENTRIC or SIMSCI or bankid} or { BANK=PROII_8.0:SIMSCI, LIBRARY1:USER1, LIBRARY1:USER2, LIBRARY1:bankid...} <optional data statements> ...
For details see
or DENSITY(V)
or DENSITY(L)
Enthalpy Options, Optional

ENTHALPY(VL) {BANK = SIMSCI or NONE } or { BANK=PROII_8.0:SIMSCI, LIBRARY1:USER1, LIBRARY1:USER2, DIPPR, bankid...} {ALPHA = ACENTRIC or SIMSCI or bankid} or { BANK=PROII_8.0:SIMSCI, LIBRARY1:USER1, LIBRARY1:USER2, LIBRARY1:bankid...} HMIX = IDEAL or GAMMA or RK1 or RK2 {BANK = SIMSCI or NONE} or { BANK=PROII_8.0:SIMSCI, LIBRARY1:USER1, LIBRARY1:USER2, DIPPR, bankid...} {ALPHA = ACENTRIC or SIMSCI or bankid} or { BANK=PROII_8.0:SIMSCI, LIBRARY1:USER1, LIBRARY1:USER2, LIBRARY1:bankid...} {BANK = SIMSCI or NONE} or { BANK=PROII_8.0:SIMSCI, LIBRARY1:USER1, LIBRARY1:USER2, DIPPR, bankid...} {ALPHA = ACENTRIC or SIMSCI or bankid} or { BANK=PROII_8.0:SIMSCI, LIBRARY1:USER1, LIBRARY1:USER2, LIBRARY1:bankid...} HMIX = NONE or GAMMA or RK1 or RK2 <optional data statements> ...
Chapters 4 & 5
or ENTHALPY(V)
and/or ENTHALPY(L)
Entropy Options, Optional

Chapters 4 & 5
II-1-6

ENTROPY(VL)
Keywords
{BANK = SIMSCI or NONE } or { BANK=PROII_8.0:SIMSCI, LIBRARY1:USER1, LIBRARY1:USER2, DIPPR, bankid...} {ALPHA = ACENTRIC or SIMSCI or bankid} or { BANK=PROII_8.0:SIMSCI, LIBRARY1:USER1, LIBRARY1:USER2, LIBRARY1:bankid...} {BANK = SIMSCI or NONE} or { BANK=PROII_8.0:SIMSCI, LIBRARY1:USER1, LIBRARY1:USER2, DIPPR, bankid...} {ALPHA = ACENTRIC or SIMSCI or bankid} or { BANK=PROII_8.0:SIMSCI, LIBRARY1:USER1, LIBRARY1:USER2, LIBRARY1:bankid...} {BANK = SIMSCI or NONE } or { BANK=PROII_8.0:SIMSCI, LIBRARY1:USER1, LIBRARY1:USER2, DIPPR, bankid...} {ALPHA = ACENTRIC or SIMSCI or bankid} or { BANK=PROII_8.0:SIMSCI, LIBRARY1:USER1, LIBRARY1:USER2, LIBRARY1:bankid...} <optional data statements> ...
For details see
or ENTROPY(V)
and/or ENTROPY(L)
User-supplied K-value Data, Optional (Use with KVALUE statements)

KVALUE(VLE or LLE) KDATA CORR=icorr, LN or LOG or EXPFAC=ipos, PREF(punit)=value DATA=i, tmax, tmin, c1, ... c8/ ... TABULAR=t1, t2, .../ i, p1, p2, .../ ..., PREF(punit)=value
Chapter 3
or KDATA
Binary Interaction Data, Optional (Use with KVALUE, PHI, DENSITY, ENTHALPY, or ENTROPY statements) BWRS Equation of State Data, Optional
BWRS i, j, kij, / ...
Chapters 4 & 5
HEXAMER Equation of State Data, Optional

HEXA(K or R) i, j, kija, kjia, kijb, kjib, kijc, kjic, cij, cji / ...
LKP Equation of State Data, Optional

LKP i, j, kij, / ...
Hayden-OConnell Data, Optional (For vapor fugacity, vapor density, vapor enthalpy, and vapor entropy)
II-1-7

HOCV i, i, nii, / i, j, nij, / ...
Keywords
For details see
Truncated Virial Data, Optional (For vapor fugacity)

TVIRIAL i, i
IDIMER Data, Optional (For vapor fugacity, vapor density, vapor enthalpy, and vapor entropy)
IDIMER i, i, Aii, Bii / i, j, Aij, Bij / ...
Redlich-Kister Excess Properties Data, Optional (Currently for heat of mixing only)
RK1 (K or KCAL or KJ) or RK2 (K or KCAL or KJ) i, j, aij, bij, cij, dij, eij, fij, gij, hij / ...
i, j, aij, bij, cij, dij, eij, fij, gij, hij / ...
Soave-Redlich-Kwong or Peng-Robinson Equation of State Interaction Parameters, Optional

SRK(K or R) or PR(K or R) or SRKKD(K or R) or SRKP(K or R) or PRP(K or R) or SRKM(K or R) or PRM(K or R) or i, j, kija, kijb, kijc / ...
Chapter 4
i, j, kija, kijb, kijc / ... i, j, kija, kjia, kijb, kjib, kijc, kjic / ...
i, j, kija, kjia, kijb, kjib, kijc, kjic, cij, cji / ...
SRKH i, j, aij, bij, cij, aji, bji, cji, ij, ij / ... (K or KCAL or KJ) or PRH (K or KCAL or KJ) or SRKS(K or R)
( ) = Keyword qualifiers;

{ } = Optional entries; Values given are defaults; Underlined keywords are defaults.
II-1-8
Table 1-1: THERMODYNAMIC DATA Category of Input Statement NRTL Data, Optional
NRTL3 (K or KCAL or KJ) NRTL (K or KCAL or KJ) NRTL6 (K or KCAL or KJ) NRTL8 (K or KCAL or KJ) i, j, bij, bji, ij / ... i, j, aij, bij, aji, bji, ij / ... i, j, aij, bij, aji, bji, ij, ij / ... i, j, aij, bij, cij, aji, bji, cji, ij, ij / ...
Keywords
For details see Chapter 5
Liquid Phase Activity Binary Interaction Data
UNIQUAC Data, Optional

UNIQUAC (K or KCAL or KJ) UNIQ4 (K or KCAL or KJ) i, j, aij, aji / ... i, j, aij, aji, bij, bji / ...
Wilson Data, Optional

WILSON (K or KCAL or KJ or NODIME) VANLAAR i, j, aij, aji / ...
Van Laar Data, Optional

i, j, aij, aji / ...
Margules Data, Optional

MARGULES i, j, aij, aji, dij / ... i, j, ij / ...
Flory-Huggins Data, Optional

FLORY
Other Binary Data for Liquid Activity Methods (For use with liquid activity methods, such as all forms of NRTL, UNIQUAC, Wilson, van Laar, and the Margules methods.)
AZEOTROPE (basis, punit, tunit) INFINITE(tunit) MUTUAL (basis, tunit) IDEAL
i, j, pres, temp, xi / ... i, j, temp, ioo, joo / ... i, j, temp, xiI, xjII / ... i, j / ...
Chapter 5 Chapter 5 Chapter 5 Chapter 5
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Table 1-1: THERMODYNAMIC DATA Category of Input Statement Henrys Law Data, Optional
SOLUTE HENDATA (punit, tunit) i, {j, ...} i, l, c1, c2, c3, c4 / ...
Keywords
UNIFAC Group Contribution Data, Optional (For K-value calculations only)

UNIFAC (K or KCAL or KJ) UNIFT1(K) or UNIFT2(K) or UNIFT3(K) UNFV (K or KCAL or KJ) UNIFT1(K) UNIFAC (K or KCAL or KJ)
Chapter 5
l, k, Alk, Akl / ... l, k, alk, akl, blk, bkl, clk, ckl / ... l, k, alk, akl, blk, bkl, clk, ckl / ... l, k, alk, akl, blk, bkl, clk, ckl / ... l, k, alk, akl / ...
UNIWAALS Modified Group Contribution Interaction Data, Optional

l, k, alk, akl, blk, bkl, clk, ckl / ... l, k, Alk, Akl / ...
Values given are defaults; Underlined keywords are defaults.
Chapter 4
{ } = Optional entries;
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Table 1-1: THERMODYNAMIC DATA Category of Input Statement Keywords For details see Chapter 4 Pure Component Alpha Formulations, Optional (Used with PR, SRK, or UNIWAALS methods)
PA01 or SA01 or VA01 PA02 or SA02 or VA02 PA03 or SA03 or VA03 PA04 or SA04 or VA04 PA05 or SA05 or VA05 PA06 or SA06 or VA06 PA07 or SA07 or VA07 PA08 or SA08 or VA08 PA09 or SA09 or VA09 PA10 or SA10 or VA10 PA11 or SA11 or VA11 property(qualifier) i, c1 / ... i, c1, c2, c3 / ... i, c1, c2 / ... i, c1, c2 / ... i, c1, c2 / ... i, c1, c2, c3 / ... i, c1 / ... i, c1, c2, c3 / ... i, c1, c2, c3 / ... i, c1, c2 / ... i, c1, c2 / ...
Special Property Methods Data, Optional

{GAMMA=value, REFINDEX=value, REFVALUE(unit)=value}, {NCFILL=ncfill}, {NCBLEND=ncblend} i, datvalue / ... i, indvalue / ...
Chapter 8
DATA(unit) INDEX
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TC(unit) PC(unit) VC(unit) ZC ACENTRIC NBP(unit) MOLVOL(unit) DIPOLE(unit) RADIUS(unit) SOLUPARA RACKETT WDELT PARACHOR PENELOUX i, value / ... i, value / ... i, value / ... i, value / ... i, value / ... i, value / ... i, value / ... i, value / ... i, value / ... i, value / ... i, value / ... i, value / ... i, value / ... i, value / ...
Keywords
Method-specific Pure Component Data, Optional
User-added Subroutine Data, Optional

(See the PRO/II Data Transfer System and User-added Subroutines Users Guide) UDATA
Chapters 6 & 8
i, value / ...
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Notes Statement (optional)

NOTES TEXT = notes line
The NOTES statement in the Thermodynamic Data Section provides a TEXT keyword that specifies the actual note.
NOTES This statement must be placed along with the METHOD statement of the specific thermodynamic set to which the information pertains. One NOTES statement is allowed per thermodynamic set. TEXT This entry specifies the actual notes line(s). The Notes Data can be specified in multiple lines, but only the first 256 characters will be scanned and the rest will be discarded.
An example of information added through NOTES statements about the thermodynamic sets used in a simulation follows:
THERMODYNAMIC DATA $Example with Set ID METHOD SYSTEM=PR, DENSITY(L)=LK, SET=PR01 NOTES TEXT= This is the default thermo set used in the & simulation. $Example without Set ID METHOD SYSTEM=SRK NOTES TEXT= The SRK method is defined for use with the & hot key flash in PROVISION.
Minimum Required User Input

General Information
The program offers a multitude of user choices and data entry options for the Thermodynamic Data Category. However, the input requirements to define the thermodynamic properties for the vast majority of applications are minimal. In most cases, selecting a predefined system (see Predefined Systems on page 1-28) is sufficient. This takes the form:
THERMODYNAMIC DATA METHOD SYSTEM=system id
Where the system id is selected from Table 1-4.
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Some unit operations require transport properties to be selected on the METHOD statement. This is not defaulted with the SYSTEM selection, and instead must be chosen separately. The simplest way to do this is to use the TRANSPORT keyword which selects a group of consistent property generators for viscosity, thermal conductivity and surface tension. Once the TRANSPORT keyword is supplied, the program uses a suitable default. The choices are given in Transport Properties on page 8-1. The input takes the form:
THERMODYNAMIC DATA METHOD SYSTEM=system id, TRANSPORT or THERMODYNAMIC DATA METHOD SYSTEM=system id, TRANSPORT=transport id
Note: The DIFFUSIVITY entry is not included with the
TRANSPORT groupings and must be entered separately when the DISSOLVER unit operation is present in the flowsheet and the Treybal method is used to calculate the mass transfer coefficient.
Examples
Typical input file segments based on recommendations given in Chapter 2, Application Guidelines, are provided below. The Thermodynamic Data Category is highlighted. 1. A petroleum refinery crude fractionator using the GraysonStreed system :
... COMPONENT DATA LIBID 1,H2O / 2,C2 / 3,C3 / 4,IC4 / 5,NC4 / 6,IC5 / 7,NC5 THERMODYNAMIC DATA METHOD SYSTEM=GS STREAM DATA ...
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2.
A deethanizer using Peng-Robinson. Transport properties are selected to support tray rating calculations:
... COMPONENT DATA LIBID 1,N2 / 2,C1 / 3,C2 / 4,C3 / 5,IC4 / 6,NC4 / & 7,IC5 / 8,NC5 / 9,NC6 / 10,NC7 THERMODYNAMIC DATA METHOD SYSTEM=PR, TRANSPORT=PURE STREAM DATA ...
3.
A three phase distillation tower containing MEK, water and toluene using NRTL:
... COMPONENT DATA LIBID 1,MEK / 2,H2O / 3,TOLUENE THERMODYNAMIC DATA METHOD SYSTEM(VLLE)=NRTL STREAM DATA ...
4.
Gas sweetening with MEA:

... COMPONENT DATA LIBID 1,CO2 / 2,H2S / 3,C1 / 4,C2 / 5,C3 / 6, IC4 / 7,NC4 / & 8,IC5 / 9,NC5 / 10,NC6 / 11, NC7 / 12,H2O / 13,MEA THERMODYNAMIC DATA METHOD SYSTEM=AMINE STREAM DATA ...
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Order of Input
The order of appearance of statements in the input file is significant, and the statements should always be given in the order shown in Table 1-1. Some general guidelines are discussed later in this section. More detailed descriptions of the various statements can be found in later sections.
Table 1-1Thermodynamic Data Order of Input Statement
THERMODYNAMIC DATA METHOD WATER <property>
Comments Section heading, required as the first statement in the section. Required as the first statement in defining each set of methods. Optional. Method-specific water options that apply only to the current method. Optional. Any KVALUE, ENTHALPY,K ENROPY, DENSITY, TRANSPORT, HENRY, or PHI statement that applies to a method declared on the METHOD statement. Optional. Additional binary interaction data statements associated with the <property> statement. Optional. Additional alpha data statements associated with the <property> statement. Optional. Any pure component data statements (Tc, Pc, etc.) that apply to the current <property> statement.
Chapter 1 1 to 5
<binary data> <alpha data> <component data> <property> ... METHOD ...
Optional additional sets of thermodynamic methods
The Thermodynamic Data Category must begin with the THERMODYNAMIC DATA heading statement. This must be followed by the definition of one or more thermodynamic system. Each system begins with a METHOD statement that declares a method for every thermodynamic property required by the problem. The entries on this statement activate the required property calculations. Available entries include SYSTEM, KVALUE, ENTHALPY, ENTROPY, DENSITY, TRANSPORT, PHI, and HENRY. If a method is not specified for a property, that property will not be calculated.
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Most of the property methods have built-in databanks that contain the required data. When desired, the user may supply additional data or overwrite the default SimSci data by including optional property statements and data statements. The property statements (SYSTEM, KVALUE, ENTHALPY, ENTROPY, DENSITY, HENRY, TRANSPORT and PHI) can appear in any order. Each may be followed by optional data statements that supply pure component data or binary interaction data for that property. These subsequent data statements must appear immediately after the property statement they affect and apply only to that property statement. The exception is that data entered after the KVALUE property statement serve as default values for all other properties that use the same method (as the KVALUE method). For example, using SYSTEM=SRK selects the SRK method for computing K-values, enthalpy, entropy, and vapor density. Binary interaction parameters (Kijs) supplied for calculating K-values also act as default values when calculating enthalpy, entropy, and vapor density.
Thermodynamic Sets
In the program, property generators predicting K-values, enthalpy, density, and, optionally, entropy and transport properties are grouped together to form thermodynamic sets. By fixing the composition of a stream and two independent stream variables (such as pressure and temperature, or pressure and enthalpy), the program can fully calculate all of the thermodynamic properties for that stream with the generators defined in that set. Each set is headed by a METHODS statement and continues until the next METHODS or STREAM DATA statement. For example, the following input section defines a thermodynamic set:
... THERMODYNAMIC DATA METHOD SYSTEM=SRK STREAM DATA ...
It uses the SRK predefined system to calculate all of the stream properties. See Predefined Systems on page 1-28 and Soave Modified Redlich-Kwong on page 4-1.
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In the following example, several different generators are assembled to create a single set:
... THERMODYNAMIC DATA METHOD KVALUE=NRTL, PHI=SRK, & ENTHALPY(V)=SRK, ENTHALPY(L)=IDEAL, & TRANSPORT=PURE, RVPMETHOD, SET=01 NOTES TEXT= This thermo set is used for RVP calcs. KVALUE NRTL 1,3,,-51.2,,2216,.200 STREAM DATA ...
In this case, NRTL liquid activity coefficients coupled with SRK vapor phase fugacities are used in combination to establish K-values. Vapor enthalpies are calculated via SRK, liquid enthalpies via pure component saturated liquid enthalpies, and transport properties via pure component blending. This thermodynamic set is defined as set 01, and is used for RVP calculations. Each unit operation that calculates stream properties has at least one associated thermodynamic set. The product streams, internal streams, and external feeds (feed streams defined on a PROPERTY statement rather than from other unit operations) all use that set for calculating the relevant thermodynamic properties. Some units, such as columns and heat exchangers, have multiple internal streams, and provision is made to allow multiple sets to be used within the same unit operation. (See Multiple Thermodynamic Sets on page 1-31.) Table 1-2 shows all of the available thermodynamic property generators. Also given in this table are chapter numbers to refer to for more information on each generator. A complete description of all keywords relevant to that generator is provided in that chapter.
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Table 1-2: Thermodynamic Generators Method Description K-values Enthalp y VL VL VL VL Entrop y VL VL Density Phi
Generalized Correlation Methods (see Chapter 3) IDEAL GS CS IGS GSE CSE CP BK10 JG LK API RACKET T COSTALD LIBRARY Ideal Grayson-Streed Chao-Seader Improved GraysonStreed Erbar Improved Grayson-Streed Erbar Improved Chao-Seader Curl-Pitzer Braun K10 Johnson-Grayson Lee-Kesler API Liquid Density Rackett Liquid Density COSTALD Liquid Density Library Liquid Entropy Soave-RedlichKwong Peng-Robinson SRK Kabadi-Danner SRK Huron-Vidal SRK Panagiotopoulos & Reid SRKP Modified VLE VLE(fw) VLE(fw) VLLE VLE(fw) VLE(fw) VLE(fw) VLE(fw) VL VL L L L
Equation of State Methods (see Chapter 4) SRK PR SRKKD SRKH SRKP SRKM VLE1(fw ) VLE1(fw ) VLLE VLLE VLLE VLLE VL VL VL VL VL VL VL VL VL VL VL VL V2 V2 V2 V2 V2 V2 yes yes yes yes yes yes
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Table 1-2: Thermodynamic Generators Method SRKS PRH PRP PRM UNIWAA L BRWS HEXAME R LKP Description SRK Simsci PR Huron-Vidal PR Panagiotopoulos & Reid PRP Modified UNIWAALS Benedict-WebbRubin-Starling Associating EOS for HF systems Lee-Kesler-Plocker K-values VLLE VLLE VLLE VLLE VLLE VLE(fw) VLLE VLLE VLE(fw) VLLE VLLE VLLE VLLE VLLE VLLE VLLE VLE VLLE VLLE VLLE VLE(fw) VLLE Enthalp y VL VL VL VL VL VL VL VL Entrop y VL VL VL VL VL VL VL VL Density V2 V2 V2 V2 V2 VL VL VL Phi yes yes yes yes yes yes yes yes
Liquid Activity Methods (see Chapter 5) NRTL UNIQUAC UNIFAC UFT1 UFT2 UFT3 UNFV WILSON VANLAA R MARGUL ES REGULA R FLORY HOCV TVIRIAL NRTL UNIQUAC UNIFAC UNIFAC Lyngby UNIFAC Dortmund Modified UNIFAC UNIFAC Free Volume option Wilson equation van Laar equation Margules equation Regular solution theory Flory Huggins Hayden-OConnell vapor fugacity Truncated virial vapor fugacity V V V yes yes
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Table 1-2: Thermodynamic Generators Method IDIMER Description IDIMER vapor fugacity K-values Enthalp y V Entrop y V Density V Phi yes
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Table 1-2: Thermodynamic Generators Method Description K-values Enthalp y L VL Entrop y VL Density Phi
Special Packages (see Chapter 6) ALCOHO L GLYCOL SOUR GPSWAT ER AMINE U1 - U15 Alcohol package Glycol package Sour water package GPA sour water package Amine package User-supplied subroutines vant Hoff solubilities User-supplied solubility data K-value data VLLE VLLE VLLE1 VLLE1 VLLE1 VLLE VL
Additional Thermodynamic Generators VANTHO FF SOLDATA DATA

Symbols VLLE VLE VLE(fw) SLE V L VL Notes 1 2 3
SLE SLE VLLE
- Vapor-liquid-liquid equilibrium - Vapor-liquid equilibrium - Vapor-liquid equilibrium with free water decant - Solid-liquid equilibrium - Applicable to vapor phase - Applicable to liquid phase - Applicable to both vapor and liquid phases - VLLE available, but not recommended - Liquid density available, but not recommended - GS is preferred to CS
Table 1-3: Features that Require Entropy Feature COMPRESSOR EXPANDER GIBBS Reactor
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Table 1-3: Features that Require Entropy Feature HCURVE Entropy Tables EXERGY
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Input Description
METHOD SYSTEM{VLE or VLLE}=method, KVALUE(SLE)=method}, {KVALUE(VLE or LLE or VLLE)=method, ENTHALPY=method, DENSITY=method, ENTROPY=method}, {PHI=method}, {HENRY},{RVPMETHOD, TVPMETHOD}, TRANSPORT=option}, {property(qualifier)=method, REFPROP=SIMSCI} SET=setid, {DEFAULT}... TEXT = Notes line (up to 256 characters) KVALUE{VLE or LLE or VLLE}=method, KVALUE(SLE)=method}, ENTHALPY=method, DENSITY=method, ENTROPY=method}, {PHI=method}, {HENRY}, {RVPMETHOD, TVPMETHOD}, {TRANSPORT=option}, {property(qualifier)=method, REFPROP=SIMSCI} SET=setid ,{DEFAULT}... TEXT = Notes line (up to 256 characters)
NOTES or METHOD
NOTES
SYSTEM
This entry selects a predefined system of thermodynamic property methods as tabulated in Table 1-4. There are no default methods. If the SYSTEM entry is missing, the user must select individual methods using the KVALUE, ENTHALPY, ENTROPY, and DENSITY entries described below. SYSTEM property methods may be overridden individually with the additional use of the KVALUE, ENTHALPY, ENTROPY, and DENSITY entries. Methods for other properties usually are optional, but may be required in a specific problem. The optional qualifier on the SYSTEM entry indicates which equilibrium calculations apply to the problem. Omitting the qualifier is the same as specifying VLE. VLE This qualifier indicates that the methods included in the selected system apply to vapor-liquid equilibrium calculations (normally, a single liquid phase is present). It is the default.
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VLLE
Include this qualifier to indicate that the selected system of methods apply to vapor-liquidliquid equilibria calculations. When used, the program rigorously models the equilibrium between the two liquid phases. If omitted, VLE is the default.
KVALUE(VLE ) KVALUE(LLE )
This entry is used to select a method from Table 12 to calculate vapor-liquid and liquid-liquid phase equilibrium K-values. The VLE qualifier may be omitted since it is the default. The METHOD statement must include KVALUE(VLE) when the SYSTEM entry is missing. This entry may be used instead of KVALUE(VLE) and KVALUE(LLE) when both use the same generators. When a problem includes solid phase components, this optional entry declares the method (chosen from Table 1-2) used to determine solid-liquid equilibria. Use of this entry does not eliminate the need to declare either a VLE or VLLE K-value method. See Chapter 7, Solid Solubility Methods. This entry is used to select a method from Table 1-2 to perform vapor and liquid density calculations when no SYSTEM entry is present. Omitting the qualifier or specifying VL as the qualifier indicates that the selected method applies to all liquid and vapor phases. To apply different methods for vapor and liquid calculations, use both DENSITY(V) and DENSITY(L). Refer to Chapter 2, Application Guidelines, for recommendations on which density method to use.
or KVALUE(VLL E) KVALUE(SLE )
DENSITY
Note: Correlations and data for solid phase component density
are supplied in the Component Data Category.
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ENTHALPY
This entry is used to select a method fromTable 12 to perform vapor and liquid enthalpy calculations when no SYSTEM entry is present. Omitting the qualifier or specifying VL as the qualifier indicates that the selected method applies to all liquid and vapor phases. To apply different methods for vapor and liquid calculations, use both ENTHALPY(V) and ENTHALPY(L).
Note: Correlations and data for solid phase component enthalpy
are supplied in the Component Data Category.

ENTROPY This entry is used to select the method from Table 1-2 used for vapor and liquid entropy calculations. Specifying VL or omitting the qualifier indicates that the selected method applies to all liquid and vapor phases. Use both ENTROPY(V) and ENTROPY(L) to apply different methods to vapor and liquid calculations. This entry usually is optional, but may be required when a problem includes any of the unit operations or options shown in Table 1-3.
Note: Not all systems available on the SYSTEM entry declare an entropy method, and the ENTROPY entry still may be required. Refer to Table 1-3 to determine which features require an entropy method. PHI This entry specifies the method from Table 1-2 used to compute pure component and mixture vapor fugacity coefficients (i). It is available only when using a liquid activity method to calculate equilibrium K-values. A fugacity method generally is used for high pressure applications. The default is PHI=IDEAL. See HaydenOConnell Vapor Fugacity on page 6-69 and Truncated Virial Vapor Fugacity on page 6-73. The HENRY option applies pre-stored or usersupplied Henry's Law data to model dissolved gases in a liquid solution. This option is available only when using a liquid activity method for Kvalue calculations. This method employs linear mixing rules to compute ln(H). See Henrys Law for Non-condensible Components on page 6-63.
HENRY
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RVPMETHO D, TVPMETHO D
These options are used to specify the thermodynamic method to be used for RVP and TVP calculations. If either RVPMETHOD or TVPMETHOD appears, the other method defaults to that method specified. If neither RVPMETHOD nor TVPMETHOD is specified, then the stream RVP and TVP are calculated by the thermodynamic method used in generating that stream. This entry requests the calculation of all transport properties, including vapor and liquid viscosities, vapor and liquid thermal conductivities, and liquid surface tension values. Alternatively, use one or more of the options described below to select transport property methods individually. The program does not calculate transport properties unless requested by the presence of these entries. Entering TRANSPORT with no argument is the same as using TRANSPORT=PURE. See Transport Properties on page 8-1. This entry requests the calculation of special refinery properties. See Special Properties on page 8-11. This keyword is used to supply the default methods for calculating special stream refinery properties. The SIMSCI option is used to specify the PRO/II v3.3 calculation methods and v3.3 properties. These properties are KVIS, CLOU, POUR, FLPT, SULF, and CETA. This entry supplies a label that uniquely identifies the method set. When a problem includes more than one method set, each set must have an assigned label. The labels allow each unit operation to select a specific set of thermodynamic methods. The setid is an unique identifier and may contain up to 12 alphanumeric characters, excluding delimiters and embedded blanks. See Multiple Thermodynamic Sets on page 1-31.
TRANSPORT
property
REFPROP
SET
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NOTES
This statement must be placed along with the METHOD statement of the specific thermodynamic set to which the information pertains. One NOTES statement is allowed per thermodynamic set. TEXT This entry specifies the actual notes line(s). The Notes Data can be specified in multiple lines, but only the first 256 characters will be scanned and the rest will be discarded.
Predefined Systems
General Information
The use of predefined systems is a convenient, shortcut method of specifying thermodynamic sets. A predefined system may be selected by using the SYSTEM keyword. This option uses a single entry to declare several property methods at once. In general, each predefined system includes methods for computing K-values, vapor and liquid enthalpies, and vapor and liquid densities. Predefined systems using generalized and equation of state methods and special package systems also include an entropy property method. Predefined liquid activity systems do not include an entropy method. As an example, the following METHOD statement uses the SRK system of thermodynamic generators (see Soave Modified Redlich-Kwong on page 4-1, for keyword definitions):
METHOD SYSTEM=SRK
From Table 1-4, we can see that this is equivalent to the following METHOD statement:
METHOD KVALUE=SRK, ENTHALPY=SRK, ENTROPY=SRK, & DENSITY(V)=SRK, DENSITY(L)=API
or even more explicitly:

METHOD KVALUE=SRK, & ENTHALPY(V)=SRK, ENTHALPY(L)=SRK, & ENTROPY(V)=SRK, ENTROPY(L)=SRK, & DENSITY(V)=SRK, DENSITY(L)=API
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Input Overview
Table 1-4 shows the predefined systems available and the property methods used for each one.
Table 1-4: Systems of Thermodynamic Methods Methods for Evaluating Properties SYSTEM IDEAL GS CS2 IGS GSE CSE BK10 VLE or VLLE VLE VLE1 VLE1 VLLE1 VLE1 VLE1 VLE1 VLE1,3 VLE1,3 VLLE VLLE VLLE VLLE VLLE VLLE VLLE VLLE VLLE VLE1 VLLE VLLE1
2
Enthalpy K-values IDEAL GS CS IGS GSE CSE BK10 vapor SATD CP CP CP CP CP JG liquid SATD CP CP CP CP CP JG Entropy CP CP CP CP CP CP Generalized Correlation Methods
Density vapor IDEAL SRK SRK SRK SRK SRK IDEAL liquid SATD API API API API API API
Equation of State Methods SRK PR SRKKD SRKH SRKP SRKM SRKS PRH PRP PRM UNIWAAL BRWS HEXAMER LKP
1
SRK PR SRKKD SRKH SRKP SRKM SRKS PRH PRP PRM UNIWAAL BRWS HEXAMER LKP
3
SRK PR SRKKD SRKH SRKP SRKM SRKS PRH PRP PRM UNIWAAL BRWS HEXA LKP
SRK PR SRKKD SRKH SRKP SRKM SRKS PRH PRP PRM UNIW BRWS HEXA LKP
SRK PR SRKKD SRKH SRKP SRKM SRKS PRH PRP PRM UNIW BRWS HEXA LKP
SRK PR SRKK D SRKH SRKP SRKM SRKS PRH PRP PRM UNIW BRWS HEXA LKP
API API API API API API API API API API API BRWS API API
May decant free water
GS preferred to CS
VLLE available, but not recommended
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Table 1-4: Systems of Thermodynamic Methods Methods for Evaluating Properties SYSTEM NRTL UNIQUAC UNIFAC UFT1 UFT2 UFT3 UNFV WILSON VANLAAR MARGULES REGULAR FLORY ALCOHOL GLYCOL SOUR GPSWATER AMINE
1
VLE or VLLE VLLE VLLE VLLE VLLE VLLE VLLE VLLE VLE VLLE VLLE VLLE VLLE VLLE VLLE VLLE3 VLLE3 VLLE3
2
Enthalpy K-values NRTL UNIQUAC UNIFAC UFT1 UFT2 UFT3 UNFV WILSON VANLAAR MARGULES REGULAR FLORY NRTL SRKM SOUR GPSWATER AMINE
3
Density Entropy SRKM SRKM SRKM SRKM SRKM vapor IDEAL IDEAL IDEAL IDEAL IDEAL IDEAL IDEAL IDEAL IDEAL IDEAL IDEAL IDEAL SRKM SRKM SRKM SRKM SRKM liquid SATD SATD SATD SATD SATD SATD SATD SATD SATD SATD SATD SATD SATD API SATD SATD SATD
vapor SATD SATD SATD SATD SATD SATD SATD SATD SATD SATD SATD SATD Special Packages SRKM SRKM SRKM SRKM SRKM
liquid SATD SATD SATD SATD SATD SATD SATD SATD SATD SATD SATD SATD SATD SRKM SATD SATD AMINE
Liquid Activity Methods
May decant free water
GS preferred to CS
VLLE available, but not recommended
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Multiple Thermodynamic Sets

General Information
In most cases, each problem includes a single set of methods for calculating all thermodynamic properties. However, a flowsheet may contain widely varying process conditions that dictate the use of more than one set. To facilitate this, the program allows up to 100 methods in each problem. All method sets defined in the Thermodynamic Data Category are available for use in the remainder of the problem. When a single method set is present, all unit operations use that set. When two or more sets appear, each unit operation may select any of the defined sets. Some units may use more than one set. For example, in PRO/II:
l
A rigorous heat exchanger may use one method set for the shell side and a second for the tube side. A chemicals column is known to have two liquid phases on only two trays. To prevent the CHEMDIST algorithm from performing CPU intensive three phase calculations on all trays, a VLLE set is declared on those two trays, and a VLE set is declared for the remainder.
The following hierarchy of defaulting governs the selection of thermodynamic methods applied to stream calculations. 1. 2. 3. Product streams use the thermodynamic methods of the unit operation from which they flow. Feed streams that are not products of unit operations use the thermodynamic methods of the unit operations they feed. In all other cases, a stream use either the default methods set or the set assigned to it in the input file.
The Default Method Set One set of thermodynamic methods serves as the default set. When an unit operation does not explicitly specify a method set, the default set prevails. Normally, the program assumes the first set declared in the Thermodynamics Data Category is the default set; however, the use may declare any set as the default by including the DEFAULT keyword on the METHOD statement of that set.
Note: Only one default set may exist in each problem. PRO/II Thermodynamic Data Keyword Input Manual II-1-31
Method Set Requirements When an input file contains two or more thermodynamic method sets, each set must be assigned a unique label (identifier). The label allows individual unit operations to select a desired set. Each method set is a complete set; that is, it contains declared methods for all required properties. Avoiding Inconsistent Methods Improper use of multiple thermodynamic methods can cause serious discontinuities that produce erroneous results. For example, both the SRK and Curl-Pitzer methods are based on deviations from ideal gas values. However, they predict different enthalpy values for a mixture at any given temperature and pressure. Thus, an adiabatic flash using the SRK method predicts an incorrect temperature value for a feed stream with a Curl-Pitzer enthalpy. The stream enthalpy first should be reset by performing an isothermal, dew point, or bubble point flash calculation (as appropriate) using the new enthalpy method. The RESET unit operation in PRO/II is provided just for that purpose. Multiple Method Sets in Distillation Columns For rigorous column calculations, provision exists to consider the column as comprised of sections, with different method sets used in the sections. This option requires great care to ensure that the data sets interface smoothly, without discontinuities when moving from one section to another. Changes in enthalpy methods will nearly always cause unrealistic temperature and flow profiles.
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Examples
1.1: A hydrocarbon-water mixture is modeled using both VLE and rigorous VLLE thermodynamics.
TITLE PROB=SETS COMPONENT DATA LIBID 1,C3/2,NC4/3,H2O THERMODYNAMIC DATA METHOD SYSTEM(VLE)=SRK, SET=2PHASE, DEFAULT METHOD SYSTEM(VLLE)=SRKM, SET=3PHASE STREAM DATA PROP STREAM=1, TEMP=60, PRES=250, COMP=50/40/10 UNIT OPERATION FLASH UID=F1 FEED 1 PROD V=2, L=3 TPSPEC PRES=160 SPEC STREAM=2, RATE, RATIO, STREAM=1, & RATE, VALUE=0.5 METHOD SET=2PHASE FLASH UID=F1 FEED 1 PROD V=4, L=5, W=6 TPSPEC PRES=160 SPEC STREAM=2, RATE, RATIO, STREAM=1, & RATE, VALUE=0.5 METHOD SET=3PHASE END
The first thermodynamic set, identified as 2PHASE, uses the predefined SRK set to calculate all thermodynamic properties. The use of the VLE argument (which is the default) implies that, although you can decant a pure water phase, you cannot perform rigorous liquid-liquid equilibrium calculations. The second set, identified as 3PHASE, uses the predefined SRKM set. This method is better suited than SRK for rigorous three phase calculations. The VLLE argument implies that all equilibrium calculations using this set will attempt to find two liquid phases.
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Free-water Decant Considerations

General Information
Free-water decant is useful when handling mixtures that form water as a nearly pure immiscible phase. Such systems are common in hydrocarbon-water mixtures in refinery and gas processing plants. For engineering purposes, it may be assumed that the water phase is pure. This reduces the computational time required to solve these problems with rigorous VLLE models. See Table 1-2 for K-value generators that support free-water decant. When free-water decant is not supported for a particular thermodynamic set, the WATER statement is disregarded by the program. When the free-water decant option is turned on, water properties except transport are calculated from the Keenan and Keyes steam tables. By default, all values are calculated as if the water were at saturated conditions, which saves a significant amount of CPU time. If superheated steam is present, the PROPERTIES=STEAM option should be selected. This will calculate steam properties based on the full Keenan and Keyes equation of state for water. The GPSA method is based on the GPSA Data Book, Figure 20-3. This option is useful for natural gas mixtures at pressures above 2000 psia. When the free-water decant option is turned off, water properties are calculated from the prevailing property generators. Beware that many of the standard generators (i.e., SRK, PR and GS), are poorly suited for calculating properties of highly polar, non-hydrocarbons such as water.
Note: A WATER statement may appear only after a METHOD statement. Therefore water properties apply only to that thermodynamic set.
For example, in the following thermodynamic data section the water solubility in hydrocarbon is calculated via the API kerosene solubility curve for thermodynamic set SRK only:
THERMODYNAMIC DATA METHOD SYSTEM=SRK, SET=SRK WATER SOLUBILITY=KEROSENE METHOD SYSTEM=GS, SET=GS
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Input Description
Water Handling Statement
WATER DECANT=ON or OFF, GPSA, SOLUBILITY=SIMSCI or KEROSENE or EOS, PROPERTY=SATURATED or STEAM
DECANT
This turns the water decant option on or off. ON This is the default when SRK, PR, GS, CS, GSE, CSE, IGS, LKP, BK10 or BWRS methods are used. Water is treated as a non-rigorous component that may be decanted as a pure aqueous phase. The hydrocarbon phase has some water dissolved in it according to the calculated solubility. K-values for water are computed from: Kw = P0 / (X ) where: P0 is the partial pressure of water, X is the solubility of water in the liquid hydrocarbon phase, is the system pressure. OFF Water is treated as a regular component and all other entries on the WATER statement are ignored.
GPSA
When DECANT=ON is selected, the presence of this keyword requests the calculation of water partial pressures based on the GPSA Data Book, Figure 20-3, instead of the steam tables. This option is useful for natural gas mixtures at pressures above 2000 psia.
SOLUBILI This statement selects the method for computing water TY solubility in the hydrocarbon phase.
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SIMSCI
This is the default. Water solubility calculations are based on the solubility of water in the following individual components: Library components in the Paraffin, Naphthalene, Unsaturated and Aromatic classes, carbon disulfide, methyl mercaptan, ammonia, argon, carbon dioxide, helium, hydrogen chloride, hydrogen sulfide, nitrogen, nitrous oxide, oxygen, sulfur dioxide, and air. For pseudocomponents, the water solubility is calculated as a function of the Watson K-factor.
Note: When the SIMSCI option is used in a problem containing
components other than those listed above, or containing NONLIB components, the program estimates the correlation parameters for these components and prints a warning message.
KEROSENE Water solubility calculations are based on the data for the solubility of water in kerosene, as presented in the API Technical Data Book, Figure 9A1.4. The water solubility in the hydrocarbon phase is calculated from the water K-value computed by the equation of state method. Water-hydrocarbon interaction parameters are retrieved from the databanks or estimated using the Kabadi-Danner method.
EOS
PROPERT Y
This option allows for the selection of the water properties calculation basis. SATURATED This is the default. Water properties are based on vapor/liquid curves. This option is adequate for most problems, and requires the least computing time. STEAM The basis for computing water properties is the Keenan and Keyes equation of state for water. It is recommended when water is present as a superheated vapor.
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Note: If the WATER option is used, the predefined system or Kvalue method in use must be able to handle free water decant, or else the WATER statement is ignored. When any of the predefined or K-value generators SRK, PR, GS, CS, GSE, CSE, IGS, LKP, BK10 or BWRS are selected, free water decant is automatically activated. If water is to be treated as any other component, or in a rigorous manner, WATER DECANT=OFF must be selected. The WATER statement applies only for that particular METHOD statement.
Examples
1.2: SRK is used to model the phase behavior of a hydrocarbon/water mixture.
TITLE PROJECT=MANUAL, USER=SIMSCI, PROB=HC-WATER COMPONENT DATA LIBID 1,H2O/ 2,C3/ 3,NC4/ 4,NC5/ 5,NC6 THERMODYNAMIC DATA METHOD SYSTEM=SRK STREAM DATA PROP STREAM=1, TEMP=100, PRES=100, COMP=20/20/20/20/20 UNIT OPERATION FLASH UID=F1 FEED 1 PROD V=2, L=3 TPSPEC PRES=50 SPEC STREAM=2, RATE, RATIO, STREAM=1, & RATE, VALUE=0.5 END
Vapor-liquid-liquid Equilibrium Considerations

General Information
Declaring a VLLE set The program provides a number of methods that can rigorously calculate vapor-liquid-liquid equilibrium. Most unit operation modules support this capability. The user must specifically request VLLE calculations on the METHOD statement in one of three ways:
l
by including the VLLE qualifier when using the SYSTEM entry (Table 1-5).
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by including the VLLE qualifier when using the KVALUE entry to declare the method used to calculate equilibrium K-values (Table 1-5). by including both a KVALUE(VLE) and KVALUE(LLE) entry to declare the method used to calculate equilibrium K-values (Table 1-5).
When entering K-value data, VLE and LLE data are entered on separate KVALUE(VLE) and KVALUE(LLE) property statements respectively. See Chapters 3 and 4. All other input requirements for VLLE are the same as for VLE method sets. Table 1-5 lists the method systems that support rigorous VLLE modeling. Often, not all the unit operations in a problem perform VLLE calculations, making it desirable to include both VLE and VLLE methods sets in a single problem. The user may define separate method sets for the VLE and VLLE methods. Unit operations that use the VLE method will not attempt VLLE calculation, substantially reducing computational time.
Table 1-5: VLLE Predefined Systems and K-value Generators K-value Method SRK1 SRKM SRKKD SRKH SRKP SRKS PR1 PRM PRP UNIWAALS IGS LKP HEXAMER
1
System SRK1 SRKM SRKKD SRKH SRKP SRKS PR1 PRM PRP UNIWAALS IGS LKP HEXAMER AMINE NRTL UNIQUAC UNIFAC UFT1 UFT2 UFT3 UNFV VANLAAR REGULAR FLORY ALCOHOL GLYCOL SOUR GPSWATER
AMINE NRTL UNIQUAC UNIFAC UFT1 UFT2 UFT3 UNFV MARGULES REGULAR FLORY SOUR GPSWATER
VLLE available, but not recommended.
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Liquid-liquid equilibrium (LLE) calculations are a subset of VLLE. For example, a VLLE methods set must be declared when modeling a liquid-liquid extraction (LLEX) unit operation.
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The following example shows three equivalent input sections that declare VLLE phase behavior. Each of these files uses the NRTL binary interaction parameters as supplied in the SIMSCI databank.
THERMODYNAMIC DATA METHOD SYSTEM(VLLE)=NRTL THERMODYNAMIC DATA METHOD KVALUE(VLLE)=NRTL, ENTHALPY=LIBRARY THERMODYNAMIC DATA METHOD KVALUE(VLE)=NRTL, KVALUE(LLE)=NRTL, & ENTHALPY=LIBRARY
Table 1-6: Available Databanks BANK= SIMSCI Method NRTL UNIQUAC Type of Data VLE and LLE interaction coefficients VLE and LLE interaction coefficients
SRK PR SRKH PRH SRKM PRM SRKP PRP SRKK SRKS BWRS RK1 / RK2 COSTALD RACKETT HENRY binary interactions interaction coefficients component critical properties component Rackett properties Henrys Law solubility data binary interactions and pure component alpha values
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Table 1-6: Available Databanks BANK= ALCOHOL GLYCOL NONE AZEOTROP E= SIMSCI NONE Method All liquid activity methods Method NRTL SRKM Type of Data binary coefficients for specific components binary interactions and pure component alphas omit all databank data Type of Data azeotropic data for pairs of components omit all azeotropic databank data
The user may specify any number of the available databanks by using the BANK option on each property statement or the AZEOTROPE option for azeotropic data. BANK=SIMSCI is the default specification for all properties except for GLYCOL and ALCOHOL package K-values. The program searches the databanks in the order they appear on the PROPERTY statement, and automatically retrieves any data required for the property method (specified on the METHOD statement). Any data supplied in the Component Data Category of input or on data statements in the Thermodynamic Data Category of input are used instead of the data retrieved from the databanks. The BANK=NONE entry suppresses all databank operations. The following thermodynamic data section,
METHOD KVALUE=NRTL, ... KVALUE BANK=SIMSCI, ALCOHOL
searches the SIMSCI databank, then the ALCOHOL databank for VLE interaction parameters.
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Specifying Key Components Specifying VLLE equilibrium on the METHOD statement allows the use of the two optional entries, L1KEY and L2KEY. These two entries allow the user to specify the dominant component in the L1 and L2 phases. If these entries are missing, the program estimates the key components during each K-value evaluation. The most dense stream forms the L2 or W phase. If one of the liquids is an aqueous phase, water will (in the majority of cases) be designated as the L2KEY component. Specifying Separate VLE and LLE Models When specifying different K-value methods for VLE and LLE calculations, or supplying different interaction parameters for VLE and LLE calculations using the same method, some thermodynamic inconsistency is necessarily introduced. Unfortunately, model parameters regressed to VLE data seldom do an adequate job of modeling LLE, and vice-versa. Using different VLE and LLE methods of data can overcome this problem. The user should be aware, however, that for a system that exists in all three phases, V, L1, L2, the L1 and L2 phases will be in equilibrium according to the LLE method data. The V-L1 and V-L2 equilibria, according to the VLE method/data, are averaged to give compromise V-bulk L equilibrium. Each L phase may not necessarily be at its bubble point, or in equilibrium with the vapor phase, at the final conditions of pressure, temperature and individual phase composition. In the following example, the first thermodynamic set uses the SRKM equation of state. The second set uses conventional SRK.
... THERMODYNAMIC DATA METHOD SYSTEM=SRK, SET=SRK_VLE METHOD SYSTEM=SRKM, SET=SRK_VLLE STREAM DATA ...
When retrieving interaction parameters from the SIMSCI databank, the program follows some special rules to minimize these inconsistencies: If no KVALUE(VLE) or KVALUE(LLE) statements are given (i. e., all data are retrieved from the SIMSCI databank), the program searches the LLE databank for interaction parameters first, and the
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VLE databank second for all data. Thus all phases will be governed by the same set of coefficients as follows:
VLE Interface LLE databank VLE databank Set interaction parameter to zero LLE Interface LLE databank VLE databank Set interaction parameter to zero
If a KVALUE(VLE) statement is given, but KVALUE(LLE) is not given, the interaction parameters for the VLE and LLE interfaces are searched for in the following order:
VLE Interface KVALUE (VLE) statement LLE databank VLE databank Use FILL option for missing parameters if requested Set interaction parameter to zero LLE Interface KVALUE (VLE) statement LLE databank VLE databank Use FILL option for missing parameters if requested Set interaction parameter to zero
If a KVALUE(LLE) statement is given, the interaction parameters are searched for in the following order:
VLE Interface KVALUE (VLE) statement VLE databank Use FILL option for missing parameters if requested Set interaction parameter to zero LLE Interface KVALUE (VLE) statement LLE databank VLE databank Use FILL option for missing parameters if requested Set interaction parameter to zero
For more information on the use of the FILL option, see Filling in Missing Parameters on page 4-27 for equations of state and Filling in Missing Parameters on page 6-57 for liquid activity methods.
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Input Description
The METHOD Statement
METHOD or METHOD or METHOD KVALUE(VLLE)=method, {L1KEY=i, L2KEY=j}, ... KVALUE(VLE)=method, and KVALUE(LLE)=method, {L1KEY=i, L2KEY=j,}... SYSTEM(VLLE)=method, {L1KEY=i, L2KEY=j,}...
SYSTEM(VLLE) or KVALUE(VLLE)
This selects the VLLE predefined thermodynamic system or K-value generator to be used in the problem. The VLLE systems and K-value generators available are given in Table 1-5. The L1KEY and L2KEY optional entries identify the most prevalent components expected in the first liquid phase and in the second liquid phase. These entries are optional, and the program will estimate the key components if they are not given. In the majority of cases, water (when present) is designated as the L2KEY component. Designation of the two key components is suggested for partially miscible systems containing little or no water.
L1KEY and L2KEY
Note: While it is not necessary to designate the key components,
it is strongly recommended. Three-phase calculations are time consuming. The algorithm uses an immiscible pair of components to initialize the distribution of components between liquid phases. Specifically declaring the key components instead of relying on the calculations to find an appropriate pair significantly reduces the time required to reach a solution.
K-value Data (Optional)

