Document 2jXD88YzzQq2r4JVw0Oxn4Xgr

A Chemical Kinetic Mechanism for 2-Bromo3,3,3-trifluoropropene (2-BTP) Flame Inhibition DONALD R. BURGESS JR.,1 VALERI I. BABUSHOK,2 GREGORY T. LINTERIS,2 JEFFREY A. MANION1 1Chemical Sciences Division, National Institute of Standards and Technology, Gaithersburg 20899 2Fire Research Division, National Institute of Standards and Technology, Gaithersburg 20899 Received 28 July 2014; revised 3 April 2015; accepted 3 April 2015 DOI 10.1002/kin.20923 Published online 22 July 2015 in Wiley Online Library (wileyonlinelibrary.com). ABSTRACT: In this work, we report a detailed chemical kinetic mechanism to describe the flame inhibition chemistry of the fire-suppressant 2-bromo-3,3,3-trifluoropropene (2-BTP), under consideration as a replacement for CF3Br. Under some conditions, the effectiveness of 2-BTP is similar to that of CF3Br; however, like other potential halon replacements, it failed an U.S. Federal Aviation Authority (FAA) qualifying test for its use in cargo bays. Large overpressures are observed in that test and indicate an exothermic reaction of the agent under those conditions. The kinetic model reported herein lays the groundwork to understand the seemingly conflicting behavior on a fundamental basis. The present mechanism and parameters are based on an extensive literature review supplemented with new quantum chemical calculations. The first part of the present article documents the information considered and provides traceability with respect to the reaction set, species thermochemistry, and kinetic parameters. In additional work, presented more fully elsewhere, we have combined the 2-BTP chemical kinetic mechanism developed here with several other submodels from the literature and then used the combined mechanism to simulate premixed flames over a range of fuel/air stoichiometries and agent loadings. Overall, the modeling results qualitatively predicted observations found in cupburner tests and FAA Aerosol Can Tests, including the extinguishing concentrations required and the lean-to-rich dependence of mixtures. With these data in hand, in a second phase of the present work, we perform a reaction path analysis of major species under several modeled conditions. This analysis leads to a qualitative understanding of the ability of 2-BTP to act as Correspondence to: Donald R. Burgess, Jr.; e-mail: dburgess@ nist.gov. Supporting Information is available in the online issue at www.wileyonlinelibrary.com. Published 2015. This article is a U.S. Government work and is in the public domain in the USA. 534 BURGESS ET AL. both an inhibitor and a fuel, depending on the conditions and suggests areas of the kinetic model that should be further investigated and refined. Published 2015. This article is a U.S. Government work and is in the public domain in the USA. Int J Chem Kinet 47: 533-563, 2015 INTRODUCTION The present paper is concerned with the development of a detailed chemical kinetic mechanism to describe the flame inhibition chemistry of the fire-suppressant 2-bromo-3,3,3-trifluoropropene (2BTP). Currently, 2-BTP is considered as a fire suppressant to replace CF3Br for use in aircraft cargo bays. Cup burner tests indicate that 2-BTP is an effective flame extinguisher at concentrations similar to those required by CF3Br [1-3]. However, it was unexpectedly found that when 2BTP is added at subinerting concentrations in the U.S. Federal Aviation Authority Aerosol Can Test (FAAACT) [4-8] a large overpressure is obtained, causing the agent to fail the test and indicating that 2-BTP is reacting exothermically under these conditions. The development of a fundamental model explaining the chemical basis of these results would be of value to help assess the range of conditions where such behavior might be expected, as well as provide insights that could lead to the development of more effective agents. To simulate the above tests, the full model must include both fuel combustion chemistry and flame suppression chemistry. Many models of the combustion of various fuels are available, and, as a first approximation, the fuel chemistry is independent of that of the fire suppression agent. Thus, the flame suppression chemistry of 2-BTP can be treated as a separate submechanism, with only the addition of a minimal number of cross-reactions appropriate to the particular fuels of interest. The intent of the present work is to develop the mechanism of 2-BTP decomposition under combustion conditions and to document the developed 2-BTP kinetic model, providing traceability with respect to the thermochemistry employed for each species, the set of reactions, and their kinetic parameters. We have combined the 2-BTP chemical kinetic mechanism presented here with several other submodels from the literature and then used the combined mechanism to simulate premixed flames over a range of fuel/air stoichiometries and agent loadings. The modeling results are presented in detail and discussed elsewhere [3,9]. Overall, the modeling results qualitatively predicted observations found in cup-burner tests and FAA-ACT, including the extinguishing concentrations required and the lean-to-rich dependence of mixtures. The FAA-ACT simulates the explosion of an aerosol spray can in a cargo bay fire. The modeling results also were able to qualitatively simulate the increase in flammability limits and overpressure when the agent was added in subinerting concentrations-- at high agent loadings and lean flames, there was an increase in flame temperature. The qualitative success of these simulations suggests that we have successfully captured key elements of the flame inhibition chemistry of 2-BTP. Nonetheless, the 2-BTP chemical kinetic mechanism presented here needs further quantitative validation against flame speeds and other physical observables. Iterative improvements are to be expected, and the present efforts should be considered to be an initial working model, rather than a fully descriptive final product. METHODOLOGY AND WORK FLOW There appear to be no previous efforts to develop a detailed chemical kinetic model of the flame inhibition chemistry of 2-BTP. Our simulations require a model that is based on the elementary reactions that describe not only the initial decomposition reactions of 2-BTP, but also the subsequent chemistry of the resulting intermediates, including pathways involving unimolecular decomposition, radical-induced decomposition, and oxidation chemistry. Although one can find relevant information on related compounds and systems scattered throughout the literature, the information is not complete, nor has it been gathered in a single location, or subjected to general review. With this in mind, the overall methodology and work program was to review the relevant literature and develop a draft set of reactions and species, compute the energetics of the reactions and stability of the species using quantum chemical methods, incorporate existing experimental data for enthalpies of formation and reaction rates into the draft chemical mechanism, augment this information with thermochemical and chemical kinetic data from our quantum chemical calculations, derived after benchmarking to appropriate reference species and reactions, International Journal of Chemical Kinetics DOI 10.1002/kin.20923 CHEMICAL KINETIC MECHANISM FOR 2-BTP FLAME INHIBITION 535 reduce the draft reaction set to only those reac- tions that are feasible on the basis of our com- puted reaction energetics, utilize Rice-Ramsperger-Kassel-Marcus (RRKM), Master Equation, and transition state theory methods to compute rate constants and rate expressions, particularly for unimolecular and chemically-activated reactions that are important, utilize the initial chemical reaction mechanism to model the chemistry of 2-BTP in a combusting hydrocarbon environment, revise the set