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Thermochemical and Chemical Kinetic Data for Fluorinated Hydrocarbons

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TECH R-IC INST °F STAND 8, NAT'L MIST PUBUCATIONS 713370 AlllOM !I '^:'-'f&?li:'!jey^:Mii{i,^r'::i^^£^'i-r-<-'-'fTSei:i'y'iXi. United States Department of Commerce Technology Administration Nisr National Institute of Standards and Technology NIST Technical Note 14 12 Thermochemical and Chemical Kinetic Data for Fluorinated /Hydrocarbons D. R. F. Burgess, Jr., M. R. Zacharlah, W. Tsang, and R R. Westmoreland CH3F CH2F2 CHF3 CH2F CF3 / ^^ /I / / CHF / \ CF2 \ =?\ / CH3O \ // CH A-^-CF V \ I CF3O ' / ^ \ / / / I / ^, I A CH2O \ \ CHFO / CF2O •-. \ 1 \ I \ CHO I ^CFO he National Institute of Standards and Technology was established in 1988 by Congress to "assist industry Jin the development of technology . needed to improve product quality, to modernize manufacturing processes, to ensure product reliability . and to facilitate rapid commercialization ... of products based on new scientific discoveries." NIST, originally founded as the National Bureau of Standards in 1901, works to strengthen U.S. industry's competitiveness; advance science and engineering; and improve public health, safety, and the environment. One of the agency's basic functions is to develop, maintain, and retain custody of the national standards of measurement, and provide the means and methods for comparing standards used in science, engineering, manufacturing, commerce, industry, and education with the standards adopted or recognized by the Federal Government. As an agency of the U.S. Commerce Department's Technology Administration, NIST conducts basic and applied research in the physical sciences and engineering, and develops measurement techniques, test methods, standards, and related services. The Institute does generic and precompetitive work on new and advanced technologies. NIST's research facilities are located at Gaithersburg, MD 20899, and at Boulder, CO 80303. 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'Some elemenis at Boulder, CO 80303. NIST Technical Note 1412 Thermochemical and Chemical Kinetic Data for Fluorinated Hydrocarbons D. R. F. Burgess, Jr., M. R. Zachariah, W. Tsang Chemical Science and Technology Laboratory National Institute of Standards and Technology Gaithersburg, MD 20899-0001 and R R. Westmoreland Department of Chemical Engineering University of Massachusetts Amherst, MA 01003-3110 July 1995 *'-4TES o« U.S. Department of Commerce Ronald H. Brown, Secretary Technology Administration Mary L. Good, Under Secretary for Technology National Institute of Standards and Technology Arati Prabhakar, Director National Institute of Standards U.S. Government Printing Office For sale by the Superintendent of and Technology Washington: 1995 Documents Technical Note 1412 U.S. Government Printing Office Natl. Inst. Stand. Technol. Washington, DC 20402 Tech. Note 1412 163 pages (July 1995) CODEN: NTNOEF EXECUTIVE SUMMARY A comprehensive, detailed chemical kinetic mechanism was developed and is presented for Ci and C2 fluorinated hydrocarbon destruction and flame suppression. Existing fluorinated hydrocarbon thermochemistry and kinetics were compiled from the literature and evaluated. For species where no or incomplete thermochemistry was available, these data were calculated through application of ab initio molecular orbital theory. Group additivity values were determined consistent with experimental and ab initio data. For reactions where no or limited kinetics was available, these data were estimated by analogy to hydrocarbon reactions, by using empirical relationships from other fluorinated hydrocarbon reactions, by ab initio transition state calculations, and by application of RRKM and QRRK methods. The chemistry was modeled considering different transport conditions (plug flow, premixed flame, opposed flow