KVALUE(VLE) BANK=SIMSCI or NONE, ... and KVALUE(LLE) BANK=SIMSCI or NONE, ...
Note: When used for entering K-value data, VLE and LLE data
must be entered on separate property statements. See Chapters 3 through 6 for details on format and definition of the data entries.
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Examples
1.3: A mixture of furfural, cyclohexane, heptane and nonane at 85 F and 1.5 atmospheres is to be modeled using NRTL thermodynamics. This system forms two liquid phases. To avoid arbitrary allocation of key components by the calculation algorithm, the key components are designated by the user. The explicit declaration of the dominant components ensures that the Liquid2 stream contains the cyclohexane-rich phase, while the Liquid1 stream contains the furfural-rich liquid.
TITLE PROB=VLLE COMPONENT DATA LIBID 1,FURFURAL/2,CYHEXANE/3,HEPTANE/4,NONANE THERMODYNAMIC DATA METHOD SYSTEM(VLLE)=NRTL, L1KEY=1,L2KEY=2 STREAM DATA PROP STREAM=1, TEMP=85, PRES(ATM)=1.5, & COMP=35/25/20/10 UNIT OPERATION FLASH UID=F1 FEED 1 PROD V=2, L=3, W=4 ADIA DP=0.0 END
1.4:
A small amount of formic acid and benzene is present in an aqueous stream. Note that, as the key components are not specified by the user, the L2KEY component (i.e., the dominant component in the second liquid product) is designated to be water.
TITLE PROBLEM=VLLE COMPONENT DATA LIBID 1,BENZENE/2,FORMIC/3,H2O/4,BENZOIC THERMODYNAMIC DATA METHOD SYSTEM(VLLE)=NRTL, TRANS=PURE, PHI=HOCV KVALUE(VLE) FILL=UNIF KVALUE(LLE) FILL=UNIF STREAM DATA PROP STREAM=1, TEMP=86, PRES=21.3, RATE(M)=162.6, & COMP(M)=1,0.1001/2,1.9059/3,160.6/4,0.0002, NORMALIZE
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UNIT OPERATION FLASH UID=F1 FEED 1 PROD V=2, L=3, W=4 ADIA DP=0.0 END
1.5:
A mixed alcohol/water feed is modeled using the VLE NRTL method. The NRTL binary interaction data are obtained from the ALCOHOL databank.
TITLE PROBLEM=VLLE COMPONENT DATA LIBID 1,DIPE/ 2,IPA/ 3,H2O/ 4,BUTANOL THERMODYNAMIC DATA METHOD KVALUE(VLE)=NRTL, ENTH(V)=SRKM, ENTH(L)=IDEA, DENS(V)=SRKM, DENS(L)=IDEA, & SET=SET01, DEFAULT KVALUE(VLE) BANK=ALCOHOL, SIMSCI STREAM DATA PROP STREAM=1, PRES=20, TEMP=150, RATE(M)=1000, & COMP(M)=1,20/2,60/3,900/4,20, NORMALIZE UNIT OPERATION FLASH UID=F1 FEED 1 PROD V=2, L=3 ADIA DP=0.0 END
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Chapter 2 Application Guidelines

This section presents simple heuristic rules for selecting suitable methods for performing thermodynamic property calculations.
Note: Although these rules were developed specifically for the
PRO/II program, the general guidelines still apply to fluid flow applications. However, the examples at the end of this section were developed specifically for this program.
General Information
Usually, there are several thermodynamic methods suitable for any given application. The user always should try to determine which methods give the best representation of the whole flowsheet, while trying to select the simplest, most appropriate thermodynamic options. The user should bear in mind that the best thermodynamic method is the one that gives the best agreement with reality. When laboratory or actual operating data are available, it may be necessary to try several options and compare the results to obtain the best possible model. The following guidelines are divided into four basic categories of applications. These are:
l l l l
Refinery and Gas Processing Natural Gas Petrochemical Chemical and Environmental
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For each application, the various types of unit operations encountered have recommended thermodynamic methods.
Refinery and Gas Processing Applications

Water Handling
For most systems containing water, it is perfectly satisfactory to use the default water decant option with the simpler hydrocarbon thermodynamic methods. These are: SRK, PR, CS, GS, CSE, GSE, IGS, BK10, BWRS. For each of these methods, the amount of water dissolved in the hydrocarbon phase is calculated using either the SIMSCI or the KEROSENE correlation. The SIMSCI method is based on the solubility of water in the pure components, while the KEROSENE correlation is based on the solubility of water in kerosene, given in the API Technical Data Book, Figure 9A1.4. In addition, SRK and PR can use the EOS method for calculating the water solubility. The remaining water may be decanted as a pure liquid water stream. The properties of this pure water stream can be calculated using saturated water properties or by using the full Keynan and Keyes equation of state for water. The Keynan and Keyes equation should be used if water is present as super-heated vapor. The program uses the vapor pressure of water at the temperature of the system to calculate the amount of water in the vapor phase. The user can select either the (default) built-in steam tables or the GPSA Data Book, Figure 20-3 for the water vapor pressure. The GPSA values should be used for natural gas systems above 2000 psia (136 atmospheres). For systems where the solubility of hydrocarbon in water is significant, a more accurate method should be used. The Kabadi-Danner modification to the SRK equation of state (SRKKD) is recommended. This method may be selected by using either SYSTEM(VLLE)=SRKKD or KVALUE(VLLE)=SRKKD on the METHOD statement. The SRKKD method performs rigorous vapor-liquid-liquid equilibrium calculations to predict the amount of water in the hydrocarbon phase and the amount of hydrocarbon in the water phase. It uses interaction parameters for the water and hydrocarbons based on the amount of water present in each phase.
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Application Guidelines
Low Pressure Crude Systems

Vacuum towers and atmospheric crude towers are representatives of low pressure crude systems. These units generally exhibit nearly ideal behavior, and simpler methods can be used very successfully. The accuracy of the results depends much more on the characterization of the crude feed than on the thermodynamic method chosen. The BK10 method usually is adequate and quicker than more complex general hydrocarbon methods such as GS, SRK or PR. The user may wish to solve the unit with BK10 as a first attempt, and then use a more complex method if the results are not satisfactory. If the results do not agree with plant data, the user should try different assay and characterization methods before employing other thermodynamic methods. The API method should be used for calculating the liquid density. Thermal cracking is a common source of error when modeling vacuum units. A laboratory analysis of the vacuum tower overhead product can be used to estimate the amount of light ends to be added to the feed stream in order to correctly model the column. In lieu of a direct analysis, methane can be added to the feed and adjusted until the temperature profiles match the plant data.
Recommended Methods BK10 Comments Fast and easy to use, and gives acceptable answers.
GS / IGS / GSE Comparable to BK10 for low pressure systems. Substituting LK for CP enthalpies may improve answer. SRK / PR The results will be somewhat better than with BK10 near the top of the tower where light ends may predominate. May require more CPU time than BK10.
High Pressure Crude Systems, FCCU, and Main Coker Fractionators

Towers above atmospheric pressure usually contain greater concentrations of lighter components and therefore require more complex thermodynamic methods. BK10 has been used extensively in the past for these types of applications, but PR, SRK, GSE, IGS, and GS can be expected to give better answers. The user should remember that the characterization of the petroleum fractions is more important than the thermodynamic method for obtaining good
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agreement with plant data. The API method should be used for the liquid density. For Fluidised Catalytic Cracker Unit (FCCU) main fractionators, the petroleum fractions are much more hydrogen deficient than are crude fractions. Since most characterization correlations are derived from crude petroleum data, it is expected that the results will be less accurate than for crude fractions.
Recommende d Methods Comments
GS / GSE / IGS Usually faster than SRK or PR, but less accurate in the presence of a high concentration of light components. Substituting LK for CP enthalpies may improve the answers. SRK / PR Use SRK or PR if light crudes dominate the top of the tower.
Reformers and Hydrofiners

These units contain streams with a high hydrogen content. For the SRK and PR methods the component databanks contain extensive binary interaction parameters for component pairs involving hydrogen. The API method should be used for the liquid density. Historically, GS has been used successfully with hydrogen rich systems. In general, SRKM and PRM should give better results with the improvement in interaction parameters over previous versions.
Recommended Methods SRKM / PRM Comments Recommended because of the high concentration of hydrogen present.
Lube Oil and Solvent De-asphalting Units

These units generally have non-ideal components present and require a more complex thermodynamic method. SRKM or PRM is recommended, but the answers will only be as good as the interaction parameters supplied by the user for the non-ideal components. This complex method should not be used unless such data are available. If no specific data are available, SRKM yields results comparable to SRK, and the general SRK or PR method should be used. The API method should be used for the liquid density.
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Recommended Methods SRKM / PRM SRK / PR
Comments Recommended when using user-supplied interaction data for non-ideal components. Use in place of SRKM or PRM when no usersupplied interaction data are available. These methods require less CPU time than SRKM or PRM.
Natural Gas Systems

For systems with less than 5 percent N2, CO2 or H2S, general equations of state such as SRK, PR, or BWRS provide excellent answers. The interaction parameters for hydrogen, carbon dioxide, nitrogen, and hydrogen sulfide are estimated using general correlations when user-supplied interaction parameters are not available. The BWRS method should be used with more caution, since it does not extrapolate as well as SRK or PR into the supercritical region. For systems with higher concentrations of the sour gases, the default interaction parameters may not produce the best possible answers. A general equation of state should still be used, but the user should supply better interaction parameters to obtain good results. The default water decant option is usually acceptable. However, for high pressure systems where the solubility of hydrocarbon in water is significant and the solubility correlations of water in hydrocarbon break down, the Kabadi-Danner modification to SRK should be used with the VLLE option. The Kabadi-Danner option as implemented has been extended to include nitrogen, hydrogen, carbon dioxide, carbon monoxide, and hydrogen sulfide as specific components. Petroleum fraction components are approximately identified as paraffins, olefins, aromatics, or naphthenes, according to their Watson characterization parameters, when suitable interaction parameters are supplied by the user. For systems containing non-hydrocarbon components (such as methanol and glycol acting as inhibitors), more complex mixing rules must be used to obtain good results. The SRKM and PRM methods work well for these systems, but the user must ensure that all the relevant interaction data are entered. These methods automatically access the SIMSCI databank to retrieve all available interaction data, but the user may have to supply additional data if the
data for a component pair are not in the bank. The VLLE option must be specified on the METHOD statement if two liquid phases are expected. Use the COSTALD method to calculate the liquid density for Tr < 0.95. This option is not the default method and must be specifically requested.
Recommended Methods SRK / PR / BWRS SRKKD Comments These methods give good results for most hydrocarbon and hydrocarbon-water systems. Use SRKKD(VLLE) for high pressure systems containing hydrocarbons and water. SRKKD uses more CPU time than SRK. Do not use SRKKD if other polar components, such as methanol, are present. Use these methods for systems containing water and other polar components, such as methanol. Always use the VLLE option with these methods for this type of system. Simpler versions of SRKM and PRM. These methods are not as good as SRKM or PRM and do not significantly reduce CPU time.
SRKM / PRM / SRKS
SRKP / PRP
Glycol Dehydration Systems

The GLYCOL bank of interaction parameters for the SRKM method has been created for these systems. This bank is a sub-section of the general SRKM interaction bank, and the data have been fitted over a narrow range of typical temperatures and pressures for TEG, and, to a lesser extent, EG, and DEG dehydration systems. Invoking the GLYCOL system automatically retrieves the GLYCOL interaction parameters.
Recommended Methods GLYCOL Comments The program includes special interaction coefficients for typical TEG, and, to a lesser extent, EG, and DEG dehydration systems.
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Sour Water Systems

There are two methods available for the prediction of vapor-liquid equilibrium. They are identified on the METHODS statement as SOUR and GPSWATER. SOUR This method is based on a combination of the API/EPA SWEQ (Sour Water EQuilibrium) model for sour water components (H2O, H2S, CO2 and NH3) and SRKM for all other components. The recommended range of application is:
Temperature (F) Pressure Composition 68 < T < 300 F P < 1500 psia xwtNH3 + xwtCO2+ xwtH2S< 0.30
where xi is the weight fraction in the aqueous phase.
In general, this method is recommended over the GPSWATER when CPU time is a consideration. GPSWATER This method is based on the GPSWAT program for calculating sour water equilibrium. The GPSWAT method is used for generating Kvalues for sour water components (H2O, H2S, CO2, NH3, CO, CS2, COS, MeSH and EtSH). All other components are calculated using SRKM. The recommended range of application is:
Temperature (F) Pressure Composition Sour gas partial pressure 68 < T < 600 F P < 2000 psia xwtNH3 < 0.40 PCO2+ PH2S < 1200 psia
The GPSWATER method is valid for a broader range of applications than the SOUR method, but requires significantly more computation time.
Amine Systems
The AMINE package is used for generating K-values for aqueous amine systems and sour gases including H2S, CO2, H2O, MEA, DEA, DGA, DIPA, and MDEA. All other component K-values are calculated using SRKM. Water and exactly one amine must be present when using the package.
Data for the equilibrium constants are provided for MEA, DEA, DGA, DIPA, and MDEA. However, the DIPA data are not recommended for use in final designs. For MDEA, the model is modified to include composition effects. be specified by the user. These corrections are only appropriate for systems involving MDEA or DGA. For all other amines, the entry is ignored if it appears. The user can override the default value of 0.3 under the KVALUE keyword in the THERMO DATA section in order to better fit the plant data. A RESI value of 1.0 corresponds to an equilibrium model. The data package may be used over the ranges of concentrations and acid gas loadings typically encountered in gas processing. This includes the temperatures and pressures for the contactor and regenerator. MEA processes have been successfully applied in the 25-100 psig operating range. However, DEA does not perform well under these conditions and is generally used at higher pressures. Typically, contactor pressures for MEA contactors may range from 100 to 500 psig, with DEA systems ranging from 100 to 1000 psig. The amine regenerators are generally operated at temperatures less than 275 F, with a typical temperature being 255 F. Amine solution strengths for MEA and DEA are generally within 15-25 wt% and 25-35 wt%, respectively. The AMINE package accounts for heats of reactions by applying a correction to IDEAL saturated liquid enthalpies. SRKM is also used for actual vapor densities and IDEAL values are used for liquid densities.
Petrochemical Applications
Light Hydrocarbon Systems
SRK, PR, or BWRS is recommended for most light-hydrocarbon, petrochemical applications. When solubility of water in hydrocarbon and hydrocarbon in water becomes important, as it would at high pressure, SRKKD(VLLE) is recommended. Use the COSTALD method for liquid density. This option is not the default and must be requested specifically.
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Recommended Methods SRK / PR / BWRS SRKKD
Comments Good for systems containing only similar hydrocarbon types (e.g., all paraffins). Water may be decanted as a pure aqueous phase. Use SRKKD for more accurate results with hydrocarbon-water systems. SRKKD uses more CPU time than SRK.
Aromatic Systems
For systems containing all aromatic components, use the ideal method at low pressures as these systems are very close to ideal. For systems at pressures above 2 atmospheres, use GS, SRK, or PR for a more accurate result. The liquid density can be calculated using the ideal, the default API, or the COSTALD methods. The COSTALD method has data for many aromatic components, will give good results at higher temperatures, and is better than API if any light components such as methane are present. For systems at high temperatures with all aromatic components, the API method is as good and uses less CPU time. The ideal method is best at lower temperatures and should not be used if the temperature is significantly higher than the boiling point of any one component.
Recommended Methods IDEAL GS / SRK/ PR IDEAL / API / COSTALD Comments Recommended for systems at low pressures below 2 atm. Recommended for systems at pressures above 2 atm. Recommended for liquid density.
Aromatic/Non-aromatic Systems
Traditionally, these systems are difficult to model accurately.However, new equation-of-state mixing rules and alpha formulations can give excellent results when appropriate interaction parameters and alpha parameters are available. The SIMSCI databank includes a large number of interaction parameters, but the user should verify
the availability of all critical parameters to ensure getting good results. It is not necessary to use the VLLE option unless polar components, such as water, are present. For aromatic / non-aromatic extraction systems (e.g., DMF extraction of butadiene), use a liquid activity method such as NRTL. Equations of state using the advanced mixing rules can model this system as well but require more CPU time to obtain the same results. As with all systems of this type, the results are only as good as the supplied data. The SIMSCI databank has a large amount of interaction data stored for the advanced mixing rules and the NRTL and UNIQUAC liquid activity methods. However, the user must ensure that all important interactions are covered in order to get good results. The liquid activity methods have an advantage over equations of state, since they can use the UNIFAC FILL option to estimate any missing binary interaction parameters. Systems that include light gases can be modeled using the HENRY option in conjunction with the liquid activity methods. This is acceptable when the light gases are present in small quantities. However, if the gases are present in large quantities, it is better to employ an equation of state using one of the advanced mixing rule methods. These calculate the solubilities of the gases more rigorously.
Recommended Methods SRKM / PRM / SRKH / PRH Comments Use any of these methods for aromatic / nonaromatic systems. Also use them for extraction systems at high pressure, or when large quantities of supercritical gases are present. Use these liquid activity methods for extraction systems, such as the extraction of butadiene using DMF. Use the Henry option to model any supercritical gases present in small quantities. Use the UNIFAC FILL option to estimate missing binary pairs.
NRTL / UNIQUAC
Non-hydrocarbon Systems
These systems typically contain oxygen, halogen, or nitrogen derivatives of hydrocarbon components and tend to be highly non-ideal. For low pressure systems, use a liquid activity coefficient method. For single phase systems, the WILSON, NRTL, and UNIQUAC methods are equally good. The Wilson method is the simplest and
requires the least amount of computer time. Simpler methods, such as VANLAAR and MARGULES, are not as good, since they often do not model the more non-ideal systems accurately. For systems containing two liquid phases, the NRTL or UNIQUAC method should be used. The SIMSCI databank contains a large number of binary interaction coefficients for both VLE and LLE systems. In order to get good results, the user must ensure that all significant binaries are supplied in the input. The UNIFAC FILL option can be used to fill in any missing binary data, but should be used only if interaction data are available for most of the binary pairs. If the user has no data, the SYSTEM= UNIFAC option can be used, since it has group interaction data available for both VLE and LLE applications. For high pressure systems, the program offers several methods for modeling the vapor phase fugacity. These methods should be used only if the system pressure is significantly higher than the pressure at which the interaction coefficients were regressed. Interaction coefficients regressed from high pressure data may already include any vapor phase non-ideality in the liquid phase interaction coefficients. The user should always determine whether or not any usersupplied interaction parameters include vapor phase fugacity. All of the parameters in the SIMSCI databank except for components such as carboxylic acids were regressed without a vapor phase fugacity method. For systems with carboxylic acids such as acetic acid, it would therefore be appropriate to use PHI=HOCV. Supercritical gases present in small quantities can be modeled using the Henry option. If they are present in large quantities, or if the system is at high pressures (usually greater than 10 atmospheres), an equation of state using one of the advanced mixing rules should be selected. These are the SRKH, PRH, SRKM, PRM, SRKS, SRKP and PRP methods. The SRKM, SRKS or PRM methods are recommended for the non-hydrocarbon systems discussed here.
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Recommended Methods WILSON
Comments Use WILSON for slightly non-ideal systems. Use the HENRY option to model small amounts of noncondensible gases. Use the UNIFAC FILL option to fill in missing binary interaction data.Do not use WILSON for VLLE systems. Use either of these methods for all non-ideal systems. Use the Henry option to model small amounts of non-condensible gases. Both methods model VLLE systems as well as VLE systems. Use the UNIFAC FILL option to fill in missing binary interaction data. Use for systems at higher pressure or when large quantities of non-condensible gases are present. Can be used for VLE and VLLE systems. Can be used as comparable alternatives to SRKS, SRKM and PRM. SRKS / SRKH / PRH / SRKM / PRM normally yield better results than SRKP and PRP in these applications.
NRTL / UNIQUAC
SRKM / PRM / SRKS SRKH / PRH SRKP / PRP
Alcohol Dehydration Systems

A special bank of interaction coefficients for the NRTL method has been created for alcohol dehydration systems. The coefficients are applicable over a much narrower range than the general NRTL bank coefficients. The user may specify either BANK=ALCOHOL on the KVALUE statement or SYSTEM=ALCOHOL on the METHOD statement. The SYSTEM=ALCOHOL option calculates the vapor enthalpy and density using the SRKM method.
Recommended Methods ALCOHOL NRTL / UNIQUAC Comments Use for all alcohol dehydration systems. Use when valid user-supplied interaction data are available.
HF Systems
A special equation of state, HEXAMER, has been created for systems containing molecules that hexamerize in the vapor phase. This
method is recommended for HF systems such as the HF alkylation process, and for the manufacture of refrigerants and other halogenated compounds using HF.
Chemical and Environmental Applications

Non-Ionic Systems
Non-ionic systems typically contain oxygen, halogen, or nitrogen derivatives of hydrocarbon components and tend to be highly nonideal. For low pressure systems, use a liquid activity coefficient method. For single liquid phase systems, the WILSON, NRTL, and UNIQUAC methods are equally good. The Wilson method is the simplest and requires the least amount of computer time. Simpler methods such as VANLAAR and MARGULES are less applicable, since they often do not model the more non-ideal systems accurately. The NRTL or UNIQUAC method should be used for systems containing two liquid phases. The SIMSCI bank contains a large number of binary interaction coefficients for both VLE and LLE systems. In order to get good results, the user must ensure that all significant binaries are included in the input. The UNIFAC FILL option can be used to estimate any missing binary data but should be used only if interaction data are available for most of the binary pairs. If the user has no data, the SYSTEM=UNIFAC option can be used, since it has group interaction data available for both VLE and LLE systems. The program offers several methods for modeling the vapor phase fugacity in high pressure systems. These should be used only if the system pressure is significantly higher than the pressure at which the interaction coefficients were regressed. Interaction coefficients regressed from high pressure data may already include any vapor phase non-ideality in the liquid phase interaction coefficients. Supercritical gases present in small quantities may be modeled using the Henry option. If they are present in large quantities or if the system is at high pressures, an advanced equation of state such as SRKH, PRH, SRKM, PRM, SRKS SRKP, and PRP should be selected
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.
Recommended Methods WILSON Comments Use WILSON for slightly non-ideal systems. Use the Henry option to model small quantities of noncondensible gases.Do not use WILSON for VLLE systems. Use either of these methods for all non-ideal systems. Use the Henry option to model small quantities of non-condensible gases. Both methods model VLLE systems as well as VLE systems. Use the UNIFAC FILL option to estimate missing binary interaction data. Use at higher pressures or when large quantities of non-condensible gases are present. All three of these methods can be used for VLE and VLLE systems. These methods often yield less satisfactory results than the SRKH, PRH, SRKM, SRKS, and PRM methods in these applications.
NRTL / UNIQUAC
SRKM / PRM / SRKS SRKP / PRP
Carboxylic Acid Systems

Carboxylic acids form dimers in the vapor phase. To obtain accurate values for vapor fugacity, enthalpy, and density, use the Hayden-O'Connell method to calculate the vapor phase properties. Note that HOCV vapor phase fugacities must be used in conjunction with a liquid activity method.
Recommended Methods HOCV Comments The Hayden-O'Connell method produces the best values for vapor phase properties in these applications. Use the PHI=HOCV, ENTHALPY(V)=HOCV, DENSITY(V)=HOCV options on the METHOD statement.
Environmental Applications
These systems usually involve stripping dilute pollutants out of water. The normal liquid activity methods, such as NRTL, do not usually model these very dilute systems with sufficient accuracy. A better approach is to use Henry's Law data for the components in water. The Henry's Law data can be obtained from data sources,
such as the U.S. Environmental Protection Agency( EPA), or are often available in the SIMSCI databank. In order to model the systems accurately, the user should supply temperature-dependent values for the Henry data whenever possible. Non-temperature dependent data often over-predict the required amount of stripping steam.
Solid Applications
Solid-liquid equilibria for most systems can be represented by the van't Hoff (ideal) solubility method or by using user-supplied solubility data. In general, for those systems where the solute and solvent components are chemically similar and form a near ideal solution, the van't Hoff method is appropriate. For non-ideal systems, solubility data should be supplied. For most organic crystallization 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 VANLAAR methods.
Examples
2.1: You are required to model a hydrocarbon-water mixture which contains less than 10% of water. The SRK method is chosen.
TITLE PROB=HC-WATER PRINT INPUT=ALL COMP DATA LlBID 1,H2O/2,C2/3,NC4/4,NC5/5,NC6 THERMO DATA METHOD SYSTEM=SRK WATER DECANT=ON STREAM DATA PROP STREAM=1,TEMP=100,PRES=100, & COMP=40/100/100/100/100 UNIT OPERATIONS FLASH FEED 1 PROD V=2,L=3,W=4 ISOT TEMP=100,PRES=100 END
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2.2
Refinery Application: A mixture of topped crude and dissolved steam is to be modeled. The BK10 method gives satisfactory results for this low pressure crude application.
TITLE PROB=VACUUM DIMEN METRIC, PRES=MMHG COMP DATA LIBID 1,H2O/ 2,C2/ 3,C3 THERMO DATA METHOD SYSTEM=BK10 STREAM DATA PROP STREAM=1, TEMP=330, PRES=8000, RATE(V)=99.37, & ASSAY=LV TBP STREAM=1, PRES(MMHG)=760, & DATA=0,257/ 5,324/ 10,380/ 20,399/ 30,435/ 40,455/ & 50,505/ 60,541/ 70,596/ 75,634 SPGR AVERAGE=0.9833, STREAM=1 PROP STREAM=2, TEMP=30, PRES=8000, RATE(V)=3.0, & COMP=2,75/ 3,25 PROP STREAM=3, TEMP=330, PRES=8000, RATE(W)=318, & COMP=1,100 PROP STREAM=4, TEMP=355, PRES=8500, PHASE=V, & RATE(W)=908, COMP=1,100 UNIT OPERATIONS MIXER FEED 1,2,3 PROD L=5 COLUMN PARA TRAY=2 FEED 5,1/ 4,2 PROD OVHD=6, BTMS=7,100 VAPOR 1,300/ 2,50 TEMP 1,355/ 2,371 HEAT 1,1 PRES 1,98/ 2,115 SPEC STREAM=7, RATE(V), VALUE=50.88 VARY HEAT=1 END
2.3
Sour Water Application: A sour water stream containing CO2, H2S, NH3 and HCN is to be modeled. The amount of HCN in the feed is small, and its distribution between the liquid and vapor phases is not important. Either the SOUR or GPSWAT methods could be used. However, an examination of the feed shows that the sum of the weight fractions of the sour gases exceeds 0.30. The GPSWAT method is therefore preferred over the SOUR method.
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TITLE PROB=SOUR PRINT INPUT=ALL COMPONENT DATA LIBID 1,N2/ 2,CH4/ 3,H2S/ 4,NH3/ & 5,CO2/6,HCN/7,H2O THERMODYNAMIC DATA METHODS SYSTEM=GPSWAT STREAM DATA PROP STREAM=1, TEMP=120, PRES=25, PHASE=L, & COMP(W)=1,2/ 2,3/3,8000/4,4000/ & 5,1200/6,0.238/7,25584.7 PROP STREAM=2, PRES=50, PHASE=V, COMP(M)=7,2000 UNIT OPERATIONS COLUMN PARA TRAY=7, IO=25, DAMP=0.5 FEED 1,1/ 2,7, NOTSEP PROD OVHD=3, BTMS=4,24446 PSPEC TOP=20.8, DPCOL=2.1678 ESTI MODEL=CONV END
2.4
Natural Gas Application: You wish to study a natural gas stream that contains less than 1 percent of N2. Therefore, the SRK equation of state method is used along with the COSTALD liquid density method to model this application.
TITLE PROB=LNG PRINT INPUT=ALL COMPONENT DATA LIBID 1,N2/ 2,CH4/ 3,C2/ 4,C3/ & 5,NC4/ 6,NC5/ 7,NC6 THERMODYNAMIC DATA METHODS SYSTEM=SRK, DENSITY(L)=COSTALD STREAM DATA PROP STREAM=1, TEMP=10, PRES=50, PHASE=V, & COMP(M)=1,2.6/2,93.7/3,1.94/4,0.95/ & 5,0.38/6,0.23/7,0.2 UNIT OPERATIONS PHASE ENVELOPE EVALUATE STREAM=1, LFRAC=0.90, IPLOT=OFF END
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2.5
Petrochemical Application: A binary aromatic mixture of n-methyl-formamide (NMF) and tert-butylformamide (TBUTFORM) is to be modeled at a pressure of 3 atmospheres. The SRK K-value method provides good results for aromatic systems above 2 atmospheres. The COSTALD liquid density method provides good results for aromatic systems at low temperatures.
TITLE PROB=AROM PRINT INPUT=ALL COMP DATA LIBID 1,NMF/ 2,TBUTFORM THERMO DATA METHOD SYSTEM=SRK, DENS(L)=COSTALD STREAM DATA PROP STREAM=1, TEMP=80, PRES(ATM)=1, RATE(W)=1000, & COMP=1,25/ 2,75 UNIT OPERATIONS COLUMN PARA TRAY=10, CHEM=40, DAMP=0.6 FEED 1,5 PROD OVHD=2, BTMS=3,700 COND TYPE=BUBB, PRES(ATM)=3 PSPEC PTOP(ATM)=3, DPCOL=0.5 DUTY 1,1,10/ 2,10,10 SPEC RRATIO, VALUE=5 SPEC STREAM=3, COMP=2, FRAC, VALUE=0.9 VARY DUTY=1,2 ESTI MODEL=CONV END
2.6
Chemical and Environmental Application: A waterhydrocarbon stream is to be flashed at 1 atmosphere. The presence of acetic and acrylic acids in the stream necessitates the use of the Hayden-O'Connell vapor fugacity method to account for the vapor phase dimer formation. The NRTL method will be used to calculate VLE equilibria. The HENRY option is selected to model the supercritical components.
TITLE PROB=ACIDS PRINT INPUT=ALL COMP DATA LIBID 1,H2O/ 2,O2/ 3,N2/ 4,C3/ 5,IC4/ 6,NC4/ & 7,NC5/ 8,ACETIC/ 9,ACRYLIC
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THERMO DATA METHOD SYSTEM=NRTL, PHI=HOCV, ENTH(V)=HOCV , & DENS(V)=HOCV, HENRY KVALUE BANK=SIMSCI, POYNTING=YES, FILL=IDEAL HENRY BANK=SIMSCI SOLUTE 2,3 STREAM DATA PROP STREAM=1, TEMP=80, PRES(ATM)=1, RATE(W)=1000, & COMP=1,0.80/ 2,2.0E-02/ 3,0.04/ 4,2E-02/ 5,5.0E-02/ & 6,0.05/ 7,1.0E-03/ 8,0.01/ 9,0.01 UNIT OPERATIONS FLASH FEED 1 PROD L=2, V=3 ISOT TEMP(C)=90, DP=0.0 END
2.7
Solid Application: Urea is to be precipitated from an aqueous solution. Some library properties for urea and water such as vapor pressure and heat capacity are overridden with user-supplied values. The urea-water mixture is non-ideal and so user solubility data are supplied.
TITLE PROB=SOLIDS PRINT INPUT=ALL COMP DATA LIBID 1,UREA/ 2,H2O PHASE VLS=1 ATTR COMP=1, PSD(MIC)=147,208,295,417,589,833,1168 TTP(K) 1,4.0585E+02 PTP(PA) 1,9.31306E+01 FORMATION(V,J/KG,MOLE) 1,-2.458E+08,-1.582E+08 HFUS(J/KG,MOLE) 1,1.479E+07 VP(L,PA,K) CORR=20, LN, DATA=1, & 3.6805E+02,2.981E+02,2.8209E+01,-1.05E+04, & 1.0272E-01,0.0,0.0,0.0 LATENT(J,KG/K,MOLE) CORR=1, DATA=1, & 2.981E+02,2.981E+02,8.7864E+07,0.0, & 0.0,0.0,0.0,0.0 CP(S,J/KG,K,MOLE) CORR=1, DATA=1, & 4.0E+02,8.0E+01,1.725E+04,2.318E+02, & 7.9E-02,0.0,0.0,0.0 DENS(S,K,KG/M3,WT) CORR=1, DATA=1, & 300.0,20.0,1335.036 SVTB 1,-7.701601E-03 SLTB 1,1.889548E+02 SLTM 1,1.639447E+01
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HVTB 1,-9.317743E-03 HLTB 1,8.7864E+04 HLTM 1,7.127574E+03 THERMO DATA METHOD SYSTEM(VLE)=VANLAAR, KVALUE(SLE)=SOLDATA KVALUE(VLE) VANLAAR 1,2,0.8255,100.0 KVALUE(SLE) SOLUTE 1 SOLDATA(K) 1,2,0.0,-1310.37,0.533619 STREAM DATA PROP STREAM=1, TEMP=80, PRES(ATM)=1, RATE(W)=1000, & COMP=1,25/ 2,75 UNIT OPERATIONS CRYSTALLIZER FEED 1 PROD OVHD=2, BTMS=3 RATING VOLUME=200 OPER SOLU=1, SOLVENT=2, TEMP=20, DP=0.0 GROWTH KG(M/S)=1.0E-07, GEXP=0.2 NUCLEATION KB=8.0E+13, RPM=100 END
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Chapter 3 Generalized Correlations

These general purpose data generators may be used for a variety of industrial applications but are primarily applicable to systems of non-polar hydrocarbons. The program also allows the user to input K-value data directly.
Ideal and Library Methods

Typical Usage
...
COMPONENT DATA LIBID 1, IC4/ 2, NC4/ 3, NC5 THERMO DATA METHOD SYSTEM=IDEAL STREAM DATA . . .
General Information
The IDEAL method calculates K-values, vapor and liquid densities, and vapor and liquid enthalpies. LIBRARY methods to calculate liquid entropies were discontinued starting with PRO/II version 4.1. These methods should be used with pure component streams and streams with very similar components; for instance: o-xylene / m-xylene / p-xylene / ethylbenzenestyrene.
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Table 3-1: Attributes of IDEAL and LIBRARY Methods Properties predicted by IDEAL and LIBRARY methods K-values Liquid densities Vapor densities Liquid enthalpies Vapor enthalpies
Required pure component properties1 K-values Liquid enthalpy Vapor enthalpy Liquid densities Vapor densities Pressure Free-water decant VLLE
1
- Vapor pressure correlations - Liquid enthalpy correlations - Liquid enthalpy and heat of vaporization correlations - Liquid density correlations - Molecular weight - Low pressures - Not supported - Not supported
Suggested application ranges Two liquid phase behavior
Automatically supplied for library and petroleum components. Must be supplied by the user for non-library components.
Input Description
The THERMODYNAMIC DATA statement and the METHOD statement are discussed in full in Chapter 1, Thermodynamic Data Overview. The keywords relevant to the IDEAL method are discussed here. The METHOD Statement
METHOD or METHOD SYSTEM=IDEAL, ... KVALUE=IDEAL, ENTHALPY=IDEAL, DENSITY=IDEAL
SYSTEM
Selects a combination of compatible thermodynamic property generators. When SYSTEM=IDEAL is chosen, IDEAL K-values, densities, and enthalpies are assumed.
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Generalized Correlations
KVALUE
Selects the method for K-value calculations. Only VLE K-value calculations are available with the IDEAL method. Pure component vapor pressures and Raoult's law: Pi = i Pisat are used to calculate K-values.
ENTHALPY (VL or V and/or L) DENSITY (VL or V and/or L)
Selects the method for enthalpy calculations. IDEAL methods may be selected for liquid and/or vapor phase calculations. Selects the method for density calculations. IDEAL methods may be selected for liquid and/or vapor phase calculations.
Examples
3.1: Using the IDEAL methods, model a 50/50 mix of propane and normal butane at 50 psia and 100 F. By choosing the IDEAL system, Curl-Pitzer enthalpies are invoked.
TITLE PROB=IDEAL, PROJ=THERMO DESC THERMO MANUAL PROBLEM PRINT INPUT=ALL COMPONENT DATA LIBID 1,IC4/ 2,NC4 THERMODYNAMIC DATA METHOD SYSTEM=IDEAL STREAM DATA PROP STREAM=1, TEMP=100, PRES=100, COMP=50/50 UNIT OPERATION FLASH UID=FL1 FEED 1 PROD V=2, L=3 TPSPEC PRES=50 SPEC STREAM=2, RATE, RATIO, STREAM=1, & RATE, VALUE=0.5 END
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3.2:
For the same problem, explicitly declare IDEAL K-values, enthalpies, IDEAL vapor density, and API liquid densities.
THERMODYNAMIC DATA METHOD KVALUE=IDEAL, ENTHALPY=IDEAL, & DENSITY(V)=IDEAL, DENSITY(L)=API
3.3:
For the same problem, use SRK for K-values and enthalpies, and IDEAL densities.
THERMO DATA METHOD KVALUE=SRK, ENTHALPY=SRK, DENSITY=IDEAL or THERMO DATA METHOD SYSTEM=SRK, DENSITY=IDEAL
3.4:
For the same problem, use SRK for everything except liquid enthalpies. Use the IDEAL method instead for liquid enthalpy calculations.
THERMODYNAMIC DATA METHOD SYSTEM=SRK, ENTHALPY(L)=IDEAL
Grayson-Streed
Typical Usage
...
COMPONENT DATA LIBID 1, IC4/ 2, NC4/ 3, NC5 THERMO DATA METHOD SYSTEM=GS STREAM DATA . . .
General Information
The Grayson-Streed method calculates K-values. It is generally useful for light to mid-range refinery hydrocarbons. It is also useful for vacuum column and coker simulations when API87 is used. Refer to the PRO/II Reference Manual for additional limitations.
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Table 3-2: Attributes of Grayson-Streed Methods Properties predicted by GS methods K-values Required pure component properties1 Molecular weight Critical temperature Critical pressure Suggested application ranges Pressure Temperature Two liquid phase behavior Free-water decant VLLE - Supported - Not supported < 3000 psia 0 - 800 F Liquid molar volume Acentric factor Solubility parameter
1 Automatically supplied for library and petroleum components. Must be supplied by the user for nonlibrary components.
Input Description
METHOD or METHOD SYSTEM=GS, ... KVALUE=GS, ...
SYSTE M
Selects a combination of compatible thermodynamic property generators. When SYSTEM=GS is chosen, GS K-values, Curl-Pitzer (CP) enthalpies, CP entropies, API liquid densities, and SRK vapor densities are assumed. Selects the method for K-value calculations. Only VLE K-value calculations are available with the GS method.
KVALU E
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Water Handling Options (optional)

WATER DECANT=ON or OFF, GPSA, SOLUBILITY=SIMSCI or KEROSENE or EOS PROPERTY=SATURATED or STEAM
The GS K-value generator supports the free-water decant option. Refer to Free-water Decant Considerations on page 1-34 for a description of these input options. Method-specific Pure Component Properties (optional)
TC(unit) PC(unit) MOLVOL(unit) ACENTRIC SOLUPARA ... i, value / ... i, value / ... i, value / ... i, value / ... i, value / ...
Properties may be supplied that are active only when a specific method is used. For a further description of these input parameters, see Chapter 9, Method-specific Pure Component Data.
Examples
3.5: Using the GS methods, model a 50/50 mix of propane and normal butane at 50 psia and 100 F. By choosing the GS system, Curl-Pitzer enthalpies are invoked.
TITLE PROB=GS, PROJ=THERMO DESC THERMO MANUAL PROBLEM PRINT INPUT=ALL COMPONENT DATA LIBID 1,C3/ 2,NC4 THERMO DATA METHOD SYSTEM=GS STREAM DATA PROP STREAM=1, TEMP=100, PRES=100, COMP=50/50 UNIT OPERATION FLASH UID=FLSH FEED 1 PROD V=2, L=3 TPSPEC PRES=50 SPEC STREAM=2, RATE, RATIO, STREAM=1, & RATE, VALUE=0.5 END
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3.6:
For the same problem, use GS K-values, Lee-Kesler enthalpies and densities.
THERMO DATA METHOD KVALUE=GS, ENTHALPY=LK, DENSITY=LK
3.7:
The same system as in Example 3.5 now contains 20% water at a higher pressure. Use the GPSA Data Book, water solubility by the API Technical Data Book, Fig. 9A1.4. Pure water properties are calculated using the Keenan and Keyes steam tables.
TITLE PROB=GS, PROJ=THERMO DESC THERMO MANUAL PROBLEM PRINT INPUT=ALL COMPONENT DATA LIBID 1,C3/ 2,NC4 THERMO DATA METHOD SYSTEM=GS STREAM DATA PROP STREAM=1, TEMP=100, PRES=100, COMP=50/50 UNIT OPERATION FLASH UID=F1 FEED 1 PROD V=2, L=3 TPSPEC PRES=50 SPEC STREAM=2, RATE, RATIO, STREAM=1, & RATE, VALUE=0.5 END
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Chao-Seader
Typical Usage
...
COMPONENT DATA LIBID 1, IC4/ 2, NC4/ 3, NC5 THERMO DATA METHOD SYSTEM=CS STREAM DATA . . .
General Information
The Chao-Seader method calculates K-values. It is generally useful for light to mid-range refinery hydrocarbons. SimSci recommends that the Grayson-Streed method (GS) be used in preference to CS. Refer to the PRO/II Reference Manual for additional limitations.
Table 3-3: Attributes of the Chao-Seader Methods Properties predicted by CS Methods K-values Chao-Seader Required pure component properties1 Molecular weight Critical temperature Critical pressure Liquid molar volume Acentric factor Solubility parameter C2 & Higher Pressure Temperature Free-water decant VLLE
1
Suggested application ranges H2 & C1 < 8000 psia -100 to 500F
< 2000 psia 0 to 800 F Supported Not supported
Two liquid phase behavior
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Input Description
METHOD or METHOD SYSTEM=CS, ... KVALUE=CS, ...
SYSTEM
Selects a combination of compatible thermodynamic property generators. When SYSTEM=CS is chosen, CS K-values, Curl-Pitzer (CP) enthalpies, CP entropies, API liquid densities, and SRK vapor densities are assumed. Selects the method for K-value calculations. Only VLE K-value calculations are available with the CS method.
KVALUE

The CS K-value generator supports the free-water decant option. Refer to Free-water Decant Considerations on page 1-34, for a description of these input options. Method-specific Pure Component Properties (optional)
TC(unit) PC(unit) MOLVOL(unit) ACENTRIC SOLUPARA ... i, value / ... i, value / ... i, value / ... i, value / ... i, value / ...
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Examples
3.8: Using the CS methods, model a 50/50 mix of propane and normal butane at 100 psia and 100 F. By choosing the CS system, Curl-Pitzer enthalpies are invoked.
TITLE PROB=CS, PROJ=THERMO DESC THERMO MANUAL PROBLEM PRINT INPUT=ALL COMPONENT DATA LIBID 1,C3/ 2,NC4 THERMO DATA METHOD SYSTEM=CS STREAM DATA PROP STREAM=1, TEMP=100, PRES=100, COMP=50/50 UNIT OPERATION FLASH UID=FLSH FEED 1 PROD V=2, L=3 TPSPEC PRES=50 SPEC STREAM=2, RATE, RATIO, STREAM=1, & RATE, VALUE=0.5 END
3.9:
For the same problem, use CS K-values, Lee-Kesler enthalpies and densities.
THERMO DATA METHOD KVALUE=CS, ENTHALPY=LK, DENSITY=LK
3.10:
The system in Example 3.8 now contains 20% water at a higher pressure. Use the GPSA Data Book charts, water solubility by the API Technical Data Book, Fig. 9A1.4. Pure water properties are calculated using the Keenan and Keyes steam tables.
TITLE PROB=GS, PROJ=THERMO DESC THERMO MANUAL PROBLEM PRINT INPUT=ALL COMPONENT DATA LIBID 1,H2O/ 2,C3/ 3,NC4 THERMO DATA METHOD SYSTEM=CS WATER DECANT=ON, GPSA, SOLUBILITY=KEROSENE, & PROPERTY=STEAM STREAM DATA PROP STREAM=1, TEMP=100, PRES=1000, COMP=20/40/40
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UNIT OPERATION FLASH UID=F1 FEED 1 PROD V=2, L=3, W=4 TPSPEC TEMP=100 SPEC STREAM=2, RATE, RATIO, STREAM=1, & RATE, VALUE=0.5 END
Modifications to GS and CS
Typical Usage
...
COMPONENT DATA LIBID 1, IC4/ 2, NC4/ 3, NC5 THERMO DATA METHOD SYSTEM=IGS STREAM DATA . . .
General Information
The Erbar modification to the Chao-Seader and Grayson-Streed methods offers improved liquid fugacity coefficients for N2, H2S and CO2. These methods do not support rigorous three-phase calculations, but they do support free water decant. The Improved Grayson-Streed method has better liquid fugacity coefficients for N2, H2S, CO, CO2, H2O, and O2. This method supports a rigorous three phase calculation but can also be used with the free water decant option turned on. These methods are generally useful for petroleum refinery applications. Refer to the PRO/II Reference Manual for additional limitations.
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Table 3-4: Attributes of the Modified GS and CS Methods Properties predicted by modified GS and CS Methods K-values (VLE) Erbar modified Grayson-Streed Erbar modified Chao-Seader Improved Grayson-Streed Improved Grayson-Streed
K-values (VLLE)
Required pure component properties1 Molecular weight Critical temperature Critical pressure Pressure Temperature Free-water decant VLLE Acentric factor Water solubility parameter (IGS only)
Suggested application ranges < 3000 psia 0 to 800 F Supported by GSE, CSE and IGS Not supported by GSE and CSE Supported by IGS
1Automatically supplied for library and petroleum components. Must be supplied by the user for nonlibrary components.
Input Description
The METHOD Statement Improved Grayson-Streed
METHOD or METHOD SYSTEM(VLE or VLLE)=IGS, ... KVALUE(VLE and/or LLE or VLLE)=IGS, ...
Erbar modifications to Grayson-Streed and Chao-Seader

METHOD or METHOD SYSTEM=GSE or CSE, ... KVALUE=GSE or CSE, ...
SYSTEM
Selects a combination of compatible thermodynamic property generators. When SYSTEM=IGS, GSE or CSE is chosen, GS K-values, Curl-Pitzer (CP) enthalpies, CP entropies, API liquid densities, and SRK vapor enthalpies are default.
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KVALUE
Selects the method for K-value calculations. Only VLE K-value calculations are available with the GSE and CSE methods. The IGS method supports VLLE as well.
Water Handling Options (optional) These options are not valid when the VLLE option is active.
The IGS, GSE, and CSE K-value generators support the free-water decant option. Refer to Free-water Decant Considerations on page 1-34, for a description of these input options. Method-specific Pure Component Properties (optional)
TC(unit) PC(unit) MOLVOL(unit) ACENTRIC SOLUPARA WDELT ... i, value / ... i, value / ... i, value / ... i, value / ... i, value / ...
Properties may be supplied that are active only when a specific method is used. For IGS, the water solubility parameter, WDELT, is applied asymmetrically to the water phase. For a further description of these input parameters, see Chapter 9, Method-specific Pure Component Data.
Examples
3.11: Using the IGS methods, model a 50/50 mix of propane and normal butane at 100 psia and 100 F. By choosing the IGS system, Curl-Pitzer enthalpies are invoked.
TITLE PROB=IGS, PROJ=THERMO DESC THERMO MANUAL PROBLEM PRINT INPUT=ALL COMPONENT DATA LIBID 1,C3/ 2,NC4 THERMO DATA METHOD SYSTEM=IGS STREAM DATA PROP STREAM=1, TEMP=100, PRES=1000, COMP=50/50
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UNIT OPERATION FLASH UID=F1 FEED 1 PROD V=2, L=3 TPSPEC TEMP=50 SPEC STREAM=2, RATE, RATIO, STREAM=1, & RATE, VALUE=0.5 END
3.12:
For the same problem, use GSE K-values, Lee-Kesler enthalpies and densities.
THERMO DATA METHOD KVALUE=GSE, ENTHALPY=LK, DENSITY=LK
3.13:
The Improved Grayson-Streed (IGS) method, compare the results using rigorous VLLE calculations with those obtained using the water decant option. Use all the defaults for the water decant option. Both thermodynamic systems will be tried in the same run by assigning different thermodynamic sets to the two flash units.
TITLE PROB=GS, PROJ=THERMO COMPONENT DATA LIBID 1,H2O/ 2,C3/ 3,NC4 THERMO DATA METHOD SYSTEM(VLLE)=IGS, SET=RIGOROUS METHOD SYSTEM=IGS, SET=DECANTING WATER DECANT=ON, GPSA, SOLUBILITY=KEROSENE, & PROPERTY=STEAM STREAM DATA PROP STREAM=1, TEMP=100, PRES=1000, COMP=20/40/4 UNIT OPERATION FLASH UID=DEC FEED 1 PROD V=2D, L=3D, W=4D TPSPEC TEMP=100 SPEC STREAM=2D, RATE, RATIO, STREAM=1, & RATE, VALUE=0.5 METHOD SET=DECANTING FLASH UID=RIG FEED 1 PROD V=2R, L=3R, W=4R TPSPEC TEMP=100 SPEC STREAM=2R, RATE, RATIO, STREAM=1, & RATE, VALUE=0.5 METHOD SET=RIGOROUS END
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Curl-Pitzer
Typical Usage
...
COMPONENT DATA LIBID 1, IC4/ 2, NC4/ 3, NC5 THERMO DATA METHOD SYSTEM=SRKM, ENTHALPY=CP STREAM DATA . . .
General Information
The Curl-Pitzer method calculates enthalpies and entropies. It is generally useful for refinery hydrocarbons Refer to the PRO/II Reference Manual for additional limitations.
Table 3-5: Attributes of CP Methods Properties predicted by CP methods Enthalpies Entropies Required pure component properties1 Critical temperature Critical pressure Acentric factor
Input Description
METHOD or METHOD or SYSTEM=GS or CS or IGS or GSE or CSE or BK10, ... ..., ENTHALPY(VL)=CP, ENTHALPY(V)= CP and/or ENTHALPY(L)=CP, ENTROPY(VL)=CP, ... or ENTROPY(V)=CP and/or ENTROPY(L)=CP, ...
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SYSTEM
Selects a combination of compatible thermodynamic property generators. Selecting GS, CS, IGS, GSE or CSE will cause Curl-Pitzer enthalpies and entropies to be used. Selecting BK10 will cause CP entropies to be used.
ENTHALPY Selects the method for enthalpy calculations. By (VL or V and/or L) default both vapor and liquid (VL) enthalpies are calculated using the same method. You may select different methods for the vapor and liquid enthalpies by providing both an ENTHALPY(V) and ENTHALPY(L) entry. ENTROPY Selects the method for entropy calculations. By (VL or V and/or L) default both vapor and liquid (VL) entropies are calculated using the same method. You may select different methods for the vapor and liquid entropies by providing both an ENTROPY(V) and ENTROPY(L) entry.
Method-specific Pure Component Properties (optional)