of reactions and species based on the results of the simulations, and employ additional computations to refine the most important rate expressions. COMPILATION AND SURVEY OF PREVIOUS RELATED WORK There are relatively few measurements and computations of the reactivity of species closely related to 2-BTP. There is, however, a significant body of work detailing the fire suppression chemistry of CF3Br and other fluorinated hydrocarbons. This chemistry involves many of the same intermediates and provides a chemical basis for understanding and developing a chemical kinetic mechanism for inhibition by 2-BTP. As part of our assessment we have, in particular, reviewed the literature for information pertaining to inhibition of flames by 2-BTP and related compounds. This includes global characterizations of flames and their inhibition, including, for example, measurements of flame speeds, flammability limits, strain rates, reaction products, species profiles, etc. These types of data and studies provide very valuable insights, but usually do not contain the information directly needed to create detailed chemical kinetic models, which require the properties of individual molecules and the kinetics of elementary reactions. We have therefore also examined previous models involving the combustion of halogenated fire suppressants and other halocarbons, and conducted an extensive search of the literature for the needed molecular property data, including experimental, computed, or estimated enthalpies of formation of relevant compounds, and the rate constants of relevant reactions. The literature pertaining to inhibition by halogenated species has not been extensively compiled and assessed for about 10 years, and one of the outcomes of the present work is an extensive bibliographic database that can be utilized as a basis for future work. Our literature review encompasses about 650 articles and a wide range of data types and topics. The sheer volume of information precludes a detailed discussion within the limited space of the current presentation. We do, however, provide an annotated bibliography and summary of the accumulated information in the form of tables in the Supporting Information. Various aspects of the assembled data will be subsequently discussed in more detail, but an overview of the information is provided here to orient the reader. Data specifically used in our model are provided in Tables AI-AIV in the Appendix. Table AI provides unambiguous identification of each species contained in our model, including molecular formula, symbol employed, CAS number, and systematic name. Table AII summarizes the adopted enthalpies of formation, and includes the value of fHo(298 K), our estimated uncertainty, the source, and method of determination. Available fHo(298 K) data on selected species for which values were re-evaluated in the course of this work are given in Table AIII. Table AIV summarizes the reactions and rate parameters as used in the full model, with rate parameters given in the standard modified Arrhenius form, k = ATb exp(-E/RT), together with the source of the data and the method by which the value was derived. DEVELOPMENT AND REFINEMENT OF THE 2-BTP MODEL The first major objective was to develop a draft set of species and associated reactions. The extensive literature review yielded little direct information on the initial reactions involved in the breakdown of 2-BTP. Nonetheless, a survey of the reactions of related compounds together with a thermochemical kinetic analysis results in a number of a priori conclusions. In particular, the C-F, C-H, and C-C bonds in 2-BTP are quite strong and not susceptible to simple bond fission under the relatively moderate conditions associated with chain initiation processes. Its unimolecular decomposition is therefore expected to proceed by more facile reactions, either by fission of the relatively weak C-Br bond or via the molecular elimination of HBr. 2-BTP will also be subject to bimolecular attack by active radicals that are present in combusting systems, notably H and OH. From the literature, it is known that abstraction of F by such radicals is slow, as is the abstraction of the vinylic hydrogens present in 2-BTP. In general, direct abstraction of Br by H atoms is known to be reasonably fast, although no measurements for 2-BTP are available. One further expects that addition of radicals to the double bond of 2-BTP, particularly by H and OH, will be extremely rapid, and this will lead to unstable International Journal of Chemical Kinetics DOI 10.1002/kin.20923 536 BURGESS ET AL. Table I Possible Decomposition and Oxidation Pathways for 2-BTP and Related Compounds Reactant Products Reaction Type 2-Bromotrifluoropropene (2-BTP) CH2=CBr-CF3 CH2=CBr-CF3 + H CH2=CBr-CF3 + OH CH2=CBr-CF3 + CF3 HCC-CF3 + HBr CH2=C-CF3 + Br CH2=CH-CF3 + Br CH2=CH2 + CF3 CH2=C-CF3 + HBr CH=CBr-CF3 + H2 CH2=C(OH)-CF3 + Br CH3-C(=O)-CF3 + Br CH=CBr-CF3 + H2O CH2=C-CF3 + CF3Br CH=CBr-CF3 + CHF3 Elimination Bond fission Addition/beta-scission Addition/beta-scission Abstraction Abstraction Addition/beta-scission Add/isomerization/beta-scission Abstraction Abstraction Abstraction Trifluoropropene (TFPe) CH2=CH-CF3 + H CH2=CH-CF3 + OH CH2=CH2 + CF3 CH2=C-CF3 + H2 CH=CH-CF3 + H2 CH2=CH(OH) + CF3 CH3-C(=O)H + CF3 CF3-C(=O)H + CH3 Addition/beta-scission Abstraction Abstraction Addition/beta-scission Add/isomerization/beta-scission Add/isomerization/beta-scission Trifluoropropyne (TFPy) HCC-CF3 + H HCC-CF3 + CH3 HCC-CF3 + OH HCCH + CF3 HCC-CH3 + CF3 CH2=C=O + CF3 Addition/beta-scission Addition/beta-scission Add/isomerization/beta-scission intermediates that will rapidly fragment, producing Br, CF3, and other intermediates. The above analysis results in an initial set of potential decomposition and oxidation reactions involving 2-BTP and its intermediate products. These reactions lead in turn to a collection of directly accessible radical fragments and closed shell products, as well as oxygen-containing species that can be formed as the fragments oxidize further. Some of the involved reactions are provided in Table I and indicate the classes of reactions that were initially anticipated to be the most important (although the ensuing model suggests that not all are significant). Provided in Table AIV of the Appendix is the full list of reactions that were ultimately used in this work to model the chemistry of 2-BTP. This list includes suspected minor channels added for completeness, as well as additional reactions related to the subsequent chemistry of the system, and associated only indirectly with 2-BTP decomposition. With the initial mechanism in hand, experimental data for enthalpies of formation were compiled and rates of reaction were taken from the literature or estimated by analogy or rate rules. However, reliable data were available for only a few of the species and reac- tions in Table I and even fewer of those in the large table provided in Table AIV. As a result, we have used quantum chemical calculations to compute the stability of the species and the energetics of many of the indicated reactions. The Gaussian software package was used to compute the structures and stationary point energies of the examined reactions, including transition states, using the G3MP2B3 and G3B3 composite ab initio methods [10,11]. Geometries, vibrational frequencies, and zero-point energies of species were calculated at the B3LYP/6-31G(d) level of theory. This level has generally been observed to perform well for the types of species and reactions under current consideration. Some comparisons of the presently computed enthalpy values with other experimental and computational results can be found for selected molecules in Table AIII. Good to excellent agreement (often within 1-5 kJ mol-1) is observed in cases where reliable data are available. In