The ASTM Computer Program for Chemical Thermodynamic and Energy Release Evaluation

Transcription

1 B. Keith Harrison The ASTM Computer Program for Chemical Thermodynamic and Energy Release Evaluation CHETAH Version 10.0 User Guide ASTM Stock Number: DS51G Contents Foreword iv Acknowledgments V 1. INTRODUCTION 1 Overview of CHETAH 1 Capabilities 2 What s New in CHETAH Program Requirements 3 Installation 4 Installation to C Drive Only 4 Technical Support 5 2. BUILDING A MOLECULE USING A MOLECULAR DRAWING PROGRAM 7 Overview 7 Example 1 8 Example 2 13 Example BUILDING A MOLECULE USING DIRECT TABLE ENTRY 21 Overview 21 Selecting Category 21 Building Gas Molecules 23 Building a Molecule Using Benson Group by Direct Choice of Groups 23 Building Crystals 24 Menu Order 24 Searching for Elements, Groups, and Molecules 25 Adding an Element, Group, or Molecule 26 Selecting Group Count 26 Deleting an Element, Group, or Molecule 26 Changing Compound Properties 26 Symmetry Number 27

2 Optical Isomers 27 Saving Built Compounds 28 Opening Built Compounds CHETAH DATABASE 29 Examining the Database 29 Elements 29 Gas Molecules 29 Crystal Molecules 29 onic Groups 30 Benson Groups 30 Overview 32 Benson Group Notation 32 Examples of Benson Group Notation 35 Benson Groups for Solid and Liquid Compounds 36 Overview of Solid Benson Groups 36 Overview of Liquid Benson Groups 36 Benson Group Notation for Solid and Liquid Benson Groups 37 Species in Aqueous Solution PRIVATE DATABASE 41 Entering Private Data 41 Benson Groups 41 Whole-Molecule Data for Gases 42 Data for Crystal Solids 43 Deleting User-Entered Groups 43 Modifying User-Entered Groups THERMODYNAMIC TABLES 45 Overview 45 Performing Thermodynamic Calculations ENERGY RELEASE EVALUATION 51 ERE Criteria 52 Criterion 1: Maximum Heat of Decomposition 52 Criterion 2: Fuel Value Heat of Decomposition 52 Criterion 3: Oxygen Balance 53 Criterion 4: CHETAH ERE 53 Criterion 5: Overall Energy Release Potential 53 Criterion 6: Net Plosive Density 54 Performing ERE Calculations 54 Example HEAT OF COMBUSTION 59 Overview 59 Performing Heat of Combustion Calculations 59 Example REACTION THERMOCHEMISTRY 63 Overview 63

3 Performing Chemical Reaction Calculations 63 Example FLAMMABILITY 69 Lower Flammable Limit 69 Bothwell s Method for LFL 69 Britton s Method for LFL 69 Other Flammability-Related Calculations 70 Definitions 71 Performing Flammabilty Calculations 72 Example 72 REFERENCES 77 APPENDIX A Estimation of Missing Benson Group Data of Organic Species for Use in CHETAH 91 APPENDIX B Definition of Symmetry Numbers and Optical Isomers Used in CHETAH Calculations and a Simple Method for Choosing These Numbers 107 APPENDIX C Treatment of Heat Capacity 123 APPENDIX D Elements 125 APPENDIX E Gas Molecules 127 APPENDIX F Benson Groups 149 APPENDIX G Crystal Molecules 165 APPENDIX H Ionic Groups 171 APPENDIX I Solid Benson Groups 173 APPENDIX J Liquid Benson Groups 177 APPENDIX K Aqueous Species 183 INDEX 195

4 ASTM International 100 Barr Harbor Drive West Conshohocken, PA Printed in the U.S.A. ASTM makes no warranty, express or implied, regarding this product, and it is expressly agreed that ASTM will not be liable, or in any way responsible for the content of, or an error or omission in, this product. Copyright 2016 ASTM International, West Conshohocken, PA. All rights reserved. This material may not be reproduced or copied, in whole or in part, in any printed, mechanical, electronic, film, or other distribution and storage media, without the written consent of the publisher. Photocopy Rights Authorization to photocopy items for internal, personal, or educational classroom use, or the internal, personal, or educational classroom use of specific clients, is granted by ASTM International provided that the appropriate fee is paid to the Copyright Clearance Center, 222 Rosewood Drive, Danvers, MA 01923, Tel: (978) ; Printed in Bayshore, NY February, 2016 VERSION 10.0 PREPARED FOR ASTM COMMITTEE E27 Subcommittee E27.07, Estimation Methods Version 10.0 program prepared primarily by: B. Keith Harrison Department of Chemical Engineering University of South Alabama Mobile, AL Dan Detman Consultant Daphne, AL Foreword ASTM Committee E27 has been responsible for the computer program CHETAH since it was first introduced in Although there is no official ASTM standard practice or guide designation for this program, the committee has worked diligently to build an extensive, reliable, and traceable database and associated application software. The committee continues to coordinate, review, and test further refinements to CHETAH. To provide more complete documentation on the use of CHETAH, Appendixes A and B in this manual were adapted from internal Dow Chemical Company reports released to ASTM Committee E The consensus of the committee is that the techniques outlined in these two appendixes are useful in exploiting the full power of CHETAH. The latest version was largely prepared by a team at the University of South Alabama in close coordination with Committee E27

5 Acknowledgments The development of CHETAH has taken place over the years with the generous support and invaluable technical assistance of a great many people too numerous to list. However, special acknowledgement is in order for Dr. William Seaton, who for many years spearheaded the continued development of the program. With many omissions, others who have made major contributions to the program include Dave Fruip (Dow), Carol Davies (Dow), Gary Buckley (Cameron University), Eli Friedman (Eli Friedman and Associates), G. Hertel (University of South Florida), Josee Audet (Meck), Jeff Niemeyer (Lilly), Donna Loftin (University of South Alabama), Srinath Balaraman (University of South Alabama), Malcolm Chase (National Institute of Standards and Technology), and Larry Britton (retired). Special thanks to the graduate assistants who helped support CHETAH and participated in the early-stage development of this version: Akilesh Akula, Rahul Badaru, and Bharatan Vijaykumar. A major code rewrite was undertaken by independent consultant Dan Detman with the support of ASTM funding. Dan accomplished a translation of the program from Visual Basic to a Microsoft Access application. In addition, Dr. Kevin West (University of South Albama) and two graduate students, Reggie Ross and Weisin Chai, were involved in a project related to database development supported by Pfizer Inc. This project was also beneficial to CHETAH CHETAH 10.0 represents an upgrade from the Visual Basic language to an application based on Microsoft Access. The coding for this new version was accomplished by Dan Detman, with content input from several ASTM E27 committee members.