TC(unit) PC(unit) ACENTRIC ... i, value / ... i, value / ... i, value / ...
The Curl-Pitzer method requires Tc, Pc, acentric factors and ideal enthalpies. Tc, Pc and acentric factors may be overridden here for a specific method set. The ideal enthalpies may only be specified globally for all sets in the Component Data Category. For a further description of these input parameters, see Chapter 9, Method-specific Pure Component Data.
Examples
3.14: Using the CS system, model a 50/50 mix of propane and normal butane at 100 psia and 100 F. By choosing the CS system, Curl-Pitzer enthalpies and entropies are invoked.
TITLE PROB=CP, PROJ=THERMO DESC THERMO MANUAL PROBLEM PRINT INPUT=ALL COMPONENT DATA LIBID 1,C3/ 2,NC4
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THERMO DATA METHOD SYSTEM=CS STREAM DATA PROP STREAM=1, TEMP=100, PRES=100, COMP=50/50 UNIT OPERATION FLASH UID=FLSH FEED 1 PROD V=2, L=3 TPSPEC PRES=50 SPEC STREAM=2, RATE, RATIO, STREAM=1, & RATE, VALUE=0.5 END
3.15:
For the same problem, specify CP enthalpies and entropies explicitly.
THERMO DATA METHOD KVALUE=CS, ENTHALPY=CP, ENTROPY=CP, & DENSITY=API
3.16:
For the same problem, use Curl-Pitzer methods in the vapor phase and IDEAL methods in the liquid phase for enthalpy and entropy calculations. For liquid density, use API and for vapor density, use the IDEAL method.
TITLE PROB=CP, PROJ=THERMO DESC THERMO MANUAL PROBLEM PRINT INPUT=ALL COMPONENT DATA LIBID 1,C3/ 2,NC4 THERMO DATA METHOD KVALUE=CS, ENTHALPY(V)=CP, & ENTHALPY(L)=IDEAL, ENTROPY(V)=CP, DENSITY(L)=API, & DENSITY(V)=IDEA STREAM DATA PROP STREAM=1, TEMP=100, PRES=100, COMP=50/50 UNIT OPERATION FLASH UID=FLSH FEED 1 PROD V=2, L=3 TPSPEC PRES=50 SPEC STREAM=2, RATE, RATIO, STREAM=1, & RATE, VALUE=0.5 END
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Braun K10
Typical Usage
...
COMPONENT DATA LIBID 1, IC4/ 2, NC4/ 3, NC5 THERMO DATA METHOD SYSTEM=BK10 STREAM DATA . . .
General Information
The Braun K10 method calculates K-values. It is generally useful for heavy refinery hydrocarbons at low pressures. Refer to the PRO/II Reference Manual for additional limitations.
Table 3-6: Attributes of the Braun K10 Methods Properties predicted by BK10 method K-values Required pure component properties1 Molecular weight Critical temperature Critical pressure Pressure Temperature Composition Free-water decant VLLE
1
Acentric factor Normal boiling point
Suggested application ranges 0 to 100 psia 100 to 1200 F C6 & Heavier Supported Not supported
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Input Description
METHOD or METHOD SYSTEM=BK10, ... KVALUE=BK10, ...
SYSTEM
Selects a combination of compatible thermodynamic property generators. When SYSTEM=BK10 is chosen, BK10 K-values, Johnson-Grayson (JG) enthalpies, Curl-Pitzer (CP) entropies, IDEAL vapor densities, and API liquid densities are assumed. Selects the method for K-value calculations. Only VLE K-value calculations are available with the BK10 method.
KVALUE

The BK10 K-value generator supports the free-water decant option. Refer to Free-water Decant Considerations on page 1-34, for a description of these input options. Method-specific Pure Component Properties (optional)
NBP(unit) TC(unit) PC(unit) ACENTRIC ... i, value / ... i, value / ... i, value / ... i, value / ...
Examples
3.17: Using the BK10 method, model a 50/50 mix of propane and normal butane at 100 psia and 100 F. By choosing the SYSTEM=BK10, Johnson-Grayson enthalpies are invoked.
TITLE PROB=BK10, PROJ=THERMO DESC THERMO MANUAL PROBLEM PRINT INPUT=ALL
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COMPONENT DATA LIBID 1,C3/ 2,NC4 THERMO DATA METHOD SYSTEM=BK10 STREAM DATA PROP STREAM=1, TEMP=100, PRES=100, COMP=50/50 UNIT OPERATION FLASH UID=FL1 FEED 1 PROD V=2, L=3 TPSPEC PRES=50 SPEC STREAM=2, RATE, RATIO, STREAM=1, & RATE, VALUE=0.5 END
3.18:
For the same problem, use BK10 K-values, Lee-Kesler enthalpies and densities.
THERMO DATA METHOD KVALUE=BK10, ENTHALPY=LK, DENSITY=LK
3.19:
The system in Example 3.17 now contains 20% water at a higher pressure. Calculate water partial pressures using the GPSA Data Book, water solubilities using the API Technical Data Book, and, because of the conditions, pure water properties using the Keenan and Keyes steam tables.
TITLE PROB=BK10, PROJ=THERMO DESC THERMO MANUAL PROBLEM PRINT INPUT=ALL COMPONENT DATA LIBID 1,H2O/ 2,C3/ 3,NC4 THERMO DATA METHOD SYSTEM=BK10 WATER DECANT=ON, GPSA, & SOLUBILITY=KEROSENE, PROPERTY=STEAM STREAM DATA PROP STREAM=1, TEMP=100, PRES=1000, COMP=20/40/40 UNIT OPERATION FLASH UID=DRUM FEED 1 PROD V=2, L=3, W=4 TPSPEC TEMP=100 SPEC STREAM=2, RATE, RATIO, STREAM=1, & RATE, VALUE=0.5 END
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Johnson-Grayson
Typical Usage
...
COMPONENT DATA LIBID 1, IC4/ 2, NC4/ 3, NC5 THERMO DATA METHOD SYSTEM=SRKM, ENTHALPY=JG STREAM DATA . . .
General Information
The Johnson-Grayson method calculates enthalpies. It is generally useful for heavy refinery hydrocarbons. When using the JohnsonGrayson enthalpy method, it is recommended that the JohnsonGrayson method be used for both liquid and vapor phases.Refer to the PRO/II Reference Manual for additional limitations.
Table 3-7: Attributes of JG Methods Properties predicted by JG methods Enthalpies Required pure component properties1 Critical temperature Critical pressure Normal boiling point
1
Automatically supplied for library and petroleum components. must be supplied by the user for non-library components.
Input Description
METHOD or METHOD SYSTEM=BK10, ... ..., or ENTHALPY(VL)=JG, ... ENTHALPY(V)= JG and/or ENTHALPY(L)=JG
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SYSTEM
Selects a combination of compatible thermodynamic property generators. When SYTEM=BK10 is chosen, Johnson-Grayson vapor and liquid enthalpies are assumed. Selects the method for enthalpy calculations. By default both vapor and liquid (VL) enthalpies are calculated using the same method. You may select different methods for the vapor and liquid enthalpies by providing both an ENTHALPY(V) and ENTHALPY(L) entry, although this is not recommended.
ENTHALPY (VL or V and/or L)

TC(unit) PC(unit) NBP(unit) i, value / ... i, value / ... i, value / ...
The Johnson-Grayson method requires Tc, Pc, and NBP. Tc, Pc, and NBP may be overridden here for a specific method set. For a further description of these input parameters, see Chapter 9, Method-specific Pure Component Data.
Examples
3.20: Using the BK10 system, model a 50/50 mix of propane and normal butane at 100 psia and 100 F. By choosing the BK10 system, Johnson-Grayson enthalpies are invoked.
TITLE PROB=JG, PROJ=THERMO DESC THERMO MANUAL PROBLEM PRINT INPUT=ALL COMPONENT DATA LIBID 1,C3/ 2,NC4 THERMO DATA METHOD SYSTEM=BK10 STREAM DATA PROP STREAM=1, TEMP=100, PRES=100, COMP=50/50 UNIT OPERATION FLASH UID=D101 FEED 1 PROD V=2, L=3 TPSPEC PRES=50 SPEC STREAM=2, RATE, RATIO, STREAM=1, & RATE, VALUE=0.5 END
II-3-22
3.21:
For the same problem, specify JG enthalpies explicitly.
THERMO DATA METHOD KVALUE=BK10, ENTHALPY=JG, ENTROPY=CP, & DENSITY=API
Lee-Kesler
Typical Usage
...
COMPONENT DATA LIBID 1, IC4/ 2, NC4/ 3, NC5 THERMO DATA METHOD SYSTEM=SRKM, ENTHALPY=LK STREAM DATA . . .
General Information
The Lee-Kesler method calculates enthalpies, entropies and densities. It is generally useful for refinery hydrocarbons. The liquid density method is not recommended for hydrocarbons heavier than C8. Refer to the PRO/II Reference Manual for additional limitations.
Table 3-8: Attributes of the Lee-Kesler Methods Properties predicted by LK methods Enthalpies Entropies Densities Suggested application ranges Composition C8 & lighter (for liquid density method) Required pure component properties1 Critical temperature Critical pressure Normal boiling point
1
Automatically supplied for library and petroleum components. must be supplied by the user for non-library components.
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Input Description
METHOD or ENTHALPY(VL)=LK, ENTHALPY(V)= LK and/or ENTHALPY(L)=LK, ENTROPY(VL)=LK, ... or ENTROPY(V)= LK and/or ENTROPY(L)=LK, ... DENSITY(VL)=LK, ... or DENSITY(V)= LK and/or DENSITY(L)=LK, ...
Selects the method for enthalpy calculations. By default both vapor and liquid (VL) enthalpies are calculated using the same method. You may select different methods for the vapor and liquid enthalpies by providing both an ENTHALPY(V) and ENTHALPY(L) entry. Selects the method for entropy calculations. By default both vapor and liquid (VL) entropies are calculated using the same method. You may select different methods for the vapor and liquid entropy by providing both an ENTROPY(V) and ENTROPY(L) entry. Selects the method for density calculations. By default both vapor and liquid (VL) densities are calculated using the same method. You may select different methods for the vapor and liquid densities by providing both a DENSITY(V) and DENSITY(L) entry.
ENTROPY (VL or V and/or L)
DENSITY (VL or V and/or L

TC(unit) PC(unit) NBP(unit) ... i, value / ... i, value / ... i, value / ...
The Lee-Kesler method requires Tc, Pc, NBP and ideal gas enthalpies. Tc, Pc and NBP may be overridden here for a specific method set. The ideal gas enthalpies may only be specified globally for all sets in the Component Data Category. For a further description of these input parameters, see Chapter 9, Method-specific Pure Component Data.
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Examples
3.22: Using the SRK system and Lee-Kesler enthalpies, model a 50/50 mix of propane and normal butane at 100 psia and 100 F. By choosing the SRK system, SRK entropies, vapor densities, and API liquid densities are invoked.
TITLE PROB=LK, PROJ=THERMO DESC THERMO MANUAL PROBLEM PRINT INPUT=ALL COMPONENT DATA LIBID 1,C3/ 2,NC4 THERMO DATA METHOD SYSTEM=SRK, ENTHALPY=LK STREAM DATA PROP STREAM=1, TEMP=100, PRES=100, COMP=50/50 UNIT OPERATION FLASH UID=FLSH FEED 1 PROD V=2, L=3 TPSPEC PRES=50 SPEC STREAM=2, RATE, RATIO, STREAM=1, & RATE, VALUE=0.5 END
3.23:
For the same problem, specify SRK K-values, LK enthalpies, entropies and densities explicitly.
THERMO DATA METHOD KVALUE=SRK, ENTHALPY=LK, & ENTROPY=LK, DENSITY=LK
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API Liquid Density

Typical Usage
...
COMPONENT DATA LIBID 1, IC4/ 2, NC4/ 3, NC5 THERMO DATA METHOD SYSTEM=SRKM, DENSITY(L)=API STREAM DATA . . .
General Information
The API method calculates liquid densities. It is generally useful for refinery hydrocarbons. Refer to the PRO/II Reference Manual for additional limitations.
Table 3-9: Attributes of API Methods Properties predicted by API methods Liquid densities Required pure component properties1 Critical temperature Critical pressure Normal boiling point
Input Description
METHOD SYSTEM=SRK or SRKKD or SRKH or SRKP or SRKM or PR or PRH or PRP or PRM or BK10 or GS or IGS or CS or UNIWAAL or GLYCOL ..., DENSITY(L)=API, ...
or METHOD
SYSTEM
Selects a combination of compatible thermodynamic property generators. When one of the above systems is chosen, API liquid densities are assumed.
II-3-26
DENSITY(L)
Selects the method for liquid density calculations.

TC(unit) PC(unit) NBP(unit) i, value / ... i, value / ... i, value / ...
The API method requires Tc, Pc, and NBP. Tc, Pc and NBP may be overridden here for a specific method set. For a further description of these input parameters, see Chapter 9, Method-specific Pure Component Data.
Examples
3.24: Using the SRK system, model a 50/50 mix of propane and normal butane at 100 psia and 100 F. By choosing SYSTEM= SRK, API liquid densities are automatically invoked.
TITLE PROB=API, PROJ=THERMO COMPONENT DATA LIBID 1,C3/ 2,NC4 THERMO DATA METHOD SYSTEM=SRK STREAM DATA PROP STREAM=1, TEMP=100, PRES=100, COMP=50/50 UNIT OPERATION FLASH UID=D121 FEED 1 PROD V=2, L=3 TPSPEC PRES=50 SPEC STREAM=2, RATE, RATIO, STREAM=1, & RATE, VALUE=0.5 END
3.25:
For the same problem, specify SRK K-values, SRK enthalpies, SRK entropies, SRK vapor densities, and API liquid densities explicitly.
THERMO DATA METHOD KVALUE=SRK, ENTHALPY=SRK, & ENTROPY=SRK, DENSITY(V)=LK, & DENSITY(L)=API
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Rackett Liquid Density

Typical Usage
...
COMPONENT DATA LIBID 1, IC4/ 2, NC4/ 3, NC5 THERMO DATA METHOD SYSTEM=SRKM, DENSITY(L)=RACKETT STREAM DATA . . .
General Information
The RACKETT method calculates liquid densities. It is generally useful for refinery hydrocarbons as well as non-hydrocarbons. Refer to the PRO/II Reference Manual for additional limitations.
Table 3-10: Attributes of RACKETT Methods Properties predicted by RACKETT methods Liquid densities Required pure component properties1 Critical temperature Critical pressure Rackett parameter Critical compressibility factor
1 Automatically supplied for some library and petroleum components. Must be supplied by the user for non-library components.
Input Description
METHOD ..., DENSITY(L)=RACKETT, ...
DENSITY(L)

TC(unit) PC(unit) RACKETT ZC i, value /... i, value /... i, value /... i, value /...
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The RACKETT method requires Tc, Pc, the Rackett parameter, and the critical compressibility factor. Either RACKETT or Zc may be provided. If both are given, the Rackett parameter is used. Tc, Pc, RACKETT and Zc may be overridden here for a specific method set. For a further description of these input parameters, see Chapter 9, Method-specific Pure Component Data.
Examples
3.26: Using the SRK system and RACKETT liquid densities, model a 50/50 mix of propane and normal butane at 100 psia and 100 F. The DENSITY(L)=RACKETT overrides the default API liquid densities.
TITLE PROB=RACKETT, PROJ=THERMO DESC THERMO MANUAL PROBLEM PRINT INPUT=ALL COMPONENT DATA LIBID 1,C3/ 2,NC4 THERMO DATA METHOD SYSTEM=SRK, DENSITY(L)=RACKETT STREAM DATA PROP STREAM=1, TEMP=100, PRES=100, COMP=50/50 UNIT OPERATION FLASH UID=FL1 FEED 1 PROD V=2, L=3 TPSPEC PRES=50 SPEC STREAM=2, RATE, RATIO, STREAM=1, & RATE, VALUE=0.5 END
3.27:
For the same problem, specify SRK K-values, SRK enthalpies, entropies, Lee-Kesler vapor densities, and RACKETT liquid densities explicitly.
THERMO DATA METHOD KVALUE=SRK, ENTHALPY=SRK, & ENTROPY=SRK, DENSITY(V)=LK, & DENSITY(L)=RACKETT
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Costald Liquid Density

Typical Usage
...
COMPONENT DATA LIBID 1, IC4/ 2, NC4/ 3, NC5 THERMO DATA METHOD SYSTEM=SRKM, DENSITY(L)=COSTALD STREAM DATA . . .
General Information
The COSTALD method calculates liquid densities. It is generally useful for aromatics and other light refinery hydrocarbons up to reduced temperatures of 0.95. Refer to the PRO/II Reference Manual for additional limitations.
Table 3-11: Attributes of COSTALD Methods Properties predicted by COSTALD methods Liquid densities Required pure component properties1 Critical temperature Acentric factor
1
Critical volume
Automatically supplied for some library and petroleum components. Must be supplied by the user for non-library components.
Input Description
METHOD . ..., DENSITY(L)=COSTALD, ...
DENSITY(L)

TC(unit) ACENTRIC VC(unit) ... i, value / ... i, value / ... i, value / ...
The COSTALD method requires Tc, the acentric factor, and critical volumes. Tc and w may be overridden here for a specific method
II-3-30 Generalized Correlations
set. The parameter Vc is used by COSTALD as a characteristic volume, not a critical volume, and is retrieved (along with Tc and the acentric factor) from the COSTALD databank. Pure component critical volumes will however be used when the characteristic volume is not supplied or is missing from the COSTALD databank. For petroleum and assay components however, a characteristic volume is back calculated in order to provide a correct specific gravity for the pseudocomponent. For a further description of these input parameters, see Chapter 9, Method-specific Pure Component Data.
Examples
3.28: Using the SRK system, and COSTALD liquid densities, model a 50/50 mix of propane and normal butane at 100 psia and 100 F. The DENSITY(L)=COSTALD overrides the default (API) liquid densities.
TITLE PROB=COSTALD, PROJ=THERMO DESC THERMO MANUAL PROBLEM PRINT INPUT=ALL COMPONENT DATA LIBID 1,C3/ 2,NC4 THERMO DATA METHOD SYSTEM=SRK, DENSITY(L)=COSTALD STREAM DATA PROP STREAM=1, TEMP=100, PRES=100, COMP=50/50 UNIT OPERATION FLASH UID=FLSH FEED 1 PROD V=2, L=3 TPSPEC PRES=50 SPEC STREAM=2, RATE, RATIO, STREAM=1, & RATE, VALUE=0.5 END
3.29:
For the same problem, specify SRK K-values, SRK enthalpies, entropies, Lee-Kesler vapor densities, and COSTALD liquid densities explicitly.
THERMO DATA METHOD KVALUE=SRK, ENTHALPY=SRK, & ENTROPY=SRK, DENSITY(V)=LK, & DENSITY(L)=COSTALD
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User-supplied K-value Data

Typical Usage
...
COMPONENT DATA LIBID 1, IC4/ 2, NC4/ 3, NC5 THERMODYNAMIC DATA METHOD KVALUE=DATA KVALUE(VLE) KDATA TABU=50, 100, 150/ 1, 0.4, 0.6, 0.7/ & 2, 0.3, 0.4, 10.8/ 3, 0.5, 0.7, 0.9, PREF=50 or COMPONENT DATA LIBID 1,IC4/ 2,NC4/ 3,NC5 THERMODYNAMIC DATA METHOD KVALUE=DATA KVALUE(VLE) KDATA TABU=50, 100, 150/1, 0.4, 0.6, 0.7, PREF=50 STREAM DATA . . .
General Information
All K-value data supplied by the user may be chosen as the primary VLE or LLE K-value method by designating DATA as the K-value method on the METHOD statement. K-value data may also be used as a secondary K-value method, overriding some or all of the values generated by the principal K-value method. VLE or LLE K-value data may be supplied. However, if a VLLE method is selected, both LLE and VLE K-value data may be supplied. KDATA may be supplied in either tabular or correlation forms.
Table 3-12: Attributes of User-Supplied K-value Data Properties predicted by K-value Data K-values Required pure component properties None Two liquid phase behavior Free-water decant VLLE II-3-32 Not supported Supported Generalized Correlations
Input Description
METHOD KVALUE(VLE)=DATA, ... KVALUE(VLE)=DATA, KVALUE(LLE)=method, ... KVALUE(LLE)=DATA, SYSTEM(VLLE)=method, ... KVALUE(LLE)=DATA, KVALUE(VLE)=method, ...
or
METHOD
or
METHOD
or
METHOD
K-value Data (required)

KVALUE(VLE or LLE) KDATA CORR=icorr, LN or LOG or EXPFAC=ipos, PREF(punit)=value, DATA=i, tmax, tmin, c1, ...c8/ ...
or
KDATA TABU=t1, t2, .../ i, p1, p2, .../ ..., PREF(punit)=value
Note: If KVALUE(VLE)=DATA is used, all components of phase type VL or VLS must have KDATA information. Note: If KVALUE(LLE)=DATA is used, all component of phase type VL, VLS, or LS must have KDATA information.
KDATA This statement allows entry of K-value data in either tabular or correlation forms. CORR Selects the correlation form of the supplied Kvalue data. icorr is one of the 29 available correlation forms. See Volume I, Component Properties, for further details on data entry for thes equation-based correlations. Selects the tabular form of the supplied K-value data. See Volume I, Component Properties, for further details on data entry for tabular based data. Tabular data will interpolated using:
a ln ( K ) = --+b T
TABU
where a and b are constants, and T is Kelvin.
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PREF
This keyword is required and provides the reference pressure at which K-value data are being supplied. K-value data at any other pressure P will be calculated using the following equations: For VLE: For LLE:
PREF K ( P ) = K ( PREF ) -------------P K ( P ) = K ( PREF )
Note: Supplied KDATA will apply to VLE by default. If VLLE methods are used, both LLE or VLE KDATA may be supplied.
Examples
3.30: Using tabular data, predict the bubble point temperature at 50 psia for an equal molar mixture of propane, n-butane and n-pentane. The K-value data to be entered are as follows:
50F 2.2492 0.58776 0.16308 100F 2.08300 0.68216 0.23487 150F 1.9088 0.76869 0.32252
Temperature propane n-butane n-pentane
TITLE PROB=KDATA BP COMPONENT DATA LIBID 1, C3/2, NC4 /3, NC5 THERMODYNAMIC DATA METHOD SYST=DATA, ENTH=PR, DENS(V)=PR, DENS(L)=API KVALUE KDATA TABU= 50, 100, 150 / & 1, 2.2492, 2.08300, 1.9088 / & 2, 0.58776,0.68216, 0.76869 / & 3, 0.16308, 0.23487, 0.32252, PREF=50 STREAM DATA PROP STREAM=1, TEMP=90, PRES=50, COMP=50/50/50 UNIT OPERATIONS FLASH UID=1 FEED 1 PROD L=2 BUBB PRES=50 END
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3.31:
Using the SRKM method for VLE K-values, supply VLE K-values for H2O in a 50/40/10 mixture of propane, nbutane, and water at 100 F and 100 psia.
TITLE PROB=KDATA, PROJ=THERMO DESC THERMO MANUAL PROBLEM PRINT INPUT=ALL COMPONENT DATA LIBID 1,C3/ 2,NC4/ 3,H20 THERMO DATA METHOD SYSTEM=SRKM KVALUE KDATA TABU=50,100,150,6.0387,10.822,18.773, PREF=100 STREAM DATA PROP STREAM=1, TEMP=100, PRES=100, COMP=50/40/10 UNIT OPERATION FLASH UID=FD23 FEED 1 PROD V=2, L=3 TPSPEC PRES=75 SPEC STREAM=2, RATE, RATIO, STREAM=1, & RATE, VALUE=0.5 END
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II-3-36
Chapter 4 Equations of State

Historically, equations of state have been successfully applied to petroleum and refining hydrocarbon systems and light gases. Recent advances in mixing rules and alpha forms have extended their applicability to many non-ideal systems.
Soave Modified Redlich-Kwong

Typical Usage
...
COMPONENT DATA LIBID 1,IC4/ 2,NC4/ 3,NC5 THERMO DATA METHOD SYSTEM=SRK STREAM DATA . . .
General Information
The Soave modified Redlich-Kwong equation of state predicts Kvalues, enthalpies, entropies, and vapor densities. It is most often used in gas and refining processes. Without significant modification, it is generally not useful for highly non-ideal systems. Liquid densities and VLLE behavior can be predicted with the SRK equation of state, but are not recommended without using an advanced form (seeModified Soave-Redlich-Kwong and Peng-Robinson on page 4-13).
II-4-1
Table 4-1: Attributes of the Soave-Redlich-Kwong Equation of State Properties predicted by SRK K-values Enthalpies Entropies Vapor densities Liquid densities (not recommended)
Required pure component properties1 Molecular weight Critical temperature Critical pressure Pressure Temperature Free-water decant VLLE
1
Acentric factor Ideal vapor enthalpy
Suggested application ranges 0 to 5000 psia -460 to 1200 F Supported Not recommended
Automatically supplied for library and petroleum components. Must be supplied by the user for nonlibrary components.
Input Description
METHOD or METHOD SYSTEM=SRK, ... KVALUE=SRK, ENTHALPY=SRK, ENTROPY=SRK, DENSITY(V)=SRK, DENSITY(L)=API,...
Note: DENSITY(L)=SRK is supported but not recommended. KVALUE(VLLE)=SRK is supported but not recommended. SYSTEM Selects a combination of consistent thermodynamic property generators. When SYSTEM=SRK is chosen, SRK K-values, SRK enthalpies, SRK entropies, API liquid densities, and SRK vapor densities are assumed. Selects the method for K-value calculations. Only VLE K-value calculations are recommended with the SRK method. Selects the method for enthalpy calculation. By default, both vapor and liquid enthalpies use this method. Equations of State
KVALUE
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ENTROPY (VL or V and/or L) DENSITY (V)
Selects the method for entropy calculation. By default, both vapor and liquid entropies use this method. Selects the method for vapor density.
Note: If DENSITY=SRK without the V qualifier is used, liquid
density will also be calculated from the SRK equation of state. This method is not recommended for this purpose. K-value Data (optional)
KVALUE BANK=PROCESS or SIMSCI or NONE or bankid, FILL=NONE or GAO or GOR or CPHC, ALPHA=ACENTRIC or SIMSCI or bankid SRK(K or R) i, j, kija, kijb, kijc/ ... SA01to SA11 i, c1, c2, c3/ ...
Note: The SRK and SAxx statements must follow the KVALUE
statement.
BAN K This option selects one or more banks from which to retrieve vapor and/or liquid phase binary interaction data. PROCESS SIMSCI NONE bankid Selects the SimSci PROCESS databank. Selects the SimSci standard databank (default). This option disables all data retrieval from databanks for interaction parameters. This option selects the user-created databank named bankid that is created and maintained by the LIBMGR program.
FILL
Selects the method used for estimating values for hydrocarbon/hydrocarbon binary interaction data missing from the input file and any selected databank libraries. This option is not valid for all modified equations of state. See Filling in Missing Parameters on page 4-27 for further information on the methods given below. NONE GOR This option disables estimation of any missing binary interaction data(default). This option estimates binary interaction parameters between methane and ethane and heavier hydrocarbons. This option estimates binary interaction parameters between methane through propane and heavier hydrocarbons.
GAO
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CPHC ALPHA
This option estimates binary interaction parameters for all hydrocarbon pairs.
This option allows access to the databank for alpha formulations. ACENTRIC Uses the original Soave acentric form for alpha (default). SIMSCI bankid Selects the SimSci alpha form and values supplied from the SIMSCI databank. This option selects the user-created databank named bankid that is created and maintained by the LIBMGR program.
SRK
This statement allows entry of the binary interaction parameters (kijs) for the SRK equation of state. Entries correspond to the following temperature-dependent correlation: kij = kija + kijb/T + kijc/T2 Temperature units may be K (default) or R.
SA01 to SA11
These entries permit various formulations of the pure component Alpha correlations. See Cubic Equation Of State Alpha Formulations on page 4-29, for further details.
Enthalpy, Entropy, and Density Data (optional)

ENTHALPY BANK=PROCESS or SIMSCI or NONE or bankid, ALPHA=ACENTRIC or SIMSCI or bankid ENTROPY BANK=PROCESS or SIMSCI or NONE or bankid, ALPHA=ACENTRIC or SIMSCI or bankid BANK=PROCESS or SIMSCI or NONE or bankid, ALPHA=ACENTRIC or SIMSCI or bankid i, j, kija, kijb, kijc/ ... i, c1, c2, c3/ ...
DENSITY
SRK(K or R) SA01to SA11
SRK interaction parameters and alpha formulations may be provided for enthalpy, entropy, and density methods. Normally, these data are provided for the K-value method and are automatically carried over for other properties using the same method, i.e., SRK. If, however, the K-value method is not SRK, you can supply the interaction parameters and/or alpha formulations independently.
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Equations of State
See above under K-value Data for format and definition of these entries. Water Handling Options (optional)
The SRK K-value generator supports the free-water decant option. Refer to Free-water Decant Considerations on page 1-34 for a description of these input options. Method-specific Pure Component Properties (optional)
Examples
4.1: Using the SRK method with default interaction parameters and using acentric factors for alpha formulation, calculate the temperature of a 50/50 mix of propane and normal butane at 50 psia and 50% vaporization.
TITLE PROB=SRK, PROJ=THERMO DESC THERMO MANUAL PROBLEM PRINT INPUT=ALL COMPONENT DATA LIBID 1,C3/ 2,NC4 THERMODYNAMIC DATA METHOD SYSTEM=SRK STREAM DATA PROP STREAM=1, TEMP=100, PRES=100, COMP=50/50 UNIT OPERATION FLASH UID=FLSH FEED 1 PROD V=2, L=3 TPSPEC PRES=50 SPEC STREAM=2, RATE, RATIO, STREAM=1, & RATE, VALUE=0.5 END
II-4-5
4.2:
For the same problem, explicitly specify SRK K-values, enthalpies, entropies, and vapor densities. Specify API liquid densities.
THERMODYNAMIC DATA METHOD KVALUE=SRK, ENTHALPY=SRK, ENTROPY=SRK,& DENSITY(V)=SRK, DENSITY(L)=API
4.3:
Use the SOUR thermo methods but apply SRK to vapor density.
THERMODYNAMIC DATA METHOD SYSTEM=SOUR, DENSITY(V)=SRK
4.4:
Supply SRK kij binaries for components 1-2 and 2-3. Note that unless binary 1-3 is available in the databank, the kij will have a value of 0.0. Note that the SRK statement must follow the KVALUE statement even though there are no additional entries on the KVALUE statement.
THERMODYNAMIC DATA METHOD SYSTEM=SRK KVALUE SRK 1,2,0.01/ 2,3,0.025...
4.5:
For the previous example, also supply parameters for the Twu-Bluck-Cunningham alpha formulation for components 1 and 3. See Cubic Equation Of State Alpha Formulations on page 4-29.
THERMODYNAMIC DATA METHOD SYSTEM=SRK KVALUE SRK 1,2,0.01/ 1,3,0.025 SA06 1,0.75,0.93,1.6/ 3,0.61,0.81,2.1
4.6:
For the previous example, use alpha parameters from the PROCESS instead of the default SIMSCI databank for entropy calculations. Also, supply parameters for the Twu alpha formulation for entropy calculations for components 1 and 3.
TITLE PROB=SRK, PROJ=THERMO COMPONENT DATA LIBID 1,C3/ 2,NC4/ 3,H2O/ 4,NH3/ 5,CO2 THERMO DATA METHOD SYSTEM=SRK
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Equations of State
KVALUE SRK 1,2,0.01/ 1,3,0.025 SA06 1,0.75,0.93,1.6/ 3,0.61,0.81,2.1 ENTROPY BANK=SIMSCI, ALPHA=SIMSCI SA05 1,0.7,0.85/ 3,0.6,0.71 STREAM DATA PROP STREAM=1, TEMP=100, PRES=100, COMP=50/50/2/2/2 UNIT OPERATION FLASH UID=F1 FEED 1 PROD V=2, L=3 TPSPEC PRES=50 SPEC STREAM=2, RATE, RATIO, STREAM=1, & RATE, VALUE=0.5 END
Peng-Robinson
Typical Usage
...
COMPONENT DATA LIBID 1,IC4/ 2,NC4/ 3,NC5 THERMODYNAMIC DATA METHOD SYSTEM=PR STREAM DATA . . .
General Information
The Peng-Robinson (PR) equation of state predicts K-values, enthalpies, entropies, and vapor densities. It is most often used for gas and refining processes. Without significant modification, it is generally not useful for highly non-ideal systems. Liquid densities and VLLE behavior predictions are not recommended without using an advanced form of the PR equation of state (see Modified Soave-Redlich-Kwong and Peng-Robinson on page 4-13).
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Table 4-2: Attributes of the PR Equation of State Properties predicted by PR K-values Enthalpies Entropies Vapor densities Liquid densities (not recommended)
Required pure component properties1 Molecular weight Critical pressure Critical temperature Pressure Temperature Free-water decant VLLE
1
Ideal vapor enthalpy Acentric factor
Suggested application ranges 0 to 5000 psia -460 to 1200 F Supported Not recommended
Input Description
METHOD or METHOD SYSTEM=PR, .. KVALUE=PR, ENTHALPY=PR, ENTROPY=PR, DENSITY(V)=PR, DENSITY(L)=API,...
Note: DENSITY(L)=PR is supported but not recommended.
KVALUE(VLLE)=PR is supported but not recommended.

SYSTEM Selects a combination of consistent thermodynamic property generators. When SYSTEM=PR is chosen, PR K-values, PR enthalpies, PR entropies, API liquid densities, and SRK vapor densities are assumed. Selects the method for K-value calculations. VLE and VLLE are both supported, but only VLE Kvalue calculations are recommended with the PR method.
KVALUE
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Equations of State
ENTHALPY (VL or V and/or L) ENTROPY (VL or V and/or L) DENSITY (V)
Selects the method for enthalpy calculation. By default, both vapor and liquid enthalpies use this method. Selects the method for entropy calculation. By default, both vapor and liquid entropies use this method. Selects the method for vapor density.
Note: If DENSITY=PR without the V qualifier is used, liquid density will also be calculated from the PR equation of state. This method is not recommended for this purpose.
K-value Data (optional)

KVALUE BANK=PROCESS or SIMSCI or NONE or bankid, FILL=NONE or GOR or GAO or CPHC ALPHA=ACENTRIC or SIMSCI or bankid i, j, kija, kijb, kijc/ ... i, c1, c2, c3/ ...
PR(K or R) PA01to PA11
Note: The PR and PAxx statements must follow the KVALUE
statement.
BAN K This option selects one or more banks from which to retrieve vapor and/or liquid phase binary interaction data. PROCESS SIMSCI NONE bankid Selects the SimSci PROCESS databank. Selects the SimSci standard databank (default). This option disables all data retrieval from databanks for interaction parameters. This option selects the user-created databank named bankid that is created and maintained by the LIBMGR program.
FILL
Selects the method used for estimating values for hydrocarbon/hydrocarbon binary interaction data missing from the input file and any selected databank libraries. This option is not valid for all modified equations of state. See Filling in Missing Parameters on page 4-27 for further information on the methods given below. NONE This option disables estimation of any missing binary interaction data(default).
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GOR
This option estimates binary interaction parameters between methane and ethane and heavier hydrocarbons. This option estimates binary interaction parameters between methane through propane and heavier hydrocarbons. This option estimates binary interaction parameters for all hydrocarbon pairs.
GAO
CPHC ALPHA
This option allows access to the databank for alpha formulations. ACENTRI C SIMSCI bankid Uses the original Soave acentric form for alpha (default). Selects the SimSci alpha form and values supplied from the SIMSCI databank. This option selects the user-created databank named bankid that is created and maintained by the LIBMGR program.
PR
This statement allows entry of the binary interaction parameters (kijs) for the PR equation of state. Entries correspond to the following temperature-dependent correlation: kij = kija + kijb/T + kijc/T2 Temperature units may be K (default) or R.
PA01 to PA11 These entries permit various formulations of the pure component Alpha correlations. See Cubic Equation Of State Alpha Formulations on page 4-29, for further details.

ENTHALPY BANK=PROCESS or SIMSCI or NONE or bankid, ALPHA=ACENTRIC or SIMSCI or bankid ENTROPY BANK=PROCESS or SIMSCI or NONE or bankid, ALPHA=ACENTRIC or SIMSCI or bankid DENSITY BANK=PROCESS or SIMSCI or NONE or bankid, ALPHA=ACENTRIC or SIMSCI or bankid PR(K or R) i, j, kija, kijb, kijc/ ... PA01to PA11 i, c1, c2, c3/ ...
PR interaction parameters and alpha formulations may be selected for enthalpy, entropy, and density methods. Normally, these features are selected for the K-value method and are automatically carried
II-4-10 Equations of State
over for these other methods. If, however, the K-value method is not SRK, you can supply the interaction parameters and/or alpha formulations independently. See above under K-value Data for format and definition of these entries. Water Handling Options (optional)
The PR K-value generator supports the free-water decant option. Refer to Free-water Decant Considerations on page 1-34 for a description of these input options. Method-specific Pure Component Properties (optional)
Examples
4.7: Using the PR method with default interaction parameters and using acentric factors for alpha formulation, calculate the temperature of a 50/50 mix of propane and normal butane at 50 psia and 50% vaporization.
TITLE PROB=PR, PROJ=THERMO DESC THERMO MANUAL PROBLEM PRINT INPUT=ALL COMPONENT DATA LIBID 1,C3/ 2,NC4 THERMODYNAMIC DATA METHOD SYSTEM=PR STREAM DATA PROP STREAM=1, TEMP=100, PRES=100, COMP=50/50 UNIT OPERATION FLASH UID=F203 FEED 1 PROD V=2, L=3 TPSPEC PRES=50 SPEC STREAM=2, RATE, RATIO, STREAM=1, &
II-4-11
RATE, VALUE=0.5 END
4.8:
For the same problem, explicitly specify PR K-values, enthalpies, entropies, and vapor densities. Specify API liquid densities.
THERMODYNAMIC DATA METHOD KVALUE=PR, ENTHALPY=PR, ENTROPY=PR,& DENSITY(V)=PR, DENSITY(L)=API...
4.9:
Use the SOUR thermo methods but apply PR to vapor density.

THERMODYNAMIC DATA METHOD SYSTEM=SOUR, DENSITY(V)=PR
4.10:
Supply PR kij binaries for components 1-2 and 2-3. Note that unless binary 1-3 is available in the databank, the kij will have a value of 0.0. Note that the PR statement must follow the KVALUE statement even though there are no additional entries on the KVALUE statement.
THERMODYNAMIC DATA METHOD SYSTEM=PR KVALUE PR 1, 2, 0.01/ 2, 3, 0.025
4.11:
THERMODYNAMIC DATA METHOD SYSTEM=PR KVALUE PR 1, 2, 0.01/ 2, 3, 0.025 PA06 1, 0.75, 0.93, 1.6/ 3, 0.61, 0.81, 2.1
4.12:
For the previous example, use binary parameters from the PROCESS databank instead of the default SIMSCI databank for entropy calculations. Also, supply parameters for the Twu alpha formulation for entropy calculations for components 1 and 3.
II-4-12
Equations of State
TITLE PROB=PR, PROJ=THERMO DESC THERMO MANUAL PROBLEM PRINT INPUT=ALL COMPONENT DATA LIBID 1,C3/ 2,NC4/ 3,H2O/ 4,NH3/ 5,CO2 THERMO DATA METHOD SYSTEM=PR KVALUE PR 1, 2, 0.01/ 1, 3, 0.025 PA06 1, 0.75, 0.93, 1.6/ 3, 0.61, 0.81, 2.1 ENTROPY BANK=SIMSCI, ALPHA=SIMSCI PA05 1, 0.7, 0.85/ 3, 0.6, 0.71 STREAM DATA PROP STREAM=1, TEMP=100, PRES=100, COMP=50/50/2/2/2 UNIT OPERATION FLASH UID=F209 FEED 1 PROD V=2, L=3 TPSPEC PRES=50 SPEC STREAM=2, RATE, RATIO, STREAM=1, & RATE, VALUE=0.5 END
Modified Soave-Redlich-Kwong and Peng-Robinson

Typical Usage
...
COMPONENT DATA LIBID 1,IC4/ 2,NC4/ 3,NC5 THERMO DATA METHOD SYSTEM=SRKM STREAM DATA . . .
General Information
The modified SRK and PR equations of state predict K-values, enthalpies, entropies, and vapor densities. They are most often used in gas and refining processes and are generally useful for non-ideal systems. VLLE behavior can be predicted with the modified SRK and PR equations of state. Liquid densities can also be predicted but are not recommended.
II-4-13
Table 4-3: Attributes of the Modified SRK and PR Equations of State Properties predicted by Modified SRK and PR Equations K-values Entropies Enthalpies Vapor densities Liquid densities (not recommended)
Required pure component properties1 Molecular weight Critical temperature Critical pressure Ideal vapor enthalpy Acentric factor (needed only if ACENTRIC alpha formulation is selected) 0 to 5000 psia -460 to 1200 F Not supported Supported
Suggested application ranges Pressure Temperature Free-water decant VLLE

1
Input Description
The METHOD Statement Modified Panagiotopoulos-Reid modifications to SRK
METHOD SYSTEM(VLE or VLLE)=SRKM, ... or METHOD KVALUE(VLE and/or LLE or VLLE)=SRKM, ENTHALPY=SRKM, ENTROPY=SRKM, DENSITY(V)=SRKM, DENSITY(L)=API, ...
Note: DENSITY(L)=SRKM is supported but not recommended.
Huron-Vidal modifications to SRK

METHOD SYSTEM(VLE or VLLE)=SRKH, ... or METHOD KVALUE(VLE and/or LLE or VLLE)=SRKH, ENTHALPY=SRKH, ENTROPY=SRKH, DENSITY(V)=SRKH, DENSITY(L)=API, ...
Note: DENSITY(L)=SRKH is supported but not recommended. II-4-14 Equations of State
SimSci modifications to SRK

METHOD or METHOD SYSTEM(VLE or VLLE)=SRKS, ... KVALUE(VLE and/or LLE or VLLE)=SRKS, ENTHALPY=SRKS, ENTROPY=SRKS, DENSITY(V)=SRKS, DENSITY(L)=API, ...
Note: DENSITY(L)=SRKS is supported but not recommended.
Panagiotopoulos-Reid modifications to SRK

METHOD or METHOD SYSTEM(VLE or VLLE)=SRKP, ... KVALUE(VLE and/or LLE or VLLE)=SRKP, ENTHALPY=SRKP, ENTROPY=SRKP, DENSITY(V)=SRKP, DENSITY(L)=API, ...
Note: DENSITY(L)=SRKP is supported but not recommended.
Kabadi-Danner modifications to SRK

METHOD or METHOD SYSTEM(VLE or VLLE)=SRKKD, ... KVALUE(VLE and/or LLE or VLLE)=SRKKD, ENTHALPY=SRKKD, ENTROPY=SRKKD, DENSITY(V)=SRKKD, DENSITY(L)=API, ...
Note: DENSITY(L)=SRKKD is supported but not recommended.
Modified Panagiotopoulos-Reid modifications to PR

METHOD or METHOD SYSTEM(VLE or VLLE)=PRM, ... KVALUE(VLE and/or LLE or VLLE)=PRM, ENTHALPY=PRM, ENTROPY=PRM, DENSITY(V)=PRM, DENSITY(L)=API, ...
Note: DENSITY(L)=PRM is supported but not recommended.
Huron-Vidal modifications to PR
METHOD or METHOD SYSTEM(VLE or VLLE)=PRH, ... KVALUE(VLE and/or LLE or VLLE)=PRH, ENTHALPY=PRH, ENTROPY=PRH, DENSITY(V)=PRH, DENSITY(L)=API, ...
Note: DENSITY(L)=PRH is supported but not recommended.
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Panagiotopoulos-Reid modifications to PR
METHOD or METHOD SYSTEM(VLE or VLLE)=PRP, ... KVALUE(VLE and/or LLE or VLLE)=PRP, ENTHALPY=PRP, ENTROPY=PRP, DENSITY(V)=PRP, DENSITY(L)=API, ...
Note: DENSITY(L)=PRP is supported but not recommended. SYSTEM Selects a combination of consistent thermodynamic property generators. When SYSTEM=SRKM (or SRKS or SRKH or SRKP or SRKKD or PRM or PRH or PRP) is chosen, SRKM (or SRKS or SRKH or SRKP or SRKKD or PRM or PRH or PRP) K-values, enthalpies, entropies, vapor densities, and API liquid densities are assumed. Selects the method for K-value calculations. Both VLE and LLE K-value calculations are available with the modified SRK and PR methods. The VLLE option automatically selects both.SRKM (or PRM) selects the modified PanagiotopoulosReid SRK (or PR) method, SRKS selects the SimSci modified SRK method, SRH (or PRH) selects the Huron-Vidal modified SRK (or PR) method, SRP (or PRP) selects the Panagiotopoulos-Reid modified SRK (or PR), and SRKKD selects the Kabadi-Danner modified SRK.
KVALUE

KVALUE(VLE or LLE or VLLE) BANK=SIMSCI or NONE or bankid, FILL=NONE or GOR or GAO or CPHC ALPHA=SIMSCI or ACENTRIC or bankid SRKM or PRM(K or R) or SRKS(K or R) or SRKH or PRH(K or KCAL or KJ) i, j, aij, bij, cij, aji, bji, cji, ij, ij/ ... or SRKP or PRP(K or R) or SRKKD(K or R) i, j, kija, kijb, kijc/ ... i, j, kija, kjia, kijb, kjib, kijc, kjic/... i, j, kija, kjia, kijb, kjib, kijc, kjic, cij, cji /... i, j, kija, kjia, kijb, kjib, kijc, kjic, cij, cji /...
II-4-16
Equations of State
SA01 to SA11 or PA01 to PA11
i, c1, c2, c3/ ...
Note: If used for calculating K-values, the SRKM or PRM or
SRKH or PRH or SRKP or PRP or SRKKD or SRKS and SAxx or PAxx statements must follow the KVALUE statement.
BAN K This option selects one or more databanks from which to retrieve vapor and/or liquid phase binary interaction data. SIMSCI NONE bankid Selects the SimSci standard databank (default). This option disables all data retrieval from databanks for interaction parameters. This option selects the user-created databank named bankid that is created and maintained by the LIBMGR program.
The SRKM and SRKS databanks are the only databanks that contain extensive binary interaction parameter data. The databanks for the advanced PR equations of state are especially limited in the binary interaction data they contain. Providing binary interaction parameters regressed from experimental data is highly recommended when using advanced SRK and PR equations of state for non-ideal components. FILL Selects the method used for estimating values for hydrocarbon/hydrocarbon binary interaction data missing from the input file and any selected databank libraries. This option is not valid for all modified equations of state. See Filling in Missing Parameters on page 4-27 for further information on the methods given below. NONE GOR This option disables estimation of any missing binary interaction data(default). This option estimates binary interaction parameters between methane and ethane and heavier hydrocarbons. This option estimates binary interaction parameters between methane through propane and heavier hydrocarbons. This option estimates binary interaction parameters for all hydrocarbon pairs.
GAO
CPHC ALPHA
This option allows access to the databank for alpha formulations. II-4-17
SIMSCI
Selects the SimSci alpha form and values supplied from the SIMSCI databank (default). Uses the original Soave acentric form for alpha (default). This option selects the user-created databank named bankid that is created and maintained by the LIBMGR program.
ACENTRI C bankid
SRKM or PRM
This statement allows entry of the binary interaction parameters (kijs) for the SRKM or PRM equation of state.Entries correspond to the following temperature dependent correlation:
kij = kija + kijb / T + kijc / T2

Temperature units may be K (default) or R. The cij's are additional non-ideal interactions. SRKS This statement allows entry of the binary interaction parameters (kijs) for the SRKS equation of state. Entries correspond to the following temperature dependent correlation:
kij = kija + kijb / T + kijc / T 2

Temperature units may be K (default) or R. The cij's are additional non-ideal interactions. SRKH or PRH This statement allows entry of the binary interaction parameters (kijs) for the SRKH or PRH equation of state. Entries correspond to the following temperature dependent correlation:
kij = aij + bijl / T + kijl / T2

Temperature units may be K (default) or KCAL or KJ. ij and ij are two-parameter interactions. SRKP or PRP This statement allows entry of the binary interaction parameters (kijs) for the SRKP or PRP equation of state. Entries correspond to the following temperature dependent correlation:
kij = kija + kijb / T + kijc / T2

Temperature units may be K (default) or R. SRKKD This statement allows entry of the binary interaction parameters (kijs) for the SRKKD equation of state. Entries correspond to the following temperature dependent correlation:
II-4-18
Equations of State
kij = kija + kijb / T + kijc /T 2

Temperature units may be K (default) or R. SA01 to SA11 These entries permit various formulations of the pure PA01 to PA11 component Alpha correlations. See Cubic Equation Of State Alpha Formulations on page 4-29 for further details.