addition to the assembled data set on the intermediates and products directly relevant to the decomposition, oxidation, and flame chemistry of 2-BTP, we also considered a more comprehensive set of species International Journal of Chemical Kinetics DOI 10.1002/kin.20923 CHEMICAL KINETIC MECHANISM FOR 2-BTP FLAME INHIBITION 537 and reactions involving related chloro- and fluorosubstituted analogs. This additional work was done to benchmark the quantum chemical calculations with reference species and reactions, to provide a means of self-consistency checks and uncertainty analysis for the quantum chemical calculations, and to screen the experimental data to identify cases where the data may be in error or have high uncertainties. We believe this additional benchmarking is very important to validate the results, particularly for the present system where reliable experimental data are limited. The large preliminary set of species and reactions was critically considered, and the pathways that were obviously noncompetitive for energetic reasons were removed. Further calculations and estimation methods were employed to develop the preliminary chemical reaction mechanism that was used to model the flame chemistry of 2-BTP. The results of this preliminary modeling work were subsequently analyzed to again refine the chemical reaction mechanism--the revision of the mechanism after modeling was iterated several times. If reliable kinetic parameters for pathways appearing to be significant were unavailable, values were computed using transition state theory in conjunction with the computed reaction energetics. Under combustion conditions, many of the unimolecular reactions have pressure-dependent rate constants due to the falloff effects that result in non-Boltzmann energy distributions. This is an additional complication in providing accurate rate constants. For key reactions, we have carried out RRKM/Master Equation modeling using the ChemRate software program to produce rate constants and rate expressions that can be used for modeling purposes. As previously noted, the sources and methodologies employed in the derivation of specific parameters are given in the Appendix tables. As a whole, our compilation of the literature, together with the additional computations performed in this work, and our subsequent analysis and evaluation, has resulted in a significant database of thermochemical and chemical kinetic data for species and reactions derived from halogenated hydrocarbon systems. These data are important to not only flame inhibition chemistry (for 2-BTP and other compounds) but are also relevant to the atmospheric chemistry of halogenated compounds that impact global warming and ozone depletion. 2-BTP AS AN INHIBITOR VERSUS PROMOTER istry of 2-BTP. One of the objectives is to provide a chemical basis for explaining the effectiveness of 2BTP inhibition (and enhanced combustion) under different conditions. In the course of this work, we have performed reaction path analyses of major species involved in the decomposition and oxidation of 2-BTP under several conditions. These analyses lead to an understanding of the ability of 2-BTP to act as both an inhibitor and a promoter (or as a fuel), depending on the conditions. Flame inhibition in 2-BTP systems is a result of the decomposition of the agent and the subsequent chemical reactions of its breakdown products. It is seen from Table I that some of these reactions ultimately produce HBr and Br atoms, which are known to catalytically removed H-atoms and thereby suppress flame chemistry through the following set of simple reactions: HBr + H Br + H2 (R1) 2 Br Br2 (R2) Br2 + H HBr + Br (R3) The first reaction, HBr + H Br + H2, is the most important in the sense that it suppresses the superequilibrium concentration of hydrogen atoms in the flame. During inhibition, this reaction operates with high reversibility: Br + H2 HBr + H [reverse of (R1)] (R4) The other two reactions are responsible for catalytically recycling HBr. One of the important factors is that 2-BTP can act as a fuel itself, and hence, rather than inhibit combustion, it has the potential enhance or accelerate combustion in two ways. First, the alkenylmoiety "=CH2" in 2-BTP (CF3-CBr=CH2) is a fuel "component" that will eventually produce CO2 and H2O, which are exothermic products producing heat. Our reaction path analysis, given later, will demonstrate that ethene is the primary hydrocarbon involved in this process. Second, the Br-atom itself is a radical that can react with and cause the decomposition of a fuel just like HOx radicals in a flame. R - H + H, O, OH R + H2, OH, H2O (R5) R - H + Br R + HBr (R6) The goal of this work was to develop a chemical reaction mechanism for use in modeling the flame chem- It is important to understand the nature of this chemistry. The conditions where 2-BTP accelerates International Journal of Chemical Kinetics DOI 10.1002/kin.20923 538 BURGESS ET AL. combustion and acts as a fuel is where it and its decomposition products impact combustion before the catalytic destruction of H-atoms by HBr is able to occur. The experimental observation that at high agent loadings and lean flames, there is an increase in flame temperature (promotion of combustion) is related to the perturbation of the important HBr + H Br + H2 reaction, as will be demonstrated in more detail in the reaction path analysis given later. HBr can be reformed from bromine atoms by (R4), Br + H2 HBr + H, which is the reverse of (R1). HBr can also be regenerated by other reactions, including HO2 + Br O2 + HBr RH + Br R + HBr H2O + Br OH + HBr HBr (high T; product region) HBr (low T; reactant region) (R7) (R8) (R9) (R10) The first reaction above, reaction (R7), is important to inhibition during the chain initiation stage of the flame. Generic reaction (R8) above occurs as the fuel is decomposing. Here, RH indicates a hydrocarbon species, such as CH4 and C2H6, or an oxidized hydrocarbon, such as CH2O and CHO. Reaction (R9) is important in the high-temperature postflame region where the product molecule water (H2O) is the main significant source of H and reacts with Br atoms to regenerate the important HBr species. "Reaction" (R10) is meant to indicate a physical diffusion process, not a "chemical reaction," but is included above to reflect that it is important to recognize that HBr formed "later" in the combustion process or in the postflame zone can diffuse back into other regions. This overall picture is of consumption of HBr via the highly exothermic (R1) in the chain initiation and flame zones where H atoms are relatively plentiful, the regeneration of HBr in the H-depleted postflame regions where free Br atoms are no longer sustainable, and then backdiffusion of HBr into the flame zone. The chemistries of both inhibition and enhancement are driven by the breakdown of 2-BTP and are thus intertwined. Elevated temperatures increase the rates of the decomposition chemistry that leads to inhibition as well as the exothermic oxidation steps that produce heat and accelerate combustion. Radical chemistry initiates much of the decomposition of 2BTP (see the subsequent reaction path analysis), and the radicals produced during decomposition can lead, variously, to chain termination if they are particularly stable or catalyze termination steps, to chain propagation if they are reactive, or to chain branching if they lead to multiple reactive radicals. Heat release increases the temperature and accelerates reactions. Conversely, heat loss by endothermic processes, or by mixing with cool gas regions, results in decreasing temperatures and slower reactions. The slower reactions result in fewer radicals to drive the chemistry, consequently a further reduced rate of heat release, still lower temperatures, and eventually the extinguishment of any flames. Although