diffusion flame) and using different fuels (methane, ethylene), equivalence ratios, agents (fluoromethanes, fluoroethanes) and agent concentrations. This report provides a compilation and analysis of the thermochemical and chemical kinetic data used in this work. Ill Table of Contents 1. Introduction 1 1.1. Overview 1 1.2. Background 3 1.3. Mechanism Development 5 1.4. Acknowledgments 5 2. Thermochemistry 7 2.1. Overview 7 2.2. H/O/F and Hydrocarbon Species 11 2.3. Ci Fluorinated Hydrocarbons 13 2.3.1. Fluoromethanes 13 2.3.2. Fluoromethyl Radicals 14 2.3.3. Fluoromethylenes and Fluoromethylidyne Radical 16 2.3.4. Carbonyl Fluorides and Fluoromethoxy Radicals 17 2.4. C2 Fluorinated Hydrocarbons 19 2.4.1. Fluoroethanes 19 2.4.2. Fluoroethyl Radicals 21 2.4.3. Fluoroethylenes and Fluorovinyl Radicals 22 2.4.4. Fluoroacetylenes, Fluoroketenes, and Fluoroketyl Radical 24 2.5. BAC-MP4 Ab Initio Predictions 25 2.6. Thermochemical Tables 29 2.6.1. Table 1: AHf°, S°, Cp°(T) - H/0 Species, Hydrocarbons 29 2.6.2. Table 2: AHf^ S^ Cp°(T) - H/F/0 Species, Ci Fluorocarbons 30 2.6.3. Table 3: AUf, S°, Cp°(T) - C2 Fluorocarbons 31 2.6.4. Table 4: AR° - Calculated, Literature Values, Uncertainties 32 3. Reaction Kinetics 35 3.1. Overview 35 3.1.1. Figure 1. Fluorinated Hydrocarbon Reaction Pathways 37 3.2. Hydrocarbon and H/O/F Chemistry 39 3.3. Cj Fluorinated Hydrocarbon Chemistry 41 3.3.1. Overview 41 3.3.2. Fluoromethanes: Decompositions 42 3.3.3. Fluoromethanes: H Abstractions by H Atoms 44 3.3.4. Fluoromethanes: H Abstractions by O Atoms and OH Radicals 46 3.3.5. Fluoromethanes: H Abstractions by F and F Abstractions by H 48 3.3.6. Fluoromethanes: Metathetical Reactions 50 3.3.7. Fluoromethyl Radical Destruction 51 3.3.8. Fluoromethylene Destruction 54 3.3.9. Fluoromethylidyne Destruction 56 3.3.10. Carbonyl Fluoride Chemistry 57 3.4. C2 Fluorinated Hydrocarbon Chemistry 59 3.4.1. Overview 59 3.4.2. Fluoroethanes: Thermally and Chemically Activated Decompositions .... 60 3.4.3. Fluoroethanes: Fluoromethyl/methylene Disproportionations/Insertions ... 62 3.4.4. Fluoroethanes: Abstractions 63 3.4.5. Fluoroethyl Radical Destruction 65 3.4.6. Fluoroethylene Chemistry 66 3.4.7. Fluorovinyl Radical Destruction 69 3.4.8. Fluoroethyne, Fluoroketene, and Fluoroketyl Radical Chemistry 70 3.5. BAC-MP4 Ab Initio Predictions 71 4. Future Mechanism Refinement 75 4.1. Overview 75 4.2. Thermochemistry 79 4.3. Kinetics 83 5. Reaction Set (Table 5) 85 5.1. Description of Listing 85 5.2. H/0 Reactions 89 5.3. Hydrocarbon Reactions 90 5.4. NIST HFC Mechanism 95 5.4.1. H/F/0 Species 95 5.4.2. Fluoromethanes 96 5.4.3. Fluoromethyl Radicals 98 5.4.4. Fluoromethylenes 99 5.4.5. Fluoromethylidyne Radical, Fluoromethoxy Radical 100 5.4.6. Carbonyl Fluorides 101 5.4.7. Fluoroethanes: Decompositions 102 5.4.8. Fluoroethanes: Abstractions 106 5.4.9. Fluoroethyl Radicals 110 5.4.10. Fluoroethylenes 112 5.4.11. Fluorovinyl Radicals 115 5.4.12. Fluoroethynes, Fluoroketenes 116 5.4.13. F Atom Reactions 117 5.5. Reference Reactions 118 5.6. Notation 122 5.7. Citation Index 123 VI 6. Bibliography 127 6.1. Overview 127 6.2. General Thermochemistry and Kinetics 129 6.3. Hydrocarbon Chemistry 133 6.4. Fluorine Chemistry 135 6.5. Fluorocarbon Thermochemistry 137 6.6. Oxidized Fluorocarbon Thermochemistry 145 6.7. Fluorocarbon Kinetics (Decompositions) 147 6.8. Fluorocarbon Kinetics (Abstractions) 151 6.9. Fluorocarbon Kinetics (Oxidations) 155 6.10. Oxidized Fluorocarbon Kinetics 159 6.11. Fluorocarbon Kinetics (Other) 163 6.12. Flame Inhibition (Halogens) 169 6.13. Flame Inhibition (non-Halogens) 173 Vll 1. Introduction 1.1. Overview The thermochemical and chemical kinetic data presented here were compiled as a part of flame-inhibition modeling that was part of a large, short-term, intensive effort at NIST that evaluated (for the U.S. Air Force, Navy, Army and Federal Aviation
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