ENTHALPY BANK=SIMSCI or NONE or bankid, ALPHA=SIMSCI or ACENTRIC or bankid ENTROPY BANK=SIMSCI or NONE or bankid, ALPHA=SIMSCI or ACENTRIC or bankid BANK=SIMSCI or NONE or bankid, ALPHA=SIMSCI or ACENTRIC or bankid i, j, kija, kjia, kijb, kjib, kijc, kjic, cij, cji /... i, j, kija, kjia, kijb, kjib, kijc, kjic, cij, cji /...
DENSITY
SRKM or PRM(K or R) or SRKS(K or R) or
SRKH or PRH(K or KCAL or KJ) i, j, aij, bij, cij, aji, bji, cji, ij, ij/ ... or SRKP or PRP(K or R) or SRKKD(K or R) i, j, kija, kijb, kijc/ ... i, c1, c2, c3/ ... i, j, kija, kjia, kijb, kjib, kijc, kjic/...
SA01 to SA11 or PA01 to PA11
All these interaction parameters and alpha formulations may be selected for enthalpy, entropy, and density methods. Normally, these features are selected for the K-value method and are automatically carried over for these other methods. If, however, the K-value method is not any of the modified SRK or PR methods, you can supply the interaction parameters and/or alpha formulations independently. See above under K-value Data for format and definition of these entries. Method-specific Pure Component Properties (optional)
II-4-19
Examples
4.13: Using the SRKM method with default interaction parameters, model a 50/40/10 mix of propane, normal butane, and water at 50 psia and 50% vaporization.
TITLE PROB=SRKM COMPONENT DATA LIBID 1,C3/ 2,NC4/ 3,H2O THERMODYNAMIC DATA METHOD SYSTEM(VLLE)=SRKM STREAM DATA PROP STREAM=1, TEMP=100, PRES=100, COMP=1,50/ 2,40/ 3,10 UNIT OPERATION FLASH UID=FL2 FEED 1 PROD V=2, L=3 TPSPEC PRES=50 SPEC STREAM=2, RATE, RATIO, STREAM=1, & RATE,VALUE=0.5 END
4.14:
For the same problem, explicitly specify SRKKD Kvalues, enthalpies, entropies, and vapor densities. Specify API liquid densities.
THERMODYNAMIC DATA METHOD KVALUE(VLLE)=SRKKD, ENTHALPY=SRKKD, & ENTROPY=SRKKD, DENSITY(V)=SRKKD, & DENSITY(L)=API
4.15:
Use the SOUR thermo methods but apply PRM to vapor density.
THERMODYNAMIC DATA METHOD SYSTEM=SOUR, DENSITY(V)=PRM...
4.16:
Supply SRKM kij binaries for components 1-2 and 2-3. Note that unless binary 1-3 is available in the databank, the kij will have a value of 0.0. Note that the SRKM statement must follow the KVALUE statement even though there are no additional entries on the KVALUE statement.
Equations of State
II-4-20
THERMODYNAMIC DATA METHOD SYSTEM=SRKM KVALUE SRKM 1, 2, 0.01, -0.02/ 2, 3, 0.025, 0.04
4.17:
THERMODYNAMIC DATA METHOD SYSTEM=SRKM KVALUE SRKM 1,2,0.01,-0.02/2,3,0.025,0.04 SA06 1,0.75,0.93,1.6/3,0.61,0.81,2.1...
4.18:
For the previous example, supply binary interaction parameters for component pairs 1-2 and 1-3. Disable all entropy binary interaction data except those input directly. Also, supply Twu alpha parameters for entropy calculations for components 1 and 3, and use the acentric databank to supply values for component 2.
TITLE PROB=SRKM PRINT INPUT=ALL COMPONENT DATA LIBID 1,C3/ 2,NC4/ 3,H2O THERMODYNAMIC DATA METHOD SYSTEM=SRKM $,ENTROPY=SRKH KVALUE SRKM 1,2,0.01/2,3,0.025 SA06 1,0.75,0.93,1.6/3,0.61,0.81,2.1 ENTROPY BANK=NONE, ALPHA=ACENTRIC $ SRKH(KJ) 1,2,0.06/1,3,0.10 $ SA05 1,0.7,0.85/3,0.6,0.71 STREAM DATA PROP STREAM=1, TEMP=100, PRES=100, COMP=1,50/ 2,40/ 3,10 UNIT OPERATION FLASH UID=F101 FEED 1 PROD V=2, L=3 TPSPEC PRES=50 SPEC STREAM=2, RATE, RATIO, STREAM=1, & RATE, VALUE=0.5 END
II-4-21
4.19:
For the previous example, compare the results obtained from using rigorous VLLE calculations with those obtained from using the water decant option. Take all the defaults for the water handling option. Both thermodynamic systems will be tried in the same run by assigning different thermodynamic sets.
TITLE PROB=SRKM PRINT INPUT=ALL COMPONENT DATA LIBID 1,C3/ 2,NC4/ 3,H2O THERMODYNAMIC DATA METHOD SYSTEM(VLLE)=SRKM, SET=RIGOROUS KVALUE SRKM 1,2,0.01 SA06 1,0.75,0.93,1.6/3,0.61,0.81,2.1 ENTROPY BANK=NONE, ALPHA=ACENTRIC METHOD SYSTEM=SRK, SET=DECANTING KVALUE SRK 1,2,0.01 SA06 1,0.75,0.93,1.6/3,0.61,0.81,2.1 ENTROPY BANK=NONE, ALPHA=ACENTRIC WATER DECANT=ON STREAM DATA PROP STREAM=1, TEMP=100, PRES=100, COMP=1,50/ 2,40/ 3,10 UNIT OPERATION FLASH UID=RIG FEED 1 PROD V=2R, L=3R, W=4R TPSPEC PRES=100 $,TEMP=100 SPEC STREAM=2R, RATE, RATIO, STREAM=1, & RATE, VALUE=0.5 METHOD SET=RIGOROUS FLASH UID=DEC FEED 1 PROD V=2D, L=3D, W=4D TPSPEC PRES=100 $,TEMP=100 SPEC STREAM=2D, RATE, RATIO, STREAM=1, & RATE, VALUE=0.5 METHOD SET=DECANTING END
II-4-22
Equations of State
UNIWAALS
Typical Usage
...
COMPONENT DATA LIBID 1,IC4/ 2,NC4/ 3,NC5 THERMODYNAMIC DATA METHOD SYSTEM=UNIWAAL STREAM DATA . . .
General Information
The UNIWAALS equation of state predicts K-values, enthalpies, entropies, and vapor and liquid densities. It is most often useful for highly non-ideal systems if group contribution parameters are supplied either from the built-in databanks or by the user. VLLE behavior can also be predicted with the UNIWAALS equation of state.
Table 4-4: Attributes of the UNIWAALS Equation of State Properties predicted by UNIWAALS K-values Enthalpies Entropies Vapor densities Liquid densities
Required pure component properties1 Molecular weight Critical temperature Critical pressure Low to mid temperatures Two liquid phase behavior Free-water decant VLLE
1
Suggested application ranges
Not supported Supported
II-4-23
Input Description
METHOD or METHOD SYSTEM(VLE or VLLE)=UNIWAAL, ... KVALUE(VLE and/or LLE or VLLE)=UNIWAAL, ENTHALPY=UNIWAAL, ENTROPY=UNIWAAL, DENSITY(V)=UNIWAAL, DENSITY(L)=API, ...
Note: DENSITY(L)=UNIWAAL is also supported, but is not rec-
ommended.
SYSTEM Selects a combination of consistent thermodynamic property generators. When SYSTEM=UNIWAAL is chosen, UNIWAAL Kvalues, enthalpies, entropies, and API liquid densities are assumed. Selects the method for K-value calculations. Both VLE and LLE K-value calculations are available with the UNIWAAL method. The VLLE option automatically selects both.
KVALUE

KVALUE(VLE and/or LLE or VLLE) BANK=SIMSCI or NONE or bankid, ALPHA=SIMSCI or ACENTRIC or bankid UFT1(K) m, k, amk, akm, bmk, bkm, cmk, ckm/ ... UNIFAC(K or KCAL or KJ) VA01 to VA11 m, k, Amk, Akm/... i, c1, c2, c3/ ...
Note: The UFT1, UNIFAC and VAxx statements must follow the KVALUE statement. BAN K This option selects one or more banks from which to retrieve vapor and/or liquid phase binary group contribution data. SIMSCI NONE bankid Selects the SimSci standard databank (default). This option disables all data retrieval from databanks for interaction parameters. This option selects the user-created databank named bankid that is created and maintained by the LIBMGR program.
II-4-24
Equations of State
ALPHA
This option allows access to the databank for alpha formulations. SIMSCI Selects the SimSci alpha form and values supplied from the SIMSCI databank (default). Uses the original Soave acentric form for alpha. This option selects the user-created databank named bankid that is created and maintained by the LIBMGR program.
ACENTRI C bankid
UFT1 and/or UNIFAC
This statement allows entry of the temperature dependent Lyngby modification of the UNIFAC method (UFT1) and non-temperature dependent UNIFAC group contribution data for groups m and k for the UNIWAAL equation of state. UFT1 entries correspond to the following temperature dependent correlation:
Amk = amk + bmk(T-To) + cmk(T ln{To / T} + T - To)

For UNIFAC, units may be K (default) or KCAL or KJ. VA01 to VA11 These entries permit various formulations of the pure component Alpha correlations. See Cubic Equation Of State Alpha Formulations on page 4-29 for further details.

ENTHALPY BANK=SIMSCI or NONE or bankid, ALPHA=SIMSCI or ACENTRIC or bankid BANK=SIMSCI or NONE or bankid, ALPHA=SIMSCI or ACENTRIC or bankid BANK=SIMSCI or NONE or bankid, ALPHA=SIMSCI or ACENTRIC or bankid m, k, amk, akm, bmk, bkm, cmk, ckm/ ... m, k, Amk, Akm/... i, c1, c2, c3/ ...
ENTROPY DENSITY
UFT1(K) UNIFAC(K or KCAL or KJ) VA01 to VA11
UNIWAALS UFT1 and UNIFAC binary group contribution data and alpha formulations VA01-VA11 may be selected for enthalpy, entropy, and density methods. Normally, these features are selected for the K-value method and are automatically carried over for these other methods. If, however, the K-value method is not UNIWAALS, you can supply these parameters independently.
See above under K-value Data for format and definition of these entries.

Properties may be supplied that are active only when a specific method is used. If UFT1 and/or UNIFAC data are specified, van der Waals area and volume data (VANDERWAALS) may also be input. However, VANDERWAALS data may only be specified globally for all thermodynamic sets in the Component Data Category. For a further description of these input parameters see Chapter 9, Method-specific Pure Component Data.
Examples
4.20: Using the UNIWAALS method with default group contribution data, calculate the temperature of a 50/50 mix of propane and normal butane at 50 psia and 50% vaporization.
TITLE PROB=UNIWAAL PRINT INPUT=ALL COMPONENT DATA LIBID 1,C3/ 2,NC4 THERMODYNAMIC DATA METHOD SYSTEM=UNIWAAL STREAM DATA PROP STREAM=1, TEMP=100, PRES=100, & COMP=50/50 UNIT OPERATION FLASH UID=FL30 FEED 1 PROD V=2, L=3 TPSPEC PRES=50 SPEC STREAM=2, RATE, RATIO, STREAM=1, & RATE, VALUE=0.5 END
4.21:
For the same problem, use explicitly specified UNIWAALS K-values, enthalpies, entropies, and vapor densities. Specify API liquid densities.
Equations of State
II-4-26
THERMODYNAMIC DATA METHOD KVALUE=UNIWAAL, ENTHALPY=UNIWAAL, & ENTROPY=UNIWAAL, DENSITY(V)=UNIWAAL, & DENSITY(L)=API
4.22:
For the previous example, also supply parameters for the Twu-Bluck-Cunningham alpha formulation for components 1 and 2, propane and butane. See Cubic Equation Of State Alpha Formulations on page 4-29.
THERMODYNAMIC DATA METHOD KVALUE=UNIWAAL, ENTHALPY=UNIWAAL, & ENTROPY=UNIWAAL, DENSITY(V)=UNIWAAL, & DENSITY(L)=API KVALUE VA06 1,0.34,0.85,2.54/ 2,0.19,0.87,2.96
4.23:
Use the SOUR thermo methods but apply UNIWAAL to vapor density.
THERMODYNAMIC DATA METHOD SYSTEM=SOUR, DENSITY(V)=UNIWAAL
Filling in Missing Parameters

Typical Usage
...
COMPONENT DATA LIBID 1,C1/ 2,C2/ 3,C3/ 4,NC4/ 5,C5 THERMO DATA METHOD SYSTEM=SRK KVALUE FILL=GAO $ or GOR or CPHC STREAM DATA . . .
General Information
PRO/II has an extensive facility to backfill missing binary interaction data between hydrocarbons for cubic equations of state (i.e., SRK, PR, and their modifications). Table 4-5 shows the methods developed by SIMSCI that can be used for estimating binary interaction parameters.
II-4-27
Table 4-5: FILL options available for Cubic Equations of State FILL Options Description GOR Provides cubic equation of state binary interaction parameters between methane and ethane and heavier hydrocarbons. This method is based on correlations of existing experimental data. Provides cubic equation of state binary interaction parameters between methane, ethane, and propane and heavier hydrocarbons. This method is based on a modified Gao et al approach. Provides cubic equation of state binary interaction parameters for all hydrocarbon pairs. This method is based on the work of Chueh and Prausnitz.
GAO
CPHC
Input Description
METHOD or METHOD SYSTEM=SRK or PR or SRKM or PRM or SRKS or SRKP or PRP, ... KVALUE=SRK or PR or SRKM or PRM or SRKS or SRKP or PRP, ...
SYSTEM
One of the cubic equations of state shown above must be selected if one of the three hydrocarbon/ hydrocarbon FILL options is used. Selects the method for K-value calculations. Only the above cubic equations of state can be used with the hydrocarbon/hydrocarbon FILL option.
KVALUE
K-value Data
KVALUE FILL=NONE or GOR or GAO or CPHC
II-4-28
Equations of State
FILL
This selects the method used for estimating values for hydrocarbon/hydrocarbon binary interaction data missing from the input file and any selected databank libraries. Missing parameters are regressed using the option selected to fit the previously specified K-value cubic equation of state method. A description of the FILL options shown in Table 4-5. The options are ordered such that each subsequent method in the table generates more and more binary interaction parameters, so they provide a spectrum of results that can be selected based on the goodness of fit to the specific production data being modeled.
Cubic Equation Of State Alpha Formulations

Typical Usage
...
COMPONENT DATA LIBID 1,IC4/ 2,NC4/ 3,NC5 THERMO DATA METHOD SYSTEM=SRKM KVALUE SA06 2, 0.19, 0.87, 2.96 STREAM DATA . . .
General Information
The pure component alpha formulations are used for methods based on the cubic equation of state. The alpha function controls pure component properties (vapor pressure, enthalpies and entropy) as opposed to the interaction parameter (kij), which controls the mixture properties. Alpha formulations are available with all cubic equations of state. The SAxx entries are associated with SRK and modified SRK equations of state. The PAxx entries are associated with the PR and modified PR equations of state. The VAxx entries are associated with the UNIWAAL equation of state. PRO/II will use all data supplied on the SAxx, PAxx, or VAxx statements. The constants to be supPRO/II Thermodynamic Data Keyword Input Manual II-4-29
plied on the SAxx, PAxx, or VAxx statements can be regressed from experimental data using REGRESSTM. Components not entered here will default to the method selected on the ALPHA entry.
K-value Data
KVALUE ALPHA=SIMSCI or ACENTRIC or bankid, ... ..., SA01 or PA01 or VA01 i, c1/ ... or SA02 or PA02 or VA02 or SA03 or PA03 or VA03 or SA04 or PA04 or VA04 or SA05 or PA05 or VA05 or SA06 or PA06 or VA06 or SA07 or PA07 or VA07 or SA08 or PA08 or VA08 or SA09 or PA09 or VA09 or SA10 or PA10 or VA10 or SA11 or PA11 or VA11 i, c1, c2/ ... i, c1, c2/ ... i, c1, c2, c3/ ... i, c1, c2, c3/ ... i, c1/ ... i, c1, c2, c3/ ... i, c1, c2/ ... i, c1, c2/ ... i, c1, c2/ ... i, c1, c2, c3/ ...
Note: The SAxx, PAxx and VAxx statements must follow the KVALUE statement. ALPHA This option allows access to the databank for alpha formulations for components not given on SAxx, PAxx, or VAxx statements. SIMSCI Selects the SimSci alpha form and values supplied from the SIMSCI databank (default). Uses the original Soave acentric form for alpha (default). This option selects the user-created databank named bankid that is created and maintained by the LIBMGR program.
ACENTRI C bankid
II-4-30
Equations of State
SA01 to SA11 These entries permit various formulations of the pure component alpha correlations. Statements that have an or S prefix may be used with any form of the SoavePA01 to PA11 Redlich- Kwong equation of state, those with P apply or to the Peng-Robinson equation of state, while those VA01 to VA11 statements prefixed with V apply to the UNIWAALS equation of state. For each component i, c1, c2, and c3 are dimensionless coefficients that define the alpha correlation for that component.
Table 4-6 gives the equations for the eleven alpha formulations that are available.
Table 4-6: Alpha Formulations SA01 to SA22 or PA01 to PA11 or VA01 to VA11
xx = Equation 01 02 03 = [ 1 + C1 ( 1 Tr
0.5
Reference )]
2
Soave (1972)
2
= [ C1 + C2 ( 1 Tr ) ]
C3
Peng-Robinson (1980) Soave (1979)
C2 = 1 + ( 1 Tr ) C 1 + ---- Tr = exp [ C 1 ( 1 T r ) ] = Tr = Tr
2 ( C2 1 ) C2
04 05 06
Boston-Mathias (1980)
2C 2
exp [ C 1 ( 1 Tr
)] )]
Twu (1988) Twu-Bluck-Cunningham (1990) (Recommended by SimSci) Alternative for form (04)
C3 ( C2 1 )
exp [ C 1 ( 1 T r
C2 C3
07
2C 1 ( Cr + 1 ) 2 = exp --------------- ( 1 T r ) 1 + C1 = T r exp [ C 1 ( 1 Tr ) ] = [ 1 + C1 ( 1 Tr

0.5 C3 C2
08 09
Alternative for form (06)

0.5 2
) + C2 ( 1 Tr
) + C3 ( 1 Tr
2
0.5 2
) + C3 ( 1 Tr
0.5 3 2
) ] ] Mathias-Copeman (1983) Mathias (1983) Melhem-Saini-Goodwin (1989)
10 11
= [ 1 + C1 ( 1 Tr
0.5
) + C 2 ( 1 T r ) ( 0.7 T r ) ]
0.5 2
= exp [ C 1 ( 1 T r ) + C 2 ( 1 T r
) ]
II-4-31

ENTHALPY ALPHA=SIMSCI or ACENTRIC or bankid, ... ENTROPY DENSITY ALPHA=SIMSCI or ACENTRIC or bankid, ... ALPHA=SIMSCI or ACENTRIC or bankid, ...
SA01 to SA11i, c1, c2, c3/ ... or PA01 to PA11i, c1, c2, c3/ ... or VA01 to VA11i, c1, c2, c3/ ...
Alpha formulations SA01-SA11 or PA01-PA11 or VA01-VA11 may be selected for enthalpy, entropy, and density methods. Normally, these features are selected for the K-value method and are automatically carried over for these other methods. If, however, the K-value method is not the same as the enthalpy or entropy or density methods, you can supply these parameters independently. See above under K-value Data for format and definition of these entries.
Vapor Phase Fugacity Data (optional) Available only when liquid activity methods are used.
PHI ALPHA=SIMSCI or ACENTRIC or bankid, ... i, c1, c2, c3/ ... i, c1, c2, c3/ ... i, c1, c2, c3/ ...
SA01 to SA11 PA01 to PA11 VA01 to VA11
Alpha formulations SA01-SA11 or PA01-PA11 or VA01-VA11 may be selected for vapor phase fugacities when liquid activity methods are used. See above under K-value Data for format and definition of these entries.
II-4-32
Equations of State
Examples
4.24: Using the SRK method with default data, model a 50/50 mix of propane and normal butane at 50 psia and 50% vaporization. Supply parameters for the Twu-BluckCunningham alpha formulation SA06 for components 1 and 2, propane and butane.
TITLE PROB=ALPHA COMPONENT DATA LIBID 1,C3/ 2,NC4 THERMODYNAMIC DATA METHOD KVALUE=SRK, ENTHALPY=SRK, & ENTROPY=SRK, DENSITY(V)=SRK, & DENSITY(L)=API KVALUE SA06 1, 0.34, 0.85, 2.54/ 2, 0.19, 0.87, 2.96 STREAM DATA PROP STREAM=1, TEMP=100, PRES=100, COMP=50/50 UNIT OPERATION FLASH UID=FL2 FEED 1 PROD V=2, L=3 TPSPEC PRES=50 SPEC STREAM=2, RATE, RATIO, STREAM=1, RATE, VALUE=0.5 END
Benedict-Webb-Rubin-Starling
Typical Usage
...
COMPONENT DATA LIBID 1,IC4/ 2,NC4/ 3,NC5 THERMO DATA METHOD SYSTEM=BRWS STREAM DATA . . .
II-4-33
General Information
The Benedict-Webb-Rubin-Starling equation of state predicts Kvalues, enthalpies, entropies, and vapor and liquid densities. It is most often useful for light to heavy refinery hydrocarbons. Rigorous two liquid phase behavior is not supported with the BWRS equation of state.
Table 4-7: Attributes of the BWRS Equation of State Properties predicted by BWRS K-values Enthalpies Entropies Vapor densities Liquid densities
Required pure component properties1 Molecular weight Critical temperature Critical volume Pressure Temperature Components Free-water decant VLLE
1
Suggested application ranges 0 to 2000 psia -460 to 200 F C1 & heavier Supported Not supported

METHOD or METHOD SYSTEM=BWRS, ... KVALUE=BWRS, ENTHALPY=BWRS, ENTROPY=BWRS, DENSITY=BWRS, ...
SYSTEM
Selects a combination of consistent thermodynamic property generators. When SYSTEM=BWRS is chosen, BWRS K-values, BWRS enthalpies, BWRS entropies, BWRS liquid and vapor densities are assumed.
II-4-34
Equations of State
KVALUE
Selects the method for K-value calculations. Only VLE K-value calculations are available with the BRWS method. Selects the method for enthalpy calculation. By default, both vapor and liquid enthalpies use this method. Selects the method for entropy calculation. By default, both vapor and liquid entropies use this method. Selects the method for density calculation. By default, both liquid and vapor densities use this method.
ENTHALPY (VL or V and/or L) ENTROPY (VL or V and/or L) DENSITY (VL or V and/or L)

KVALUE BWRS BANK=SIMSCI or NONE or bankid i, j, kij/ ...
Note: The BWRS statements must follow the KVALUE state-
ment.
BAN K This option selects one or more banks from which to retrieve vapor and/or liquid phase binary interaction data. SIMSCI NONE bankid Selects the SimSci standard databank (default). This option disables all data retrieval from databanks for interaction parameters. This option selects the user-created databank named bankid that is created and maintained by the LIBMGR program.
BWRS
This statement allows entry of interaction parameters for component pairs that use the BWRS equation of state. Each entry includes the component ID number for each component in the pair, followed by the interaction parameter value.

ENTHALPY BANK=SIMSCI or NONE or bankid ENTROPY BANK=SIMSCI or NONE or bankid
DENSITY BANK=SIMSCI or NONE or bankid BWRS i, j, kij ...
II-4-35
BWRS binary interaction data may be selected for enthalpy, entropy and density methods. Normally, these features are selected for the K-value method and are automatically carried over for these other methods. If, however, the K-value method is not BWRS, you can supply these parameters independently. See above under K-value Data for format and definition of these entries. Water Handling Options (optional)
The BWRS K-value generator supports the free-water decant option. Refer to Free-water Decant Considerations on page 1-34 for a description of these input options. Method-specific Pure Component Properties (optional)
Properties may be supplied that are active only when a specific method is used. However, ideal vapor enthalpy data may only be specified globally for all thermodynamic sets in the Component Data Category. For a further description of these input parameters, see Chapter 9, Method-specific Pure Component Data.
Examples
4.25: Using the BWRS method with default binary interaction data, model a 50/50 mix of propane and normal butane at 50 PSIA AND 50% vaporization.
TITLE PROB=BWRS PRINT INPUT=ALL COMPONENT DATA LIBID 1,C3/ 2,NC4 THERMODYNAMIC DATA METHOD SYSTEM=BWRS STREAM DATA PROP STREAM=1, TEMP=100, PRES=100, & COMP=50/50
II-4-36
Equations of State
UNIT OPERATION FLASH UID=DRUM FEED 1 PROD V=2, L=3 TPSPEC PRES=50 SPEC STREAM=2, RATE, RATIO, STREAM=1,& RATE, VALUE=0.5 END
4.26:
For the same problem, use explicitly specified BWRS Kvalues, enthalpies, entropies, and vapor densities. Specify API liquid densities.
THERMODYNAMIC DATA METHOD KVALUE=BWRS, ENTHALPY=BWRS, & ENTROPY=BWRS, DENSITY(V)=BWRS, & DENSITY(L)=API
4.27:
Use the SOUR thermo methods but apply BWRS to vapor density.
THERMODYNAMIC DATA METHOD SYSTEM=SOUR, DENSITY(V)=BWRS...
Associating Hexamer Equation Of State

Typical Usage
...
COMPONENT DATA LIBID 1,IBTE/ 2,IC4/ 3,HF THERMO DATA METHOD SYSTEM=HEXAMER STREAM DATA . . .
General Information
The HEXAMER equation of state1 predicts K-values, enthalpies, entropies, and vapor densities. It is most often useful for HF alkyla-
1. Twu, C.H., J.E. Coon, and J. Cunningham, 1993, An Equation of State for Hydrogen Fluoride, Fluid Phase Equilibria, 86, 47-62. PRO/II Thermodynamic Data Keyword Input Manual II-4-37
tion and refrigerant synthesis. Rigorous two liquid phase behavior is supported with the HEXAMER equation of state.
Table 4-8: Attributes of the HEXAMER Equation of State Properties predicted by HEXAMER K-values Enthalpies Entropies Vapor densities Liquid densities (not recommended)
Required pure component properties1 Molecular weight Critical temperature Critical volume Components Acentric factor Ideal vapor enthalpy
Suggested application ranges Only 1 hexamerizing component and no H2 O Not supported Supported
Two liquid phase behavior Free-water decant VLLE

1

METHOD or METHOD SYSTEM(VLE or VLLE)=HEXAMER, ... KVALUE(VLE and/or LLE or VLLE)=HEXAMER, ENTHALPY=HEXAMER, ENTROPY=HEXAMER, DENSITY(V)=HEXAMER, DENSITY(L)=API, ...
SYSTEM
Selects a combination of consistent thermodynamic property generators. When SYSTEM=HEXAMER is chosen, HEXAMER K-values, HEXAMER enthalpies, HEXAMER entropies, HEXAMER vapor densities, and API liquid densities are assumed. Selects the method for K-value calculations. VLE and VLLE K-value calculations are available with the HEXAMER method.
KVALUE
II-4-38
Equations of State
ENTHALPY (VL or V and/or L) ENTROPY (VL or V and/or L) DENSITY (V)
Selects the method for enthalpy calculation. By default, both vapor and liquid enthalpies use this method. Selects the method for entropy calculation. By default, both vapor and liquid entropies use this method. Selects the method for vapor density.
Note: If DENSITY=HEXAMER without the V qualifier is used, liquid density will also be calculated from the HEXAMER equation of state. This method is not recommended for this purpose.

KVALUE BANK=SIMSCI or NONE or bankid, i, j, kija, kjia, kijb, kjib, kijc, kjic, cij, cji / ... HEXA(K or R)
Note: The HEXA statements must follow the KVALUE state-
ment.
BAN K This option selects one or more banks from which to retrieve vapor and/or liquid phase binary group contribution data. SIMSCI NONE bankid Selects the SimSci standard databank (default). This option disables all data retrieval from databanks for interaction parameters. This option selects the user-created databank named bankid that is created and maintained by the LIBMGR program.
HEXA
This statement allows entry of interaction parameters for component pairs that use the Associating Hexamer equation of state. Each entry includes the component ID number for each of the two components in the pair, followed by the interaction parameters.

ENTHALPY ENTROPY DENSITY BANK=SIMSCI or NONE or bankid BANK=SIMSCI or NONE or bankid BANK=SIMSCI or NONE or bankid
II-4-39
HEXA(K or R)
HEXAMER binary interaction data may be selected for enthalpy, entropy, and density methods. Normally, these features are selected for the K-value method and are automatically carried over for these other methods. If, however, the K-value method is not HEXAMER, you can supply these parameters independently. See above under K-value Data for format and definition of these entries.

Properties may be supplied that are active only when a specific method is used. However, ideal vapor enthalpy data may only be specified globally for all thermodynamic sets in the Component Data Category. For a further description of these input parameters see Chapter 9, Method-specific Pure Component Data.
Examples
4.28: The HEXAMER equation of state is used to model a hydrocarbon stream containing HF.
TITLE PROJ=MANUAL, PROB=HEXAMER DIME LIQV=BBL, TIME=DAY, XDEN=API COMPONENT DATA LIBID 1,C3/ 2,IC4/ 3,NC4/ 4,IC5/ 5,HF/ 6,NC7 THERMODYNAMIC DATA METHOD SYSTEM=HEXAMER, SET=SET01, DEFAULT METHOD SYSTEM(VLLE)=HEXAMER, & L1KEY=1, L2KEY=5, SET=SET02 STREAM DATA PROP STREAM=F, TEMP=140, PRES=169, RATE(LV)=65952, & COMP(V)=17.1/58.4/9.8/1.1/2.1/11.5 PROP STREAM=REFL, TEMP=86, PRES=158, RATE=56250, & COMP=0.59/0.39/0.02
II-4-40
Equations of State
UNIT OPERATION COLUMN UID=12C2, NAME=ISOSTRIPPER PARA TRAY=49, IO=30 FEED F,7/ REFL,1 PROD OVHD=DF, BTMS=1, 20600, VDRAW=IR, 9, 167672 DUTY 1,42,1200/ 2,49,1000 PRES 1,161/ 7,164/ 49,174 ESTI MODEL=CONV SPEC STREAM=IR, COMP=2, RATE, RATIO, STREAM=F, & RATE, VALUE=O.75 SPEC TRAY=1, TEMP, VALUE=114.8 VARY DUTY=2, DRAW=IR FLASH UID=F1, NAME=CONDENSER FEED DF PROD L=DF1, W=HF1 ISO PRES=50, TEMP=85 METHOD SET=SET02 END
Lee-Kesler-Plocker
Typical Usage
...
COMPONENT DATA LIBID 1,IC4/ 2,NC4/ 3,NC5 THERMO DATA METHOD SYSTEM=LKP STREAM DATA . . .
General Information
The LKP method is derived from a corresponding states approach combined with the Benedict-Webb-Rubin-Starling (BWRS) equation of state (see Benedict-Webb-Rubin-Starling on page 4-33). The LKP method predicts K-values, enthalpies, entropies, and vapor and liquid densities. It is most often used for light hydrocarbons and for reformer systems containing high quantities of hydrogen. VLLE behavior can also be predicted with the LKP method.
II-4-41
Table 4-9: Attributes of the LKP Method Properties predicted by LKP K-values Enthalpies Entropies Vapor densities Liquid densities
Required pure component properties1 Molecular weight Critical temperature Critical volume Temperature Components Free-water decant VLLE
1
Acentric factor Ideal vapor enthalpy Specific gravity Below reduced temperatures of 0.96 Light hydrocarbons Not supported Supported
Suggested application ranges
Input Description
METHOD or METHOD SYSTEM(VLE or VLLE)=LKP, ... KVALUE(VLE or VLLE)=LKP, ENTHALPY=LKP, ENTROPY=LKP, DENSITY=LKP
SYSTEM
Selects a combination of consistent thermodynamic property generators. When SYSTEM=LKP is chosen, LKP K-values, LKP enthalpies, LKP entropies, LKP liquid and vapor densities are assumed. Selects the method for K-value calculations. Both VLE and LLE K-value calculations are available with the LKP method. The VLLE option automatically selects both.
KVALUE
II-4-42
Equations of State
Selects the method for enthalpy calculation. By default, both vapor and liquid (VL) enthalpies are calculated using the same method. You may select different methods for the vapor and liquid enthalpies by providing both an ENTHALPY(V) and ENTHALPY(L) entry. Selects the method for entropy calculation. By default, both vapor and liquid (VL) entropies are calculated using the same method. You may select different methods for the vapor and liquid enthalpies by providing both an ENTROPY(V) and ENTROPY(L) entry. Selects the method for density calculation. By default, both vapor and liquid (VL) densities are calculated using the same method. You may select different methods for the vapor and liquid enthalpies by providing both an DENSITY(V) and DENSITY(L) entry.
ENTROPY (VL or V and/or L)
DENSITY (VL or V and/or L)

KVALUE(VLE or LLE or VLLE) BANK=SIMSCI or NONE or bankid LKP i, j, kij / ...
Note: The LKP statements must follow the KVALUE statement. BAN K This option selects one or more banks from which to retrieve vapor and/or liquid phase binary interaction data. SIMSCI NONE bankid Selects the SimSci standard databank (default). This option disables all data retrieval from databanks for interaction parameters. This option selects the user-created databank named bankid that is created and maintained by the LIBMGR program.
SRK
This statement allows entry of the interaction parameters for component pairs that use the Lee-Kesler-Plocker method. Each entry includes the component ID number for each of the two components in the pair, followed by the interaction parameter value.
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ENTHALPY BANK= SIMSCI or NONE or bankid ENTROPY DENSITY LKP BANK= SIMSCI or NONE or bankid BANK=SIMSCI or NONE or bankid i, j, kij / ...
LKP binary interaction data may be selected for enthalpy, entropy, and density methods. Normally, these features are selected for the K-value method and are automatically carried over for these other methods. If, however, the K-value method is not LKP, you can supply these parameters independently. See above under K-value Data for format and definition of these entries. Method-specific Pure Component Properties (optional)
Properties may be supplied that are active only when a specific method is used. However, ideal vapor enthalpy data may only be specified globally for all thermodynamic sets in the Component Data Category. For a further description of these input parameters, see Chapter 9, Method-specific Pure Component Data.
Examples
4.29: Using the LKP method, calculate the temperature of a 50/ 50 mix of propane and normal butane at 50 psia and 50% vaporization.
TITLE PROB=SRK, PROJ=THERMO DESC THERMO MANUAL PROBLEM PRINT INPUT=ALL COMPONENT DATA LIBID 1,C3/ 2,NC4 THERMODYNAMIC DATA METHOD SYSTEM=LKP STREAM DATA PROP STREAM=1, TEMP=100, PRES=100, COMP=50/50
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Equations of State
UNIT OPERATION FLASH UID=FLSH FEED 1 PROD V=2, L=3 TPSPEC PRES=50 SPEC STREAM=2, RATE, RATIO, STREAM=1, & RATE, VALUE=0.5 END
4.30:
For the same problem, explicitly specify LKP K-values, enthalpies, entropies, and vapor densities. Specify API liquid densities.
THERMODYNAMIC DATA METHOD KVALUE=LKP, ENTHALPY=LKP, ENTROPY=LKP, & DENSITY(V)=LKP, DENSITY(L)=API
4.31:
Use the SOUR thermo methods but apply LKP to vapor density.
THERMODYNAMIC DATA METHOD SYSTEM=SOUR, DENSITY(V)=LKP
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II-4-46
Equations of State
Chapter 5 Special Packages

Several special thermodynamic packages have been incorporated into the program. These packages have been developed for particular applications containing systems of components commonly found in refining or chemicals processing. Systems available include alcohols, glycols, sour water and amines.
Alcohols
Typical Usage
... COMPONENT DATA LIBID 1,ETOH/ 2, MEOH/ 3, H2O THERMO DATA METHOD SYSTEM=ALCOHOL STREAM DATA . . .
General Information
The ALCOHOL package is used to predict VLE and/or LLE phase behavior. This method does not support free water decant. This system uses a special set of NRTL binary interaction data for systems containing alcohols, water, and other polar components. The ALCOHOL package is generally useful for applications involving alcohols, especially for azeotropic distillation common in
alcohol dehydration plants. Refer to the PRO/II Reference Manual for information.
Table 5-1:Attributes of the ALCOHOL Package Properties predicted by the ALCOHOL method K-values Required pure component properties1 Vapor pressure Vapor pressure Critical temperature Critical pressure Acentric factor Vapor pressure Liquid molar volume Suggested application ranges Pressure Temperature Components Free-water decant VLLE
1
PHI=IDEAL and POYNTING=OFF PHI=SRK or PR or SRKM or PRM or SRH or PRH or SRP or PRP or SRKS or SRKKD or HOCV or BWRS or UNIWAAL
When used with POYNTING=ON
- up to 1500 psia - 122-230 F (H2O-Alcohol), 150-230 F (Other systems) - Alcohols, water, other polar components - Not supported - Supported
Input Description
METHOD or METHOD SYSTEM(VLE or VLLE)=ALCOHOL, PHI=IDEAL, {HENRY} KVALUE(VLE and/or LLE or VLLE)=ALCOHOL, ENTHALPY(V)=SRKM, ENTHALPY(L)=IDEAL, ENTROPY=SRKM, DENSITY(V)=SRKM, DENSITY(L)=IDEAL, PHI=IDEAL, {HENRY}, ...
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Special Packages
SYSTEM
Selects a combination of consistent thermodynamic property generators. When SYSTEM=ALCOHOL is chosen, NRTL K-values, SRKM vapor enthalpies, IDEAL liquid enthalpies, SRKM entropies, IDEAL liquid densities, and SRKM vapor densities are default. Interaction parameters are defaulted to the ALCOHOL databank. Selects the method for K-value calculations. Both VLE and LLE K-value calculations are available with the ALCOHOL package. The VLLE option automatically selects both. See Vapor-liquid-liquid Equilibrium Considerations on page 1-37 for more details on liquid-liquid equilibrium calculations. Selects the option used to calculate pure component and mixture vapor phase fugacity coefficients (i). A vapor fugacity method should generally be selected for high pressure applications. The options are the equations of state methods SRK, PR, SRKM, PRM, SRKH, PRH, SRKP, PRP, SRKS, SRKKD, BWRS and UNIWAAL (see Chapter 4) and HOCV (the Hayden-O'Connell method), TVIRIAL (the Truncated Virial method) and the IDIMER method. See Hayden-OConnell Vapor Fugacity on page 6-69; Truncated Virial Vapor Fugacity on page 6-73; and IDIMER Vapor Fugacity on page 6-78 for details on these last three options. The default is PHI=IDEAL. This option selects Henry's Law data (either usersupplied or from databanks) to model dissolved gases in a liquid solution. See Henrys Law for Noncondensible Components on page 6-63 for further details.
KVALUE
PHI
HENRY
Note: A heat of mixing option, HMIX, is available for the
enthalpy method selected. See Redlich-Kister, Gamma Heat of Mixing on page 6-82 for further information on the use of this option.
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K-value Data (Optional)

KVALUE(VLE or LLE or VLLE) POYNTING=OFF or ON, MOLVOL=STANDARD or RACKETT or RCK2 or LIBRARY, BANK=ALCOHOL and SIMSCI or NONE or bankid, FILL=NONE or UNIFAC or UFT1 or FLORY or REGULAR, AZEOTROPE=SIMSCI or NONE or bankid, WRITE=fileid NRTL3(K or KCAL or KJ) and/or NRTL(K or KCAL or KJ) and/or NRTL6(K or KCAL or KJ) and/or NRTL8(K or KCAL or KJ) and/or AZEOTROPE(basis, punit, tunit) and/or INFINITE(tunit) and/or MUTUAL(basis, tunit) and/or IDEAL i, j/ ... i, j, temp, xiI, xiII / ... i, j, temp, ioo, joo / ... i, j, pres, temp, xi / ... i, j, aij, bij, cij, aji, bji, cji, ij, ij/... i, j, aij, bij, aji, bji, ij, ij /... i, j, aij, bij, aji, bji, a ij / ... i, j, bij, bji, aij / ...
Note: The NRTL3, NRTL, NRTL6, NRTL8, AZEOTROPE, INFINITE, MUTUAL and/or IDEAL statements must follow the KVALUE statement. POYNTING This option selects whether to apply the Poynting correction to fugacities of components in the liquid phase. The default is OFF unless a PHI method is selected, in which case the default is ON. This selects the method used to calculate the liquid molar volume necessary for computing the Poynting correction factor. Options are: STANDAR The default. Selects the standard method D for calculating the liquid molar volume at standard conditions (25 C, 1 atm). RACKETT Selects the Rackett liquid density method. RCK2 LIBRARY Selects the Rackett 2 liquid density method. Selects the LIBRARY liquid density method.
MOLV OL
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Special Packages
BANK
This option selects the alcohol databank from which to retrieve vapor and/or liquid phase binary interaction data. ALCOHOL Selects the ALCOHOL databank. This databank contains binary coefficients for a special set of components including many alcohols, water and other polar components. See Table 5-2 for the components available in this databank and Table 5-3 for the binary interaction data available. This is the default databank when SYSTEM=ALCOHOL or KVALUE=ALCOHOL is selected. SIMSCI Selects the SIMSCI databank. If selected, this should follow the ALCOHOL entry. The program will search the ALCOHOL databank first for NRTL interaction parameters, then attempt to find missing parameters in the SIMSCI databank. This option disables all data retrieval from databanks for interaction parameters. This option selects a user-created databank named bankid that is created and maintained with the LIBMGR program.
NONE
bankid
FILL
This selects the method used for estimating values for binary interaction data missing from the input file and any selected databank libraries. See Filling in Missing Parameters on page 6-57 for further details on these options. This selects the azeotrope databank used for retrieving azeotropic data for binary pairs. Current options are SIMSCI (default) or NONE or bankid. This option writes the binary interaction parameters for the liquid activity coefficient K-value method to a file. The format of this file is suitable for inclusion into an input file.
AZEOTROPE
WRITE
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fileid
This name identifies the file containing the binary interaction data. It may be any valid file name allowed on the particular operating system being used, but must not include a suffix. The program will automatically add a suffix (e.g., .FIL on PCs).
NRTL3 and/or NRTL and/or NRTL6 and/or NRTL8
This statement allows entry of the binary interaction data parameters for the NRTL K-value method used in the ALCOHOL package. The statements can be mixed in order to enter the data in the most convenient form. The binary parameters aij, bij, cij, aji, bji, cji, ij and ij are related to the liquid activity coefficients i by the following equations:
xk kj Gkj G X j ij j k In i = -------------------- + --------------------- ij -------------------------- G kj X k GkiXk j Gkj Xk k
ji
k
b ij C ij - + ----- ij = a ij + ----T T2 C ij b ij - + ---------- ij = a ij + -----RT R 2 T 2
(when unit is K)
(when unit is KCAL or KJ)
G ji = exp ( i ji ), i = a' ji + ' ji T
AZEOTROPE and/or INFINITE and/or MUTUAL and/or IDEAL
These statements are used to enter data for binary pairs. This data will be regressed to the coefficients for the liquid activity method used to generate the K-values. Multiple statements may be used to enter data with different units, or the data can be entered on a single statement. This statement sets the binary interaction parameters to zero.
Data input using the NRTL3, NRTL, NRTL6, NRTL8, AZEOTROPE, INFINITE, MUTUAL and IDEAL statements are used in preference to any data retrieved from the databanks or estimated using FILL options. See Filling in Missing Parameters on page 657 for further details.
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Special Packages

ENTHALPY(V) BANK=SIMSCI or NONE or bankid ALPHA=SIMSCI or ACENTRIC or bankid ENTROPY BANK=SIMSCI or NONE or bankid, ALPHA=SIMSCI or ACENTRIC or bankid BANK=SIMSCI or NONE or bankid, ALPHA=SIMSCI or ACENTRIC or bankid i, j, kija, kjia, kijb, kjib, kijc, kjic, cij, cji / ... i, c1, c2, c3/ ...
DENSITY(V)
SRKM(K or R) SA01 to SA11
BANK
Selects databank from which to retrieve binary interaction data. SIMSCI NONE bankid Selects the SimSci standard databank(default). This option disables all data retrieval from databanks for interaction parameters. This option selects a user-created databank named bankid that is created and maintained with the LIBMGR program.
ALPH A
This option allows access to the databank for alpha formulations. SIMSCI Selects the SimSci alpha form and values supplied from the SIMSCI databank (default). Uses original Soave acentric form for alpha (default). This option selects a user-created databank named bankid that is created and maintained with the LIBMGR program.
ACENTRI C bankid
Note: The SRKM and SAxx statements may follow each ENTHALPY(V), ENTROPY or DENSITY(V) STATEMENT.
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Table 5-2:ALCOHOL Databank Components Component Formula LIBID Water Alcohols Methanol Ethanol N-propanol Isopropanol N-butanol Isobutanol Sec-butanol Tert-butanol 3-Methyl-1 butanol N-Pentanol Ethers Isopropyl Ether Ethyl Ether Methyl Ether Acids Acetic Acid Formic Acid Ketones Methyl Ethyl Ketone Acetone Esters Ethyl Acetate Methyl Formate Miscellaneous Acetaldehyde Sulfolane Light Gases Hydrogen Nitrogen Oxygen Carbon Dioxide H2 N2 O2 CO2 H2 N2 O2 CO2 C2H4O C4H8O2S ACH SULFLN C4H8O2 C2H4O2 EOQC MFOR C4H8O C3H6O MEK DMK C2H4O2 CH2O2 HAC, HDAC HFOR C6H14O C4H10O C2H6O IPE, DIPE, DEE DME CH4O C2H6O C3H8O C3H8O C4H10O C4H10O C5H12O C5H12O MEOH ETOH NPRA IPA IBA SBA TBA 3M1BA H2O H2O
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Special Packages
Table 5-2:ALCOHOL Databank Components Component Formula LIBID Hydrocarbons Isopentane N-Pentane Cyclopentane 2 Methylpentane 1-Hexene N-Hexane Methylcyclopentane Benzene Cyclohexane 2-4 Dimethylpentane 3-Methylhexane 1-Trans-2Dimethylcyclopentane N-Heptane Methylcyclohexane Toluene 2-4 Dimethylhexane 1-Trans-2-Cis-4-TriMethylcyclopentane C5H12 C5H12 C5H10 C6H14 C6H12 C6H14 C6H12 C6H6 C6H12 C7H16 CYH16 C7H14 C7H16 C7H14 C7H8 C8H18 C8H16 IC5 NC5 CP 2MP 1HEXENE NC6 MCP C6H6 CH 24DMP 3MHX 1T2MCP NC7 MCH TOLU 24DMHX 1T2C4MCP
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Table 5-3:Binary Interaction Data

Nitrogen Nitrogen Oxygen CarbonOxygen Dioxide Carbon Dioxide Isopentane Isopentane n-Pentane n-Pentane 2-Methylpentane 2-Methylpentane n-Hexane n-Hexane 2,4,-Dimethylpentane 2,4,-Dimethylpentane 3-Methylhexane 3-Methylhexane n-Heptane n-Heptane 2,4-Dimethylhexane 2,4-Dimethylhexane Cyclopentane Cyclopentane Methylcyclopentane Methylcyclopentane Cyclohexane Cyclohexane 1-T-2DM-Cyclopentane 1-T-2DM-Cyclopentane Methylcyclohexane Methylcyclohexane 1-T,2-C-4 TMCP TMCP 1-T,2-C-4 1-Hexene 1-Hexene Benzene Benzene Toluene Toluene DIPE DIPE DEE DEE DME DME Acetic Acid Acetic Acid Formic Acid Formic MEK Acid MEK Acetone EthylAcetone Acetate Acetate Ethyl Mrthyl Formate Formate Methyl Acetaldehyde Acetaldehyde Sulfolane Sulfolane n-Pentanol n-Pentanol 3-M-1-Butanol 3-M-1-Butanol n-Butanol n-Butanol Isobutanol Isobutanol sec -Butanol sec tert-Butanol -Butanol tert -Butanol n-Propanol n-Propanol Isopropanol Isopropanol Ethanol Ethanol Methaol Methanol Water Water X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X
X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X
X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X
X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X
X X X X X X X X X X X X X X X X X X X X X X X X X X X X
X X X X X X X X X X X X X X X X X X X X X X X X X X
X X X X X X X X X X X X X X X X X X X X X X X X
X X X X X X X X X X X X X X X X X X X X X X
X X X X X X X X X X X X X X X X X X X X
X X X X X X X X X X X X X X X X X X
X X X X X X X X X X X X X X X X
X X X X X X X X X X X X X X
X X X X X X X X X X X X
X X X X X X X X X X
X X X X X X X X
X X X X X X X X X X X X X X X X X X X X X X X X
X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X
X X X X X X X X X X
X X X X X X X X
X X X X X X
X X
X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X
X X X X
X X X X X X X X X X X X X X X X X X X X X X
X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X
X X X X X X X X X X X X X X X X X X
X X X X X X X X X X X X X X X X
X X X X X X X X X X X X X X
X X X X X X X X X X
X X X X X X X X

TC(unit) PC(unit) ACENTRIC MOLVOL(unit) VP ... i, value / ... i, value / ... i, value / ... i, value / ...
Properties may be supplied that are active only when a specific method is used. For a further description of these input parameters, see Chapter 9, Method-specific Pure Component Data. Note that only vapor pressure has any direct effect on the calculation of liquid activity coefficients. Tc, Pc and the acentric factor will have an
II-5-10 Special Packages
impact if a cubic equation of state is chosen for vapor phase fugacities. Molar volume will have an impact on the Poynting correction factor.
Examples
6.1: Using the ALCOHOL system, model a 50/25/20/5 mix of water, benzene, ethanol and cyclohexane at 50 psia and 20% vaporization. Use SRK for vapor phase fugacity calculations, and supply NRTL binary interaction data.
TITLE PROB=ALCOHOL PRINT INPUT=ALL COMPONENT DATA LIBID 1,H2O/2,BENZENE/3,ETOH/4,CHEN THERMO DATA METHOD SYSTEM=ALCOHOL, PHI=SRK KVALUE FILL=UNIFAC, POYNTING=ON NRTL 1,2,5.256,219.685,-5.645,288.34,0.2/ & 1,3,1.015,536.264,0.4985,-456.0,0.1448/ & 2,3,-2.748,1472.24,-0.449,440.51,0.5355 STREAM DATA PROP STREAM=1,TEMP=100,PRES=100, & COMP=50/25/20/5 UNIT OPERATION FLASH UID=FL2B FEED 1 PROD V=2, L=3 TPSPEC PRES=50 SPEC STREAM=2, RATE, RATIO, STREAM=1, & RATE, VALUE=0.2 END
6.2:
For the same problem, use ALCOHOL K-values, IDEAL enthalpies and liquid densities and SRK vapor densities.
THERMO DATA METHOD KVALUE=ALCOHOL, ENTHALPY=IDEAL, & DENSITY(L)=IDEAL, DENSITY(V)=SRK, PHI=SRK
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Glycols
Typical Usage
...
COMPONENT DATA LIBID 1,H2O/ 2, CH/ 3, TEG THERMO DATA METHOD SYSTEM=GLYCOL STREAM DATA . . .
General Information
The GLYCOL package is used to predict VLE and/or LLE phase behavior. This method does not support free water decant. It uses a special set of SRKM binary interaction data and alpha parameters for systems containing glycol, water, and other components. The GLYCOL package is generally useful for applications involving triethylene glycol, and to a lesser extent, diethylene glycol, and ethylene glycol. It is useful especially for TEG dehydration plants. Refer to the PRO/II Reference Manual for information.
Table 5-4:Attributes of the GLYCOL Package Properties predicted by GLYCOL method K-values Required pure component properties1 Critical temperature Critical pressure Pressure Temperature Components Free-water decant VLLE
1
Acentric factor
Suggested application ranges - up to 2000 psia - 80-400 F - A glycol or water must be present - Not supported - Supported
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Special Packages
Input Description
METHOD or METHOD SYSTEM(VLE or VLLE)=GLYCOL KVALUE(VLE and/or LLE or VLLE)=GLYCOL, ENTHALPY(V)=SRKM, ENTHALPY(L)=SRKM, ENTROPY=SRKM, DENSITY(V)=SRKM, DENSITY(L)=API,... BANK=GLYCOL
and KVALUE
SYSTEM
Selects a combination of consistent thermodynamic property generators. When SYSTEM=GLYCOL is chosen, SRKM K-values, SRKM vapor enthalpies, IDEAL liquid enthalpies, SRKM entropies, IDEAL liquid densities, and SRKM vapor densities are default. Selects the method for K-value calculations. Both VLE and LLE K-value calculations are available with the SRKM method, which is used by the GLYCOL package. The VLLE option automatically selects both. See Vapor-liquidliquid Equilibrium Considerations on page 1-37 for more details on liquid-liquid equilibrium calculations.
KVALUE

KVALUE(VLE or LLE or VLLE) BANK=GLYCOL and SIMSCI or NONE or bankid, ALPHA=SIMSCI or ACENTRIC or bankid SRKM(K or R) SA01 to SA11 i, j, kija, kjia, kijb, kjib, kijc, kjic, cij, cji / ... i, c1, c2, c3/ ...
Note: If used for calculating K-values, the SRKM and SAxx
statements must follow the KVALUE statement.
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BANK
This option selects the GLYCOL databank from which to retrieve vapor and/or liquid phase binary interaction data. GLYCOL Selects the GLYCOL databank. This databank contains binary coefficients and alpha parameters for a special set of components including many glycols, water and other components. See Table 5-5 for the components available in this databank. This is the default databank when SYSTEM=GLYCOL or KVALUE=GLYCOL is selected. Selects the SimSci standard databank. If selected this should follow the GLYCOL entry. The program will search the GLYCOL databank first for SRKM interaction parameters, then attempt to find missing parameters in the SIMSCI databank. This option disables all data retrieval from databanks for interaction parameters. This option selects a user-created databank named bankid that is created and maintained with the LIBMGR program.
SIMSCI
NONE
bankid
ALPHA
This option allows access to the databank for alpha formulations. SIMSCI Selects the SimSci alpha formulation and values supplied from the SimSci databank (default). Uses original Soave acentric form for alpha (default). This option selects a user-created databank named bankid that is created and maintained with the LIBMGR program.
ACENTRIC bankid
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Special Packages
SRKM and/or SA01 to SA11
This statement inputs binary interaction parameters and alpha formulation data for the SRKM method used to calculate K-values for the GLYCOL package. See Modified Soave-Redlich-Kwong and PengRobinson on page 4-13 for further details.