the effects are related and are overlapping, one can broadly consider the effects as being either of a physical nature (related to heat capacity and temperature) or of a chemical nature (related to competing reaction rates). The nature of substituents on the molecule (e.g., fluorine vs. bromine) and the degree of substitution (e.g., CH3CF3 vs. CF3CF3) impact the chemical nature of the species and hence can significantly impact the reaction rates. Chemical substitution can also change the heat release since it influences the heat of reaction and hence the temperature. The heat capacity of the agent/fuel mixture can also significantly influence the temperature. All agents, Halon 1301, 2-BTP, HFCs, etc. will eventually decompose and burn, forming stable and exothermic products, e.g., CO, H2O, HBr, and HF, and liberating heat in the process. Stable fluorinated compounds and radicals such as CF3 are slower to burn than hydrocarbons, in large part because of the strength of C-F bonds. Fluorinated intermediates, including radicals, thus "inhibit" the chemistry simply by delaying or interrupting the chemistry. They are effectively products of incomplete combustion and can increase rates of termination steps, in contrast to driving the chemistry with chain-propagating radical reactions. On the other hand, at high enough temperatures, the stability of the fluorinated intermediates is overcome and they decompose, becoming chain carriers. They can lead to additional heat release through reactions that lead to the highly exothermic formation of HF, which has an exceptionally strong bond. There is thus a complex interplay of thermodynamic and kinetic properties that will determine the behavior of a combusting 2-BTP/fuel mixture under a particular set of conditions. The decomposition of 2-BTP leads to many possible intermediates and products, including partially oxidized species. If the inhibiting HBr and Br atoms are not produced in sufficient quantities or sufficiently fast, the catalytic destruction of H-atoms is delayed, and thermal considerations may thereby lead to enhanced combustion. International Journal of Chemical Kinetics DOI 10.1002/kin.20923 CHEMICAL KINETIC MECHANISM FOR 2-BTP FLAME INHIBITION 539 THE CURRENTLY RECOMMENDED 2-BTP CHEMICAL KINETIC MECHANISM Species Identification Table AI in the Appendix provides a list of all the species included in the 2-BTP chemical kinetic submechanism developed as part of this work. It also contains a number of auxillary species used as reference compounds in the derivation of enthalpies of formation from the G3MP2B3 quantum chemical results. It does not include most species from the larger models developed previously, such as the USC Mech 2.0 C1C4 hydrocarbon model [12], or the NIST HFC C1-C2 mechanism [13]. Given for each species is the chemical formula, the "Species Symbol" used in the current model, the Chemical Abstracts Registry Number (if available), and an IUPAC-based systematic name. Enthalpies of Formation for Species Table AII in the Appendix provides enthalpies of formation, with uncertainties, for all species listed in Table I. The reference for each value is indicated, together with the method by which it was determined. Enthalpies of formation are provided for approximately 90 species in Table AII. About 55 of the values were selected from other reviews, evaluations, and thermochemical network studies that we judged to be of high quality. These were accepted without further review other than to verify that the data were properly transcribed and were self-consistent with our preferred values for related compounds. About 10 of the species in Table AII have experimental values from the literature where there is essentially only one value that is available. We selected these values for use after verifying that the enthalpies of formation are self-consistent with computed values (if available) and with values for related compounds. An additional eight enthalpies of formation are derived from our G3MP2B3 calculations where we have benchmarked the calculated values to reference molecules using isodesmic reactions. For example, trifluoropropyne can be benchmarked to molecules with well-defined enthalpies of formation through the reaction CF3CCH + CH3CH3 CH3CCH + CF3CH3. Finally, for 14 species there were multiple values in the literature, but there were either no evaluations, or there were measurements more recent than the last evaluation. In these cases, the available values are compiled in Table AIII, and we provide a preferred number based on our own assessment. These preferred values generally agree with the listed experiments and calculations within the stated uncertainties. In some cases, generally where the experimental values are either limited or have high uncertainties, the selected value is based on high level ab initio calculations. In these instances, we refer the reader to the cited references for a discussion of the accuracy of the ab initio value in comparison with experiment. Reactions in 2-BTP Submechanism Table AIV in the Appendix provides a list, subdivided by class, of the reactions included in the 2-BTP chemical kinetic submodel. Rate constants have been parameterized using the extended Arrhenius form, k = ATbexp(-E/RT), and values of A, b, and E are provided. Sources of the rate constants are given, together with notes about the methodology used, which ranged from review, to shock tube experiments, to quantum chemical methods, to simply "estimated." Where possible, the selected values are from evaluations or are those accepted and used in other models. In some cases, we were able to estimate the rate constants by analogy to similar reactions with known values. For other reactions, we computed the rate constants employing barriers calculated using the G3MP2B3 quantum chemical method. In such cases, we took care to validate the results by also computing barriers for similar reactions where experimental data exist. Good agreement was generally observed, giving confidence to the computed barriers. In general, many rate expressions of Table AIV should be considered as estimates that could be improved upon. In a few cases, we provide two rate expressions for a reaction. One of the rate expressions-- identified with "(b)"--is that which was used in the initial modeling work that we report more fully elsewhere [3,9]. The other rate expression--identified with "(a)"--is a revised rate expression based on new measurements or a revised evaluation that was carried out in the latter stages of this work. Such revisions typically reflect that analysis of the initial modeling work suggested that these reactions warranted further scrutiny, and we were then able to develop sufficient information to provide a better estimate. The revised rate expressions are suggested for use in future work. In the first column of Table AIV, we assign a qualitative importance to the reactions, labeling them as the primary ("1"), secondary ("2"), and minor ("3") reaction pathways. Unlabeled reactions were found to be negligible (less than 1%) in contributing to the reaction flux under the modeled conditions. Note, however, that the relative importance of these reactions could change under substantially different conditions such as different agents, very high agent loadings, or where there is no hydrocarbon fuel (only the agent and O2). These International Journal of Chemical Kinetics DOI 10.1002/kin.20923 540 BURGESS ET AL. reactions should therefore be retained in the mechanism for use under other conditions. One of the purposes of characterizing the reactions in this manner is to identify the reactions that could most benefit from further scrutiny. It should be noted that these characterizations identify the reactions most important to the formation or destruction of particular species: They are not