ENTHALPY BANK=SIMSCI or NONE or bankid, ALPHA=SIMSCI or ACENTRIC or bankid ENTROPY BANK=SIMSCI or NONE or bankid, ALPHA=SIMSCI or ACENTRIC or bankid BANK=SIMSCI or NONE or bankid, ALPHA=SIMSCI or ACENTRIC or bankid
DENSITY
SRKM(K or R) i, j, kija, kjia, kijb, kjib, kijc, kjic, cij, cji /... SA01 to SA11 i, c1, c2, c3/ ...
All these interaction parameters and alpha formulations may be selected for enthalpy, entropy, and density methods. Normally for the GLYCOL package, these features are selected for the K-value method and are automatically carried over for these other methods. However, you can supply the interaction parameters and/or alpha formulations independently. See above under K-value Data for format and definition of these entries.
Table 5-5:Components Available for GLYCOL Package Gas Component Formula LIBID Hydrogen Nitrogen Oxygen Carbon Dioxide Hydrogen Sulfide Methane Ethane Propane Isobutane N-butane H2 N2 O2 CO2 H2S CH4 C2H6 C3H8 C4H10 C4H10 H2 N2 O2 CO2 H2S C1 C2 C3 IC4 NC4
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Table 5-5:Components Available for GLYCOL Package Liquid Formula LIBID Components Isopentane Pentane Hexane Heptane Cyclohexane Methylcyclohexane Ethylcyclohexane Benzene Toluene O-xylene M-xylene P-xylene Ethylbenzene Ethylene Glycol Diethylene Glycol Triethylene Glycol Water C5H12 C5H12 C6H14 C7H16 C6H12 C7H14 C8H16 C6H6 C7H8 C8H10 C8H10 C8H10 C8H10 C2H6O2 C4H10O3 C6H14O4 H2O IC5 NC5 NC6 NC7 CH MCH ECH BNZN TOLU OXYL MXYL PXYL EBZN EG DEG TEG H2O

Examples
6.3: Using the GLYCOL system, model a 50/25/20/5 mix of water, benzene, ethanol and TEG at 50 psia and 20% vaporization. Supply SRKM binary interaction data.
TITLE PROB=GLYCOL COMPONENT DATA LIBID 1,H2O/2,BENZENE/3,ETOH/4,TEG THERMO DATA METHOD SYSTEM=GLYCOL KVALUE SRKM 2,4,0.05,0.0,0.0,0.3,0.07,0.0,0.0,0.3 STREAM DATA PROP STREAM=1, TEMP=100, PRES=100, &
II-5-16
Special Packages
COMP=50/25/20/5 UNIT OPERATION FLASH UID=FLSH FEED 1 PROD V=2, L=3 TPSPEC TEMP=100 SPEC STREAM=2, RATE, RATIO, STREAM=1, & RATE, VALUE=0.2 END
6.4:
For the same problem, use K-values and IDEAL liquid densities.
THERMO DATA METHOD KVALUE=GLYCOL, ENTHALPY=SRKM, & DENSITY(L)=IDEAL, DENSITY(V)=SRKM
Sour Water
Typical Usage
... COMPONENT DATA LIBID 1,H2O/ 2, NH3/ 3, CO2 THERMO DATA METHOD SYSTEM=SOUR STREAM DATA . . .
General Information
The SOUR package is used to predict VLE and/or LLE phase behavior. This method does not support free water decant. This system uses the API/EPA SWEQ (Sour Water EQuilibrium) method developed by Grant Wilson to model sour water components NH3, H2S, CO2, and H2O. SRKM generates phase equilibria for all other components. The SOUR package is generally useful for applications involving sour water containing less than 30% by weight of sour components.
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Table 5-6:Attributes of the SOUR Package Properties predicted by SOUR method K-values Required pure component properties1 Critical temperature Critical pressure Acentric factor Suggested application ranges Pressure Temperature Components - up to 1500 psia - 68-300 F
wt wt - xwt NH3 + x CO2+ x H2S< 0.30 (H2O, NH3, and one acid gas required)

1
- Not supported - Supported
Input Description
METHOD or METHOD SYSTEM(VLE or VLLE)=SOUR,... KVALUE(VLE and/or LLE or VLLE)=SOUR, ENTHALPY(V)=SRKM, ENTHALPY(L)=IDEAL, ENTROPY=SRKM, DENSITY(V)=SRKM, DENSITY(L)=IDEAL, ...
SYSTE M
Selects a combination of consistent thermodynamic property generators. When SYSTEM=SOUR is chosen, SOUR K-values, SRKM vapor enthalpies, IDEAL liquid enthalpies, SRKM entropies, IDEAL liquid densities, and SRKM vapor densities are default. Selects the method for K-value calculations. Both VLE and VLLE K-value calculations are available with the SOUR package.
KVALU E
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Special Packages

DENSITY
All these interaction parameters and alpha formulations may be selected for enthalpy, entropy, and density methods. Normally, for the SOUR package, these features are selected for the K-value method and are automatically carried over for these other methods. However, you can supply the interaction parameters and/or alpha formulations independently.
BANK This option selects the databank from which to retrieve vapor and/or liquid phase binary interaction data. SIMSCI NONE Selects the SimSci standard databank (default). This option disables all data retrieval from databanks for interaction parameters. This option selects a user-created databank named bankid that is created and maintained with the LIBMGR program.
bankid
ALPH A
This option allows access to the databank for alpha formulations. SIMSCI Selects the SimSci alpha formulation and values supplied from the SimSci databank (default).
ACENTRIC Uses original Soave acentric form for alpha (default). bankid This option selects a user-created databank named bankid that is created and maintained with the LIBMGR program.
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This statement inputs binary interaction parameters and alpha formulation data for the SRKM method used to calculate vapor enthalpies, vapor densities and liquid and vapor entropies for the SOUR package. See Modified Soave-Redlich-Kwong and Peng-Robinson on page 4-13 for further details.

Examples
6.5: Using the SOUR system, model a 80/5/10/5 mix of water, H2S, CO2 and NH3 at 50 psia and 20% vaporization.
TITLE PROB=SOUR PRINT INPUT=ALL COMPONENT DATA LIBID 1,H2O/2,H2S/3,CO2/4,NH3 THERMO DATA METHOD SYSTEM=SOUR STREAM DATA PROP STREAM=1, TEMP=100, PRES=100, & COMP=80/5/10/5 UNIT OPERATION FLASH UID=FL7 FEED 1 PROD V=2, L=3 TPSPEC PRES=50 SPEC STREAM=2, RATE, RATIO, STREAM=1,& RATE, VALUE=0.2 END
6.6:
For the same problem, supply SRKM vapor enthalpy interaction data for component pairs 1-2 and 1-4.
THERMO DATA METHOD SYSTEM=SOUR ENTHALPY(V) SRKM 1, 2, 0.38, -26.7, 7, 0.0, 1.64, 0.3, -168, 10011, 0.3/ & 1, 4, -0.08, -54, 0.0, 2.5, -0.18, -28, 0.0, 0.5
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Special Packages
GPA Sour Water

Typical Usage
... COMPONENT DATA LIBID 1, H2O/2, H2S/3, CO2/4, NH3 THERMO DATA METHOD SYSTEM=GPSWATER STREAM DATA . . .
General Information
The GPSWATER package predicts VLE and/or LLE phase behavior for Sour Water systems. This method does not support free water decant. It uses the Gas Processors Association GPSWAT method to model sour water components H2O, NH3, H2S, CO, CS2, MeSH, EtSH and CO2. SRKM is used for all other components. The GPSWATER package is generally valid for a wider range of applications involving sour water than the SOUR package (See Sour Water on page 5-17).
Table 5-7:Attributes of GPSWATER Package Properties predicted by GPSWATER method K-values Required pure component properties1 Critical temperature Critical pressure Pressure Temperature Components Acentric factor
Suggested application ranges - up to 2000 psia - 68-600 F - xwt NH3 < 0.40, PCO2+ PH2S < 1200 psia (H2O, NH3, H2S, and CO2 required) Two liquid phase behavior Free-water decant VLLE
1
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Input Description
METHOD or METHOD SYSTEM(VLE or VLLE)=GPSWATER,... KVALUE(VLE and/or LLE or VLLE)=GPSWATER, ENTHALPY(V)=SRKM, ENTHALPY(L)=IDEAL, ENTROPY=SRKM, DENSITY(V)=SRKM, DENSITY(L)=IDEAL, ...
SYSTE M
Selects a combination of consistent thermodynamic property generators. When SYSTEM=GPSWATER is chosen, GPSWATER K-values, SRKM vapor enthalpies, IDEAL liquid enthalpies, SRKM entropies, IDEAL liquid densities, and SRKM vapor densities are default. Selects the method for K-value calculations. Both VLE and VLLE K-value calculations are available with the GPSWATER package.
KVALU E

ENTHALPY BANK=SIMSCI or NONE or bankid, ALPHA=SIMSCI or ACENTRIC or bankid ENTROPY BANK=SIMSCI or NONE or bankid, ALPHA=SIMSCI or ACENTRIC or bankid BANK=SIMSCI or NONE or bankid, ALPHA=SIMSCI or ACENTRIC or bankid i, j, kija, kjia, kijb, kjib, kijc, kjic, cij, cji /... i, c1, c2, c3/ ...
DENSITY
SRKM(K or R) SA01 to SA11
All these interaction parameters and alpha formulations may be selected for enthalpy, entropy, and density methods. Normally, for the GPSWATER package, these features are selected for the Kvalue method and are automatically carried over for these other methods. However, you can supply the interaction parameters and/ or alpha formulations independently.
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Special Packages
BANK
This option selects the databank from which to retrieve vapor and/or liquid phase binary interaction data. SIMSCI NONE Selects the SimSci standard databank (default). This option disables all data retrieval from databanks for interaction parameters. This option selects a user-created databank named bankid that is created and maintained with the LIBMGR program.
bankid
ALPH A
This option allows access to the databank for alpha formulations. SIMSCI Selects the SimSci alpha formulation and values supplied from the SimSci databank (default).
ACENTRIC Uses original Soave acentric form for alpha (default). bankid This option selects a user-created databank named bankid that is created and maintained with the LIBMGR program.
This statement inputs binary interaction parameters and alpha formulation data for the SRKM method used to calculate vapor enthalpies, vapor densities and liquid and vapor entropies for the GPSWATER package. See Modified Soave-Redlich-Kwong and Peng-Robinson on page 4-13 for further details.

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Examples
6.7: Using the GPSWATER system, model a 80/5/10/5 mix of water, H2S, CO2 and NH3 at 50 psia and 20% vaporization.
TITLE PROB=GPSWATER COMPONENT DATA LIBID 1,H2O/2,H2S/3,CO2/4,NH3 THERMO DATA METHOD SYSTEM=GPSWATER STREAM DATA PROP STREAM=1, TEMP=100, PRES=100,& COMP=80/5/10/5 UNIT OPERATION FLASH UID=F405 FEED 1 PROD V=2, L=3 TPSPEC PRES=50 SPEC STREAM=2, RATE, RATIO, STREAM=1, & RATE, VALUE=0.2 END
6.8:
For the same problem, supply SRKM enthalpy interaction data for component pairs 1-2 and 1-4.
THERMO DATA METHOD SYSTEM=GPSWATER ENTHALPY(V) SRKM 1, 2, 0.38, -26, 0.0, 1.6, 0.3, -168, 10011, 0.3/ & 1, 4, -0.08, -54, 0.0, 2.5,- 0.18, -28, 0.0, 0.5
Amines
Typical Usage
... COMPONENT DATA LIBID 1, H20/2, H2S/3, MEA/4, C1 THERMO DATA METHOD SYSTEM=AMINE STREAM DATA ...
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Special Packages
General Information
The AMINE package is used to predict VLE and/or LLE phase behavior. This method does not support free water decant. This system uses the Kent-Eisenberg model for reaction equilibria with MEA, DEA, or DIPA and an additional residence time correction for MDEA or DGA. A correction is applied to IDEAL liquid enthalpies to account for heats of reaction. The DIPA data are not recommended for final design purposes. The AMINE package is generally useful for gas sweetening processes with a single amine. Only one amine at a time is allowed.
Table 5-8:Attributes of the AMINE Package Properties predicted by the AMINE method K-values Required pure component properties1 Critical temperature Critical pressure Suggested application ranges MEA Pressure, psig Temperature, F Acid gas loading, (mol gas/mol amine) Free-water decant VLLE
1
Acentric factor
DEA
<275 ~25-35 0.45
DGA
<275 ~55-65 0.50
MDEA
<275 ~50 0.4
DIPA
<275 ~30 0.4
25-500 <275
100-1000 100-1000 100-1000 100-1000
Concentration, wt.% ~15-25

0.5-0.6
Two liquid phase behavior - Not supported - Supported
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Input Description
METHOD or METHOD SYSTEM(VLE or VLLE)=AMINE,... KVALUE(VLE and/or LLE or VLLE)=AMINE, ENTHALPY(V)=SRKM, ENTHALPY(L)=AMINE, ENTROPY=SRKM, DENSITY(V)=SRKM, DENSITY(L)=IDEAL, ...
SYSTEM
Selects a combination of consistent thermodynamic property generators. When SYSTEM=AMINE is chosen, AMINE K-values, SRKM vapor enthalpies, AMINE liquid enthalpies, SRKM entropies, IDEAL liquid densities, and SRKM vapor densities are default. Selects the method for K-value calculations. Both VLE and VLLE K-value calculations are available with the AMINE package.
KVALUE

KVALUE(VLE or LLE or VLLE)RESI=0.3
RESI
Specifies the dimensionless residence time correction for systems involving MDEA or DGA. The default value is 0.3. A RESI value of 1.0 corresponds to an equilibrium model. For amines MEA, DEA or DIPA, the entry is ignored if it appears.
Note: If used for correcting the dimensionless residence time for
systems involving MDEA or DGA, the RESI statement must follow the KVALUE statement.
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Special Packages

DENSITY
All these interaction parameters and alpha formulations may be selected for enthalpy, entropy, and density methods. You can supply the interaction parameters and/or alpha formulations independently.
BANK This option selects the databank from which to retrieve vapor and/or liquid phase binary interaction data. SIMSCI NONE bankid Selects the SimSci standard databank (default). This option disables all data retrieval from databanks for interaction parameters. This option selects a user-created databank named bankid that is created and maintained with the LIBMGR program.
ALPHA
This option allows access to the databank for alpha formulations. SIMSCI Selects the SimSci alpha formulation and values supplied from the SIMSCI databank (default). Uses original Soave acentric form for alpha (default). This option selects a user-created databank named bankid that is created and maintained with the LIBMGR program.
ACENTRI C bankid
This statement inputs binary interaction parameters and alpha formulation data for the SRKM method used to calculate vapor enthalpies, vapor densities and liquid and vapor entropies for the AMINE package. See Modified Soave-Redlich-Kwong and Peng-Robinson on page 4-13 for further details.
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Examples
6.9: Using the AMINE system, model a mix of water, H2S, CO2, MEA, and NH3 at 50 psia and 20% vaporization.
TITLE PROB=AMINE PRINT INPUT=ALL COMPONENT DATA LIBID 1,H2O/2,H2S/3,CO2/4,NH3/5,MEA THERMO DATA METHOD SYSTEM=AMINE STREAM DATA PROP STREAM=1, TEMP=100, PRES=100, & COMP=30/5/10/5/50 UNIT OPERATION FLASH UID=FL3 FEED 1 PROD V=2, L=3 TPSPEC PRES=50 SPEC STREAM=2, RATE, RATIO, STREAM=1, & RATE, VALUE=0.2 END
6.10:
For the same problem, use MDEA and supply a residence time correction factor of 1.0.
COMPONENT DATA LIBID 1,H2O/2,H2S/3,CO2/4,NH3/5,MDEA THERMO DATA METHOD SYSTEM=AMINE KVALUE RESI=1.0
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Special Packages
User-added Subroutines
Typical Usage
... COMPONENT DATA LIBID 1,IC4/ 2, NC4/ 3, H2O THERMO DATA METHOD KVALUE=U1, ENTHALPY=U2, DENSITY=U3 STREAM DATA . . .
General Information
User-added subroutines can be supplied to calculate equilibrium Kvalues and to generate liquid and/or vapor enthalpy data, liquid and/ or vapor entropy data and liquid and/or vapor density data.
Table 5-9:Attributes of User-Added Subroutines Properties predicted by User-Added Subroutines K-values Liquid/vapor densities Liquid/vapor entropies Liquid/vapor enthalpies
Required pure component properties1 As required by the subroutine Two liquid phase behavior Free-water decant VLLE - Supported - Supported
Automatically supplied for library and petroleum II-5-29
components. Must be supplied by the user for non-library components
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Special Packages
Input Description
METHOD KVALUE(VLE and/or LLE or VLLE)=U1 or U2 or ... U15, ENTHALPY(VL or V and/or L)=U1 or U2 or ... U15, ENTROPY(VL or V and/or L)=U1 or U2 or ... U15, DENSITY(VL or V and/or L)=U1 or U2 or ... U15
KVALUE and/or ENTHALPY and/or ENTROPY and/or DENSITY
Selects the user-added method for K-value, liquid/ vapor enthalpy, liquid/vapor entropy, and liquid/vapor density calculations. Both VLE and LLE K-value calculations are available when supplying user-added subroutines. The VLLE option automatically selects both. See the PRO/II Data Transfer System and UserAdded Subroutines Users Guide for more details on specifying these subroutines.

KVALUE(VLE or LLE or VLLE) UDATA i, value /...
Note: If used for calculating K-values, the UDATA statement
must follow the KVALUE statement.

UDATA This statement supplies method-specific data that will be used by the user-added subroutine for the calculation of equilibrium K-values. See the PRO/II Data Transfer System and User-added Subroutines User's Guide for more information.

ENTHALPY ENTROPY DENSITY UDATA i, value /...
See above under K-value Data for format and definition of these entries.
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Examples
6.11: Using a user-supplied liquid enthalpy method U1 and the GLYCOL package, model a 50/25/20/5 mix of water, benzene, ethanol and TEG at 50 psia and 20% vaporization. Supply data for U1 for components 2 and 4.
TITLE PROB=UASENTH COMPONENT DATA LIBID 1,H2O/2,BENZENE/3,ETOH/4,TEG THERMO DATA METHOD SYSTEM=GLYCOL, ENTHALPY(L)=U1 ENTHALPY(L) UDATA 2,2.5/4,3.0 STREAM DATA PROP STREAM=1,TEMP=100,PRES=100, & COMP=50/25/20/5 UNIT OPERATION FLASH UID=FL3D FEED 1 PROD V=2, L=3 TPSPEC PRES=50 SPEC STREAM=2, RATE, RATIO, STREAM=1, & RATE, VALUE=0.2 END
CAPE-OPEN
Typical Usage
.. COMPONENT DATA LIBID 1,PROPANE/2,BENZENE/3,METHANE, BANK=PROCESS,SIMSCI THERMODYNAMIC DATA
METHOD SYSTEM=CO, PID=SIMSCI.THERMOSYSTEM.1, & PNAME=COC3C6C1SRK, SET=CO01 . . .
The PRO/II CAPE-OPEN thermodynamics capability enables users to add a third party CAPE-OPEN property packages to perform thermodynamic property calculations for streams on flow sheet. CAPE-OPEN standards are the uniform standards for interfacing
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process modeling software components developed specifically for the design and operation of chemical processes. These standards allow integration of different software components like Unit Operations and Thermodynamic Property Packages from different vendors into a single simulation.
Input Description
The Method Statement
Method SYSTEM=CO, PID=SIMSCI.THERMOSYSTEM.1, PNAME=COC3C6C1SRK SYSTEM Selects a combination of consistent thermodynamic property generators. When SYSTEM = CO is chosen, all property calculations and flash calculations will done in property package. Program Id of COM identifier for property package. This is to identify and instantiate the property package on computer system If CAPE-OPEN thermodynamics is thermo system, it gives package name. If it is a property package, PNAME will be NULL
PID
PNAME
EXAMPLE
TITLE =CAPE-OPEN DESC TEST SAMPLE CAPEOPEN THERMO DIMENSION SI, STDTEMP=273.15, STDPRES=101.325 SEQUENCE SIMSCI CALCULATION RVPBASIS=APIN, TVP=310.93 COMPONENT DATA LIBID 1,PROPANE/2,BENZENE/3,METHANE, BANK=PROCESS,SIMSCI THERMODYNAMIC DATA METHOD SYSTEM=SRK, SET=SRK01, DEFAULT
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METHOD SYSTEM=CO, PID=SIMSCI.THERMOSYSTEM.1, PNAME=COC3C6C1SRK, & SET=CO01 METHOD SYSTEM=CO, PID=COPROPPACK.CPROPPACK, PNAME=NULL, SET=CO02 STREAM DATA PROPERTY STREAM=S1, TEMPERATURE=250, PRESSURE=1400, PHASE=M, & RATE(M)=300, COMPOSITION(M)=1,1/2,1/3,1, & NORMALIZE, SET=DEFAULT UNIT OPERATIONS FLASH UID=F1 FEED S1 PRODUCT V=S2, L=S3 ADIABATIC END
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Special Packages
Chapter 6 Liquid Activity Methods

These are primarily applicable to highly non-ideal systems, particularly non-hydrocarbons. These methods are also useful for predicting VLLE behavior.
NRTL
Typical Usage
...
COMPONENT DATA LIBID 1, IPA/ 2, H2O/ 3, CH THERMO DATA METHOD SYSTEM=NRTL STREAM DATA . . .
General Information
The Non-Random Two Liquid (NRTL) liquid activity method is used to predict VLE and/or LLE phase behavior. This method does not support free water decant. The NRTL method is generally useful for non-ideal applications, especially for partially immiscible systems. Refer to the PRO/II Reference Manual for additional information.
II-6-1
Table 6-1: Attributes of NRTL methods Properties predicted by NRTL methods K-values Required pure component properties1 Vapor pressure Vapor pressure Critical temperature Critical pressure Acentric factor
PHI=IDEAL and POYNTING=OFF When used with PHI=SRK or PR or SRKM or PRM or SRH or PRH or SRP or PRP or SRKS or SRKKD or BWRS or UNIWAAL or HOCV
When used with POYNTING=ON Vapor pressure Liquid molar volume

1
Not supported Supported
Input Description
METHOD or METHOD SYSTEM(VLE or VLLE)=NRTL, PHI=IDEAL, {HENRY},... KVALUE(VLE and/or LLE or VLLE)=NRTL, PHI=IDEAL, {HENRY},..
SYSTEM
Selects a combination of consistent thermodynamic property generators. When SYSTEM=NRTL is chosen, NRTL K-values, LIBRARY enthalpies, IDEAL liquid densities and IDEAL vapor densities are default. Selects the method for K-value calculations. Both VLE and LLE K-value calculations are available with the NRTL method. The VLLE option automatically selects both. See Vaporliquid-liquid Equilibrium Considerations on page 1-37 for more details on liquid-liquid equilibrium calculations.
KVALUE
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PHI
Selects the option used to calculate pure component and mixture vapor phase fugacity coefficients (i). A vapor fugacity method should generally be selected for high pressure applications. The options are the equations of state methods SRK, PR, SRKM, PRM, SRKH, PRH, SRKP, PRP, SRKS, SRKKD, BWRS and UNIWAAL (see Chapter 4) and HOCV (the Hayden-O'Connell method), TVIRIAL (the Truncated Virial method) and the IDIMER method. See Hayden-OConnell Vapor Fugacity on page 6-69, Truncated Virial Vapor Fugacity on page 6-73, and IDIMER Vapor Fugacity on page 6-78, for details on these last three options. The default is PHI=IDEAL. This option selects Henry's Law data (either user-supplied or from databanks) to model dissolved gases in a liquid solution. See Henrys Law for Non-condensible Components on page 6-63 for further details.
HENRY
Note: A heat of mixing option, HMIX, is available for the enthalpy method selected. See Redlich-Kister, Gamma Heat of Mixing on page 6-82, for further information on the use of this option.

KVALUE(VLE or LLE or VLLE) POYNTING=OFF or ON, MOLVOL=STANDARD or RACKETT or RCK2 or LIBRARY, BANK=SIMSCI or ALCOHOL or NONE or bankid, FILL=NONE or UNIFAC or UFT1 or FLORY or REGULAR, AZEOTROPE = SIMSCI or NONE or bankid, WRITE=fileid NRTL3(K or KCAL or KJ) and/or NRTL(K or KCAL or KJ) and/or NRTL6(K or KCAL or KJ) and/or NRTL8(K or KCAL or KJ) i, j, bij, bji, ij / ... i, j, aij, bij, aji, bji, ij / ... i, j, aij, bij, aji, bji, ij, ij / ... i, j, aij, bij, cij, aji, bji, cji, ij, ij / ...
and/or AZEOTROPE(basis, punit, tunit) i, j, pres, temp, xi / ... and/or INFINITE(tunit) i, j, temp, ioo , joo / ...
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and/or MUTUAL(basis, tunit) and/or IDEAL i, j, temp, xiI, xjII / ... i, j / ...
Note: The NRTL3, NRTL, NRTL6, NRTL8, AZEOTROPE,
INFINITE, MUTUAL and/or IDEAL statements must follow the KVALUE statement.
POYNTING
This option selects whether to apply the Poynting correction to fugacities of components in the liquid phase. The default is OFF unless a PHI method is selected, in which case the default is ON. This selects the method used to calculate the liquid molar volume necessary for computing the Poynting correction factor. Options are: STANDARD The default. Selects the standard method for calculating the liquid molar volume at standard conditions (25 C, 1 atm). RACKETT RCK2 LIBRARY Selects the Rackett liquid density method. Selects the Rackett 2 liquid density method. Selects the LIBRARY liquid density method.
MOLVOL
BAN K
This option selects one or more banks from which to retrieve vapor and/or liquid phase binary interaction data. SIMSCI ALCOHOL Selects the SimSci standard databank (default). Selects the Alcohol databank. This databank contains binary coefficients for systems with alcohols, water and other polar components. This option disables all data retrieval from databanks for interaction parameters. Liquid Activity Methods
NONE
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bankid
This option selects a usercreated databank named bankid that is created and maintained with the LIBMGR program.
FILL
This selects the method used for estimating values for binary interaction data missing from the input file and any selected databank libraries. See Filling in Missing Parameters on page 6-57, for further details on these options. This selects the azeotrope databank used for retrieving azeotropic data for binary pairs. Current options are SIMSCI (default) or NONE or bankid. This option writes the binary interaction parameters for the liquid activity coefficient Kvalue method to a file. The format of this file is suitable for inclusion into an input file. fileid This name identifies the file containing the binary interaction data. It may be any valid file name allowed on the particular operating system being used, but must not include a suffix. The program will automatically add a suffix (e.g., .FIL on PCs).
AZEOTROPE
WRITE
NRTL3 and/or NRTL and/or NRTL6 and/or NRTL8
This statement allows entry of the binary interaction data parameters for the NRTL liquid activity coefficient method. The statements can be mixed in order to enter the data in the most convenient form. The binary parameters aij, bij, cij, aji, bji, cji, ij, and ij are related to the liquid activity coefficients gi by the following equations:
xk kj Gkj x G j ij j k ij --------------------------ln i = ------------------------ + -------------------- G x G x G x ki k j kj k kj k k
ji Gji xj
k
b ij c ij - + ---- ij = a ij + ----T T2
(when unit is K)
II-6-5
c ij b ij - + ---------- ij = a ij + ------ (when unit is KCAL or RT 2 2 R T
KJ)
G ji = exp ( ji ji ) and ij = ij + ij T
AZEOTROPE and/or INFINITE and/ or MUTUAL
These statements are used to enter data for binary pairs. This data will be regressed to the coefficients for the liquid activity method used to generate the K-values. Multiple statements may be used to enter data with different units or the data can be entered on a single statement. This statement sets the binary interaction parameters to zero.
and/or IDEAL
Data input using the NRTL3, NRTL, NRTL6, NRTL8, AZEOTROPE, INFINITE, MUTUAL and IDEAL statements is used in preference to any data retrieved from the databanks or estimated using FILL options. See Filling in Missing Parameters on page 657, for further details.

TC(unit) PC(unit) ACENTRIC MOLVOL(unit) ... i, value / ... i, value / ... i, value / ... i, value / ...
Properties may be supplied that are active only when a specific method is used. For a further description of these input parameters see Chapter 9, Method-specific Pure Component Data. Note that only the vapor pressure has any direct effect on the calculation of K-values. The vapor pressure may only be supplied globally for all sets in the Component Data Category. Tc, Pc and the acentric factor will have an impact on the K-values if a cubic equation of state is chosen for vapor phase fugacities. Molar volume will have an impact on the Poynting correction factor.
Examples
5.1: Using the NRTL system, model a 50/40/10 mix of DIPE, IPA and water at 50 psia and 50% vaporization.
TITLE PROB=NRTL PRINT INPUT=ALL
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COMPONENT DATA LIBID 1,H2O/ 2,BENZENE/ 3,ETOH/ 4,CHEN THERMO DATA METHOD SYSTEM=NRTL, PHI=SRK KVALUE FILL=UNIFAC, POYNTING=ON NRTL 1,2,5.256,219.685,-5.645,288.34,0.2/ & 1,3,1.015,536.264,0.4985,-456.0,0.1448/ & 2,3,-2.748,1472.24,-0.449,440.51,0.5355 STREAM DATA PROP STREAM=1, TEMP=100, PRES=100, & COMP=50/25/20/5 UNIT OPERATION FLASH UID=F204 FEED 1 PROD V=2, L=3 TPSPEC PRES=50 SPEC STREAM=2, RATE, RATIO, STREAM=1, & RATE, VALUE=0.2 END
5.2:
For the same problem, use NRTL K-values, IDEAL enthalpies and liquid densities and SRK vapor densities.
THERMO DATA METHOD KVALUE=NRTL, ENTHALPY=IDEAL, & DENSITY(L)=IDEAL, DENSITY(V)=SRK
UNIQUAC
Typical Usage
...
COMPONENT DATA LIBID 1, IPA/ 2, H2O/ 3, CH THERMO DATA METHOD SYSTEM=UNIQUAC STREAM DATA . . .
General Information
The UNIQUAC liquid activity method is used to predict both VLE and VLLE phase behavior. This method does not support free water decant.
II-6-7
The UNIQUAC method is generally useful for highly non-ideal applications, especially for partially immiscible systems. Refer to the PRO/II Reference Manual for additional information.
Table 6-2: Attributes of UNIQUAC Methods Properties predicted by UNIQUAC methods K-values Required pure component properties1 Vapor pressure van der Waals area and volume Vapor pressure Critical temperature Critical pressure Acentric factor van der Waals area and volume Vapor pressure Liquid molar volume van der Waals area and volume Two liquid phase behavior Free-water decant VLLE
1
PHI=IDEAL and POYNTING=OFF
When used with PHI=SRK or PR or SRKM or PRM or SRH or PRH or SRP or PRP or SRKS or SRKKD or BWRS or UNIWAAL or HOCV
Input Description
METHOD or METHOD SYSTEM(VLE or VLLE)=UNIQUAC, PHI=IDEAL, {HENRY},... KVALUE(VLE and/or LLE or VLLE)=UNIQUAC, PHI=IDEAL, {HENRY},...
SYSTEM
Selects a combination of consistent thermodynamic property generators. When SYSTEM=UNIQUAC is chosen, UNIQUAC Kvalues, LIBRARY enthalpies, IDEAL liquid densities and IDEAL vapor densities are default.
II-6-8
KVALUE
Selects the method for K-value calculations. Both VLE and LLE K-value calculations are available with the UNIQUAC method. The VLLE option automatically selects both. See Vapor-liquidliquid Equilibrium Considerations on page 1-37 for more details on liquid-liquid equilibrium calculations. Selects the option used to calculate pure component and mixture vapor phase fugacity coefficients (i). A vapor fugacity method should generally be selected for high pressure applications. The options are the equations of state methods SRK, PR, SRKM, PRM, SRKH, PRH, SRKP, PRP, SRKS, SRKKD, BWRS and UNIWAAL (see Chapter 4) and HOCV (the Hayden-O'Connell method), TVIRIAL (the Truncated Virial method) and the IDIMER method. See Hayden-OConnell Vapor Fugacity on page 6-69, Truncated Virial Vapor Fugacity on page 6-73, IDIMER Vapor Fugacity on page 6-78, for details on these last three options. The default is PHI=IDEAL. This option selects Henry's Law data (either usersupplied or from databanks) to model dissolved gases in a liquid solution. See Henrys Law for Non-condensible Components on page 6-63 for further details.
PHI
HENRY

KVALUE(VLE or LLE or VLLE) POYNTING=OFF or ON, MOLVOL=STANDARD or RACKETT or RCK2 or LIBRARY, BANK=SIMSCI or NONE or bankid, FILL=NONE or UNIFAC or UFT1 or FLORY or REGULAR, AZEOTROPE = SIMSCI or NONE or bankid, WRITE=fileid UNIQUAC(K or KCAL or KJ) and/or UNIQ4(K or KCAL or KJ) i, j, aij, aji / ... i, j, aij, aji, bij, bji / ...
and/or AZEOTROPE(basis, punit, tunit) i, j, pres, temp, xi / ...
II-6-9
and/or INFINITE(tunit) and/or MUTUAL(basis, tunit) and/or IDEAL i, j / ... i, j, temp, xiI, xjII / ... i, j, temp, ioo, joo / ...
Note: The UNIQUAC, UNIQ4, AZEOTROPE, INFINITE, MUTUAL and/or IDEAL statements must follow the KVALUE statement. POYNTING This option selects whether to apply the Poynting correction to fugacities of components in the liquid phase. The default is OFF unless a PHI method is selected, in which case the default is ON. This selects the method used to calculate the liquid molar volume necessary for computing the Poynting correction factor. Options are: STANDARD The default. Selects the standard method for calculating the liquid molar volume at standard conditions (25 C, 1 atm). Selects the Rackett liquid density method. Selects the Rackett 2 liquid density method. Selects the LIBRARY liquid density method.
MOLVOL
RACKETT RCK2 LIBRARY BAN K
This option selects one or more banks from which to retrieve vapor and/or liquid phase binary interaction data. SIMSCI NONE Selects the SimSci standard databank (default). This option disables all data retrieval from databanks for interaction parameters. This option selects a user-created databank named bankid that is created and maintained with the LIBMGR program.
bankid
II-6-10
FILL
This selects the method used for estimating values for binary interaction data missing from the input file and any selected databank libraries. See Filling in Missing Parameters on page 657, for further details on these options. This selects the azeotrope databank used for retrieving azeotropic data for binary pairs. Current options are SIMSCI (default) or NONE or bankid. This statement allows entry of the binary interaction data parameters for the UNIQUAC liquid activity coefficient method. The statements can be mixed in order to enter the data in the most convenient form. The binary parameters aij, bij, aji and bji are related to the liquid activity coefficients i by the following equations:
ln i = ln i + ln i
C R
AZEOTROPE
UNIQUAC and/or UNIQ4
i i Z i C - q i ln ---ln i = ln ---- + -- + l i ---i xi 2 i = q i 1 ln
Xj lj
j=1
ln i
j ji
j=1
j ij ---------------------- M j=1 k kj
M k=1
U ij ij = exp -----T U ij ij = exp -----RT U ij = a ij + b ij T xi qi i = -----------------M
(when unit is K) (when the unit is KCAL or KJ)
Z - ( r qj ) ( rj 1 ) l j = -2 j
xi qi
i=1
xi ri i = ----------------M
xj rj
j=1
II-6-11
A wi q i = -----------------9 2.5 10
V wi - , Z = 10 r i = -----------15.17
AZEOTROPE and/or INFINITE and/ or MUTUAL
These statements are used to enter data for binary pairs. This data will be regressed to the coefficients for the liquid activity method used to generate the K-values. Multiple statements may be used to enter data with different units or the data can be entered on a single statement. This statement sets the binary interaction parameters to zero. This option writes the binary interaction parameters for the liquid activity coefficient Kvalue method to a file. The format of this file is suitable for inclusion into an input file. fileid This name identifies the file containing the binary interaction data. It may be any valid file name allowed on the particular operating system being used, but must not include a suffix. The program will automatically add a suffix (e.g., .FIL on PCs).
and/or IDEAL WRITE
Data input using the UNIQUAC, UNQ4, AZEOTROPE, INFINITE, MUTUAL and IDEAL statements is used in preference to any data retrieved from the databanks or estimated using FILL options. See Filling in Missing Parameters on page 6-57, for further details. Method-specific Pure Component Properties (optional)
TC(unit) PC(unit) ACENTRIC MOLVOL(unit) VANDERWAALS ... i, value / ... i, value / ... i, value / ... i, value / ... i, value / ...
Properties may be supplied that are active only when a specific method is used. For a further description of these input parameters, see Chapter 9, Method-specific Pure Component Data. Note that of these properties, only the van der Waals area and volume (VANDERWAALS) has any direct effect on the calculation of liquid activity coefficients, but may only be supplied in the Component Data Category. The vapor pressure also has a direct effect on K-values, but may only be supplied globally for all sets in the Component Data Category. Tc, Pc and the acentric factor will
II-6-12 Liquid Activity Methods
have an impact if a cubic equation of state is chosen for vapor phase fugacities. Molar volume will have an impact on the Poynting correction factor.
II-6-13
Examples
5.3: Using the UNIQUAC system, model a 50/40/10 mix of DIPE, IPA and water at 50 psia and 50% vaporization.
TITLE PROB=UNIQUAC PRINT INPUT=ALL COMPONENT DATA LIBID 1,H2O/ 2,BENZENE/ 3,ETOH/ 4,CHEN THERMO DATA METHOD SYSTEM=UNIQUAC STREAM DATA PROP STREAM=1, TEMP=100, PRES=100, & COMP=50/25/20/5 UNIT OPERATION FLASH UID=DRUM FEED 1 PROD V=2, L=3 TPSPEC PRES=50 SPEC STREAM=2, RATE, RATIO, STREAM=1, & RATE, VALUE=0.2 END
5.4:
For the same problem, use UNIQUAC K-values, IDEAL enthalpies and liquid densities and SRK vapor densities.
THERMO DATA METHOD KVALUE=UNIQUAC, ENTHALPY=IDEAL, & DENSITY(L)=IDEAL, DENSITY(V)=SRK
UNIFAC
Typical Usage
...
COMPONENT DATA LIBID 1, IPA/ 2, H2O/ 3, CH THERMO DATA METHOD SYSTEM=UNIFAC STREAM DATA . . .
II-6-14
General Information
The UNIFAC liquid activity method is used to predict both VLE and VLLE phase behavior. This method does not support free water decant. The UNIFAC group contribution method is generally useful for non-ideal applications at low pressures. It is generally restricted to components with 10 or fewer different structural groups and systems containing low molecular weight polymers. Refer to the PRO/II Reference Manual for additional information.
Table 6-3: Attributes of UNIFAC Methods Properties predicted by UNIFAC methods K-values Required pure component properties1 Vapor pressure Structural groups Structure van der Waals area and volume parameters Vapor pressure Critical temperature Critical pressure Structural groups Van der Waals area and volume Vapor pressure Liquid molar volume Structural groups Van der Waals area and volume Pressure Temperature Free-water decant VLLE
1
Suggested application ranges - up to 10 atmospheres - 32-300 F - Not supported - Supported
II-6-15
Input Description
METHOD or METHOD SYSTEM(VLE or VLLE)=UNIFAC, PHI=IDEAL, {HENRY},... KVALUE(VLE and/or LLE or VLLE)=UNIFAC, PHI=IDEAL, {HENRY},..
SYSTEM
Selects a combination of consistent thermodynamic property generators. When SYSTEM=UNIFAC is chosen, UNIFAC Kvalues, LIBRARY enthalpies, IDEAL liquid densities and IDEAL vapor densities are default. Selects the method for K-value calculations. Both VLE and LLE K-value calculations are available with the UNIFAC method. The VLLE option automatically selects both. See Vapor-liquidliquid Equilibrium Considerations on page 1-37 for more details on liquid-liquid equilibrium calculations. Selects the option used to calculate pure component and mixture vapor phase fugacity coefficients (i). A vapor fugacity method should generally be selected for high pressure applications. The options are the equations of state methods SRK, PR, SRKM, PRM, SRKH, PRH, SRKP, PRP, SRKS, SRKKD, BWRS and UNIWAAL (see Chapter 4) and HOCV (the Hayden-O'Connell method), TVIRIAL (the Truncated Virial method) and the IDIMER method. See Hayden-OConnell Vapor Fugacity on page 6-69, Truncated Virial Vapor Fugacity on page 6-73, and IDIMER Vapor Fugacity on page 6-78, for details on these last three options. The default is PHI=IDEAL. This option selects Henry's Law data (either usersupplied or from databanks) to model dissolved gases in a liquid solution. See Henrys Law for Non-condensible Components on page 6-63 for further details.
KVALUE
PHI
HENRY
II-6-16

KVALUE(VLE or LLE or VLLE) POYNTING=OFF or ON, MOLVOL=STANDARD or RACKETT or RCK2 or LIBRARY, BANK=SIMSCI or NONE or bankid, AZEOTROPE = SIMSCI or NONE or bankid, WRITE=fileid UNIFAC(K or KCAL or KJ) l, k, Alk, Akl / ...
and/or AZEOTROPE(basis, punit, tunit) i, j, pres, temp, xi / ... and/or INFINITE(tunit) and/or MUTUAL(basis, tunit) and/or IDEAL i, j / ... i, j, temp, xiI, xjII / ... i, j, temp, ioo, joo / ...
Note: The UNIFAC, AZEOTROPE, INFINITE, MUTUAL and/ or IDEAL statements must follow the KVALUE statement. POYNTING This option selects whether to apply the Poynting correction to fugacities of components in the liquid phase. The default is OFF unless a PHI method is selected, in which case the default is ON. This selects the method used to calculate the liquid molar volume necessary for computing the Poynting correction factor. Options are: STANDARD The default. Selects the standard method for calculating the liquid molar volume at standard conditions (25 C, 1 atm). Selects the Rackett liquid density method. Selects the Rackett 2 liquid density method. Selects the LIBRARY liquid density method.
MOLVOL
RACKETT RCK2 LIBRARY
II-6-17
BAN K
This option selects one or more banks from which to retrieve vapor and/or liquid phase binary interaction data. SIMSCI NONE Selects the SimSci standard databank (default). This option disables all data retrieval from databanks for interaction parameters. This option selects a user-created databank named bankid that is created and maintained with the LIBMGR program.
bankid
AZEOTROPE
This selects the azeotrope databank used for retrieving azeotropic data for binary pairs. Current options are SIMSCI (default) or NONE or bankid. This option writes the binary interaction parameters for the liquid activity coefficient Kvalue method to a file. The format of this file is suitable for inclusion into an input file. fileid This name identifies the file containing the binary interaction data. It may be any valid file name allowed on the particular operating system being used, but must not include a suffix. The program will automatically add a suffix (e.g., .FIL on PCs).
WRITE
UNIFAC
This statement allows entry of the group interaction data parameters for the UNIFAC liquid activity coefficient method. The statements can be mixed in order to enter the data in the most convenient form. The group parameters Alk and Akl are related to the liquid activity coefficients i by the following equations:
ln i = ln i + ln i
C R
where:
i i i Z i C - + 1 ----ln i = ln ----- + 1 ----- -- q i ln ---- i i xi xi 2
II-6-18
xi ri xi qi i = ------------------ , i = ------------------NOC NOC
xj rj
j=1 NK
xj qj
j=1 NK
ri =
k=1
k Rk
, qi =
k Qk
k=1
Rk = volume parameter for group k Qk = surface area parameter for group k vki = number of type k groups in component i xi = liquid mole fraction of component i Z = coordination number (Z = 10) NK = number of groups in molecule i
NK
ln ( i ) =
k ( ln k ln k )
k=1
NK NK m mk ln ( k ) = Q k 1 -------------------------- ln m mk NK m = 1 n1 n nm
n=1
A nm nm = exp (where unit is K) --------T A nm nm = exp --------(where unit is KCAL or KJ) RT Qm Xm nm = ----------------------NK
Qn Xn
n=1 NOC
m xj
j=1 X m = ------------------------------NK NOC
n xj
n = 1j = 1
Anm =
group interaction parameter for the interaction between m and n. II-6-19
Data are available in PRO/II databanks for many structural groups as shown in Table 6-4. AZEOTROPE and/or INFINITE and/ or MUTUAL These statements are used to enter data for binary pairs. This data will be regressed to the coefficients for the liquid activity method used to generate the K-values. Multiple statements may be used to enter data with different units or the data can be entered on a single statement. This statement sets the binary interaction parameters to zero.
and/or IDEAL
Data input using the UNIQUAC, AZEOTROPE, INFINITE, MUTUAL and IDEAL statements is used in preference to any data retrieved from the databanks. Method-specific Pure Component Properties (optional)
Properties may be supplied that are active only when a specific method is used. For a further description of these input parameters, see Chapter 9, Method-specific Pure Component Data. Note that of these properties, only the van der Waals area and volume (VANDERWAALS) has any direct effect on the calculation of liquid activity coefficients, but may only be supplied in the Component Data Category. The vapor pressure also has a direct effect on K-values, but may only be supplied globally for all sets in the Component Data Category. Tc, Pc and the acentric factor will have an impact if a cubic equation of state is chosen for vapor phase fugacities. Molar volume will have an impact on the Poynting correction factor.
II-6-20
Table 6-4: Available UNIFAC Interaction Parameters

UNIFAC INTERACTION PARAMETERS AVAILABLE IN PROII
V L * $ @ T
11 20 21 27 30 40 43 46 50 52 55 56 59 60 70 73 76 81 84 86 87 88 90 110 114 120 122 130 140 141 143 144 150 151 153 161 162 168 170 171 203 247 250 251 260 270 281 287 290 300 320 330 340 350 360 385 388 ------------------------------------------------------------------------------------------------------------------* @ V . * V . V . . * . . @ @ V V @ @ @ * * @ @ . @ * @ . L . V . . . $ @ @ . * . V . . V V . . . V V . . . . L . | | * V . V . . . . . * . . V * . V . . . V . * V . * * * . . L * . . V V * * V . . . V . . . . . . . . . . . . * . | | . . @ V V V $ $ @ V $ @ @ V V @ @ @ * * @ @ V @ * @ @ * * @ V . V $ @ @ V * V V V V V V . V V V V . . . . * V | |
. No interactions VLE interactions - ( 634) LLE interactions - ( 208) Both VLE and LLE - ( 91) Both VLE and T - ( 48) VLE - LLE and T - ( 103) TEMP dependent - ( 1)
V V . V . . . . . V . . . . V . . . V V . V . . . . . . . . . V V V . . $ V . V V $ . V V @ . V V . $ V V V @ V . . V . . . . . V V V . . V . V V . . V V V @ . . . V . V . . @ V . V V . . . . . . . $ @ @ . V @ V . . . . . L . $ @ @ V V @ . . . . . V V V . V V * V V V V V V . . V . . . . . V V V V V V V . @ V V * $ $ @ V $ @ @ V V @ @ @ * * @ V . * $ $ V . $ @ @ V V @ @ @ V V @ . . . V . . . . . . . . . . . . . V V V @ V V * $ $ @ V $ @ @ V V @ $ @ * V @ @ . * V V V V V * V V * * V V * V * * V * * . * @ V V V . V @ V V @ @ V V @ @ @ * * @ @ V @ * . . . V V V $ . . V @ V V V V @ * V @ @ V @ * @ . . . V . . . . . * V . V V V . * V * * V * * * V . . . . . . * . . . . . . V . . V . * . . * * * . V . . . . . T * . . V . V . . $ @ L V @ V . @ * $ @ . V . . . V V . . . . V . V . V . . . . V . . V V V V . . . . . . . . . . . . . . . . . . V . V V V . . . . . . . . V . . . . . . . . . . . . . . . . . . V . . V V V . V . V . . $ . . V $ $ $ V $ $ $ V V $ $ $ V V $ $ . $ V $ $ V . $ V V V * V . * $ $ @ V $ @ @ . V @ @ @ * L @ @ . @ * @ @ * * @ . . . $ . . . V $ $ @ . $ @ @ V V @ @ @ * V @ @ . @ * @ @ * * $ . V V $ @ . . . . . . . . . V V . V V . V . V V V . V V V V V . . . . . V V V L . . L . . . . . V * . V . L * . L * V . * * * . . . L . . . . * * . V . . V . . . . . . V . V . . . . V V V . V V . V . . . . . . V V V . . . . . V . . . . . V V . V . V V . . * * . * * V . . . . V . . V V V . . . . . . . . . . . . . . . . . . V V V V V . V V . . . . . V . . . V . . . . . . . . . . . . . . . . . . . . . . V V . V V . . . . . . . . V V . . . . . . . . V V . . . V . . . . . . . . V . . V V V . . . . . . . . V . . . . . . . . V V . . . . . . . . . . . . V . . V V . . . . . . . . . . V . . . . . . V . . . . . . . . . . . . . . V V . V . . . . . . . . . . . . . . . . . . . . V . . V V . . . . . . . . V V . V V . . . . V . . . V . V . . . . . . . . . . . . . . . . . . . . . V . . V . . . V . . . . . V . . . . . . . . . . . . . . V V . V V V . V . V V . V V V V V V V . . . V . V . . . V . . . . . . . . V V . V . V V . . V . . V V V . V V . . . . V . V V . . . . . . . . . . . . . . . . . . . . V . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . V . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . V . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . V . . . . . . . . . . . . . . . . . . . . . V . . * . . V * . V . . . L . * . . * * * V * L . . . . V * . . L . . . . . . . . . . . V . V . V . V . V V . V V V V . . . . . . . V V . . . . | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 2 2 1 1 2 2 2 3 4 4 4 5 5 5 5 5 6 7 7 7 8 8 8 8 8 9 1 1 2 2 3 4 4 4 4 5 5 5 6 6 6 7 7 0 4 0 1 0 1 7 0 0 3 6 0 2 5 6 9 0 0 3 6 1 4 6 7 8 0 0 4 0 2 0 0 1 3 4 0 1 3 1 2 8 0 1 3 7
. V V V . V V V V . V V . . V V V V . V V . V V V V . . . . . . V V V V . . . . . . . . . . . . . . . . . . | |
. . . . . . . . . V . . . . . . . . V . . . . . . . . . . . . . V . . . . . . . . . . . . . . . . . . . . | |
. . . . . . . V . . . . . V . | | 2 5 0
. . . . . . . . . . . . V . | | 2 5 1
. . . . . . . . . . . . . | | 2 6 0
V . . . . . . . . . . . | | 2 7 0
. . . . . . . . . . . | | 2 8 1
V V . . . . . . . . | | 2 8 7
. . . . . . . . . | | 2 9 0
. . . . . . . . | | 3 0 0
. . . . . . . | | 3 2 0
. . . . . . | | 3 3 0
V V V . . | | 3 4 0
V V . . | | 3 5 0
V . . | | 3 6 0
. V | | 3 8 5
Examples
5.5: Using the UNIFAC system, model 50/40/10 mix of DIPE, IPA, and water at 50 psia and 50%vaporization.
TITLE PROB=UNIFAC PRINT INPUT=ALL COMPONENT DATA LIBID 1,DIPE/ 2,IPA/ 3,H2O THERMO DATA METHOD SYSTEM=UNIFAC
II-6-21
STREAM DATA PROP STREAM=1, TEMP=100, PRES=100, & COMP=50/40/10 UNIT OPERATION FLASH UID=F2 FEED 1 PROD V=2, L=3 TPSPEC PRES=50 SPEC STREAM=2, RATE, RATIO, STREAM=1, & RATE, VALUE=0.5 END
5.6:
For the same problem, use UNIFAC K-values, IDEAL enthalpies and liquid densities and SRK vapor densities.
THERMO DATA METHOD KVALUE=UNIFAC, ENTHALPY=IDEAL, & DENSITY(L)=IDEAL, DENSITY(V)=SRK
Modifications to UNIFAC
Typical Usage
...
COMPONENT DATA LIBID 1, IPA/ 2, H2O/ 3, CH THERMO DATA METHOD SYSTEM=UFT1 STREAM DATA . . .
General Information
The modified UNIFAC liquid activity methods are used to predict both VLE and VLLE phase behavior. These methods do not support free water decant. The modified UNIFAC group contribution methods are generally useful for non-ideal applications at low pressures. The Lyngby modification UFT1, the Dortmund modification UFT2, and UFT3 modified methods can be used if temperature dependent UNIFAC data is available. The UNFV free volume data method is designed to model polymer solutions and should not be used for non-polymer systems. Refer to the PRO/II Reference Manual for additional information.
Table 6-5: Attributes of Modified UNIFAC Methods Properties predicted by UNIFAC methods K-values Required pure component properties1 Vapor pressure van der Waals area and volume (UFT1,UFT2,UFT3 only) Vapor pressure Critical temperature Critical pressure Acentric factor Van der Waals area and volume (UFT1,UFT2,UFT3 only) Vapor pressure Liquid molar volume Van der Walls area and volume (UFT1,UFT2,UFT3 only) Pressure Temperature Free-water decant VLLE
1
Suggested application ranges - up to 10 atmospheres - 70-300 F - Not supported - Supported
Input Description
METHOD or METHOD KVALUE(VLE and/or LLE or VLLE)=UF1 or UFT2 or UFT3 or UNFV, PHI=IDEAL,{HENRY},.. SYSTEM(VLE or VLLE)=UF1 or UFT2 or UFT3 or UNFV, PHI=IDEAL, {HENRY},...
II-6-23
SYSTEM
Selects a combination of consistent thermodynamic property generators. The options available are: UFT1 When SYSTEM=UFT1 is chosen, UFT1 K-values, LIBRARY enthalpies, IDEAL liquid densities and IDEAL vapor densities are default. When SYSTEM=UFT2 is chosen, UFT2 K-values, LIBRARY enthalpies, IDEAL liquid densities and IDEAL vapor densities are default. When SYSTEM=UF3 is chosen, UFT3 K-values, LIBRARY enthalpies, IDEAL liquid densities and IDEAL vapor densities are default. When SYSTEM=UNFV is chosen, UNFV K-values, LIBRARY enthalpies, IDEAL liquid densities and IDEAL vapor densities are default.
UFT2
UFT3
UNFV
KVALUE
Selects the method for K-value calculations. Both VLE and LLE K-value calculations are available with the UFT1, UFT2, UFT3 AND UNFV methodS. The VLLE option automatically selects both. See Vapor-liquidliquid Equilibrium Considerations on page 1-37 for more details on liquid-liquid equilibrium calculations. Selects the option used to calculate pure component and mixture vapor phase fugacity coefficients (i). A vapor fugacity method should generally be selected for high pressure applications. The options are the equations of state methods SRK, PR, SRKM, PRM, SRKH, PRH, SRKP, PRP, SRKS, SRKKD, BWRS and UNIWAAL (see Chapter 4) and HOCV (the Hayden-O'Connell method), TVIRIAL (the Truncated Virial method) and the IDIMER method. See Hayden-OConnell Vapor Fugacity on page 6-69, Truncated Virial Vapor Fugacity on page 6-73, and IDIMER Vapor Fugacity on page 6-78 for details on these last three options. The default is PHI=IDEAL. This option selects Henry's Law data (either user-supplied or from databanks) to model dissolved gases in a liquid solution. See Henrys Law for Non-condensible Components on page 6-63 for further details. Liquid Activity Methods
PHI
HENRY
II-6-24
K-value Data (optional) UFT1-Lyngby modified UNIFAC

KVALUE(VLE or LLE or VLLE) POYNTING=OFF or ON, MOLVOL=STANDARD or RACKETT or RCK2 or LIBRARY, BANK=SIMSCI or NONE or bankid, AZEOTROPE = SIMSCI or NONE or bankid, WRITE=fileid UNIFAC(K or KCAL or KJ) and/or l, k, Alk, Akl / ...
UFT2-Dortmund modified UNIFAC

UFT3-Modified UNIFAC
UNFV-Free Volume modification

KVALUE(VLE or LLE or VLLE) POYNTING=OFF or ON, MOLVOL=STANDARD or RACKETT or RCK2 or LIBRARY, BANK=SIMSCI or NONE or bankid, AZEOTROPE = SIMSCI or NONE or bankid, WRITE=fileid UNIFAC(K or KCAL or KJ) l, k, Alk, Akl / ...
and/or AZEOTROPE(basis, punit, tunit) i, j, pres, temp, xi / ... and/or INFINITE(tunit) and/or i, j, temp, ioo , joo / ...
II-6-25
MUTUAL(basis, tunit) and/or IDEAL
i, j, temp, xiI, xjII / ... i, j / ...
Note: The AZEOTROPE, INFINITE, MUTUAL and/or IDEAL statements may be used with the UFT1, UFT2, UFT3 and UNFV methods. The data statements must follow the KVALUE statement. UNIFAC data statements may be used with any of the modified UNIFAC methods if non-temperature dependent data are entered. The UNIFT1, UNIFT2, UNIFT3 and/or UNFV data statements may not be mixed, i.e., they may not follow the same KVALUE statement. UFT1, UFT2, and UFT3 are aliases for the UNIFT1, UNIFT2, and UNIFT3 data keywords.
POYNTING This option selects whether to apply the Poynting correction to fugacities of components in the liquid phase. The default is OFF unless a PHI method is selected, in which case the default is ON. MOLVOL This selects the method used to calculate the liquid molar volume necessary for computing the Poynting correction factor. Options are: STANDARD The default. Selects the standard method for calculating the liquid molar volume at standard conditions (25 C, 1 atm). Selects the Rackett liquid density method. Selects the Rackett 2 liquid density method Selects the LIBRARY liquid density method.
RACKETT RCK2 LIBRARY BANK
This option selects one or more banks from which to retrieve vapor and/or liquid phase binary interaction data. SIMSCI NONE Selects the SimSci standard databank (default). This option disables all data retrieval from databanks for interaction parameters.
II-6-26
bankid
This option selects a usercreated databank named bankid that is created and maintained with the LIBMGR program.
AZEOTROP This selects the azeotrope databank used for retrieving E azeotropic data for binary pairs. Current options are SIMSCI (default) or NONE or bankid. WRITE This option writes the binary interaction parameters for the liquid activity coefficient K-value method to a file. The format of this file is suitable for inclusion into an input file. fileid This name identifies the file containing the binary interaction data. It may be any valid file name allowed on the particular operating system being used, but must not include a suffix. The program will automatically add a suffix (e.g., FIL on PCs).
UNIFAC
This statement allows entry of the group interaction data parameters for the UNIFAC liquid activity coefficient method. See UNIFAC on page 6-14 for further details. This selects the Lyngby modification of the UNIFAC method. The data entered are the temperature-dependent group interaction parameters alk, blk and clk. The liquid activity for each component is calculated from: Similar to the UNIFAC method except
To A mk = a mk + b mk ( T T o ) + c mk + T T o T ln ---- T
UFT1
where:
T o = 298.25 K ri xi i i c ln i = ln ---- + 1 ---- , i = ------------------------NOC xi xi 23 rj xj
j=1 23
II-6-27
UFT2
This statement allows entry of the temperaturedependent group interaction data for the Dortmund modification of the UNIFAC method. The liquid activity coefficients are calculated from the following equations: Similar to the UNIFAC method, except
A mk = a mk + b mk T + c mk T
2
i i Zq i ln i i c - ---------ln i = ln ---- + 1 ---- ------- + 1 ----2 x x

i i i i
ri xi i = ------------------------NOC
34
rj
j=1
34
xj
UFT3
This selects temperature-dependent group interaction data for a modification of the UNIFAC method. The liquid activity coefficients are computed using the equations following: Similar to the UNIFAC method, except
A mk = a mk + b mk T + c mk T
3
UNFV
This option is for entering free volume data for polymer systems. This model uses the same liquid activity coefficient combinatorial and residual terms as UNIFAC, in addition to a free volume effect term. The liquid activity equations are given by:
ln i = ln i + ln i + ln i
C R FV
ln i
FV
1 3 1 V i ------------------3 C i ln 1 3 - V m 1
V i - 1 ----- V m C i --------------------- 1 1 ---------1 3 Vi 1r' i = ----Mi

NK
Vi = --------------------V -, i 15.17 br' i
k Rk
k=1
Vi wi + Vj wj = ------------------------------------------------- , b = 1.28 V m 15.17 b ( r' i w i + r' j w j )
where:
II-6-28
Vi = volume per gram of solvent i Mi = molecular weight of solvent i Wi = weight fraction of component i Ci = number of degrees of freedom per molecule of solvent i (=3.3) AZEOTROP E and/or INFINITE and/or MUTUAL and/or IDEAL These statements are used to enter data for binary pairs. This data will be regressed to the coefficients for the liquid activity method used to generate the K-values. Multiple statements may be used to enter data with different units or the data can be entered on a single statement. This statement sets the binary interaction parameters to zero.
Data input using the UNIFAC, UFT1, UFT2, UFT3, UNFV, AZEOTROPE, INFINITE, MUTUAL and IDEAL statements is used in preference to any data retrieved from the databanks or estimated using FILL options. See Filling in Missing Parameters on page 6-57, for further details. Method-specific Pure Component Properties (optional)
Properties may be supplied that are active only when a specific method is used. VANDERWAALS may be supplied only if UNFV is used. For a further description of these input parameters see Chapter 9, Method-specific Pure Component Data. Note that of these properties, only the van der Waals area and volume (VANDERWAALS) has any direct effect on the calculation of liquid activity coefficients, but may only be supplied in the Component Data Category. The vapor pressure also has a direct effect on K-values, but may only be supplied globally for all sets in the Component Data Category. Tc, Pc and the acentric factor will have an impact if a cubic equation of state is chosen for vapor phase fugacities. Molar volume will have an impact on the Poynting correction factor.
II-6-29
Examples
5.7: Using the UFT1 liquid activity method, model a 50/40/10 mix of DIPE, IPA and water at 50 psia and 50% vaporization.
TITLE PROB=UFT1 PRINT INPUT=ALL COMPONENT DATA LIBID 1,DIPE/ 2,IPA/ 3,H2O THERMO DATA METHOD SYSTEM=UFT1 STREAM PROP STREAM=1, TEMP=100, PRES=100, & COMP=50/50 UNIT OPERATION FLASH UID=FLSH FEED 1 PROD V=2, L=3 TPSPEC PRES=50 SPEC STREAM=2, RATE, RATIO, STREAM=1, & RATE, VALUE=0.5 END
5.8:
For the same problem, use UFT2 K-values, IDEAL enthalpies and liquid densities and SRK vapor densities..
THERMO DATA METHOD KVALUE=UFT2, ENTHALPY=IDEAL, & DENSITY(L)=IDEAL, DENSITY(V)=SRK
Wilson
Typical Usage
...
COMPONENT DATA LIBID 1, IPA/ 2, H2O/ 3, CH THERMO DATA METHOD SYSTEM=WILSON STREAM DATA . . .
II-6-30
General Information
The WILSON liquid activity method is used to predict VLE phase behavior. This method does not support free water decant. The WILSON liquid activity method is generally useful for slightly non-ideal applications. Refer to the PRO/II Reference Manual for additional information.
Table 6-6: Attributes of WILSON Methods Properties predicted by WILSON methods K-values Required pure component properties1 Vapor pressure Liquid molar volume Vapor pressure Critical temperature Critical pressure Acentric factor Liquid molar volume Two liquid phase behavior Free-water decant VLLE
1
PHI=IDEAL and POYNTING=OFF When used with PHI=SRK or PR or SRKM or PRM or SRH or PRH or SRP or PRP or SRKS or SRKKD or BWRS or UNIWAAL or HOCV
Input Description
METHOD or METHOD SYSTEM(VLE)=WILSON, PHI=IDEAL, {HENRY},.. KVALUE(VLE)=WILSON, PHI=IDEAL, {HENRY}, ...
SYSTE M
Selects a combination of compatible thermodynamic property generators. When SYSTEM=WILSON is chosen, WILSON K-values, LIBRARY vapor enthalpies, IDEAL vapor densities, IDEAL liquid densities, and LIBRARY liquid enthalpies are default. Selects the method for K-value calculations. Only VLE K-value calculations are available with the WILSON method.
KVALU E
II-6-31
PHI
Selects the option used to calculate pure component and mixture vapor phase fugacity coefficients (i). A vapor fugacity method should generally be selected for high pressure applications. The options are the equations of state methods SRK, PR, SRKM, PRM, SRKH, PRH, SRKP, PRP, SRKS, SRKKD, BWRS and UNIWAAL (see Chapter 4) and HOCV (the Hayden-O'Connell method), TVIRIAL (the Truncated Virial method) and the IDIMER method. See Hayden-OConnell Vapor Fugacity on page 6-69, Truncated Virial Vapor Fugacity on page 6-73, and IDIMER Vapor Fugacity on page 6-78 for details on these last three options. The default is PHI=IDEAL. This option selects Henry's Law data (either usersupplied or from databanks) to model dissolved gases in a liquid solution. See Henrys Law for Noncondensible Components on page 6-63 for further details.
HENRY
K-value Data (optional )

KVALUE(VLE) POYNTING=OFF or ON, MOLVOL=STANDARD or RACKETT or RCK2 or LIBRARY, FILL=NONE or UNIFAC or UFT1 or FLORY or REGULAR, AZEOTROPE=SIMSCI or NONE or bankid, WRITE=fileid WILSON(K or KCAL or KJ or NODIME) and/or AZEOTROPE(basis, punit, tunit) and/or INFINITE(tunit) and/or MUTUAL(basis, tunit) and/or IDEAL i, j, temp, xiI, xjII / ... i, j / ... I, j, temp, ioo , j oo / ... I, j, aij, aji / ... i, j, pres, temp, xi / ...
II-6-32
Note: The WILSON, AZEOTROPE, INFINITE, MUTUAL and/ or IDEAL statements must follow the KVALUE statement.
POYNTIN G
This option selects whether to apply the Poynting correction to fugacities of components in the liquid phase. The default is OFF unless a PHI method is selected, in which case the default is ON. This selects the method used to calculate the liquid molar volume necessary for computing the Poynting correction factor. Options are: STANDARD The default. Selects the standard method for calculating the liquid molar volume at standard conditions (25 C, 1 atm).
MOLVOL
FILL
This selects the method used for estimating values for binary interaction data missing from the input file and any selected databank libraries. See Filling in Missing Parameters on page 6-57 for further details on these options. This selects the azeotrope databank used for retrieving azeotropic data for binary pairs. Current options are SIMSCI (default) or NONE or bankid. This option writes the binary interaction parameters for the liquid activity coefficient K-value method to a file. The format of this file is suitable for inclusion into an input file. fileid This name identifies the file containing the binary interaction data. It may be any valid file name allowed on the particular operating system being used, but must not include a suffix. The program will automatically add a suffix (e.g., .FIL on PCs).
AZEOTRO PE WRITE
II-6-33
WILSON
This statement allows entry of the binary interaction data for the WILSON liquid activity coefficient method. The statements can be mixed in order to enter the data in the most convenient form. If the NODIME option is used, however, different unit statements cannot be mixed. The binary parameters aij and aij are related to the liquid activity coefficients i by the following equations:
N N
ln i = 1 ln
xj Aij --------------------N j=1 k=1 xj Akj

j=1
x k A ki
where:
A ij Vj a ij - exp -------= ----L T Vi
L L
(when unit is K)
Vj a ij - exp -------A ij = ----L RT Vi A ij = a ij
(when unit is KCAL or KJ)
(when unit is NODIME)
and VLi is the liquid molar volume of component i. AZEOTRO PE and/or INFINITE and/or MUTUAL and/or IDEAL These statements are used to enter data for binary pairs. These data will be regressed to the coefficients for the liquid activity method used to generate the Kvalues. Multiple statements may be used to enter data with different units, or the data can be entered on a single statement. This statement sets the binary interaction parameters to zero.
Data input using the WILSON, AZEOTROPE, INFINITE, MUTUAL and IDEAL statements is used in preference to any data retrieved from the databanks or estimated using FILL options. See Filling in Missing Parameters on page 6-57 for further details. Method-specific Pure Component Properties (optional)
II-6-34
Properties may be supplied that are active only when a specific method is used. For a further description of these input parameters see Chapter 9, Method-specific Pure Component Data. Note that of these properties only the molar volume (MOLVOL) has any direct effect on the calculation of liquid activity coefficients. The vapor pressure also has a direct effect on K-values, but may only be supplied globally for all sets in the Component Data Category. Tc, Pc and the acentric factor will have an impact if a cubic equation of state is chosen for vapor phase fugacities. Molar volume will also have an impact on the Poynting correction factor.
Examples
5.9: Using the WILSON system, model a 50/40/10 mix of DIPE, IPA and water at 50 psia and 50% vaporization.
TITLE PROB=WILSON PRINT INPUT=ALL COMPONENT DATA LIBID 1,DIPE/ 2,IPA/ 3,H2O THERMO DATA METHOD SYSTEM=WILSON STREAM DATA PROP STREAM=1, TEMP=100, PRES=100, & COMP=50/40/10 UNIT OPERATION FLASH UID=FLSH FEED 1 PROD V=2, L=3 TPSPEC PRES=50 SPEC STREAM=2, RATE, RATIO, STREAM=1, & RATE, VALUE=0.5 END
5.10:
For the same problem, use WILSON K-values, IDEAL enthalpies and liquid densities and SRK vapor densities..
THERMO DATA METHOD KVALUE=WILSON, ENTHALPY=IDEAL, & DENSITY(L)=IDEAL, DENSITY(V)=SRK
Van Laar
Typical Usage
... PRO/II Thermodynamic Data Keyword Input Manual II-6-35
COMPONENT DATA LIBID 1, IPA/ 2, H2O/ 3, CH THERMO DATA METHOD SYSTEM=VANLAAR STREAM DATA . . .
General Information
The VANLAAR liquid activity method is used to predict VLE and VLLE phase behavior. This method does not support free water decant. The VANLAAR liquid activity method is generally useful for slightly non-ideal applications. Refer to the PRO/II Reference Manual for additional information.
Table 6-7: Attributes of VANLAAR Methods Properties predicted by VANLAAR methods K-values Required pure component properties1 Vapor pressure Vapor pressure Critical temperature Critical pressure Acentric factor Vapor pressure Liquid molar volume Two liquid phase behavior Free-water decant VLLE - Not supported - Supported
PHI=IDEAL and POYNTING=OFF When used with PHI=SRK or PR or SRKM or PRM or SRH or PRH or SRP or PRP or SRKS or SRKKD or BWRS or UNIWAAL or HOCV When used with POYNTING=ON
Input Description
METHOD or SYSTEM(VLE or VLLE)=VANLAAR, PHI=IDEAL, {HENRY},...
II-6-36
METHOD
KVALUE(VLE and/or LLE or VLLE)=VANLAAR, PHI=IDEAL, {HENRY}, ....
SYSTEM
Selects a combination of compatible thermodynamic property generators. When SYSTEM=VANLAAR is chosen, VANLAAR Kvalues, LIBRARY vapor enthalpies, IDEAL vapor densities, IDEAL liquid densities, and LIBRARY liquid enthalpies are default. Selects the method for K-value calculations. Both VLE and LLE K-value calculations are available with the VANLAAR method. The VLLE option automatically selects both. See Vapor-liquidliquid Equilibrium Considerations on page 1-37 for more details on liquid-liquid equilibrium calculations. Selects the option used to calculate pure component and mixture vapor phase fugacity coefficients (i). A vapor fugacity method should generally be selected for high pressure applications. The options are the equations of state methods SRK, PR, SRKM, PRM, SRKH, PRH, SRKP, PRP, SRKS, SRKKD, BWRS and UNIWAAL (see Chapter 4) and HOCV (the Hayden-O'Connell method), TVIRIAL (the Truncated Virial method) and the IDIMER method. See Hayden-OConnell Vapor Fugacity on page 6-69, Truncated Virial Vapor Fugacity on page 6-73, and IDIMER Vapor Fugacity on page 6-78 for details on these last three options. The default is PHI=IDEAL. This option selects Henry's Law data (either usersupplied or from databanks) to model dissolved gases in a liquid solution. See Henrys Law for Non-condensible Components on page 6-63 for further details.
KVALUE
PHI
HENRY
II-6-37

KVALUE(VLE OR LLE OR VLLE) POYNTING=OFF or ON, MOLVOL=STANDARD or RACKETT or RCK2 or LIBRARY, FILL=NONE or UNIFAC or UFT1 or FLORY or REGULAR, AZEOTROPE=SIMSCI or NONE or bankid, WRITE=fileid VANLAAR and/or AZEOTROPE(basis, punit, tunit) and/or INFINITE(tunit) and/or MUTUAL(basis, tunit) and/or IDEAL i, j, temp, xiI, xjII / ... i, j / ... I, j, temp, ioo , j oo / ... I, j, aij, aji / ... i, j, pres, temp, xi / ...
Note: The VANLAAR, AZEOTROPE, INFINITE, MUTUAL and/or IDEAL statements must follow the KVALUE statement.
POYNTING
This option selects whether to apply the Poynting correction to fugacities of components in the liquid phase. The default is OFF unless a PHI method is selected, in which case the default is ON. This selects the method used to calculate the liquid molar volume necessary for computing the Poynting correction factor. Options are: STANDARD The default. Selects the standard method for calculating the liquid molar volume at standard conditions (25 C, 1 atm). Selects the Rackett liquid density method. Selects the Rackett 2 liquid density method. Selects the LIBRARY liquid density method.
MOLVOL
II-6-38
FILL
This selects the method used for estimating values for binary interaction data missing from the input file and any selected databank libraries. See Filling in Missing Parameters on page 6-57 for further details on these options. This selects the azeotrope databank used for retrieving azeotropic data for binary pairs. Current options are SIMSCI (default) or NONE or bankid. This option writes the binary interaction parameters for the liquid activity coefficient K-value method to a file. The format of this file is suitable for inclusion into an input file. fileid This name identifies the file containing the binary interaction data. It may be any valid file name allowed on the particular operating system being used, but must not include a suffix. The program will automatically add a suffix (e.g., .FIL on PCs).
AZEOTROPE
WRITE
VANLAAR
This statement allows entry of the binary interaction data for the VANLAAR liquid activity coefficient method. The binary parameters aij and aij are related to the liquid activity coefficients i by the following equations:
N N
ln i =
ail Zl
i=1 j=1
1 a ij Z i Z j -2
j = 1k = 1 j, k i
-Z Z ajk ----a ji j k
a ij
where:
xl Z l = ------------------------N a il ---- xj a li
j=1
AZEOTRO PE and/or INFINITE and/or MUTUAL and/or IDEAL
These statements are used to enter data for binary pairs. This data will be regressed to the coefficients for the liquid activity method used to generate the Kvalues. Multiple statements may be used to enter data with different units, or the data can be entered on a single statement. This statement sets the binary interaction parameters to zero. II-6-39
Data input using the VANLAAR, AZEOTROPE, INFINITE, MUTUAL and IDEAL statements is used in preference to any data retrieved from the databanks or estimated using FILL options. See Filling in Missing Parameters on page 6-57 for further details. Method-specific Pure Component Properties (optional)
Properties may be supplied that are active only when a specific method is used. For a further description of these input parameters, see Chapter 9, Method-specific Pure Component Data. The vapor pressure also has a direct effect on K-values, but may only be supplied globally for all sets in the Component Data Category. Tc, Pc and the acentric factor will have an impact if a cubic equation of state is chosen for vapor phase fugacities. Molar volume will have an impact on the Poynting correction factor.
Examples
5.11: Using the VANLAAR system, model a 50/40/10 mix of DIPE, IPA and water at 50 psia and 50% vaporization.
TITLE PROB=VANLAAR PRINT INPUT=ALL COMPONENT DATA LIBID 1,DIPE/ 2,IPA/ 3,H2O THERMO DATA METHOD SYSTEM=VANLAAR STREAM DATA PROP STREAM=1, TEMP=100, PRES=100, & COMP=50/40/10 UNIT OPERATION FLASH UID=FLSH FEED 1 PROD V=2, L=3 TPSPEC PRES=50 SPEC STREAM=2, RATE, RATIO, STREAM=1, & RATE, VALUE=0.5 END
5.12:
For the same problem, use VANLAAR K-values, IDEAL enthalpies and liquid densities and SRK vapor densities.
II-6-40
THERMO DATA METHOD KVALUE=VANLAAR, ENTHALPY=IDEAL, & DENSITY(L)=IDEAL, DENSITY(V)=SRK
II-6-41
Margules
Typical Usage
...
COMPONENT DATA LIBID 1, IPA/ 2, H2O/ 3, CH THERMO DATA METHOD SYSTEM=MARGULES STREAM DATA . . .
General Information
The MARGULES liquid activity method is used to predict VLE and VLLE phase behavior. This method does not support free water decant. The MARGULES liquid activity method is generally useful for slightly non-ideal applications. Refer to the PRO/II Reference Manual for additional information.
Table 6-8: Attributes of MARGULES Methods Properties predicted by MARGULES methods K-values Required pure component properties1 Vapor pressure Vapor pressure Critical temperature Critical pressure Acentric factor Vapor pressure Liquid molar volume Free-water decant VLLE
PHI=IDEAL and POYNTING=OFF When used with PHI=SRK or PR or SRKM or PRM or SRH or PRH or SRP or PRP or SRKS or SRKKD or BWRS or UNIWAAL or HOCV When used with POYNTING=ON
Two liquid phase behavior - Not supported - Supported
II-6-42
Input Description
METHOD or METHOD SYSTEM(VLE or VLLE)=MARGULES, PHI=IDEAL, {HENRY},... KVALUE(VLE and/or LLE or VLLE)=MARGULES, PHI=IDEAL, {HENRY}, ...
SYSTEM
Selects a combination of compatible thermodynamic property generators. When SYSTEM=MARGULES is chosen, MARGULES K-values, LIBRARY vapor enthalpies, IDEAL vapor densities, IDEAL liquid densities, and LIBRARY liquid enthalpies are default. Selects the method for K-value calculations. Both VLE and LLE K-value calculations are available with the Margules method. The VLLE option automatically selects both. See Vapor-liquid-liquid Equilibrium Considerations on page 1-37 for more details on liquid-liquid equilibrium calculations. Selects the option used to calculate pure component and mixture vapor phase fugacity coefficients (i). A vapor fugacity method should generally be selected for high pressure applications. The options are the equations of state methods SRK, PR, SRKM, PRM, SRKH, PRH, SRKP, PRP, SRKKD, BWRS and UNIWAAL (see Chapter 4) and HOCV (the Hayden-O'Connell method) and TVIRIAL (the Truncated Virial method). See Hayden-OConnell Vapor Fugacity on page 6-69, Truncated Virial Vapor Fugacity on page 6-73, and IDIMER Vapor Fugacity on page 6-78 for details on these last three options. The default is PHI=IDEAL. This option selects Henry's Law data (either usersupplied or from databanks) to model dissolved gases in a liquid solution. See Henrys Law for Non-condensible Components on page 6-63 for further details.
KVALUE
PH I
HENRY
enthalpy method selected. See Henrys Law for Non-condensible Components on page 6-63 for further information on the use of this option.
II-6-43

KVALUE(VLE or LLE or VLLE) POYNTING=OFF or ON, MOLVOL=STANDARD or RACKETT or RCK2 or LIBRARY, FILL=NONE or UNIFAC or UFT1 or FLORY or REGULAR, AZEOTROPE=SIMSCI or NONE or bankid, WRITE=fileid MARGULES and/or AZEOTROPE(basis, punit, tunit) and/or INFINITE(tunit) and/or MUTUAL(basis, tunit) and/or IDEAL i, j / ... i, j, temp, xiI, xjII / ... I, j, temp, ioo , j oo / ... I, j, aij, aji, dij / ... i, j, pres, temp, xi / ...
Note: The MARGULES, AZEOTROPE, INFINITE, MUTUAL
and/or IDEAL statements must follow the KVALUE statement.

POYNTING This option selects whether to apply the Poynting correction to fugacities of components in the liquid phase. The default is OFF unless a PHI method is selected, in which case the default is ON. This selects the method used to calculate the liquid molar volume necessary for computing the Poynting correction factor. Options are: STANDAR The default. Selects the standard D method for calculating the liquid molar volume at standard conditions (25 C, 1 atm). RACKETT Selects the Rackett liquid density method. RCK2 LIBRARY FILL Selects the Rackett 2 liquid density method. Selects the LIBRARY liquid density method.
MOLVOL
This selects the method used for estimating values for binary interaction data missing from the input file and any selected databank libraries. See Filling in Missing Parameters on page 6-57 for further details on these options. This selects the azeotrope databank used for retrieving azeotropic data for binary pairs. Current options are SIMSCI (default) or NONE or bankid. Liquid Activity Methods
AZEOTROP E
II-6-44
WRITE
This option writes the binary interaction parameters for the liquid activity coefficient K-value method to a file. The format of this file is suitable for inclusion into an input file. fileid This name identifies the file containing the binary interaction data. It may be any valid file name allowed on the particular operating system being used, but must not include a suffix. The program will automatically add a suffix (e.g., .FIL on PCs).
MARGULE S
This statement allows entry of the binary interaction data for the MARGULES liquid activity coefficient method. The binary parameters aij, aji and dij are related to the liquid activity coefficients i by the following equations:
ln i = ( 1 x i ) [ A i + 2 ( B i A i D i ) x i + 3 D i x i ]
2 2
where:
N
Ai =
xj aij
j=1 N
Bi =
xj aji
j=1 N
Di =
xj dij
j=1
d ij = d ji
AZEOTROPE and/or INFINITE and/or MUTUAL and/or IDEAL
These statements are used to enter data for binary pairs. This data will be regressed to the coefficients for the liquid activity method used to generate the K-values. Multiple statements may be used to enter data with different units or the data can be entered on a single statement. This statement sets the binary interaction parameters to zero.
Data input using the MARGULES, AZEOTROPE, INFINITE, MUTUAL and IDEAL statements is used in preference to any data
II-6-45
retrieved from the databanks or estimated using FILL options. See Filling in Missing Parameters on page 6-57 for further details. Method-specific Pure Component Properties (optional)
Properties may be supplied that are active only when a specific method is used. For a further description of these input parameters, see Chapter 9, Method-specific Pure Component Data. The vapor pressure also has a direct effect on K-values, but may only be supplied globally for all sets in the Component Data Category. Tc, Pc and the acentric factor will have an impact if a cubic equation of state is chosen for vapor phase fugacities. Molar volume will have an impact on the Poynting correction factor.
Examples
5.13: Using the MARGULES system, model a 50/40/10 mix of DIPE, IPA and water at 50 psia and 50% vaporization.
TITLE PROB=MARGULES PRINT INPUT=ALL COMPONENT DATA LIBID 1,DIPE/ 2,IPA/ 3,H2O THERMO DATA METHOD SYSTEM=MARGULES STREAM DATA PROP STREAM=1, TEMP=100, PRES=100, & COMP=50/40/10 UNIT OPERATION FLASH UID=FLSH FEED 1 PROD V=2, L=3 TPSPEC PRES=50 SPEC STREAM=2, RATE, RATIO, STREAM=1, & RATE, VALUE=0.5 END
5.14:
For the same problem, use MARGULES K-values, IDEAL enthalpies and liquid densities and SRK vapor densities..
II-6-46
THERMO DATA METHOD KVALUE=MARGULES, ENTHALPY=IDEAL, & DENSITY(L)=IDEAL, DENSITY(V)=SRK
Regular Solution
Typical Usage
...
COMPONENT DATA LIBID 1, IPA/ 2, H2O/ 3, CH THERMO DATA METHOD SYSTEM=REGULAR STREAM DATA . . .
General Information
The REGULAR liquid activity method is used to predict VLE and VLLE phase behavior. It is generally useful for slightly non-ideal applications. Refer to the PRO/II Reference Manual for additional information.
Table 6-9: Attributes of REGULAR Methods Properties predicted by REGULAR methods K-values Required pure component properties1 Vapor pressure Liquid molar volume Solubility parameter Vapor pressure Critical temperature Critical pressure Acentric factor Liquid molar volume Solubility parameter Two liquid phase behavior Free-water decant VLLE - Supported - Supported
II-6-47
Input Description
METHOD or METHOD SYSTEM(VLE or VLLE)=REGULAR, PHI=IDEAL, {HENRY}, ... KVALUE(VLE and/or LLE or VLLE)=REGULAR, PHI=IDEAL, {HENRY}, ...
SYSTEM
Selects a combination of compatible thermodynamic property generators. When SYSTEM=REGULAR is chosen, REGULAR K-values, LIBRARY vapor enthalpies, IDEAL vapor densities, IDEAL liquid densities, and LIBRARY liquid enthalpies are default. Selects the method for K-value calculations. Both VLE and LLE K-value calculations are available with the Regular method. The VLLE option automatically selects both. See Vapor-liquid-liquid Equilibrium Considerations on page 1-37 for more details on liquid-liquid equilibrium calculations. Selects the option used to calculate pure component and mixture vapor phase fugacity coefficients (i). A vapor fugacity method should generally be selected for high pressure applications. The options are the equations of state methods SRK, PR, SRKM, PRM, SRKH, PRH, SRKP, PRP, SRKS, SRKKD, BWRS and UNIWAAL (see Chapter 4) and HOCV (the Hayden-O'Connell method), TVIRIAL (the Truncated Virial method) and the IDIMER method. See Hayden-OConnell Vapor Fugacity on page 669, Truncated Virial Vapor Fugacity on page 6-73, and IDIMER Vapor Fugacity on page 6-78 for details on these last three options. The default is PHI=IDEAL. This option selects Henry's Law data (either usersupplied or from databanks) to model dissolved gases in a liquid solution. See Henrys Law for Non-condensible Components on page 6-63 for further details.
KVALUE
PHI
HENRY
II-6-48
enthalpy method selected. See Redlich-Kister, Gamma Heat of Mixing on page 6-82 for further information on the use of this option. K-value Data (optional)
KVALUE(VLE or LLE or VLLE) POYNTING=OFF or ON, MOLVOL=STANDARD or RACKETT or RCK2 or LIBRARY
POYNTING
This option selects whether to apply the Poynting correction to fugacities of components in the liquid phase. The default is OFF unless a PHI method is selected, in which case the default is ON. This selects the method used to calculate the liquid molar volume necessary for computing the Poynting correction factor. Options are: STANDAR The default. Selects the standard D method for calculating the liquid molar volume at standard conditions (25 C, 1 atm). RACKETT Selects the Rackett liquid density method. RCK2 Selects the Rackett 2 liquid density method.
MOLVOL
LIBRARY Selects the LIBRARY liquid density method.
The Regular Solution Method is derived from the Scatchard-Hildebrand equation where the liquid activity coefficient i of a solution is given by the following equations:
Vi ( i m ) ln i = -----------------------------RT
L 2
where: VLi = Liquid molar volume of component i i = Solubility parameter of component i and
II-6-49
xi Vi i
=1 m = i ------------------------N
xi Vi
i=1

TC(unit) PC(unit) ACENTRIC MOLVOL(unit) SOLUPARA ... i, value / ... i, value / ... i, value / ... i, value / ... i, value / ...
Properties may be supplied that are active only when a specific method is used. For a further description of these input parameters, see Chapter 9, Method-specific Pure Component Data. Note that only two of these properties (MOLVOL and SOLUPARA) have any direct effect on the calculation of liquid activity coefficients, but may only be supplied in the Component Data Category. The vapor pressure also has a direct effect on K-values, but may only be supplied globally for all sets in the Component Data Category. Tc, Pc and the acentric factor will have an impact if a cubic equation of state is chosen for vapor phase fugacities. Molar volume will also have an impact on the Poynting correction factor.
Examples
5.15: Using the REGULAR system, model a 50/40/10 mix of DIPE, IPA and water at 50 psia and 50% vaporization.
TITLE PROB=REGULAR PRINT INPUT=ALL COMPONENT DATA LIBID 1,DIPE/ 2,IPA/ 3,H2O THERMO DATA METHOD SYSTEM=REGULAR STREAM DATA PROP STREAM=1, TEMP=100, PRES=100, & COMP=50/40/10 UNIT OPERATION FLASH UID=FLSH FEED 1 PROD V=2, L=3 TPSPEC PRES=50 SPEC STREAM=2, RATE, RATIO, STREAM=1, & RATE, VALUE=0.5
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END
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5.16:
For the same problem, use REGULAR K-values, IDEAL enthalpies and liquid densities and SRK vapor densities.
THERMO DATA METHOD KVALUE=REGULAR, ENTHALPY=IDEAL, & DENSITY(L)=IDEAL, DENSITY(V)=SRK
Flory-Huggins
Typical Usage
...
COMPONENT DATA LIBID 1, IPA/ 2, H2O/ 3, CH THERMO DATA METHOD SYSTEM=FLORY STREAM DATA . . .
General Information
The FLORY-HUGGINS liquid activity method is used to predict VLE and VLLE phase behavior. This method does not support free water decant. The FLORY-HUGGINS liquid activity method is generally useful for mixtures of components that differ vastly in size, e.g., polymer solutions. Refer to the PRO/II Reference Manual for additional information.
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Table 6-10: Attributes of FLORY Methods Properties predicted by FLORY methods K-values Required pure component properties1 Vapor pressure Liquid molar volume Solubility parameter Vapor pressure Critical temperature Critical pressure Acentric factor Liquid molar volume Solubility parameter Two liquid phase behavior Free-water decant VLLE
1
Input Description
METHOD or METHOD SYSTEM(VLE or VLLE)=FLORY, PHI=IDEAL, {HENRY},... KVALUE(VLE and/or LLE or VLLE)=FLORY, PHI=IDEAL, {HENRY}, ...
SYSTEM
Selects a combination of compatible thermodynamic property generators. When SYSTEM=FLORY is chosen, FLORY K-values, LIBRARY vapor enthalpies, IDEAL vapor densities, IDEAL liquid densities, and LIBRARY liquid enthalpies are default.
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KVALUE
Selects the method for K-value calculations. Both VLE and LLE K-value calculations are available with the Margules method. The VLLE option automatically selects both. See Vaporliquid-liquid Equilibrium Considerations on page 1-37 for more details on liquid-liquid equilibrium calculations. Selects the option used to calculate pure component and mixture vapor phase fugacity coefficients (i). A vapor fugacity method should generally be selected for high pressure applications. The options are the equations of state methods SRK, PR, SRKM, PRM, SRKH, PRH, SRKP, PRP, SRKS, SRKKD, BWRS and UNIWAAL (see Chapter 4) and HOCV (the Hayden-O'Connell method), TVIRIAL (the Truncated Virial method) and the IDIMER method. See Hayden-OConnell Vapor Fugacity on page 6-69, Truncated Virial Vapor Fugacity on page 6-73, and IDIMER Vapor Fugacity on page 6-78 for details on these last three options. The default is PHI=IDEAL. This option selects Henry's Law data (either user-supplied or from databanks) to model dissolved gases in a liquid solution. See Henrys Law for Non-condensible Components on page 6-63 for further details.
PHI
HENRY
enthalpy method selected. See Redlich-Kister, Gamma Heat of Mixing on page 6-82 for further information on the use of this option. K-value Data (optional)
KVALUE(VLE or LLE or VLLE) POYNTING=OFF or ON, MOLVOL=STANDARD or RACKETT or RCK2 or LIBRARY, WRITE=fileid FLORY I, j, cij / ..
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POYNTIN G
MOLVOL
RACKETT RCK2 LIBRARY WRITE
This option writes the binary interaction parameters for the liquid activity coefficient K-value method to a file. The format of this file is suitable for inclusion into an input file. fileid This name identifies the file containing the binary interaction data. It may be any valid file name allowed on the particular operating system being used, but must not include a suffix. The program will automatically add a suffix (e.g., .FIL on PCs).
FLORY
This statement allows entry of the c binary interaction parameters for the Flory-Huggins liquid activity coefficient method. It should be noted that ij = ji Therefore, the order of the indices (i,j or j,i) is unimportant. The binary parameters are related to the liquid activity coefficients by the following equation:
i ln j = 1 + ln ---- mi xi
n n n
ij j jk j k
ji j k>j
II-6-55
where: xi, i, and mi are the mole fraction, volume fraction and number of segments of component i. The volume fraction is defined by:
xi vi i = --------------n
xi vi
i
where: vi = the liquid molar volume of component i. The number of segments is calculated as:
vi m i = --------v min
where: vmin = the smallest molar volume in the system. Missing parameters are estimated as:
v min - ( k )2 jk = --------RT j
where: j and k are solubility parameters of components j and k, respectively.