specifically related to the overall mass flow through the system. A better way of characterizing the dominant pathways in the overall chemistry is in a reaction flux diagram such as given later in our reaction path analysis. In summary, the present reaction set and the associated kinetic parameters have been developed following a comprehensive literature review of available kinetic and thermochemical data, with extension by quantum chemical calculations. Nonetheless, the present model should be considered to be an initial working version that can be refined and improved through more calculations and kinetic experiments on key reactions. As a first test of the mechanism's performance, predicted and measured burning velocities of methane-air flames with added 2-BTP are discussed below, followed by reaction path analysis of the flames. Of course, other studies comparing measured and predicted species profiles would be highly desirable and hopefully will be available in the future. EXPERIMENTAL AND MODELING RESULTS To test the mechanism and understand flame inhibition by 2-BTP, premixed flame simulations have been performed. The kinetic model for the simulations consists of four submechanisms: (1) hydrocarbon combustion, (2) fluorocarbon inhibition, (3) CH2CBrCF3 decomposition, and (4) bromine-species inhibition. In general, we limit our discussion and analysis to the chemistry most directly relevant to the decomposition of 2-BTP and its mode of action and accept for the moment the chemistry of the other submodels, which have been validated elsewhere. For the hydrocarbon mechanism, a subset of the USC H2/CO/C1-C4 hydrocarbon model (USC Mech 2.0) [12] (111 species and 784 reactions) was used (with reactions of C5 to C7 species, which are unimportant for the present simulations, removed to reduce computational time). Additional reactions for ethanol combustion were needed to simulate the FAAACT experiments, and five species and 36 reactions were taken from the Princeton ethanol decomposition model of Dryer and co-workers [14]. To describe inhibition by fluorocarbon species, the National Institute of Standards and Technology (NIST) HFC C1-C2 Figure 1 Measured and calculated premixed, laminar burning velocity (normalized by the uninhibited value) for initially stoichiometric methane-air flames with added CF3Br. Calc (Babushok) [9]. Expt: Sanogo [20], Osorio [21], Linteris [22], Pagliaro [23]. mechanism [13], was used, including updates [15-17] and additions [3,9], as summarized in the work by Linteris et al. [18]. Finally, the submodel for the reactions describing inhibition by Br-containing species (i.e., the decomposition products of 2-BTP) is based on the CF3Br flame inhibition model of Babushok et al. [19], which has been updated [9]. The complete kinetic model for the simulations with 2-BTP has 1609 reactions and 188 species. The resulting model has been used to simulate premixed flames for which experimental burning velocity data are available in the literature. Because, as discussed below, 2-BTP largely decomposes (eventually) in hydrocarbon flames to the same intermediate species as CF3Br, (CF3 and HBr) and since the CF3Br mechanism itself was updated, we first tested the mechanism against flame inhibition by CF3Br. For example, Fig. 1 shows the measured [20-23] and calculated [9] burning velocities of stoichiometric methane-air flames with added CF3Br. [Normalized burning velocities are presented because there are systematic differences in the uninhibited burning velocities from different experimental techniques, as well as in computed velocities. The uncertainty in the absolute velocities [9,21] is on the order of 5%.] As illustrated with normalized burning velocities, the agreement is good, lending confidence in the CF3Br submechanism. For the 2-BTP submechanism, experimental results have recently become available for demonstrating the performance of the present model. Pressure traces from a International Journal of Chemical Kinetics DOI 10.1002/kin.20923 CHEMICAL KINETIC MECHANISM FOR 2-BTP FLAME INHIBITION 541 Figure 2 Measured and calculated burning velocity of methane-air mixtures with added 2-BTP (initial conditions: solid lines, 298 K, 0.10133 MPa; dotted lines, 400 K, 0.304 MPa; and initial CH4-air equivalence ratios of 0.6 and 1.0) (see the text). constant-volume combustion sphere (volume 2 L) were used to infer the experimental burning velocity for laminar, spherical, premixed methane-air flames (as a function of temperature and pressure) with added 2-BTP [23]. In later work [9], the burning velocity was numerically simulated for the same conditions, using the SANDIA PREMIX code [24] using the kinetic mechanism described above. The measured and predicted burning velocities are shown in Fig. 2, for 2BTP added to methane air flames of equivalence ratios () of 0.6 and 1.0, and initial conditions of ambient, and slightly compressed reactant gases. As shown, the agreement is good. Of course, while such comparisons are a necessary first step in model validation, more work is required to more thoroughly test and develop the mechanism. To understand the decomposition and oxidation of 2-BTP, the numerical simulations are interpreted below using reaction flux analyses via the XSenkplot reaction analysis software [25]. MODELING AND REACTION PATH ANALYSIS General Discussion The main reaction pathways associated with the flame chemistry of 2-BTP are given in Table II. These have Table II Primary Reaction Paths for 2-BTP Flame Chemistry 1 BTP + H CF3CHCH2 + Br a CF3CHCH2 + H C2H4 + CF3 b CF3CHCH2 + H CF3CCH2 + H2 a.1 CF3 + CH3 CH2=CF2 + HF CH2 = CF2 C2HF + HF CH2 = CF2 + H CH2=CHF + F a.2 CF3 + HBr CHF3 + Br CHF3 CF2 + HF 2 BTP + H, OH, CF3 CF3CBrCH + H2, H2O, CHF3 a CF3CBrCH CF3CCH + Br CF3CCH + H C2H2 + CF3 CF3CCH + OH CH2CO + CF3 CF3CCH + CH3 pC3H4 + CF3 3 BTP + H, CF3 CF3CCH2 + HBr, CF3Br a CF3CCH2 CF3CCH + H b CF3BR + H CF3 + HBR been culled from the full model given in Table AIV. The pathways given in Table II reflect those observed in our simulations: atmospheric pressure, equivalence ratios of = 0.67 to = 1.33 for methane, loadings of 2-BTP ranging from 0.5% to 3.0%, and adiabatic flame temperatures of 1600-2200 K. Reactions were identified on the basis of their contributions to the net reaction flux for each of the species in the model. One should be aware, however, that other reactions may also be important in the sense that they contribute to establishing quasi-equilibrium conditions, or contribute to establishing steady state reaction networks. Figure 3 provides a reaction path analysis of the decomposition of 2-BTP and the flame chemistry of its decomposition products. The pathways are an ensemble of those observed in our modeling over a range of conditions from an equivalence ratio of = 0.67- 1.33 and loadings of 2-BTP from 0.5% to 3.0%. Each pathway that involves the production of the important inhibition species Br, HBr, and CF3 is identified. The weights of the lines in Fig. 3 are qualitative indications of the relative importance of the net flux from one species to another. More precise representations are problematic as the relative reaction flux changes with flame temperature, fuel/air ratio, and agent loading. We found that the relative importance of each reaction pathway was fully consistent with what one might expect with changes in flame temperature and agent loading. In particular, lower flame temperatures result in the shutting down of reactions with high barriers, International Journal of Chemical Kinetics DOI 10.1002/kin.20923 542 BURGESS ET AL. Figure 3 Reaction path network for 2-BTP flame chemistry. and high agent loadings increase bimolecular reaction rates involving intermediate radicals derived from the agent. The reaction path analysis indicates that the primary and secondary decomposition pathways for 2-BTP involve reactions with H atoms. There is also a secondary pathway of CF3 abstracting Br to form CF3Br. Unimolecular decompositions of 2-BTP by molecular elimination of HBr and by C-Br bond fission (Br atom elimination) were found to be negligible. Under the modeled conditions, on the order of 70-80% of the 2-BTP (CF3CBr=CH2) decomposes via a net displacement reaction that generates trifluoropropene (CF3CH=CH2) and a bromine atom: CF3CBr=CH2 + H CF3CH=CH2 + Br (R11) On an elementary level, this reaction involves addition of H to the unsaturated center to form a chemically activated halopropyl radical intermediate that subsequently decomposes by beta scission [i.e., breaking of a bond adjacent ("beta") to the radical site, in this case the weak C-Br bond]. CF3CBr=CH2 + H [CF3CHBrCH2] (R12) [CF3CHBrCH2] CF3CH=CH2 + Br (R13) Decomposition of the intermediate is effectively instantaneous at flame temperatures, and the behavior is that of a single-step reaction. The trifluoropropene produced then decomposes through another similar chemically activated radical addition/elimination reaction, where in this case, CF3 is displaced by an H-atom CF3CH=CH2 + H [CF3CH2CH2] CH2=CH2 + CF3 (R14) Overall, these two facile steps involving H-atoms can be written as CF3CBr=CH2 + 2H CH2=CH2 + CF3 + Br (R15) This shows that 2-BTP quickly produces ethene (CH2=CH2), CF3, and Br. The first species is highly combustible, releasing heat as it reacts further and ultimately forms CO2 and water, whereas the latter two species can contribute to inhibition of the flame. International Journal of Chemical Kinetics DOI 10.1002/kin.20923 CHEMICAL KINETIC MECHANISM FOR 2-BTP FLAME INHIBITION 543 There are several secondary decomposition pathways including CF3CBr=CH2 + CF3 CF3CBr=CH + CHF3 (R16) + CF3 CF3C=CH2 + CF3Br (R17) + H CH2=CHBr + CF3 (R18) Reactions (R16) and (R17) are abstractions by CF3, whereas reaction (R18) is a chemically activated radical addition/elimination where CF3 is displaced by H-atom. The halogenated propenyl radicals CF3CBr=CH* and CF3C*=CH2 produced in reactions (R16) and (R17) quickly undergo betascission reactions breaking the C-Br or C-H bonds, respectively, adjacent to the radical site to form trifluoropropyne (CF3CCH). Trifluoropropyne decomposes through reactions with flame radicals H, CH3, and OH to form readily combustible products propyne (CH3CCH), acetylene (HCCH), and ketene (CH2=C=O), respectively. A detailed inspection of the reaction paths reveals the nature of the behavior of 2-BTP in both inhibiting and promoting hydrocarbon flames and provides a explanation for experimental observations. In the FAAACT, overpressures were observed (indicating an increase in flammability) [4,5]. Similarly, in a constantvolume apparatus at high agent loadings in lean flames, increases in pressure, burning velocity, and flame temperature were observed [23]. Our modeling results show that at high agent loadings and lean flames, there was an increase in flame temperature consistent with the overpressure observed in the FAA-ACT and the observations in the cup-burner tests. Under these conditions, the release of Br-atoms or HBr (and thus inhibition) is overcome by the heat release of from HF formation and hydrocarbon/fuel species oxidation reactions (like C2H2) derived from the agent 2-BTP acting as a fuel/promoting combustion. We report elsewhere more details of the simulations along with experimental results from flame measurements [3,9]. Our detailed inspection of the modeled species profiles in the flame and the reaction pathways reveals fundamental differences in the chemical behavior of the agents CF3Br and 2-BTP in all regions of the flame, including A. Chain Initiation, where the increase in concentrations of radicals become significant, B. Decomposition of agent, where HBr and Br atoms are released, C. Flame reaction zone, where radical concentrations are at their maximums, and D. Postflame zone (products), where radical concentrations fall and products are formed. These differences explain the observations of the different actions of 2-BTP as an agent compared to CF3Br. Chain Initiation Pathways In the radical chain initiation stage for CF3Br, reactive Br atoms (radicals) are initially formed via unimolecular decomposition CF3Br CF3 + Br (R19) For 2-BTP, where the C-Br bond is about 40 kJ/mol stronger, this does not happen, and instead Br atoms can only be created after H atom concentrations have increased via CF3CBr=CH2 + H CF3CH=CH2 + Br (R11) This delay in Br atom formation in the case of 2BTP also results in Br atoms not participating in the early stages of ignition in the important termination step HO2 + Br O2 + HBr (R7) Decomposition of Agent Pathways The primary reaction responsible for inhibition involves HBr HBr + H Br + H2 (R1) This important inhibitor species HBr is formed in the primary reaction responsible for the decomposition of CF3Br CF3Br + H CF3 + HBr (R20) In contrast, Br atoms (not HBr) are formed in the primary reaction responsible for the decomposition of 2-BTP CF3CBr=CH2 + H CF3CH=CH2 + Br (R11) This means HBr is not readily available for suppression of H atoms immediately during the initial International Journal of Chemical Kinetics DOI 10.1002/kin.20923 544 BURGESS ET AL. decomposition of 2-BTP--it must be produced after further reactions. Combustion (Flame Reaction Zone) Pathways This conversion of one reactive radical (H atoms) into another (Br atoms) has great implications on the decomposition of the fuel. We find that the primary decomposition pathways for the fuel (methane, in this modeling work) and other hydrocarbon species are reactions with Br atoms: CH4 + Br CH3 + HBr (R21) C2H6 + Br C2H5 + HBr (R22) CH2O + Br CHO + HBr (R23) CHO + Br CO + HBr (R24) Thus, the presence of Br atoms-in much higher concentrations than H atoms-in the case of 2-BTP, can promote combustion by causing the decomposition of the fuel and intermediate hydrocarbon species. Postflame Zone (Products) Pathways The most significant differences between the chemistry of CF3Br (inhibition) and 2-BTP (inhibition/promotion) appears to occur in the postflame zone, where HOx flame radical concentrations have fallen, and combustion products have been formed. This is particularly true in the case of lean flames. In order for bromine-containing species to inhibit combustion, the HBr consumed in the scavenging of H atoms HBr + H Br + H2 (R1) must be recycled through conversion of the Br atoms back to HBr. In lean flames, which are depleted in fuel and thus, in hydrogen, the dominant brominecontaining species in the postcombustion zone are Br atoms and not HBr. In the absence of H2, the important reverse reaction becomes slow Br + H2 HBr + H (R4) In lean flames, the high concentration of Br atoms in the postcombustion zone results in Br atoms diffusing back into the flame reaction (and preheating) zones-- resulting in promotion of combustion via Br atom- mediated decomposition of the fuel. SUMMARY In this paper, we report the development, and full documentation, of a detailed chemical kinetic mechanism of the flame inhibition chemistry of 2-BTP (2bromotrifluoropropene). To our knowledge, prior to this work, such a chemical kinetic mechanism did not exist. The suggested mechanism includes both the initial breakdown processes for 2-BTP and the subsequent pyrolysis and oxidation chemistry of its decomposition products. Some of the latter chemistry includes species and reactions that are present in various existing models of hydrocarbon combustion and flame inhibition by C1-C2 fluorocarbons and bromine-containing compounds. We have made direct use of this data where possible. Additional kinetic and thermochemical parameters have been developed following a comprehensive literature review of available kinetic and thermochemical data, augmented by quantum chemical