TC(unit) PC(unit) ACENTRIC MOLVOL(unit) SOLUPARA ... i, value / ... i, value / ... i, value / ... i, value / ... i, value / ...
Properties may be supplied that are active only when a specific method is used. For a further description of these input parameters, see Chapter 9, Method-specific Pure Component Data. Note that only two of these properties (MOLVOL and SOLUPARA) have any direct effect on the calculation of liquid activity coefficients. The vapor pressure also has a direct effect on K-values. Tc, Pc and the acentric factor will have an impact if a cubic equation of state is chosen for vapor phase fugacities. Molar volume will also have an impact on the Poynting correction factor.
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Examples
5.17: Using the FLORY-HUGGINS system, model a 50/40/10 mix of DIPE, IPA, and water at 50 psia and 50% vaporization.
TITLE PROB=FLORY PRINT INPUT=ALL COMPONENT DATA LIBID 1,DIPE/ 2,IPA/ 3,H2O THERMO DATA METHOD SYSTEM=FLORY STREAM DATA PROP STREAM=1, TEMP=100, PRES=100, & COMP=50/40/10 UNIT OPERATION FLASH UID=FL1 FEED 1 PROD V=2, L=3 TPSPEC PRES=50 SPEC STREAM=2, RATE, RATIO, STREAM=1, & RATE, VALUE=0.5 END
5.18:
For the same problem, use FLORY K-values, IDEAL enthalpies and liquid densities and SRK vapor densities.
THERMO DATA METHOD KVALUE=FLORY, ENTHALPY=IDEAL, & DENSITY(L)=IDEAL, DENSITY(V)=SRK
Filling in Missing Parameters

Typical Usage
...
COMPONENT DATA LIBID 1, IPA/ 2, H2O/ 3, CH THERMO DATA METHOD SYSTEM=NRTL KVALUE FILL=UNIFAC STREAM DATA . . .
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General Information
The program has an extensive facility to backfill missing binary interaction data for liquid activity methods. If liquid activity coefficients are unavailable, they may be estimated automatically if mutual solubility, infinite dilution or azeotropic data are supplied. If none of these is available, the program seeks to find azeotropic data in the SIMSCI databank. If these data are unavailable, the FILL option can be used to estimate the required coefficients using group contribution methods (UNIFAC or UFT1), regular solution theory, or Flory-Huggins. If none of these methods are possible, the program then sets the binary interaction parameters to zero. For solidliquid equilibria, the FILL option may be used to estimate solubility data missing from the databank, or not given by the user. Missing values may be estimated using the ideal (vant Hoff) solubility equation, or the solubilities may be set to 1.0 (completely soluble), or solvents missing solubility data may be ignored in the solubility calculation.
Table 6-11: Attributes of the FILL Option Properties predicted by FILL Binary interaction parameters Binary solubilities (liquid activity methods) (solid-liquid equilibria)
Required pure component properties1 None Solubility parameters and liquid molar volumes UNIFAC structure and group area and volume data
1
FILL=NONE or VANTHOFF or ONE or FREE FILL=REGULAR or FLORY FILL=UNIFAC or UFT1
Input Description
METHOD SYSTEM=NRTL or UNIQUAC or WILSON or VANLAAR or MARGULES ... KVALUE=NRTL or UNIQUAC or WILSON or VANLAAR or MARGULES or SOLDATA ...
or METHOD
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SYSTEM KVALUE
A liquid activity method system must be chosen if the FILL option is to be used. Selects the method for K-value calculations. Only liquid activity methods and the usersupplied solubility method SOLDATA can be used with the FILL option.
K-value Data
KVALUE(VLE) FILL=NONE or UNIFAC or UFT1 or REGULAR or FLORY, AZEOTROPE=SIMSCI or NONE or bankid FILL=NONE or UNIFAC or UFT1 or REGULAR or FLORY, AZEOTROPE=SIMSCI or NONE or bankid FILL=VANTHOFF or ONE or FREE
or KVALUE(LLE)
or KVALUE(SLE)
FILL
This statement is used to supply parameters missing for the calculation of liquid activity coefficients. The FILL option regresses the missing parameters from the option selected to fit the previously specified K-value liquid activity method. The FILL options are detailed in Table5-. It should be noted that, of the VLE and LLE FILL options, only FILL=UNIFAC will produce LLE parameters that are different from the VLE parameters. The VANTHOFF or ONE or FREE fill options may only be used if the KVALUE(SLE)= SOLDATA statement has been specified. If the FILL=UNIFAC or UFT1 option is selected, and a component has no defined UNIFAC structure or includes a group that is missing its area and volume parameters, then a warning message is issued. The FILL option then sets the interaction parameters to zero for any pair containing that component. The UNIFAC component structure and UNIFAC group area and volume data can be supplied in the COMPONENT DATA section. See Volume I, UNIFAC Structural Groups for more information on entering UNIFAC structural data.
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AZEOTROPE
This statement is used to supply parameters missing for the calculation of liquid activity coefficients. By default, the AZEOTROPE option regresses the missing parameters from the azeotropic databank.
II-6-60
Table 6-12: Data Estimation Options KVALUE( ) DESCRIPTION FILL= NONE UNIFAC UFT1 REGULAR FLORY ONE VLE, LLE VLE, LLE VLE, LLE VLE, LLE SLE
No Estimates For Missing Data. UNIFAC group contribution method. Modified UNIFAC method Regular Solution Theory Flory Huggins method Missing binary solubilities set to 1.0 (i.e., all unspecified solids are completely soluble). Missing binary solubilities calculated with the vant Hoff equation Solvents missing binary solubility data are ignored in the solubility calculation.
VANTHOFF FREE
SLE SLE
AZEOTROPE= SIMSCI NONE bankid VLE, LLE

Estimates for missing data made from azeotropic data. No estimates for missing data. Estimates for missing data made from user-created databank.
Examples
5.19: Using the VLLE NRTL liquid activity method, and the Henrys Law option, determine the solubility of O2 in a methanol/ethanol/benzene/water/IPA system. NRTL binary interaction parameters are provided for the ethanol-IPA and benzene-ethanol pairs. Data are provided for the azeotrope formed between ethanol and water. Mutual solubility data are provided between water and benzene, while infinite dilution data are given for the methanol-water pair. The pairs ethanol-methanol and methanol-IPA are defined as ideal pairs in the liquid phase. Supply data for the O2IPA pair via a HENDATA statement, and retrieve data for the other pairs from the SIMSCI databank. Use the
FILL=UNIFAC option to estimate any missing parameters.

TITLE PROB=MISSING PARAMETERS PRINT INPUT=ALL COMPONENT DATA LIBID 1,MEOH/ 2,H2O/ 3,ETOH/ 4,BENZENE/ 5,IPA/ 6,O2 THERMO DATA METHOD SYSTEM(VLLE)=NRTL, HENRY KVALUE(VLE) FILL=UNIFAC INFI 1, 2, 70.0, 1.79, 2.16 MUTU(W) 2, 4, 20.0, 5.823E-04, 1.732E-03 AZEO(W,F) 2, 3, 1.013, 172.7, 4.61E-02 NRT3(KCAL) 3, 5, 48.9, 49.3, 3.96E-01 NRTL(K) 4, 3, -2.75, 1472.2, -4.5E-01, 440.5, 5.34E-01 KVALUE(LLE) FILL=UNIFAC IDEAL 1, 3/ 1, 5 HENRY SOLUTE 6 HENDATA 6, 5, -36, 2000, 6.5 STREAM DATA PROP STREAM=1, TEMP=100, PRES=100, & COMP=10/50/20/10/7/3 UNIT OPERATION FLASH UID=FL1 FEED 1 PROD V=2, L=3 TPSPEC PRES=50 SPEC STREAM=2, RATE, RATIO, STREAM=1, & RATE, VALUE=0.5 END
II-6-62
Henrys Law for Non-condensible Components

Typical Usage
...
COMPONENT DATA LIBID 1, IPA/ 2, H2O/ 3, 02 THERMO DATA METHOD SYSTEM=NRTL, HENRY STREAM DATA . . .
General Information
The HENRY option is used to predict gas solubilities, especially for modeling supercritical components using a liquid activity method. It is especially useful for environmental applications such as modeling trace organics in aqueous streams.
Table 6-13: Attributes of the Henrys Law Option Properties predicted by HENRY K-values Required pure component properties1 Vapor pressure Suggested application ranges Components Two liquid phase behavior Free-water decant VLLE Not supported The HENRY option only calculates gas solubilities. However, VLLE methods may also be used. Supercritical gases, trace organics in water
II-6-63
Input Description
METHOD SYSTEM=NRTL or UNIQUAC or UNIFAC or UFT1 or UFT2 or UFT3 or UNFV or WILSON or VANLAAR or MARGULES or REGULAR or FLORY, HENRY, . . . KVALUE=NRTL or UNIQUAC or UNIFAC or UFT1 or UFT2 or UFT3 or UNFV or WILSON or VANLAAR or MARGULES or REGULAR or FLORY, HENRY, . . .
or METHOD
SYSTEM KVALUE
A liquid activity method system must be chosen if the HENRY option is to be used. Selects the method for K-value calculations. Only liquid activity methods can be used with the HENRY option. This option selects Henrys Law data (either user-supplied or from databanks) to model dissolved gases in a liquid solution. This option is only available when using a liquid activity method for K-value calculations. Table 6-14 shows some of the binary gas-solvent pairs available in PRO/II. Some additional Henrys Law data for hydrofluorocarbons (HFCs) and chlorofluorocarbons (CFCs) are also available in the databanks.
HENRY
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Table 6-14: Henrys Law Package Available Pairs Gas Components

Hydrogen Chloride Carbon Monoxide Sulfur Dioxide Nitrous Oxide Methanethiol
Liquid
Hydrogen Nitrogen Oxygen Helium Argon
Cartoon Disulfide
Hydrogen Sulfide
Carbon Dioxide
Propylene
Acetylene
Ammonia
Water
Ethylene
Methane
Propane
Ethane
Components
Acetic Acid Formic Acid m-cresol
X X
X X
X X
X X X
Methanol Ethanol n-propanol isopropanol n-butanol sec-butanol tert-butanol 3-methyl-1butanol n-pentanol Ethylene Glycol Triethylene Glycol
X X X X X X X X X
X X X X
X X X X
X X X X X X X X X
X X X X X X X X X
X X X X X X X X X
X X X X
X X X X X X
X X X X X X
Acetaldehyde
Methyl ether Ethyl ether Isopropyl ether Tetrahydrofuran Dibenzofuran
X X X
X X X
X X X
X X X X
Methyl formate Methyl acetate Ethyl acetate
X X X
X X X
X X X
X X X
Isopentane n-pentane 2-methylpentane n-hexane
X X X X
X X X X
X X X X
X X X X X X
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Ethandiol
Isobutane
N-butane

Liquid
Cartoon Disulfide
Hydrogen Sulfide
Carbon Dioxide
Acetylene
Propylene
Ammonia
Isobutane
2-4 dimethylpentane 3-methylhexane n-heptane 2-4- dimethylhexane
X X X X
X X X X
X X X X
X X X X X X
n-octane n-nonane n-decane n-dodecane n-tetradecane n-hexadecane Eicosane Docosane Dotriacontane Cyclopentane Methylcyclopentane Cyclohexane Methylcyclohexane 1-T-2-DMCP 1-T-2-C-4MCP Bicyclohexyl
X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X
Ethylene
Methane
Propane
Ethane
Components
X X X X
1-hexene Freon 113 Benzene Chlorobenzene Toluene m-xylene 1-C1-naphthalene Diphenylmethane 1,3,5-tri-C1-benzene 9,10 dihydrophenanthrene Tetralin 2-ethylanthracene 9-methylanthracene
X X
X X X
X X X X X X X X
X X
X X X X X
X X
X X
X X X X
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Ethandiol
N-butane

Liquid
Cartoon Disulfide
Hydrogen Sulfide
Carbon Dioxide
Acetylene
Propylene
Ammonia
Isobutane
Hydrogen fluoride Acetone Methyl ethyl ketone Methyl n-butyl ketone Methyl propyl ketone n-methyl-2-pyrrolidone Quinoline Sulfolane Hydrogen chloride Ammonia Chloride
X X X
X X X
X X X X X X X X X
X X
X X
X X
X X
Henrys Law Data

HENRY BANK=SIMSCI or NONE or bankid SOLUTE i, j, ... HENDATA(punit, tunit) i, l, C1, C2, C3, C4 / ...
BANK
This option selects one or more databanks from which to retrieve Henrys Law data. Options available are: SIMSCI NONE Selects the SIMSCI standard databank (default). This option disables all data retrieval from databanks for Henrys Law data. This option selects a user-created databank named bankid that is created and maintained with the LIBMGR program.
bankid
If the data for any component designated as a Henry component is missing from the supplied databank and is not supplied via a HENDATA statement, the Henrys law constant is obtained by extrapolation of the component vapor pressure data.
Ethylene
Methane
Propane
Ethane
Components
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Ethandiol
N-butane
SOLUTE HENDATA
This statement is used to enter the component ID numbers for the components to be treated as solutes. This statement allows entry of the Henry coefficients for solute i in solvent l. The coefficients C1, C2, C3,
and C4 are related to the Henrys Law constant Hi (and the K-value) by the following equations for one or more solutes in a pure solvent: C2 - + C 3 ln ( T ) + C 4 ( P ) ln ( H i ) = C 1 + ----T
and
Hi K i = ----P
For a mixture of solvents, the following mixing rules are used for determining Hi,mix and Ki:
N
ln ( H i, mix ) =
xl ln ( Hi, l )
l=1
and
Hi K i = ----P

VP ...
Vapor pressure data may only be specified globally for all thermodynamic sets in the Component Data Category in tabular or equation form. For a further description of these input parameters, see Chapter 9, Method-specific Pure Component Data.
II-6-68
Examples
5.20: Using the NRTL liquid activity method, and the Henrys Law option determine the solubility of CO in a methanol/ water system. Data for the CO-methanol pair are supplied via a HENDATA statement, while data for the other pairs are retrieved from the SIMSCI databank.
TITLE PROB=HENRY PRINT INPUT=ALL COMPONENT DATA LIBID 1,N2/ 2,CO/ 3,H2O/ 4,MEOH THERMO DATA METHOD SYSTEM=NRTL, HENRY HENRY SOLUTE 1, 2 HENDATA 2, 4, 152.4, -8000, -20, 0 STREAM DATA PROP STREAM=1, TEMP=100, PRES=100, & COMP=2/3/70/25 UNIT OPERATION FLASH UID=FLSH FEED 1 PROD V=2, L=3 TPSPEC PRES=50 SPEC STREAM=2, RATE, RATIO, STREAM=1, & RATE, VALUE=0.5 END
Hayden-OConnell Vapor Fugacity

Typical Usage
...
COMPONENT DATA LIBID 1, ACETIC/ 2, ACRYLIC/ 3, H2O THERMO DATA METHOD SYSTEM=NRTL, PHI=HOCV, & ENTHALPY(V)=HOCV, DENSITY(V)=HOCV KVALUE FILL=UNIFAC STREAM DATA . . .
II-6-69
General Information
The HOCV method predicts vapor fugacities, vapor enthalpies, vapor entropies and vapor densities. It is especially useful for systems where dimers form in the vapor phase, e.g., carboxylic acid systems. A liquid activity method must be used in conjunction with the HOCV method.
Table 6-15: Attributes of the HOCV Vapor Fugacity Method Properties predicted by HOCV Vapor fugacities vapor enthalpies Hayden-OConnell Vapor Fugacity:
Required pure component properties1 Critical temperature Critical pressure van der Waals area and volume Dipole moment Radius of gyration Components Free-water decant VLLE
PHI=HOCV
Suggested application ranges - Carboxylic acids, polar components - Not supported - HOCV only calculates vapor phase properties, but VLLE methods may be used with HOCV methods. Two liquid phase behavior
Input Description
METHOD SYSTEM=NRTL or UNIQUAC or UNIFAC or UFT1 or UFT2 or UFT3 or UNFV or WILSON or VANLAAR or MARGULES or REGULAR or FLORY, PHI=HOCV, ENTHALPY(V)=HOCV, ENTROPY(V)=HOCV, DENSITY(V)=HOCV, . . . KVALUE=NRTL or UNIQUAC or UNIFAC or UFT1 or UFT2 or UFT3 or UNFV or WILSON or VANLAAR or MARGULES or REGULAR or FLORY, PHI=HOCV, ENTHALPY(V)=HOCV, ENTROPY(V)=HOCV, DENSITY(V)=HOCV, . . .
or METHOD
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SYSTEM KVALUE
A liquid activity method system must be chosen if the HOCV method is to be used. Selects the method for K-value calculations. Only liquid activity methods can be used with the HOCV method.
PHI Selects the HOCV method for vapor phase fugacities, and/or enthalpies and/or entropies and/or densities. and/or ENTHALPY( V) and/or ENTROPY(V) and/or DENSITY(V)

KVALUE POYNTING=ON or OFF, MOLVOL=STANDARD or RACKETT or RCK2 or LIBRARY, BANK=SIMSCI or NONE or bankid, FILL=NONE or UNIFAC or UFT1 or FLORY or REGULAR.
POYNTING
MOLVOL
Vapor Fugacity Data

PHI HOCV BANK=SIMSCI or NONE or bankid i, i, nii/ i, j, nij/ . . .
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Note: The HOCV statements must follow the PHI statement.
BANK
This option selects one or more databanks from which to retrieve vapor phase binary interaction data. SIMSCI NONE Selects the SIMSCI standard databank (default). This option disables all data retrieval from databanks for interaction parameters. This option selects a user-created databank named bankid that is created and maintained with the LIBMGR program.
bankid
HOCV
This statement supplies interaction data for the Hayden-OConnell vapor fugacity method. This method may be used for components forming dimers, particularly carboxylic acids. nii is the association parameter for component i while nij is the solvation parameter for components i and j.
Enthalpy, Entropy and Density Data

ENTHALPY(V) ENTROPY(V) DENSITY(V) HOCV BANK=SIMSCI or NONE or bankid BANK=SIMSCI or NONE or bankid BANK=SIMSCI or NONE or bankid i, i, nii/ i, j, nij/ . . .
HOCV vapor interaction data may be selected for enthalpy, entropy and density methods. Normally, these features are selected for the vapor fugacity method and are automatically carried over for these other methods. If, however, the vapor fugacity method is not HOCV, you can supply these parameters independently. See above under Vapor Fugacity Data for format and definition of these entries. Method-specific Pure Component Properties (optional)
TC(unit) PC(unit) VANDERWAALS DIPOLE(unit) RADIUS ... i, value / ... i, value / ... i, value / ... i, value / ... i, value / ...
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Properties may be supplied that are active only when a specific method is used. VANDERWAALS must be supplied in the Component Data Category. For a further description of these input parameters, see Chapter 9, Method-specific Pure Component Data.
Examples
5.21: Using the HOCV vapor fugacity method with the NRTL liquid activity method, model a 50/50 mix of acetic and acrylic acids at 100 psia and 100 F.
TITLE PROB=HOCV COMPONENT DATA LIBID 1,ACETIC/ 2,ACRYLIC THERMO DATA METHOD SYSTEM=NRTL, PHI=HOCV, & ENTHALPY(V)=HOCV, ENTROPY(V)=HOCV, & DENSITY(V)=HOCV STREAM DATA PROP STREAM=1, TEMP=100, PRES=100, & COMP=50/50 UNIT OPERATION FLASH UID=FL1 FEED 1 PROD V=2, L=3 TPSPEC PRES=50 SPEC STREAM=2, RATE, RATIO, STREAM=1, & RATE, VALUE=0.5 END
5.22:
For the same problem, use HOCV for vapor fugacities and SRK for vapor enthalpies, entropies and densities. Specify API liquid densities.
THERMODYNAMIC DATA METHOD SYSTEM=NRTL, PHI=HOCV, & ENTHALPY(V)=SRK, ENTROPY(V)=SRK, & DENSITY(V)=HOCV, DENSITY(L)=API
Truncated Virial Vapor Fugacity

Typical Usage
...
COMPONENT DATA LIBID 1, ACETIC/ 2, ACRYLIC/ 3, H2O
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THERMO DATA METHOD SYSTEM=NRTL, PHI=TVIRIAL STREAM DATA . . .
General Information
The TVIRIAL method predicts vapor fugacities. It is useful for systems where dimers form in the vapor phase, e.g., carboxylic acid systems. A liquid activity method must be used in conjunction with the TVIRIAL method.
Table 6-16: Attributes of the TVIRIAL Vapor Fugacity Method Properties predicted by HOCV Vapor fugacities Required pure component properties1 Critical temperature Critical pressure Critical volume Components Free-water decant VLLE Acentric factor Dipole moment
Suggested application ranges - Carboxylic acids - Not supported - TVIRIAL only calculates vapor phase properties, but VLLE methods may be used with TVIRIAL methods. Two liquid phase behavior
Input Description
METHOD SYSTEM=NRTL or UNIQUAC or UNIFAC or UFT1 or UFT2 or UFT3 or UNFV or WILSON or VANLAAR or MARGULES or REGULAR or FLORY, PHI=TVIRIAL KVALUE=NRTL or UNIQUAC or UNIFAC or UFT1 or UFT2 or UFT3 or UNFV or WILSON or VANLAAR or MARGULES or REGULAR or FLORY, PHI=TVIRIAL
or METHOD
II-6-74
SYSTEM KVALUE
A liquid activity method system must be chosen if the TVIRIAL method is to be used. Selects the method for K-value calculations. Only liquid activity methods can be used with the TVIRIAL method. Selects the TVIRIAL method for vapor phase fugacities.
PHI

POYNTIN G
MOLVOL
Vapor Fugacity Data

PHI TVIRIAL i, i
Note: The TVIRIAL statements must follow the PHI statement.
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TVIRIAL
This statement supplies interaction data for the Truncated Virial vapor fugacity method. This method may be used for components forming dimers, particularly carboxylic acids. i is the Truncated Virial Coefficient for component i.
II-6-76

TC(unit) PC(unit) ACENTRIC DIPOLE(unit) ... i, value / ... i, value / ... i, value / ... i, value / ...
Examples
5.23: Using the TVIRIAL vapor fugacity method with the NRTL liquid activity method, model a 75/25 mix of ethanol and cyclohexane at 5 atm and 115 C.
TITLE PROB=TVIRIAL PRINT INPUT=ALL DIME METRIC, PRES=ATM, TEMP=C COMPONENT DATA LIBID 1,ETHANOL/ 2,CYHX THERMO DATA METHOD SYSTEM=NRTL, PHI=TVIRIAL KVALUE POYNTING=ON NRT6(K) 1, 2, -.1429, 472.71, -.01, 748.33, 0.3681, 2.871E-4 PHI TVIRIAL 1, 1.0/ 2, 0.0 STREAM DATA PROP STREAM=1, TEMP=115, PRES=5, & COMP=75/25 UNIT OPERATION FLASH UID=FL1 FEED 1 PROD V=2, L=3 TPSPEC PRES=50 SPEC STREAM=2, RATE, RATIO, STREAM=1, & RATE, VALUE=0.5 END
5.24:
For the same problem, use TVIRIAL for vapor fugacities and SRK for vapor enthalpies, entropies and densities. Specify API liquid densities.
THERMODYNAMIC DATA METHOD SYSTEM=NRTL, PHI=TVIRIAL, & ENTHALPY(V)=SRK, ENTROPY(V)=SRK, & DENSITY(V)=SRK, DENSITY(L)=API
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IDIMER Vapor Fugacity

Typical Usage
...
COMPONENT DATA LIBID 1, ACETIC/ 2, ACRYLIC/ 3, H2O THERMO DATA METHOD SYSTEM=NRTL, PHI=IDIMER, & ENTHALPY(V)=IDIMER, DENSITY(V)=IDIMER KVALUE FILL=UNIFAC STREAM DATA . . .
General Information
The IDIMER method predicts vapor fugacities, vapor enthalpies, vapor entropies and vapor densities. It is especially useful for systems where dimers form in the vapor phase, e.g., carboxylic acid systems. A liquid activity method must be used in conjunction with the IDIMER method.
Table 6-17: Attributes of the IDIMER Vapor Fugacity Method Properties predicted by HOCV Vapor fugacities vapor enthalpies Vapor densities Vapor entropies
Required pure component properties1 None Suggested application ranges Components Free-water decant VLLE - Carboxylic acids, polar components - Not supported - IDIMER only calculates vapor phase properties, but VLLE methods may be used with IDIMER methods. Two liquid phase behavior
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Input Description
METHOD SYSTEM=NRTL or UNIQUAC or UNIFAC or UFT1 or UFT2 or UFT3 or UNFV or WILSON or VANLAAR or MARGULES or REGULAR or FLORY, PHI=IDIMER, ENTHALPY(V)=IDIMER, ENTROPY(V)=IDIMER, DENSITY(V)=IDIMER, . . . KVALUE=NRTL or UNIQUAC or UNIFAC or UFT1 or UFT2 or UFT3 or UNFV or WILSON or VANLAAR or MARGULES or REGULAR or FLORY, PHI=IDIMER, ENTHALPY(V)=IDIMER, ENTROPY(V)=IDIMER, DENSITY(V)=IDIMER, . . .
or METHOD
SYSTEM KVALUE
A liquid activity method system must be chosen if the IDIMER method is to be used. Selects the method for K-value calculations. Only liquid activity methods can be used with the IDIMER method. Selects the IDIMER method for vapor phase fugacities, and/or enthalpies and/or entropies and/or densities.
PHI and/or ENTHALPY( V) and/or ENTROPY(V) and/or DENSITY(V)

POYNTIN G
This option selects whether to apply the Poynting correction to fugacities of components in the liquid phase. The default is OFF unless a PHI method is selected, in which case the default is ON. This selects the method used to calculate the liquid molar volume necessary for computing the Poynting correction factor. Options are:
MOLVOL
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STANDARD
The default. Selects the standard method for calculating the liquid molar volume at standard conditions (25 C, 1 atm). Selects the Rackett liquid density method. Selects the Rackett 2 liquid density method. Selects the LIBRARY liquid density method.
Vapor Fugacity Data

PHI BANK=SIMSCI or NONE or bankid IDIMER(tunit, punit, log or ln)i, i, Aii, Bii/ i, j, Aij, Bij/ . . .
Note: The IDIMER statements must follow the PHI statement.
BANK
bankid
IDIMER
This statement supplies interaction data for the IDIMER vapor fugacity method. This method may be used for components forming dimers, particularly carboxylic acids. Aii and Bii are the association parameter for component i, while Aii and Bii are the solvation parameter for components i and j.
Enthalpy, Entropy and Density Data

ENTHALPY(V) BANK=SIMSCI or NONE or bankid ENTROPY(V) BANK=SIMSCI or NONE or bankid DENSITY(V) BANK=SIMSCI or NONE or bankid IDIMER(tunit, punit, log or ln) i, i, Aii, Bii/ i, j, Aij, Bij/ . . .
IDIMER vapor interaction data may be selected for enthalpy, entropy and density methods. Normally, these features are selected
for the vapor fugacity method and are automatically carried over for these other methods. If, however, the vapor fugacity method is not IDIMER, you can supply these parameters independently. See above under Vapor Fugacity Data for format and definition of these entries.
Examples
5.25: Use the IDIMER vapor fugacity method with the NRTL liquid activity method for a mix of associating acids.
TITLE PROB=IDIMER PRINT INPUT=ALL COMPONENT DATA LIBID 1, HFOR/ 2, ACETIC/ 3, HPRP THERMO DATA METHOD SYSTEM=NRTL, PHI=IDIMER, & ENTHALPY(V)=IDIMER, ENTROPY(V)=IDIMER, & DENSITY(V)=IDIMER PHI BANK=SIMSCI IDIME(K, MMHG, LOG) 1,1,-10.743,3083.0 IDIME(K, MMHG, LOG) 2,2,-10.421,3166.0 IDIME(K, MMHG, LOG) 3,3,-10.843,3316.0 IDIME(K, MMHG, LOG) 1,2,-10.356,3193.0 STREAM DATA PROP STREAM=1, TEMP=100, PRES=700, & COMP=0.477/0.094/0.729 UNIT OPERATION FLASH UID=FL1 FEED 1 PROD V=2, L=3 TPSPEC PRES=50 SPEC STREAM=2, RATE, RATIO, STREAM=1, & RATE, VALUE=0.5 END
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Redlich-Kister, Gamma Heat of Mixing

Typical Usage
...
COMPONENT DATA LIBID 1, IPA/ 2, H2O/ 3, CH THERMO DATA METHOD SYSTEM=NRTL ENTHALPY(L) HMIX=RK1 KVALUE FILL=UNIFAC STREAM DATA . . .
General Information
The Redlich-Kister and Gamma heat of mixing methods apply a correction to IDEAL enthalpy data. A liquid activity method must be used in conjunction with the Redlich-Kister or Gamma methods.
Table 6-18: Attributes of the Redlich-Kister, Gamma Heat of Mixing Properties predicted by RK1, RK2, GAMMA Liquid enthalpy heat of mixing corrections Required pure component properties None Two liquid phase behavior Free-water decant VLLE - N/A - N/A
Input Description
METHOD SYSTEM=NRTL or UNIQUAC or UNIFAC or UFT1 or UFT2 or UFT3 or UNFV or WILSON or VANLAAR or MARGULES or REGULAR or FLORY
or
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METHOD
KVALUE=NRTL or UNIQUAC or UNIFAC or UFT1 or UFT2 or UFT3 or UNFV or WILSON or VANLAAR or MARGULES or REGULAR or FLORY, . . . , ENTHALPY(L)=IDEAL, . . .
SYSTEM KVALUE
A liquid activity method system must be chosen if the Gamma method is to be used. Selects the method for K-value calculations. Only liquid activity methods can be used with the Gamma method. Selects the IDEAL liquid enthalpy method for use with the Redlich-Kister or Gamma heat of mixing methods.
ENTHALPY(L )
Enthalpy Data
ENTHALPY BANK=SIMSCI or NONE or bankid, HMIX=NONE or RK1 or RK2 or GAMMA RK1(K or KCAL or KJ) i, j, aij, bij, cij, dij, eij, fij, gij, hij/ . . . or RK2(K or KCAL or KJ) i, j, aij, bij, cij, dij, eij, fij, gij, hij/ . . .
BANK
bankid
HMIX
This statement selects the heat of mixing method to be applied to the liquid enthalpy method. NONE RK1 or RK2 No mixing enthalpy correction is applied (default). This option selects different formulations of the Redlich-Kister correlation.
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GAMMA
The heat of mixing is calculated through activity coefficient derivatives with respect to temperature.
RK1 or RK2
The RK1 or RK2 statements are used to supply interaction parameters for the Redlich-Kister heat of mixing correlation methods RK1 and RK2. The statement given here must correspond to the entry on the ENTHALPY property data statement. The statements RK1 and RK2 are exclusive of each other and cannot be mixed in the same property data section. The Redlich-Kister equation for the excess heat of mixing is given as: when unit is K:
EX 1 H --------- = -T RT
xi xj ( aij + bij X + cij X

i j
+ d ij X + e ij X + f ij X + g ij X + h ij X )
when unit is KCAL or KJ:

EX 1H --------- = -----RT RT
xi xj ( aij + bij X + cij X

i j
+ d ij X + e ij X + f ij X + g ij X + h ij X )
where
X = xi xj xi xj X = ------------xi + xj
(form 1 of Redlich-Kister) (form 2 of Redlich-Kister)
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Examples
5.26: Using the NRTL liquid activity method, and correcting for the heat of mixing using the Redlich-Kister method RK1, model a 50/50 mix of acetic and acrylic acids at 100 psia and 100 F.
TITLE PROB=RK1 PRINT INPUT=ALL COMPONENT DATA LIBID 1, ACETIC/ 2, ACRYLIC THERMO DATA METHOD SYSTEM=NRTL, PHI=HOCV ENTHALPY(L) HMIX=RK1 STREAM DATA PROP STREAM=1, TEMP=100, PRES=100, & COMP=50/50 UNIT OPERATION FLASH UID=FL1 FEED 1 PROD V=2, L=3 TPSPEC PRES=50 SPEC STREAM=2, RATE, RATIO, STREAM=1, & RATE, VALUE=0.5 END
5.27:
For the same problem, use TVIRIAL for vapor fugacities and specify API liquid densities.
THERMODYNAMIC DATA METHOD SYSTEM=NRTL, PHI=TVIRIAL, DENSITY(L)=API ENTHALPY(L) HMIX=RK1
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Chapter 7 Solid Solubility Methods

The program provides a number of methods for handling solids, including the van't Hoff solubility method which calculates solidliquid equilibrium K-values.
Van't Hoff Solubility

Typical Usage
... COMPONENT DATA LIBID 1,H2O/ 2,TOLUENE/ 3,PXYLENE THERMODYNAMIC DATA METHOD SYSTEM=IDEAL, KVALUE(SLE)=VANTHOFF STREAM DATA . . .
General Information
The VANTHOFF solubility method is used to calculate solid-liquid equilibrium K-values for nearly ideal non-electrolyte systems using the van't Hoff ideal solubility equation.
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Table 7-1: Attributes of the VANTHOFF Method Properties predicted by the VANTHOFF method SLE K-values Required pure component properties1 Triple point temperature Two liquid phase behavior Free-water decant VLLE
1
N/A N/A
Input Description
METHOD KVALUE(SLE)=VANTHOFF, ...
KVAL UE
Selects the method for K-value calculations. Only SLE K-value calculations are available with the VANTHOFF method.
The solubility of solute i in solvent l at temperature T is given by:

Cp Tt Hm T Cp Tt - ---- 1 --------- ln ---ln x i = ----------- ---- 1 + --------RT T t R T R T
where: Hm= enthalpy change of melting at Tt Cp= heat capacity change of melting at Tt Tt= triple point temperature In practice, the more easily accessible solid melting temperature is usually used instead of the triple point temperature.
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Solid Solubility Methods
Examples
7.1: Use the VANTHOFF method for a system containing pxylene.
TITLE PROJECT=MANUAL, PROB=VANTHOFF PRINT INPUT=ALL COMP DATA LIBID 1,TOLU/ 2,PXYLENE/ 3,MXYLENE/ 4,OXYLENE/ 5,EBZN/ & 6,ETLN/ 7,C3, BANK=SIMSCI ATTR COMP=2, PSD(MIC)=0., 10., 25., 50., 75., 100., & 250., 500., 1000., 5000., 10000. THERMO DATA METHOD SYSTEM=IDEAL, KVALUE(SLE)=VANTHOFF, & TRANSPORT=PURE STREAM DATA ... END
7.2:
For the same problem, use the VANLAAR method for VLE calculations.
THERMO DATA METHOD SYSTEM(VLE)=VANLAAR, & KVALUE(SLE)=VANTHOFF, TRANSPORT=PURE
User-supplied Solubility
Typical Usage
... COMPONENT DATA LIBID 1,H2O/ 2,NACL/ 3,CACL2 THERMODYNAMIC DATA METHOD SYSTEM=IDEAL, KVALUE(SLE)=SOLDATA KVALUE(SLE) SOLUTE 2,3 SOLDATA 2,1,-2.3/ 3,1,1.937,-1213 STREAM DATA . . .
General Information
The SOLDATA solubility method is used to calculate solid-liquid equilibrium K-values using user-supplied solubility data.
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Table 7-2: Attributes of the SOLDATA Method Properties predicted by the SOLDATA method K-values Required pure component properties1 None Two liquid phase behavior Free-water decant VLLE N/A N/A
Input Description
METHOD KVALUE(SLE)=SOLDATA, ...
KVALUE
Selects the method for K-value calculations. Only SLE K-value calculations are available with the SOLDATA method.
K-value Data
KVALUE(SLE) FILL=VANTHOFF or ONE or FREE SOLUTE i, j, k,... SOLDATA(tunit) i, l, c1, c2, c3 { , tmin, tmax}.
FILL
The fill option selects the method used to estimate binary interaction data missing from the selected databank and not given via SOLDATA statements. The options available are: VANTHOFF ONE van't Hoff ideal solubility equation. This is the default. Missing binary solubilities set to 1.0 (i.e., all unspecified solids completely soluble).
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FREE
If a solvent k is missing binary solubility data for a solute, the solvent is ignored in the solubility calculation. That is, the solvent mole fractions are normalized to a k-free basis.
SOLUTE SOLDATA
Specifies the solutes i, j, k ... in the system. This statement supplies the molar solubility of a solute i in a mixture of i and solvent l, as a function of temperature according to the following equations:
c2 ln x il = c 1 + ---- + c 3 ln T T
The solubility of i in a multi-component stream is given as:

NOC
ln ( x i, mix ) =
xl ln ( xi, l )
l = 1 li
The temperature units (tunit) may only be given in Kelvin or degrees Rankine. Note: When the SOLDATA method is used for calculating the
solid-liquid equilibrium K-values, the KVALUE(SLE) statement must be utilized. The SOLUTE and SOLDATA statements must follow the KVALUE(SLE) statement. The SOLDATA statement supplies values used for equilibrium calculations.
While only 3 coefficients are recognized on the SOLDATA statement, a total of five floating point values are allowed. The final two values are the minimum and maximum applicable temperatures, respectively.
Note:
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Examples
7.3: Use the SOLDATA method and supplied solubility data, for a system containing p-xylene. Binary interaction data not supplied via SOLDATA statements are retrieved from the van't Hoff method by the selection of the FILL=VANTHOFF option.
TITLE PROJECT=MANUAL,PROB=SOLDATA PRINT INPUT=ALL COMP DATA LIBID 1,TOLU/2,PXYLENE/3,MXYLENE/4,OXYLENE/5,EBZN/ & 6,ETLN/7,C3, BANK=SIMSCI ATTR COMP=2, PSD(MIC)=0., 10., 25., 50., 75., 100., & 250., 500., 1000., 5000., 10000. THERMO DATA METHOD SYSTEM=IDEAL, KVALUE(SLE)=SOLDATA, & TRANSPORT=PURE KVALUE(SLE) FILL=VANTHOFF SOLUTE 2 SOLDATA 2,1,-0.6,0.02,0.01 STREAM DATA ... END
7.4:
For the same problem, use SRK for VLE calculations and set all missing binary interaction data for SLE calculations equal to 1.0.
THERMODYNAMIC DATA METHOD SYSTEM=SRK, KVALUE(SLE)=SOLDATA, & TRANSPORT=PURE KVALUE(SLE) FILL=ONE
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Chapter 8 Transport and Special Properties

The program provides a number of methods for calculating transport properties, and various stream properties such as kinematic viscosities, cloud and flash point temperatures and sulfur content.
Transport Properties
Typical Usage
...
COMPONENT DATA LIBID 1,C3/ 2,IC4/ 3,NC4 THERMO DATA METHOD SYSTEM=SRK, TRANSPORT=PURE STREAM DATA . . .
General Information
The TRANSPORT keyword is used to provide transport properties, including liquid and vapor viscosities, liquid and vapor thermal conductivities, and liquid surface tension values. Liquid diffusivities may be computed by selecting the DIFFUSIVITY(L) keyword.
II-8-1
Table 8-1: Attributes of the TRANSPORT Method Properties predicted by the SHELL, PURE and PETRO methods Liquid/vapor viscosities Liquid/vapor thermal conductivities Liquid surface tensions
Properties predicted by the SIMSCI and API methods Liquid viscosities Properties predicted by the TRAPP method Liquid/vapor viscosities Liquid viscosities Liquid/vapor thermal conductivities Liquid/vapor thermal conductivities Properties predicted by the TACITE method Required pure component properties1 Varies with method and property; see the PRO/II Reference Manual for more information
1
Input Description
METHOD . . .,
TRANSPORT=NONE or TRANSPORT=PURE or PETRO or TRAPP or TACITE or U1 or U2 ... or U5, DIFFUSIVITY(L)=NONE or DIFFUSIVITY(L)=WILKE or DIFDATA,{VISCOSITY(VL)=NONE or VISCOSITY(VL)= PURE or PETRO or TRAPP or U1 or U2 or ...U5, CONDUCTIVITY(VL)=NONE or CONDUCTIVITY(VL)= PURE or PETRO or TRAPP or U1 or U2 or ... U5, SURFACE(L)=NONE or SURFACE(L)=PURE or PETRO or PARACHOR or U1 or U2 ... or U5} or VISCOSITY(VL)=NONE or VISCOSITY(VL)=PURE or PETRO or TRAPP or U1 or U2 ... or U5 or VISCOSITY(V)=PURE or PETRO or TRAPP or U1 or U2 ... or U5 or API and/or VISCOSITY(L)= PURE or PETRO or TRAPP or KVIS or LBC or U1 or U2 ... or U5 or SIMSCI or API and/or CONDUCTIVITY(VL)=NONE or
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Transport and Special Properties
CONDUCTIVITY(VL or V and/or L)= PURE or PETRO or TRAPP or U1 or U2 ... or U5, and/or SURFACE(L)=NONE or SURFACE(L)=PURE or PETRO or PARACHOR or U1 or U2 ... or U5, and/or DIFFUSIVITY(L)=NONE or DIFFUSIVITY(L)=WILKE or DIFDATA
TRANSPORT
This keyword selects the method used for calculation of transport properties including liquid and vapor viscosities, liquid and vapor thermal conductivities and liquid surface tension values. If the TRANSPORT keyword is absent, the default is that no transport method is selected. If the TRANSPORT keyword is present, the available options are:
PURE
This option applies simple mixing rules to the temperature-dependent pure component values available in the selected databanks to calculate mixture transport properties. Saturation values are used and no pressure corrections apply. This method is the default if only the TRANSPORT keyword is present. This option uses predictive correlations that apply to bulk hydrocarbon mixtures. Pressure corrections apply. This option uses a one fluid conformal TRAPP model to calculate vapor and liquid viscosities and thermal conductivities for hydrocarbons. The PETRO method is used to calculate surface tension. This option uses the Lohrenz-BrayClark (LBC) liquid viscosity method, the TRAPP conductivity methods, and the PARACHOR surface tension method.
PETRO
TRAPP
TACITE
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U1-U5
This option selects one of the up to 5 user-defined subroutines that are available to compute transport properties.
VISCOSITY (VL or V and/or L)
This keyword requests the calculation of vapor and liquid viscosities. The options available with this keyword are: PURE This option applies simple mixing rules to the temperature-dependent pure component values available in the selected databanks to calculate mixture transport properties. Saturation values are used and no pressure corrections apply. This option is available for both vapor and liquid viscosity calculations. This option uses predictive correlations that apply to bulk hydrocarbon mixtures. Pressure corrections apply. This option is available for both vapor and liquid viscosity calculations. This option uses a one fluid conformal solution model to calculate vapor and liquid viscosities. This option calculates the viscosity from the values of the kinematic viscosity and the density. For purposes of this calculation, the density is computed with the API method. In order to use this option, a KVIS method must be declared on the METHOD statement. This option is only available with the VISCOSITY(L) keyword. This is the Lohrenz-Bray-Clark prediction method for calculating liquid viscosities. This option selects one of the up to 5 user-defined subroutines that are available to compute transport properties. This option is available for both vapor and liquid viscosity calculations.
PETRO
TRAPP
KVIS
LBC
U1-U5
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SIMSCI
This option uses SimSci developed liquid viscosity values. This was known as the Twu method in PROCESS. This option is available only with the VISCOSITY(L) keyword. This option uses liquid viscosities from the API Technical Data Book. This option is available only with the VISCOSITY(L) keyword.
API
CONDUCTIVI TY (VL or V and/or L)
This keyword requests the calculation of vapor and liquid thermal conductivities. The options available with this keyword are: PURE This option applies simple mixing rules to the temperature-dependent pure component values available in the selected databanks to calculate mixture thermal conductivity properties. Saturation values are used, and no pressure corrections apply. This option is available for both vapor and liquid conductivity calculations. This option uses predictive correlations that apply to bulk hydrocarbon mixtures. Pressure corrections apply. This option is available for both vapor and liquid conductivity calculations. This option uses a one fluid conformal solution model to calculate vapor and liquid conductivities. This option selects one of the up to 5 user-defined subroutines that are available to compute transport properties. This option is available for both vapor and liquid thermal conductivity calculations.
PETRO
TRAPP
U1-U5
SURFACE(L)
This keyword selects the calculation method for liquid surface tensions. Options available are: PURE This option applies simple mixing rules to the temperature-dependent pure component values available in the selected databanks to calculate mixture viscosity properties. Saturation values are used and no pressure corrections apply. II-8-5
PETRO
This option uses predictive correlations that apply to bulk hydrocarbon mixtures. Pressure corrections apply.
PARACHO This option uses the PARACHOR R prediction method. U1-U5 This option selects one of the up to 5 user-defined subroutines that are available to compute transport properties.
DIFFUSIVITY( This keyword selects the diffusivity calculation L) method and/or provides diffusivity data. If the DIFFUSIVITY(L) keyword is absent, the default is that no diffusivity method is selected. If the DIFFUSIVITY(L) keyword is present, the WilkeChang correlation (WILKE) is the default. The other option is DIFDATA, which is selected when usersupplied data only are to be used. Note: The TRANSPORT, VISCOSITY, CONDUCTIVITY, SUR-
FACE and DIFFUSIVITY statements are usually optional but are required when certain features or unit operations are used. Table 8-2 gives the PRO/II features that require transport properties.
Table 8-2: Features that Require Transport Properties Feature Property Stream Output Transport properties option HCURVE Transport properties tables COLUMN Tray vapor/liquid transport properties printout Sieve tray sizing/rating Packed columns HXRIG PIPE ROTARY DRUM FILTER FILTERING CENTRIFUGE TRANSPORT TRANSPORT
TRANSPORT VISCOSITY(VL) VISCOSITY(L)1 & SURFACE(L)2 VISCOSITY(VL) & CONDUCTIVITY(VL) VISCOSITY(VL) & SURFACE(L)3 VISCOSITY(VL) & SURFACE(L) VISCOSITY(VL) & SURFACE(L)
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Table 8-2: Features that Require Transport Properties DISSOLVER DIFFUSIVITY(L) MASSTRANS not specified
1 2 3
If a liquid viscosity method is not explicitly defined, the viscosity contribution to the correlation is omitted. Surface tension is required when the NORTON method is used for efficient capacity and HETP calculations. Surface tension used for two-phase flow.
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Diffusivity Data
DIFFUSIVITY(L) DIFDATA(tunit) i, j, c1, c2, c3/ ...
DIFFUSIVITY( The DIFFUSIVITY statement signifies that L) diffusivity data is being supplied by the user. DIFDATA This statement supplies the diffusivity of a solute i in a mixture of i and j. Diffusivity is a measure of the rate at which a solute diffuses through a given area in a given time period under a concentration gradient. The dimensions of diffusivity are always in m2/sec. The diffusivity is given as a function of temperature according to the following equation: ln Dij = c1 + c2 / T + c3 ln T where T is in absolute units (K or R). Note: The program currently allows for the calculation of liquid diffusivities only when using a KVALUE(SLE) method. The DIFDATA statements may follow the DIFFUSIVITY(L) statement.
User-supplied Viscosity, Conductivity, and Surface Tension Data (optional)