calculations. The current computations have been checked for internal consistency by comparison with experimental data on these and related reactions and species. Specific sources of the model parameters are individually documented in the tables. In other companion work, the presently developed submechanism for the decomposition and flame chemistry of 2-BTP was combined with existing models of fuel combustion and halocarbon kinetics from the literature to simulate the behavior of 2-BTP in flame inhibition tests [3,9]. Those modeling results, reported in detail elsewhere, qualitatively predicted observations found in cup-burner tests and FAA-ACT, including the extinguishing concentrations required and system behavior with the change of equivalence ratio from rich to lean fuel mixtures, and also qualitatively predicted the increase in flammability limits and overpressure for a range of fuel/air stoichiometries and agent loadings. Thus, the present submechanism for 2-BTP chemistry, when combined with appropriate fuel and halocarbon chemistry from the literature, leads to simulations that are qualitatively in accord with experimental observations. This suggests we have successfully captured key aspects of the inhibition chemistry. As part of the present work, we have performed a reaction path analysis of major species under several conditions. This analysis leads to an understanding of the ability of 2-BTP to act as both an inhibitor and a fuel, depending on the conditions. We find that there are fundamental differences between the flame International Journal of Chemical Kinetics DOI 10.1002/kin.20923 CHEMICAL KINETIC MECHANISM FOR 2-BTP FLAME INHIBITION 545 inhibition chemistry of CF3Br, an effective inhibitor, and that of 2-BTP, which strongly accelerates (promotes) combustion in lean flames at high agent loadings. These differences exist through all regimes of the flame. With CF3Br, the initial decomposition of the agent via a reaction with H atoms produces HBr--the primary species responsible for scavenging H atoms. In contrast, with 2-BTP, agent decomposition proceeds primarily via a reaction with H atoms to produce Br atoms--reactive radicals that can themselves cause decomposition of the fuel if not catalytically recycled back to HBr. In lean flames (deficient in hydrogen), Br atoms, not HBr, are the predominant brominecontaining products. This results in HBr not being reformed in the combustion zone, either through a reaction or by diffusion. This is not an issue in CF3Br inhibited flames--where much lower agent loadings are needed and the adiabatic flame temperatures are much lower. The current model should be considered to be a working version that could benefit from further refinement. As is typical for complex chemical kinetic models, we anticipate that the thermochemical data, reaction set, and rate constants will need closer scrutiny. Additional experimental data and further validation against flame speeds, product profiles, and other physical observables is still required. Analysis over a wider range of fuel/air stoichiometries and agent loadings should better identify the key species and reactions that would profit from additional study via direct experiment, appropriately benchmarked estimates, or quantum chemical methods. The work was supported by the Boeing Company. APPENDIX In this appendix, we present several tables with information utilized in developing the chemical kinetic model for flame inhibition by 2-BTP. We provide a list of the species contained in the chemical kinetic model in Table AI along with molecular formula, chemical names, and Chemical Abstracts Registry Numbers. Enthalpies of formation for these species are provided in Tables AII and AIII. The full chemical kinetic model developed as part of this work and used in the modeling reported elsewhere is given in Table AIV. A subset of this full model--the "primary reaction pathways"--is provided in the body of this article in Table II. Based on the reaction path analysis and recent experimental rate constant measurements at NIST, we have revised a number of the rate expressions--and these are noted in Table AIII, and then discussed. Lastly, in Supporting Information, we provide Tables S1-S11, giving an annotated bibliography of relevant literature that was compiled as part of this work. This set of literature provides information about the fire suppression chemistry of fluorinated hydrocarbons, CF3Br, and other species. Many of the same intermediates prevalent in these systems are important in inhibition by 2-BTP, and by analogy provide a chemical basis for the development of a chemical kinetic model for flame inhibition by 2-BTP. Reevaluated Rate Expressions in Table IV HBr + O Br + OH The rate constant used in our modeling work for HBr + O Br + OH was taken from Nava et al. [113] and has been utilized by many others in modeling work. We have revaluated this rate expression using all the experimental values by Nicovich and Wine [116], Nava et al. [113], Singleton and Cvetanovic [184], and Brown and Smith [185] and also taking into consideration the computational values by de Oliveira-Filho et al. [186] and Broida et al [187]. Fits to the experimental data and the computed values yielded nonlinear Arrhenius expressions (Tb) with b ranging from 1.92 to 2.53 and activation energies E = 5.6-7.3 kJ/mol. We fitted the experimental data utilizing an intermediate value for the temperature factor, which yielded a rate expression with A = 7.73 105, b = 2.26, and E = 6.4 kJ/mol. This rate expression has rate constants that agree with experimental values to about 9% (roughly the experimental uncertainties), but provide rate constants at 1000 K (2.1 1012 cm3/mol/s) and 1500 K (6.8 1012 cm3/mol/s) that were about 2.4 and 4.7 times faster, respectively, compared to those utilizing the rate expression of Nava et al. [113]. This temperature factor is very similar to the T2.3 we get fitting experimental data for the analogous reaction HCl + O Cl + OH and the T2.1 for the reaction HCl + O Cl + OH from the computational work of Xie et al. [188]. HBr + OH Br + H2O The rate expression used in our modeling work was taken from the IUPAC recommendation by Atkinson et al. [114]. This rate expression, however, is only valid at low temperatures (below 400 K). Liu et al. [189] used computed rate constants from quantum-calculated potential energy surface. Although the agreement was poor with the absolute rate constants from experimental measurements, the calculations imply that the rate constant minimizes at about 250-450 K. This is consistent with the measurements of Ravishankara et al. [194] that show no temperature dependence (within experimental International Journal of Chemical Kinetics DOI 10.1002/kin.20923 546 BURGESS ET AL. Table AI Identification of species contained in the 2-BTP mechanism Formula Species Symbol CAS Registry Number H1 H1O1 H1O2 H2 H2O1 H2O2 O1 O2 F1 F2 H1F2 Br1 Br1H1 Br2 Br1O1 Br1O1H1 Br1O2 C1H1 C1H2 C1H3 C1H4 C2H2 C2H3 C2H4 C2H5 C2H6 C3H4 C3H4 C3H5 C3H5 C3H6 C3H7 C3H7 C3H8 C4H4 C1H1O1 C1H2O1 C1H3O1 C1H3O1 C1H4O1 C1O1 C1O2 C2H1O1 C2H2O1 C2H3O1 C2H4O1 C2H5O1 C2H5O1 C2H5O1 C2H6O1 C3H6O1 C1F1 C1F2 H OH HO2 H2 H2O H2O2 O O2 F F2 HF Br HBr Br2 BrO BrOH BrOO CH CH2 CH3 CH4 C2H2 C2H3 C2H4 C2H5 C2H6 aC3H4 pC3H4 CH3CCH2 CH3CHCH C3H6 iC3H7 nC3H7 C3H8 CH2CHCCH HCO CH2O CH2OH CH3O CH3OH CO CO2 HCCO CH2CO CH3CO CH3CHO C2H4OH CH3CH2O CH3CHOH C2H5OH CH3COCH3 CF CF2 12385-13-6 3352-57-6 3170-83-0 1333-74-0 7732-18-5 7722-84-1 17778-80-2 7782-44-7 14762-94-8 7782-41-4 7664-39-3 10097-32-2 10035-10-6 7726-95-6 15656-19-6 13517-11-8 67177-47-3 3315-37-5 2465-56-7 2229-07-4 74-82-8 74-86-2 2669-89-8 74-85-1 14936-94-8 74-84-0 463-49-0 74-99-7 15552-77-9 6067-68-1 115-07-1 2025-55-0 2143-61-5 74-98-6 689-97-4 2597-44-6 50-00-0 2597-43-5 2143-68-2 67-56-1 630-08-0 124-38-9 51095-15-9 463-51-4 