VISCOSITY CONDUCTIVITY SURFACE UDATA i, value/...
UDATA
This statement supplies method-specific data that will be used by the user-added subroutine for the calculation of viscosity, conductivity, or surface tension values. See the PRO/II Data Transfer System and User-added Subroutines User's Guide for more information.
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VISCOSITY CONDUCTIVITY SURFACE ...
Note: These required pure component properties are all tempera-
ture dependent and may not be supplied in the Thermodynamic Data Category. They may only be supplied globally in the Component Data Category. See Component Properties in Volume I, for details on format and entry. The following data may be supplied in the Thermodynamic Data Category of input:
PARACHOR PENELOUX(volunit) i, value/... i, value/...
Examples
8.1: In this example, an HCURVE unit operation is used to generate heating curves and transport property tables for a crude feed stream.
TITLE PROBLEM=TRANSPORT DIMEN ENGLISH, LIQV=BBL PRINT RATE=M,STREAM=ALL,INPUT=ALL,TBP COMPONENT DATA LIBID 1,ETHANE/ 2,PROPANE/ 3,IBUTANE/ 4,BUTANE/ 5,PENTANE TBPCUTS 115,300,6/ 400,10/ 650,8/ 800,4/ 1500,6 THERMODYNAMIC DATA METHOD KVAUE(VLE)=BK10, ENTH(V)=JG, ENTH(L)=JG, & ENTR(V)=CP, ENTR(L)=CP, DENS(V)=IDEA, & DENS(L)=API, TRANS=PETRO STREAM DATA PROP STREAM=1,TEMP=375, PRES=300, PHASE=M, & RATE(V)=3125, ASSAY=LV D86 STREAM=1, PRES(MMHG)=760, TEMP=F, & DATA=8,135/25,210/43,370/67,565/75,665/82,800/92,990 API STREAM=1, AVG=45.37, & DATA=11.6,80.01/21.6,62.9/41.7,50.6/61.9,38.2/83.8,27.5 MW STREAM=1, AVG=162.9, & DATA=24.2,99.5/40.5,135/55,184.7/74.8,334.8/100,789 LIGHT STREAM=1, PERCENT(W)=10.4, & COMP(M)=1,0.1/2,1.4/3,0.65/4,3.15/5,5.1, NORMALIZE UNIT OPERATIONS HCURVE UID=HC1, NAME=HEATING CRV ADIA STREAM=1, TEMP=375, 690, PRES=300, 50, POINTS=20 PROP TRANSPORT END
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8.2:
Using the van't Hoff method, calculate the amount of pxylene dissolved in 10 ft3 of water at 40 F. Note that the WILKE method is used to calculate the p-xylene diffusivity.
TITLE PROB=DIFFUSIVITY COMPONENT DATA LIBID 1,H2O/2,PXYLENE/3,ETHANE, BANK=SIMSCI ATTR COMP=2, PSD(MIC)=0., 50., 200., 1000., 5000. THERMO DATA METHOD SYSTEM(VLE)=SRKM, & KVALUE(SLE)=VANTHOFF, TRANSPORT=PURE, & DIFFUSIVITY(L)=WILKE STREAM DATA PROP STREAM=1, TEMP=40, PRES(PSIG)=0, COMP(M)=1,10/3, 0.5 SOLID STREAM=1, COMP(M)=2,100 UNIT OPERATION DISSOLVER UID=DIS FEED 1 PROD OVHD=2, BTMS=3 PRINT CSD RATING VOLUME(FT3)=10 OPERATION SOLUTE=2, SOLVENT=1, DP=0 END
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Special Properties
Typical Usage
...
COMPONENT DATA LIBID 1,IC4/ 2,NC4/ 3,NC5 THERMO DATA METHOD SYSTEM=LKP, CLOUD=INDEX STREAM DATA . . .
General Information
The program provides numerous methods to compute special stream refinery properties. These properties include KVIS which calculates liquid kinematic viscosities, CLOUD and FLPT (cloud and flash point temperatures respectively), and SULF (sulfur content). Descriptions of all the stream refinery special properties available are given in Table 8-3.
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Table 8-3: Keywords for Special Stream Refinery Properties Keyword KVIS POUR CLOU FRZP CFPP FLPT RON MON IBP FBP RCR TAN OLEF CETA CETN REFR ANIL AROM WTAR NAPH WTNA PARA WTPA NPHL H2 CARB CHRA SMOK LUMI SULF Property Kinematic viscosity Pour point temperature Cloud point temperature Freeze point temperature Cold filter plug point Flash point temperature Research octane number Motor octane number Initial boiling point Final boiling point Ramsbottom carbon Total acid number Olefinic content Cetane index Cetane number Refractive index Aniline point Aromatics content Weight aromatic content Naphthene content Weight naphthenic content Paraffin content Weight paraffinic content Naphthalene content Hydrogen content Carbon content Carbon-hydrogen ratio Smoke point Luminometer number Sulfur content
II-8-12
Table 8-3: Keywords for Special Stream Refinery Properties Keyword MERC ASUL NITR OXYG CCR NICK VANA IRON ASPH PHEN ANEU BROM MEAB CABP MOAB NHV WAX ASH NOAC SOFT PEN SPROP Property Mercaptan content Aliphatic sulfur content Nitrogen content Oxygen content Conradson carbon residue Nickel content Vanadium content Iron content Asphaltene content Phenol content Neutralize number Bromine number Mean average boiling point Cubic average boiling point Molal average boiling point Net heating value Wax content Ash content Noack volatility Softening point Penetration index User-defined special property
Input Description
The METHOD Statement For all stream refinery properties, the general METHOD statement is:
METHOD ..., property(qualifier, basis)=method, {REFPROP=SIMSCI}
The appropriate qualifier, basis, and method for each property are given in Table 8-4.
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Table 8-4: Special Refinery Property Entries for the METHOD Statement Property KVIS POUR CLOU FRZP CFPP FLPT RON MON IBP FBP RCR TAN OLEF CETA CETN REFR ANIL AROM WTAR NAPH WTNA PARA WTPA NPHL H2 CARB CHRA SMOK Qualifier C or L C or L MONO C20 or C70 TOTA or RING Basis M or WT or LV M or WT or LV M or WT or LV M or WT or LV M or WT or LV M or WT or LV M or WT or LV M or WT or LV M or WT or LV M or WT or LV M or WT or LV M or WT or LV M or WT or LV M or WT or LV M or WT or LV M or WT or LV M or WT or LV M or WT or LV WT or LV WT WT WT M or WT or LV Method INDEX or SIMSCI INDEX INDEX or SIMSCI INDEX INDEX INDEX or NELSON or API INDEX or SUM INDEX or SUM SIMSCI SIMSCI INDEX or SIMSCI INDEX or SUM INDEX or SUM ASTM D976 INDEX or SUM INDEX or SUM SUM INDEX or SUM SUM INDEX or SUM SUM INDEX or SUM SUM SUM INDEX or SUM INDEX or SUM INDEX or SUM INDEX or SUM
II-8-14
Table 8-4: Special Refinery Property Entries for the METHOD Statement Property LUMI SULF MERC ASUL NITR Qualifier TOTA or BASI or NONB C5 or C7 i Basis WT M or WT or LV WT WT WT Method INDEX or SUM or D1740 INDEX or SUM SUM SUM INDEX or SUM
OXYG CCR NICK VANA IRON ASPH PHEN ANEU BROM MEAB CABP MOAB NHV WAX ASH NOAC SOFT PEN SPROP
WT M or WT or LV WT WT WT WT WT WT or LV WT or LV WT WT WT WT or LV M or WT or LV M or WT or LV
INDEX or SUM INDEX or SUM INDEX or SUM INDEX or SUM SUM INDEX or SUM SUM SUM SUM API API API API INDEX or SUM INDEX or SUM INDEX or SUM SUM INDEX or SUM INDEX or SUM
Note: The Luminometer number (LUMI) is calculated from the Smoke Point (SMOK) for the D1740 method only. Therefore the SMOK entry must be provided on the METHOD statement and data supplied if the LUMI property is required when the D1740 method is selected. Otherwise, the LUMI number will be reported as missing. PRO/II Thermodynamic Data Keyword Input Manual II-8-15
For example, when specifying the SIMSCI mixing method for KVIS using the default liquid volume basis, the METHOD statement becomes:
METHOD ..., KVIS=SIMSCI, ...
When specifying the INDEX mixing method for research octane number (RON) and using the default weight basis, the METHOD statement becomes:
METHOD ..., RON(L, WT)=INDEX, ...
REFPRO This keyword is used to supply the default methods for P calculating special stream refinery properties. The SIMSCI option is used to specify the PRO/II v3.3 calculation methods and PRO/II v3.3 properties. These properties are KVIS, CLOU, POUR, FLPT, SULF, and CETA.
The available mixing methods for special refinery properties are described below:
INDEX This mixing method sums the individual component indices on a weight or molar or liquid volume basis. The individual component index is calculated from the property itself using the following relationship:
1.0 - log ( VALUE ) + CONSTANT(1) og ( INDEX ) = ---------------------- GAMMA
The value of the CONSTANT for a particular property is calculated from the values supplied at a reference point (GAMMA, REFINDEX, REFVALUE) given using the data statement (see below for a description of these keywords). SUM SIMSCI This mixing method sums the actual individual component property values. This mixing rule is available for the cloud point (CLOU) and kinematic viscosity (KVIS) methods only. This mixing method sums the component property index values. However, a different formula than the one shown in equation (1) is used to convert to data values to indices. For CLOU, the conversion equation is:
II-8-16
( INDEX )
GAMMA
CPF + 460.0 = ----------------------------------------------------------------------------------------- (2) exp ( 6.39693 9.21034 GAMMA )
For CLOU, GAMMA defaults to a value of 0.05. For KVIS, the conversion equation is:
INDEX = 72.0509 22.1322 ln ( KVIS ) + 4.35618 { ln ( KVIS ) }
2 (3)
NELSON
The Nelson method is an alternate method used to calculate the flash point temperature. The FLPT, MEAB, CABP, MOAB, and NHV properties may all be calculated using methods based on the API Technical Data Book. The LUMI property may be calculated using the ASTM D1740 method. The Luminometer number (LUMI) is calculated from the Smoke Point (SMOK) for the D1740 method only. Therefore the SMOK entry must be provided on the METHOD statement and data supplied if the LUMI property is required when the D1740 method is selected. Otherwise, the LUMI number will be reported as missing. This method is available for the RON and MON properties. These options select a user-added method for the property. The USFORM option requires that the FORTRAN routine SPUSER.FOR be in PROCALC.EXE and PROOUT.EXE. The USINDEX option requires that the FORTRAN routine CVUSER.FOR be compiled and linked into PROIN.EXE, PROCALC.EXE and PROOUT.EXE. See the PRO/II Useradded Subroutines User's Manual for more information.
API
D1740
SYMS USFORM, USINDEX
Note: The USINDEX option requires that DATA or INDEX val-
ues or NCFILL option be provided for the property.
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Special Property Methods Data

property(qualifier, basis) {GAMMA=value, REFINDEX=value, REFVALUE(unit)=value},{NCFILL=ncfill}, {NCBLEND=ncblend} i, datvalue/ ... i, ndvalue/ ...
DATA(unit) INDEX
For KVIS only:

KVIS(M or WT or LV) {GAMMA=value, REFINDEX=value, REFVALUE(kvisunit)=value,} {NCFILL=ncfill}, {NCBLEND=ncblend} t1, t2, /i, p1, p2, /... t1, t2, /i, p1, p2, /...
DATA(tunit, kvisunit) INDEX(tunit)
The entries and qualifiers for each special refinery property are given in Table 8-5.
Table 8-5: Special Refinery Property Data Entries Propert y KVIS Qualifier1 Basis1 Unit NCFILL NCBLEND
M or WT or kvis-unit LV M or WT or temp LV M or WT or temp LV M or WT or temp LV M or WT or temp LV M or WT or temp LV M or WT or LV M or WT or LV
SIMSCI or MISS or ZERO ZERO or or EXCL NOFILL or API API or ZERO or MISS or ZERO NOFILL or EXCL ZERO or NOFILL ZERO or NOFILL ZERO or NOFILL ZERO or NOFILL ZERO or NOFILL ZERO or NOFILL MISS or ZERO or EXCL MISS or ZERO or EXCL MISS or ZERO or EXCL MISS or ZERO or EXCL MISS or ZERO or EXCL MISS or ZERO or EXCL
POUR CLOU FZPT CFPP FLPT RON MON

1
C or L C or L
For those properties with bases frac, ppm, or pct, any one of these three bases may be specified. The basis frac or ppm or pct indicated is the default for that property.
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Table 8-5: Special Refinery Property Data Entries Propert y CETA Qualifier1 Basis1 Unit No GAMMA, REFI, or REFV entries allowed NCFILL ZERO or NOFILL NCBLEND MISS or ZERO or EXCL
CETN REFR ANIL
C20 or C70
M or WT or LV M or WT or LV
ZERO or NOFILL
MISS or ZERO or EXCL
ZERO or MISS or ZERO NOFILL or API or EXCL ZERO or NOFILL MISS or ZERO or EXCL
M or WT or No GAMMA, LV REFI, or REFV entries allowed M or WT or LV, frac M or WT or LV, frac
AROM
TOTA or RING MONO
ZERO or NOFILL or SIMSCI ZERO or NOFILL or SIMSCI ZERO or NOFILL
OLEF
WTAR
No GAMMA, REFI, or REFV entries allowed
NAPH
M or WT or LV, frac M or WT or LV, frac
ZERO or NOFILL or SIMSCI ZERO or NOFILL or SIMSCI
MISS or ZERO or EXCL MISS or ZERO or EXCL
PARA
TOTA or ISO
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Table 8-5: Special Refinery Property Data Entries Propert y WTNA Qualifier1 Basis1 Unit No GAMMA, REFI, or REFV entries allowed No GAMMA, REFI, or REFV entries allowed NCFILL ZERO or NOFILL NCBLEND MISS or ZERO or EXCL
WTPA
ZERO or NOFILL
NPHL
M or WT or M or WT or No LV LV GAMMA, REFI, or REFV entries allowed WT, frac WT, frac WT M or WT or LV
ZERO or NOFILL
H2 CARB CHRA SMOK
SIMSCI ZERO or NOFILL SIMSCI ZERO or NOFILL SIMSCI ZERO or NOFILL NELSON or ZERO or SIMSCI or NOFILL ZERO or NOFILL
MISS or ZERO or EXCL MISS or ZERO or EXCL MISS or ZERO or EXCL MISS or ZERO or EXCL
LUMI
M or WT or No LV GAMMA, REFI, or REFV entries allowed M or WT or LV, frac
SULF
1
ZERO or NOFILL
II-8-20
Table 8-5: Special Refinery Property Data Entries Propert y MERC Qualifier1 Basis1 WT, frac Unit No GAMMA, REFI, or REFV entries allowed No GAMMA, REFI, or REFV entries allowed No GAMMA, REFI, or REFV entries allowed No GAMMA, REFI, or REFV entries allowed NCFILL ZERO or NOFILL NCBLEND MISS or ZERO or EXCL
ASUL
WT
ZERO or NOFILL
NITR
TOTA or BASI or NONB
TOTA or BASI or NONB WT, frac M or WT or LV, frac WT, frac WT, frac WT
ZERO or NOFILL ZERO or NOFILL ZERO or NOFILL ZERO or NOFILL ZERO or NOFILL ZERO or NOFILL
MISS or ZERO or EXCL MISS or ZERO or EXCL MISS or ZERO or EXCL MISS or ZERO or EXCL MISS or ZERO or EXCL MISS or ZERO or EXCL
OXYG CCR NICK VANA IRON
ASPH PHEN
C5 or C7
WT, frac WT
ZERO or NOFILL ZERO or NOFILL
MISS or ZERO or EXCL MISS or ZERO or EXCL
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Table 8-5: Special Refinery Property Data Entries Propert y ANEU Qualifier1 Basis1 WT or LV Unit No GAMMA, REFI, or REFV entries allowed No GAMMA, REFI, or REFV entries allowed No GAMMA, REFI, or REFV entries allowed temp temp NCFILL ZERO or NOFILL NCBLEND MISS or ZERO or EXCL
BROM
WT or LV
ZERO or NOFILL
WAX ASH SOFT
WT or LV
WT, frac WT, frac WT or LV
ZERO or NOFILL ZERO or NOFILL ZERO or NOFILL
MISS or ZERO or EXCL MISS or ZERO or EXCL MISS or ZERO or EXCL
IBP FBP PEN

1
SIMSCI SIMSCI ZERO or NOFILL
M or WT or M or WT or LV LV
Note: For the properties NOAC, MEAB, CABP, MOAB, and NHV no individual component data entries are possible. Therefore these properties do not require a special methods data statement. The program provides default values for GAMMA, REFINDEX, and REFVALUE for properties CLOU, POUR, FLSH, and KVIS only. These default values are given in Table 8-6.
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Table 8-6: property CLOU POUR FLSH KVIS
Default GAMMA, REFI, and REFV values for CLOU, POUR, FLSH, KVIS GAMMA REFINDE X 0.05 0.08 -0.06 -3.5 10000 10000 10000 71.5 REFVALUE 333.15 (degrees K) 333.15 (degrees K) 255.372 (degrees K) 1.0 (centistoke)
For user-defined special refinery properties, the data statement is:

SPROP(M or WT or LV, frac, i) {GAMMA=value, REFINDEX=value, REFVALUE=value, NAME=text} DATA INDEX i, datvalue/... i, indvalue/ ...
SPROP
The user-defined special refinery property may be supplied on a molar, weight, or liquid volume basis. i This integer value must be supplied and may be any number between 1 and 9999. The total number of SPROPs defined in any given problem must be less than or equal to 60.
NAME
This entry is valid only for the SPROP statement and is used to supply a descriptive name for the user-defined special stream property. It may contain up to 24 alphanumeric characters including embedded blanks, but excluding delimiters. It serves only to identify the userdefined stream property in the stream summary, and does not have to be unique.
The following keyword descriptions apply to all the property data statements outlined in Table 8-5:
II-8-23
GAMMA, REFINDE X,REFVA LUE
These entries must be supplied if the INDEX or SIMSCI stream mixing method is chosen on the METHOD statement. These entries are used to determine the interrelationship between a property value and its corresponding index value. The equations used to convert from data value to index depends on the property. These equations (1-3) are given on page 8-16. Estimates refinery properties for narrow cuts generated from assay streams or PETRO components. For all special refinery properties except NOAC, MEAB, CABP, MOAB, and NHV, properties for narrow cuts may be estimated using the ZERO or NOFILL options.
ZERO NOFILL SIMSCI
NCFILL
Any missing data is set to 0.0. Any missing data is flagged with a warning message before being set to 0.0. This fill option is available for KVIS, SMOK, H2, CARB, CHRA property methods. For KVIS, the Twu method is used to fill in missing data. For H2 and CARB, the missing data are estimated from the carbon-hydrogen ratio. For CHRA, the missing data are estimated from the Twu correlation for the number of carbon and hydrogen atoms. This fill option is available for the SMOK method. This fill option is available for KVIS, POUR, REFR methods. This fill option uses KSLA (option 26) methods to supply missing values.
NELSON API KSLA
NCBLEN D
There are three options for filling in missing data when assay streams are blended. For all special refinery properties except NOAC, MEAB, CABP, MOAB, and NHV, the fill options for blending streams are ZERO, EXCLUDE, and MISSING. ZERO Missing property data for narrow assay cuts is set to 0.0
EXCLUD The narrow cuts in the assay with no data are E excluded from the blend when calculating the blended narrow cut property. MISSIN G The blended narrow cut property data is set to missing if any narrow cut in the blend has missing data.
II-8-24
DATA, INDEX
These entries are used to provide data or index values for stream special properties on a component basis. The unit qualifier on the DATA entry need not be consistent with property qualified on the REFVALUE keyword. The kvisunit qualifier for kinematic viscosity may be either CST (centistokes), IN/S (inch per second), or ST (stokes). If the unit qualifier is not given, the property unit defaults to input units based on the special property units. A data and an index entry cannot be given for the same component. The data and index values are related by the equations (1), (2) and (3) above. t1, t2 These are the temperatures at which kinetic viscosity data and/or index values will be supplied. The tunit qualifier applies to t1 and t2 for temperatures. A maximum of two temperatures may be entered. If t2 is not given, it is set equal to t1. t1 and t2 must be the same for entries on the DATA and INDEX keywords in the same KVIS statement. This number provides the component id number. These entries provide the kinematic viscosity data or index values at temperatures t1 and t2. If only one temperature (t1) is given, p2 entries are not allowed and are set internally equal to p1.
i p1, p2
Most of the special properties shown in Table 8-5 may be defined on a molar (M) or weight (WT) or liquid volume (LV) basis. The following section describes the other unique qualifiers available for RON, MON, AROM, NITR, ASPH, and REFR: For RON and MON: L C For AROM: TOTA RING Total aromatic content. Aromatic ring content. Leaded 3 ml of lead tetraethyl added. Unleaded.
II-8-25
For NITR: TOTA BASIC NONB For ASPH: C5 C7 Measurements taken using a pentane-based solvent. Measurements taken using a heptane-based solvent. Total nitrogen content. Basic nitrogen content. Non-basic content.
For REFR: C20 C70 Measurements taken at 20C. Measurements taken at 70C.
Examples
8.3: Estimate the kinematic viscosity, pour point temperature, carbon to hydrogen ratio, carbon content, refractive index, hydrogen content and smoke point temperature for an assay stream at 100 F and 15 psig. Use the SIMSCI fill methods for KVIS, CHRA, H2, and CARB. Use the NELSON fill method for SMOK, and the API fill method for POUT and REFR.
II-8-26
TITLE PROB=SPECIAL DIME LIQVOL=BBL COMPONENT DATA LIBID 1,H2O/ 2,C2/ 3,C3/ 4,IC4/ 5,NC4/ 6,PENTANE THERMODYNAMIC DATA METHOD SYSTEM=SRKM, KVIS=INDEX, POUR=INDEX, & CHRA=SUM, CARB=SUM, REFR=SUM, H2=SUM, & SMOK=SUM KVIS NCFILL=SIMSCI POUR NCFILL=API REFR NCFILL=API SMOK NCFILL=NELSON CARB NCFILL=SIMSCI H2 NCFILL=SIMSCI CHRA NCFILL=SIMSCI STREAM DATA PROP STREAM=1, TEMP=375, PRES=300, ASSAY=LV, & RATE(LV)=3125 API STREAM=1, DATA=11.6,80.01/ 21.6,62.9/ 41.7,50.6/ & 61.9,38.2/ 3.8,27.5, AVG=45.37 LIGHT STREAM=1, PERC(LV)=10.4, & COMP(LV)=2, 0.1/ 1.4/ 0.65/ 3.15/ 5.0, NORM D86 STREAM=1, DATA= 8, 135/ 25, 210/ 43, 370/ 67, 565/ & 5, 665/ 82, 800/ 92, 990 UNIT OPERATION FLASH UID=FLSH FEED 1 PROD V=2, L=3 ISO TEMP=100, PRES=15 END
II-8-27
II-8-28
Chapter 9 Method-specific Pure Component Data

The calculation of thermodynamic properties requires various pure component data, e.g., critical temperature and pressure and liquid molar volume. The component data statements required for each thermodynamic generator are outlined in this section. Data are normally found in the libraries or supplied in the Component Data Category. Supplying data in the Thermodynamic Data Category allows for the user to override pure component data within each individual method set.
Method-specific Pure Component Data

Typical Usage
...
COMPONENT DATA LIBID 1, IC4/ 2, NC4/ 3, NC5 THERMO DATA METHOD SYSTEM=SRK KVALUE TC 1, 373 STREAM DATA . . .
General Information
The calculation of thermodynamic properties requires various pure component property data. The exact property data required depend on the thermodynamic methods that are selected. For example, the Soave modified Redlich-Kwong equation of state requires pure
component critical temperatures, pressures and acentric factors, but not normal boiling points. Components chosen from the SimSci library or characterized from assay data normally contain all the component data required. Non-library components must be given all the user-supplied pure component property data required for the thermodynamic method(s) selected. Data are normally found in the libraries or supplied in the Component Data Category. Supplying data in the Thermodynamic Data Category allows for the user to override pure component data within each individual method set.
Input Description
METHOD ..., property=method, ... property data(unit) i, value/j,value/...
property
This selects the thermodynamic property for which data are to be supplied. For example, this property could be the vapor density (DENSITY(V)). The calculation method could be the Soave modified Redlich-Kwong equation of state (SRK). This statement is used for inputting the data for the property method selected. Any data supplied here are used in preference to data supplied elsewhere or retrieved from data-banks. The hierarchy of data selection is discussed later on in this section. The keywords allowed for this entry appear on the following page.
data
Note: Data statements must appear immediately after a property statement. The data statement, property statement and method statement must all refer to the same property and method. Except for the K-value property, the values supplied on the data statement apply only to that property method calculation. They do not act as default values for any other property calculations. However, if values are supplied on the data statement only for the K-value property, these values act as defaults for other property calculations using the same method.
II-9-2
The pure component data required for each generator are given in Table 9-1. Only temperature independent data may be given in the Thermodynamic Data Category. See Solid Component Properties and Component Properties in Volume I, for further details on format and definition of these data entries. Hierarchy The hierarchy that governs the use of pure component data is: 1. 2. 3. 4. Any method-specific data supplied on the data statements for each property in each method set. Applicable default values supplied on data statements following a KVALUE statement in the same method set. Data supplied in the COMPONENT DATA statement. Data stored in the component libraries as selected using the BANK option.
If data are still missing after steps 1-4 are completed, an error message is printed and the program is terminated after input processing is completed.
Table 9-1: Required Pure Component Data For Property Generators Generalized Correlation Methods
Method IDEAL GS CS IGS GSE CSE CP BK10 JG LK API RACKETT COSTALD LIBRARY
X X X X X X X X X C X X X X X X X X X X X C X X X X X X X X X X X X X X C X X X X X X X X X X Tc Pc MV Vc Zc Zra vdW DM Rad NBP SP Data
SPGR or API
VP C
H0 Hvap Hliq C C C C C C C C C
C C C C C C C C C C C C C C
II-9-3
Table 9-1: Required Pure Component Data For Property Generators

Equation of State Methods Method SRK,SRKKD,SR KH SRKP,SRKM,SR KS PR,PRH,PRP,PR M UNIWAALS BWRS HEXAMER
Tc X Pc X X MV Vc Zc Zra vdW DM Rad NBP SP Data
SPGR or API
VP
H0 Hvap Hliq C
X X X
X X X
C C C
C C C
Liquid Activity Methods Method NRTL UNIQUAC, UNQ4 UNIFAC UFT 1/2/3 UNFV WILSON VANLAAR MARGULES REGULAR FLORY HOCV TVIRIAL
X X X X C C X X C X X C Tc Pc MV Vc Zc Zra vdW DM Rad NBP SP Data
SPGR or API
VP C C
H0 Hvap Hliq C C C C
C C
C C
C C
C C C C C C C C C C
C C C C C C C C
C C C C C C C C
C C C C C C C C
C C C C C C C C
Special Packages Method ALCOHOL GLYCOL SOUR GPSWATER AMINE

Tc Pc MV Vc Zc Zra vdW DM Rad NBP SP Data
SPGR or API
VP C
H0 Hvap Hliq C C C C C C C
C C C C C
II-9-4
Table 9-1: Required Pure Component Data For Property Generators

U1-U15 Additional Thermodynamic Generators Method VANTHOFF SOLDATA VISCOSITY CONDUCT SURFACE
X X X Tc Pc MV Vc Zc Zra vdW DM Rad NBP SP Data
SPGR or API
VP
H0 Hvap Hliq
C C C C C
Table 9-2: Legend Legend Tc Pc w MV Vc Zc Zra vdW DM Rad Keyword TC PC ACENTRIC MOLVOL VC ZC RACKETT VANDERWAALS DIPOLE RADIUS Description Critical temperature Critical pressure Acentric factor Liquid molar volume Critical volume Critical compressibility factor Rackett parameter van der Waals area and volume Dipole moment Radius of gyration X Legend Data Keyword Description
CONDUCTIVITY Thermal conductivity SURFACE DENSITY (L) DATA or INDEX The user may supply these data either globally in the Component Data Category or locally for a given method set in the Thermodynamic Data Category. The user may supply these data only in the Component Data Category. Surface tension Liquid density Special property data/ index values
NBP SP H0 Hvap Hliq VP SpGr API
NBP SOLUPARA ENTHALPY (V) LATENT ENTHALPY (L) VP SPGR API ETA
Normal boiling point (temperature) Hildebrand solubility parameter Ideal vapor enthalpy Latent heat of vaporization Saturated liquid enthalpies Vapor pressure Specific gravity API gravity Truncated virial equation coefficients Viscosity
The user may supply these data or index values either globally in the Component Data or Stream Data Categories or locally in the Thermodynamic Data Category for a given method sets.
VISCOSITY
II-9-5
Examples
9.1: Using SRKM, model a 50/50 mix of normal butane and normal hexane at 50 psia and 50% vaporization. Input critical temperature data for calculation of vapor densities for components propane and n-butane. Note that the critical temperatures supplied on the TC statement apply only to the vapor density calculations. They do not act as default values for any other property calculations.
TITLE PROB=COMPDATA COMPONENT DATA LIBID 1,NC4/ 2,NC6 THERMODYNAMIC DATA METHOD SYSTEM=SRKM DENSITY(V) TC(K) 1,373.15/2,401.6 STREAM DATA PROP STREAM=1, TEMP=100, PRES=100, & COMP=50/50 UNIT OPERATION FLASH UID=FLSH FEED 1 PROD V=2, L=3 TPSPEC PRES=50 SPEC STREAM=2, RATE, RATIO, STREAM=1, & RATE, VALUE=0.5 END
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9.2:
Using the same problem as above, supply the cloud point index for component 1 and the cloud point temperature for component 2.
TITLE PROB=COMPDATA CALCULATION COMPOSITIONAL, SINGLE FCODE PIPE=BBM DIMENSION ENGLISH DEFAULT TAMBIENT=65, ROUGH(IN)=0.001, IDPIPE(IN)=32 SEGMENT DLVERTICAL=6, DLHORIZONTAL=150 COMPONENT DATA LIBID 1,NC4/ 2,NC6 THERMODYNAMIC DATA METHOD SYSTEM=SRKM, CLOUD=SIMSCI DENSITY(V) TC(K) 1,373.15/2,401.6 CLOUD INDEX 1,20 DATA 2,50 STRUCTURE DATA SOURCE NAME=1, TEMP=100, PRES=100, & COMP=50/50 PIPE LENGTH=3800, ECHG=-100 END
II-9-7
II-9-8
Index
A
Alcohol Dehydration Systems , 2-12 METHOD Statement , 4-38 Method-specific Pure Component Properties , 4-40 Typical Usage , 4-37
Alcohols ALCOHOL Databank Components , 5-8 Attributes of the ALCOHOL Package , 5-2 Enthalpy, Entropy, and Density Data , 5-7 Benedict-Webb-Rubin-Starling Examples , 5-11 Attributes of , 4-34 K-value Data , 5-4 Enthalpy, Entropy, and Density Data , 4-35 METHOD Statement , 5-2 Examples , 4-36 Method-specific Pure Component Properties , 5-10 K-value Data , 4-35 Typical Usage , 5-1 METHOD Statement , 4-34 Alpha Formulations Method-specific Pure Component Properties , 4-36 Enthalpy, Entropy, and Density Data , 4-32 Typical Usage , 4-33 Examples , 4-33 Water Handling Options , 4-36 General Information , 4-29 Binary Interaction Data K-value Data , 4-30 BWRS Equation of State Data , 1-6 Typical Usage , 4-29 Hayden-OConnell Data , 1-7 Vapor Phase Fugacity Data , 4-32 HEXAMER Equation of State Data , 1-6 Amine Systems , 2-7 IDIMER Data , 1-7 Amines LKP Equation of State Data , 1-6 Attributes of the AMINE Package , 5-25 Redlich-Kister Excess Properties Data , 1-7 Enthalpy, Entropy, and Density Data , 5-27 Truncated Virial Data , 1-7 Examples , 5-28 Braun K10 K-value Data , 5-26 Attributes of , 3-18 METHOD Statement , 5-26 Examples , 3-19 Method-specific Pure Component Properties , 5-28 METHOD Statement , 3-19 Typical Usage , 5-24 Method-specific Pure Component Properties , 3-19 API Liquid Density Typical Usage , 3-18 Attributes of , 3-26 Water Handling Options , 3-19 Examples , 3-27 METHOD Statement , 3-26 Typical Usage , 3-26
Application Guidelines , 2-1 Chemical and Environmental Applications , 2-13 Examples , 2-15 Natural Gas Systems , 2-5 Petrochemical Applications , 2-8 Refinery and Gas Processing , 2-2 Aromatic Systems , 2-9 Aromatic/Non-aromatic Systems , 2-9 Associating Hexamer Equation Of State Enthalpy, Entropy, and Density Data , 4-39 Examples , 4-40 K-value Data , 4-39
Carboxylic Acid Systems , 2-14 CHAO-SEADER Examples , 3-10 Method-specific Pure Component Properties , 3-9 Chao-Seader Attributes of , 3-8 METHOD Statement , 3-9 Typical Usage , 3-8 Water Handling Options , 3-9 Chemical and Environmental Applications Carboxylic Acid Systems , 2-14
PRO/II Component and Thermophysical Properties Reference Manual
Environmental Applications , 2-14 Non-Ionic Systems , 2-13 Solid Applications , 2-15 Costald Liquid Density Attributes of , 3-30 Examples , 3-31 Input Description , 3-30 METHOD Statement , 3-30 Method-specific Pure Component Properties , 3-30 Typical Usage , 3-30 Curl-Pitzer Attributes of , 3-15 Examples , 3-16 METHOD Statement , 3-15 Method-specific Pure Component Properties , 3-16 Typical Usage , 3-15
E
Entropy Features that Require Entropy , 1-20 Environmental Applications , 2-14 Equations of State , 4-1 Associating Hexamer Equation Of State , 4-37 Benedict-Webb-Rubin-Starling , 4-33 Cubic Equation Of State Alpha Formulations , 4-29 Filling in Missing Parameters , 4-27 Lee-Kesler-Plocker , 4-41 Modified SRK and PR , 4-13 Peng-Robinson , 4-7 Soave Modified Redlich-Kwong , 4-1 UNIWAALS , 4-23
Examples Alcohol , 5-11 Alpha Formulations , 4-33 API Liquid Density , 3-27 Associating Hexamer Equation Of State , 4-40 Benedict-Webb-Rubin-Starling , 4-36 Braun K10 , 3-19 CHAO-SEADER , 3-10 Chemical and Environmental Application , 2-18 Costald Liquid Density , 3-31 Cubic Equation Of State Alpha Formulations , 4-33 Curl-Pitzer , 3-16 FCCU , 2-3 Filling in Missing Parameters for Liquid Activity Filling in Missing Parameters Methods , 6-60 Attributes of the FILL Option for Liquid Activity Flory-Huggins , 6-55 Methods , 6-58 Free-water Decant , 1-34 Cubic Equations of State FILL options , 4-28 Glycol , 5-16 Data Estimation Options for Liquid Activity Methods , 6-60 GPA Sour Water , 5-24 Grayson-Streed Method , 3-6 Examples for Liquid Activity Methods , 6-60
Hayden-OConnell Vapor Fugacity , 6-72 Henrys Law , 6-68 Ideal Methods , 3-3 IDIMER Vapor Fugacity , 6-79 Johnson-Grayson , 3-22 Lee-Kesler , 3-25 Lee-Kesler-Plocker , 4-44 Margules , 6-45 Method-specific Pure Component Data , 9-6 Minimum Required User Input , 1-13 Modifications to GS and CS , 3-13 Modifications to UNIFAC , 6-35 Modified Soave-Redlich-Kwong and PengRobinson , 4-20 Multiple Thermodynamic Sets , 1-30 Natural Gas Application , 2-17 NRTL , 6-6 Peng-Robinson , 4-11 Petrochemical Application , 2-18 Rackett Liquid Density , 3-29 Redlich-Kister, Gamma Heat of Mixing , 6-83 Refinery Application , 2-16 Regular Solution , 6-49 Soave Modified Redlich-Kwong , 4-5 Soave Redlich-Kwong , 4-5 Solid Application , 2-19 Sour Water , 5-20 Sour Water Application , 2-16 Special Properties , 8-25 Transport Properties , 8-8 Truncated Virial Vapor Fugacity , 6-75 UNIFAC , 6-21 UNIQUAC , 6-14 UNIWAALS , 4-26 User-added Subroutines , 5-32 User-supplied K-value Data , 3-34 User-supplied Solubility , 7-5 Van Laar , 6-40 Vant Hoff Solubility , 7-3 Vapor-liquid-liquid Equilibrium Considerations , 1-41
General Information for Liquid Activity Attributes of GPSWATER Package , 5-21 Methods , 6-57 Enthalpy, Entropy, and Density Data , 5-22 K-value Data for Cubic EOS , 4-28 Examples , 5-24 K-value Data for Liquid Activity Methods , 6-58 METHOD Statement , 5-22 METHOD Statement for Cubic EOS , 4-28 Method-specific Pure Component Properties , 5-23 METHOD Statement for Liquid Activity Typical Usage , 5-21 Methods , 6-58 Grayson-Streed Typical Usage for Cubic EOS , 4-27 Attributes of , 3-5 Typical Usage for Liquid Activity Methods , 6-57 METHOD Statement , 3-5 Flory-Huggins Typical Usage , 3-4 Attributes of FLORY Methods , 6-51 Water Handling Options , 3-6 Examples , 6-55 Grayson-Streed Method K-value Data , 6-52 Examples , 3-6 METHOD Statement , 6-51 Method-specific Pure Component Properties , 3-6 Method-specific Pure Component Properties , 6-54 Typical Usage , 6-50 Free-water Decant Considerations , 1-31 Examples , 1-34 General Information , 1-31 Water Handling Statement , 1-32
H
Hayden-OConnell Vapor Fugacity Attributes of the HOCV Vapor Fugacity Method , 6-69 Enthalpy, Entropy and Density Data , 6-71 Examples , 6-72 K-value Data , 6-70 METHOD Statement , 6-69 Method-specific Pure Component Properties , 6-71 Typical Usage , 6-68 Vapor Fugacity Data , 6-70 Henrys Law Attributes of the Henrys Law Option , 6-62 Examples , 6-68 Henrys Law Data , 6-66 Henrys Law Package Available Pairs , 6-64 METHOD Statement , 6-63 Method-specific Pure Component Properties , 6-67 Typical Usage , 6-62 Hierarchy of Pure Component Data , 9-3 High Pressure Crude Systems , 2-3 Hydrofiners , 2-4
G
Generalized Correlations API Liquid Density , 3-26 Braun K10 , 3-18 Chao-Seader , 3-8 Costald Liquid Density , 3-30 Curl-Pitzer , 3-15 Grayson-Streed , 3-4 Ideal and Library Methods , 3-1 Ideal Methods , 3-1 Johnson-Grayson , 3-21 Lee-Kesler , 3-23 Library Methods , 3-1 Modifications to GS and CS , 3-11 Rackett Liquid Density , 3-28 Typical Usage , 3-1 User-supplied K-value Data , 3-32 Glycol Dehydration Systems , 2-6
Glycols Attributes of the GLYCOL Package , 5-12 Components Available for GLYCOL Package , 5Ideal Method 15 Attributes of , 3-2 Enthalpy, Entropy, and Density Data , 5-15 METHOD Statement , 3-2 Examples , 5-16 Ideal Methods K-value Data , 5-13 Examples , 3-3 METHOD Statement , 5-13 IDIMER Vapor Fugacity Method-specific Pure Component Properties , 5-16 Attributes of , 6-76 Typical Usage , 5-12 Enthalpy, Entropy and Density Data , 6-78 GPA Sour Water
Liquid Phase Activity Binary Interaction Data Flory-Huggins Data , 1-8 Henrys Law Data , 1-9 Margules Data, , 1-8 Input Description , 1-21 NRTL Data , 1-8 Other Binary Data for Liquid Activity Methods , 1-8 UNIFAC Group Contribution Data , 1-9 UNIQUAC Data , 1-8 Johnson-Grayson UNIWAALS Modified Group Contribution Attributes of , 3-21 Interaction Data , 1-9 Examples , 3-22 Van Laar Data , 1-8 METHOD Statement , 3-21 Wilson Data , 1-8 Method-specific Pure Component Properties , 3-22 Low Pressure Crude Systems , 2-3 Typical Usage , 3-21
Examples , 6-79 K-value Data , 6-77 METHOD Statement , 6-77 Typical Usage , 6-76 Vapor Fugacity Data , 6-78
Van Laar , 6-35 Wilson , 6-30
Lube Oil Units , 2-4
Lee-Kesler Attributes of , 3-23 Main Coker Fractionators , 2-3 Examples , 3-25 Margules METHOD Statement , 3-24 Attributes of MARGULES Methods , 6-41 Method-specific Pure Component Properties , 3-24 Examples , 6-45 Typical Usage , 3-23 K-value Data , 6-43 Lee-Kesler-Plocker METHOD Statement , 6-42 Attributes of , 4-42 Method-specific Pure Component Properties , 6-45 Enthalpy, Entropy, and Density Data , 4-44 Typical Usage , 6-41 Examples , 4-44 METHOD Statement , 1-3 K-value Data , 4-43 Method-specific Pure Component Data , 1-11, 9-1 METHOD Statement , 4-42 Examples , 9-6 Method-specific Pure Component Properties , 4-44 General Information , 9-1 Typical Usage , 4-41 Hierarchy , 9-3 Library Method METHOD Statement , 9-2 Attributes of , 3-2 Typical Usage , 9-1 METHOD Statement , 3-2 Method-specific Water Handling Options , 1-4 Light Hydrocarbon Systems , 2-8 Minimum Required User Input , 1-12 Liquid Activity Methods Modifications to GS and CS Filling in Missing Parameters , 6-57 Attributes of the Modified GS and CS Methods , 3Flory-Huggins , 6-50 12 Hayden-OConnell Vapor Fugacity , 6-68 Erbar modifications to Grayson-Streed and ChaoHenrys Law , 6-62 Seader , 3-12 IDIMER Vapor Fugacity , 6-76 Examples , 3-13 Margules , 6-41 Improved Grayson-Streed , 3-12 Modifications to UNIFAC , 6-22 METHOD Statement , 3-12 NRTL , 6-1 Method-specific Pure Component Properties , 3-13 Redlich-Kister, Gamma Heat of Mixing , 6-80 Typical Usage , 3-11 Regular Solution , 6-46 Water Handling Options , 3-13 Truncated Virial Vapor Fugacity , 6-72 Modifications to UNIFAC UNIFAC , 6-14 Attributes of Modified UNIFAC Methods , 6-23 UNIQUAC , 6-7
Examples , 6-35 K-value Data , 6-25 METHOD Statement , 6-23 Method-specific Pure Component Properties , 629, 6-34 Typical Usage , 6-22 UFT1-Lyngby modified UNIFAC , 6-25 UFT2-Dortmund modified UNIFAC , 6-25 UFT3-Modified UNIFAC , 6-25 UNFV-Free Volume modification , 6-25
O
Order of Input , 1-15
P
Peng-Robinson , 4-7 Enthalpy, Entropy, and Density Data , 4-10 Examples , 4-11 K-value Data , 4-9 METHOD Statement , 4-8 Method-specific Pure Component Properties , 4-11 Typical Usage , 4-7 Water Handling Options , 4-11
Modified SRK and PR Enthalpy, Entropy, and Density Data , 4-19 Examples , 4-20 Huron-Vidal modifications to PR , 4-15 Huron-Vidal modifications to SRK , 4-14 Kabadi-Danner modifications to SRK , 4-15 Petrochemical Applications K-value Data , 4-16 Alcohol Dehydration Systems , 2-12 METHOD Statement , 4-14 Aromatic Systems , 2-9 Method-specific Pure Component Properties , 4-19 Aromatic/Non-aromatic Systems , 2-9 Modified Panagiotopoulos-Reid modifications to HF Systems , 2-12 PR , 4-15 Light Hydrocarbon Systems , 2-8 Modified Panagiotopoulos-Reid modifications to Non-hydrocarbon Systems , 2-10 SRK , 4-14 Panagiotopoulos-Reid modifications to PR , 4-16 Predefined Systems , 1-25 SimSci modifications to SRK , 4-15 Typical Usage , 4-13
Property Statements Density Options , 1-5 Diffusivity Options , 1-5 Multiple Thermodynamic Sets , 1-28 Enthalpy Options , 1-6 Avoiding Inconsistent Methods , 1-29 Entropy Options , 1-6 Default Method Set , 1-28 Henrys Law Options , 1-5 Examples , 1-30 Liquid-Liquid Equilibrium Options , 1-5 General Information , 1-28 Solid-Liquid Equilibrium Options , 1-5 Method Set Requirements , 1-29 Vapor Fugacity Options , 1-5 Multiple Method Sets in Distillation Columns , 1Vapor-Liquid Equilibrium Options , 1-4 29 Pure Component Alpha Formulations , 1-10
N
Natural Gas Systems , 2-5 Amine Systems , 2-7 Glycol Dehydration Systems , 2-6 Sour Water Systems , 2-7 Non-hydrocarbon Systems , 2-10 Non-Ionic Systems , 2-13
R
Rackett Liquid Density Examples , 3-29 Input Description , 3-28 METHOD Statement , 3-28 Method-specific Pure Component Properties , 3-28 Typical Usage , 3-28
Notes Statement , 1-3, 1-12 Redlich-Kister, Gamma Heat of Mixing NRTL Attributes of , 6-80 Attributes of NRTL methods , 6-2 Enthalpy Data , 6-81 Examples , 6-6 Examples , 6-83 K-value Data , 6-3 METHOD Statement , 6-80 METHOD Statement , 6-2 Typical Usage , 6-80 Method-specific Pure Component Properties , 6-6 Refinery and Gas Processing , 2-2 Typical Usage , 6-1
Refinery and Gas Processing Applications FCCU , 2-3 High Pressure Crude Systems , 2-3 Low Pressure Crude Systems , 2-3 Lube Oil and Solvent De-asphalting Units , 2-4 Main Coker Fractionators , 2-3 Reformers and Hydrofiners , 2-4 Water Handling , 2-2
Examples , 8-25 General Information , 8-10 Keywords for Special Stream Refinery Properties , 8-11 METHOD Statement , 8-12 Special Property Methods Data , 8-17 Special Refinery Property Entries , 8-13 Typical Usage , 8-10
Special Property Methods Data , 1-10 Reformers , 2-4 SRK or PR Equation of State Interaction Regular Solution Parameters , 1-7 Attributes of REGULAR Methods , 6-46 Examples , 6-49 Systems of Thermodynamic Methods , 1-26 K-value Data , 6-48 METHOD Statement , 6-47 Method-specific Pure Component Properties , 6-49 Typical Usage , 6-46 Thermodynamic Data General Information , 1-1
Thermodynamic Generators , 1-18 Thermodynamic Sets , 1-16 Transport Properties , 8-1 Diffusivity Data , 8-7 Examples , 8-8 General Information , 8-1 METHOD Statement , 8-2 Method-specific Pure Component Properties , 8-8 Typical Usage , 8-1 User-supplied Conductivity Data , 8-7 User-supplied Surface Tension Data , 8-7 User-supplied Viscosity Data , 8-7 Truncated Virial Vapor Fugacity Attributes of the TVIRIAL Vapor Fugacity Method , 6-73 Examples , 6-75 K-value Data , 6-74 METHOD Statement , 6-73 Method-specific Pure Component Properties , 6-75 Typical Usage , 6-72 Vapor Fugacity Data , 6-74
Selecting Individual Methods , 1-3 Soave Redlich-Kwong , 4-1 Attributes of , 4-2 Enthalpy, Entropy, and Density Data , 4-4 Examples , 4-5 K-value Data , 4-3 METHOD Statement , 4-2 Method-specific Pure Component Properties , 4-5 Typical Usage , 4-1 Water Handling Options , 4-5 Solid Applications , 2-15 Solid Solubility Methods , 7-1 User-supplied Solubility , 7-3 Vant Hoff Solubility , 7-1 Solvent De-asphalting Units , 2-4 Sour Water , 5-17 Attributes of SOUR Package , 5-18 Enthalpy, Entropy, and Density Data , 5-19 Examples , 5-20 METHOD Statement , 5-18 Method-specific Pure Component Properties , 5-20 Typical Usage , 5-17 Sour Water Systems , 2-7 Special Packages Alcohols , 5-1 Amines , 5-24 Glycols , 5-12 GPA Sour Water , 5-21 Sour Water , 5-17 User-added Subroutines , 5-29 Special Properties , 8-10
U
UNIFAC Attributes of UNIfAC Methods , 6-15 Available UNIFAC Interaction Parameters , 6-21 Examples , 6-21 K-value Data , 6-17 METHOD Statement , 6-16 Method-specific Pure Component Properties , 6-20 Typical Usage , 6-14 UNIQUAC
Attributes of UNIQUAC Methods , 6-8 Vapor-liquid-liquid Equilibrium Considerations , 1-34 Examples , 6-14 Available Databanks , 1-36 K-value Data , 6-9 Declaring a VLLE set , 1-34 METHOD Statement , 6-8 Examples , 1-41 Method-specific Pure Component Properties , 6-12 K-value Data , 1-40 Typical Usage , 6-7 METHOD Statement , 1-40 Specifying Key Components , 1-38 UNIWAALS , 4-23 Specifying Separate VLE and LLE Models , 1-38 Attributes of , 4-23 VLLE Predefined Systems and K-value Enthalpy, Entropy, and Density Data , 4-25 Generators , 1-35 Examples , 4-26 K-value Data , 4-24 METHOD Statement , 4-24 Method-specific Pure Component Properties , 4-26 Typical Usage , 4-23 User-added Subroutine Data , 1-11 User-added Subroutines Attributes of , 5-29 Enthalpy, Entropy, and Density Data , 5-31 Examples , 5-32 K-value Data , 5-31 METHOD Statement , 5-31 Typical Usage , 5-29, 5-32 User-supplied K-value Data , 1-6 Attributes of , 3-32 Examples , 3-34 Input Description , 3-33 K-value Data (required) , 3-33 METHOD Statement , 3-33 Typical Usage , 3-32 User-supplied Solubility Examples , 7-5 General Information , 7-3 K-value Data , 7-4 METHOD Statement , 7-4 Typical Usage , 7-3
W
Water Handling , 2-2
V
Van Laar Attributes of VANLAAR Methods , 6-36 Examples , 6-40 K-value Data , 6-37 METHOD Statement , 6-36 Method-specific Pure Component Properties , 6-39 Typical Usage , 6-35 Vant Hoff Solubility Examples , 7-3 General Information , 7-1 METHOD Statement , 7-2 Typical Usage , 7-1

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Component and Thermodynamic Data Keyword Input Manual Volume II: Thermodynamic Data PRO/II 8.

Chapter 2 Application Guidelines

Chapter 3 Generalized Correlations

Chapter 4 Equations of State

Chapter 5 Special Packages

Chapter 6 Liquid Activity Methods

Chapter 7 Solid Solubility Methods

Chapter 8 Transport and Special Properties

Chapter 9 Method-specific Pure Component Data

PRO/II Component and Thermodynamic Data Keyword Input Manual

Chapter 1 Thermodynamic Data Overview

Thermodynamic Data Overview

For details see Chapter 1 Notes Statement (optional) on page 1-13

Notes Statement, Optional

The METHOD Statement, Required Selecting a Pre-defined System of Methods

Predefined Systems on page 1-28

Selecting Individual Methods

Thermodynamic Sets on page 117

PRO/II Thermodynamic Data Keyword Input Manual

Table 1-1: THERMODYNAMIC DATA Category of Input Statement Keywords

For details see

Method-specific Water Handling Options, Optional

Free-water Decant Considerations on page 1-34

Property Statements, Optional Vapor-Liquid Equilibrium Options, Optional

calculations when the WILSON K-value method is selected.

Thermodynamic Data Overview

Liquid-Liquid Equilibrium Options, Optional

Solid-Liquid Equilibrium Options, Optional

Diffusivity Options, Optional

Vapor Fugacity Options, Optional

Henrys Law Options, Optional

Density Options, Optional

PRO/II Thermodynamic Data Keyword Input Manual

Table 1-1: THERMODYNAMIC DATA Category of Input Statement

For details see

Enthalpy Options, Optional

Entropy Options, Optional

Thermodynamic Data Overview

Table 1-1: THERMODYNAMIC DATA Category of Input Statement

For details see

User-supplied K-value Data, Optional (Use with KVALUE statements)

HEXAMER Equation of State Data, Optional

LKP Equation of State Data, Optional

PRO/II Thermodynamic Data Keyword Input Manual

Table 1-1: THERMODYNAMIC DATA Category of Input Statement

For details see

Truncated Virial Data, Optional (For vapor fugacity)

i, j, aij, bij, cij, dij, eij, fij, gij, hij / ...

Soave-Redlich-Kwong or Peng-Robinson Equation of State Interaction Parameters, Optional

i, j, kija, kjia, kijb, kjib, kijc, kjic, cij, cji / ...

i, j, kija, kjia, kijb, kjib, kijc, kjic, cij, cji / ...

Thermodynamic Data Overview

For details see Chapter 5

Liquid Phase Activity Binary Interaction Data

UNIQUAC Data, Optional

Wilson Data, Optional

Van Laar Data, Optional

Margules Data, Optional

Flory-Huggins Data, Optional

Chapter 5 Chapter 5 Chapter 5 Chapter 5

PRO/II Thermodynamic Data Keyword Input Manual

For details see Chapter 5

UNIFAC Group Contribution Data, Optional (For K-value calculations only)