3170-69-2 75-07-0 4422-54-2 2154-50-9 2348-46-1 64-17-5 67-64-1 3889-75-6 2154-59-8 Systematic Name Hydrogen atom Hydroxyl Hydroperoxy Hydrogen Water Hydrogen peroxide Oxygen atom Oxygen Fluorine atom Fluorine Hydrogen fluoride Bromine atom Hydrogen bromide Bromine Bromine oxide Bromine hydroxide Bromoperoxy Methylidyne Methylene Methyl Methane Ethyne Ethenyl Ethene Ethyl Ethane Propadiene Propyne Propen-2-yl Propen-1-yl Propene Prop-2-yl Prop-1-yl Propane Butenyne Formyl Formaldehyde Hydroxymethyl Methoxy Methanol Carbon monoxide Carbon dioxide Ethynyloxy Ethenal Ethenyloxy Ethanal 2-Hydroxyethyl Ethoxy 1-Hydroxyethyl Ethanol Propanone Fluoromethylidyne Difluoromethylene Continued International Journal of Chemical Kinetics DOI 10.1002/kin.20923 CHEMICAL KINETIC MECHANISM FOR 2-BTP FLAME INHIBITION 547 Table AI Continued Formula C1F3 C1F4 C1H1F2 C1H1F3 C1H2F1 C1H2F2 C1H3F1 C2F2 C2H1F1 C2F4 C2F5 C2F6 C2H2F5 C2H3F3 C2H4F1 C3H1F3 C3H2F3 C3H2F3 C3H3F3 C1F1O1 C1F2O1 C1F3O1 C2F3O1 C2F4O1 C3H3F3O1 C1H2Br1 C1H3Br1 C2H3Br1 C2H5Br1 C3H1Br1F3 C1Br1F3 C3H2Br1F3 C3H3Br1F3 Species Symbol CF3 CF4 CHF2 CHF3 CH2F CH2F2 CH3F C2F2 C2HF CF2=CF2 CF3-CF2 CF3-CF3 CHF2-CF3 CH3-CF3 CH2F-CH2 CF3CCH CF3CCH2 CF3CHCH CF3CHCH2 CFO CF2O CF3O CF3CO CF3COF CF3COCH3 CH2Br CH3Br C2H3Br C2H5Br CF3CBrCH CF3Br BTP CF3CHBrCH2 CAS Registry Number 2264-21-3 75-73-0 2670-13-5 75-46-7 3744-29-4 75-10-5 593-53-3 689-99-6 2713-09-9 116-14-3 3369-48-0 76-16-4 354-33-6 420-46-2 28761-00-4 661-54-1 207602-03-7 n/a 677-21-4 1871-24-5 353-50-4 21811-29-0 6185-26-8 354-34-7 421-50-1 16519-97-4 74-83-9 593-60-2 74-96-4 n/a 75-63-8 1514-82-5 n/a Systematic Name Trifluoromethyl Trifluormethane Difluoromethyl Trifluoromethane Fluoromethyl Difluoromethane Fluoromethane Difluoroethyne Fluoroethyne Tetrafluoroethene Pentafluoroethyl Hexafluoroethane Pentafluoroethane 1,1,1-Trifluoroethane 2-Fluoroethyl 3,3,3-Trifluoropropyne 3,3,3-Trifluoropropen-2-yl 3,3,3-Trifluoropropen-1-yl 3,3,3-Trifluoropropene Fluoroformyl Difluoroformaldehyde Trifluoromethoxy Trifluoroethanoyl Trifluoroethanoylfluoride 1,1,1-Trifluoropropanone Bromomethyl Bromomethane Bromoethene Bromoethane 2-Bromo-3,3,3-trifluoropropen-1-yl Bromotrifluoromethane 2-Bromo-3,3,3-trifluoropropene 2-Bromo-3,3,3-trifluoroprop-1-yl uncertainties) between 249 and 416 K. This contrasts with the low-temperature measurements of Mullen and Smith [195] at 53-125 K and by Sims et al. [196] at 23-295 K that clearly show a negative temperature dependence at these low temperatures. To provide a rate expression that is valid at flame temperatures, we fitted the low-temperature rate data, while considering the independence of the rate constants observed by Ravishankara et al. [194] and the minimization of the rate constants calculated by Liu et al. [189]. We found that a rate expression with A = 2.05 1011 cm3/mol/s, b = 0.58 (0.17), and E = -1.4( 0.1) kJ/mol agreed with the experimental data (within experimental uncertainties of about 10%) between 50 and 400 K. This expression predicts rate constants of 9.2 1012 and 1.08 1013 cm3/mol/s at 1000 and 1500 K, respectively, which are about 2.0 and 2.5 times faster than those provided by the Atkinson et al. [114] rate expres- sion with a negative temperature dependence. Wilson et al. [190] reported a rate constant derived from flame measurements for this reaction of 1.6 1013 cm3/mol/s at 1875-1975 K. Our fitted rate expression predicts a rate constant that is about 25% slower. CH3 + HBr CH4 + Br To provide a rate expression valid at flame temperatures, we fitted the low temperature (257-677 K) data of Seetula [125], Seakins et al. [71], and Nicovich et al. [197], while constraining the rate constants at 900-1100 K to be consistent with the relative temperature dependence calculated in the computational work of Ree et al. [198]. Note that no rate expressions are given in that paper--we estimated the temperature dependence from the figures provided in the paper. Computational work by Espinosa-Garcia [191], International Journal of Chemical Kinetics DOI 10.1002/kin.20923 548 BURGESS ET AL. Table AII Formula H1 H2 O1 O2 H2O1 H2O2 H1O1 H1O2 F1 F2 H1F2 Br1 Br2 Br1H1 Br1O1 Br1O1H1 Br1O2 C1H4 C1H3 C1H2 C1H1 C2H6 C2H5 C2H4 C2H3 C2H2 C3H8 C3H7 C3H7 C3H6 C3H5 C3H5 C3H4 C3H4 C4H4 C1H4O1 C1H3O1 C1H3O1 C1H2O1 C1H1O1 C1O1 C1O2 C2H6O1 Adopted Enthalpies of Formation for Species Contained in the 2-BTP Mechanism Species fHo(298 K) Unc Reference H H2 O O2 H2O H2O2 OH HO2 F F2 HF Br Br2 HBr BrO BrOH BrOO CH4 CH3 CH2 CH C2H6 C2H5 218.0 0.0 249.23 0.0 -241.8 -135.8 37.4 12.3 79.4 0.0 -273.3 111.9 30.9 -36.3 123.4 -60.5 110.2 -74.6 146.7 391.2 595.8 -84.0 120.7 0.0 1989COX/WAG [26] 0.0 1989COX/WAG [26] 0.0 2006RUS/PIN [27] 0.0 1989COX/WAG [26] 0.0 2006RUS/PIN [27] 0.2 2006RUS/PIN [27] 0.1 2006RUS/PIN [27] 0.3 2006RUS/PIN [27] 0.3 1989COX/WAG [26] 0.0 1989COX/WAG [26] 0.7 1989COX/WAG [26] 0.1 1989COX/WAG [26] 0.1 1989COX/WAG [26] 0.2 1989COX/WAG [26] 0.4 2006KIM/DOO [28] 1.1 1997HAS/IRI [29] 3.9 2011BUR/RUS [40] 0.3 2002MAN [30] 0.3 2005RUS/BOG [31] 1.6 2005RUS/BOG [31] 0.6 2005RUS/BOG [31] 0.4 2002MAN [30] 1.0 2006BOD/KER [32] C2H4 C2H3 C2H2 C3H8 nC3H7 (1-propyl) 52.4 299.6 227.4 -104.4 101.3 0.5 2002MAN [30] 3.3 1994BER/ELL [33] 0.8 2002MAN [30] 0.3 2011BUR/RUS [34] 1.0 2006BOD/KER [32] iC3H7 (2-propyl) 88.5 1.0 2006BOD/KER [32] C3H6 CH3CCH2 (propen-2-yl) CH3CHCH (propen-1-yl) pC3H4 (propyne) aC3H4 (allene) CH2CHCCH (butenyne) CH3OH CH3O CH2OH CH2O HCO CO CO2 C2H5OH 20.3 237.7 262.8 185.8 190.2 295 -201.0 21.0 -17.0 -108.7 42.0 -110.5 -393.5 -234.8 0.3 2011BUR/RUS [34] 6 1987WO/KER [35] 6 1987WO/KER [35] 0.4 2011BUR/RUS [34] 0.4 2011BUR/RUS [34] 3 1991ROT/ADA [36] 0.6 1989GUR/VEY [37] 2.1 2005RUS/BOG [31] 0.7 2005RUS/BOG [31] 0.5 1989GUR/VEY [37] 5.0 1989GUR/VEY [37] 0.2 1989COX/WAG [26] 0.1 1989COX/WAG [26] 0.5 1989GUR/VEY [37] Method Review Review Thermo network Review Thermo network Thermo network Thermo network Thermo network Review Review Review Review Review Review Photodissociation Review Thermo network Thermo network Thermo network Thermo network Thermo network Review PEPICO, Thermo network Review Review Review Thermo network PEPICO, Thermo network PEPICO, Thermo network Thermo network Kinetics allene+H=propen-2-yl Kinetics allene+H=propen-1-yl Thermo network Thermo network Heat hydrog Review Thermo network Thermo network Review Review Review Review Review Continued International Journal of Chemical Kinetics DOI 10.1002/kin.20923 Table AII Continued Formula Species C2H5O1 C2H5O1 C2H5O1 C2H4O1 C2H3O1 C2H2O1 C2H1O1 C3H6O1 C1H3F1 C1H2F2 C1H1F3 C1F4 C1H2F1 C1H1F2 C1F3 C1F2 C1F1 C2F6 C2H2F5 C2H3F3 C2F5 CH3CH2O CH3CHOH C2H4OH (2-hydroxyethyl) CH3CHO CH3CO CH2CO HCCO CH3COCH3 CH3F CH2F2 CHF3 CF4 CH2F CHF2 CF3 CF2 CF CF3-CF3 CHF2-CF3 CH3-CF3 CF3-CF2 C2H4F1 C2F4 C2F2 C1H1F1 C3H3F3 CH2F-CH2 CF2=CF2 C2F2 C2HF CF3CHCH2 C3H2F3 CF3CHCH C3H2F3 CF3CCH2 C3H1F3 CF3CCH C1F2O1 C1F1O1 C1F3O1 C2F4O1 C2F3O1 C3H3F3O1 CF2O CFO CF3O CF3COF CF3CO CF3COCH3 CHEMICAL KINETIC MECHANISM FOR 2-BTP FLAME INHIBITION 549 fHo(298 K) Unc Reference Method -12.5 -55.3 -25.8 4.0 2005RUS/BOG [31] Thermo network 4.0 2011BUR/RUS [34] Thermo network 4.0 2011BUR/RUS [34] Thermo network -165.4 -10.3 -47.7 176.6 -216.1 -235.9 -450.3 -695.0 -933.0 -31.2 -243.0 -467.4 -193.2 247.0 -1344.3 -1105 -745.6 -891 -59.4 -675.3 2.9 104.4 -623.4 -378.4 -366.4 -419.0 -607.1 -184.1 -635 -445.6 -605 -831.1 0.3 2011BUR/RUS [34] Thermo network 1.8 2005RUS/BOG [31] Thermo network 1.6 2005RUS/BOG [31] Thermo network 3.0 1997OSB/MOR [38] Photoionization 0.4 2011BUR/RUS [34] Thermo network 2.0 2012HAR/TUC [39] PEPICO, Thermo network 2.0 2012HAR/TUC [39] PEPICO, Thermo network 2.0 2012HAR/TUC [39] PEPICO, Thermo network 0.8 1998RUS/MIC [40] Thermo network 1.6 2010CSO/ROL [41] Quantum CC/cbs 3.6 2010CSO/ROL [41] Quantum CC/cbs 2.0 2005BUR/RUS [42] Thermo network 1.2 2010CSO/ROL [41] Quantum CC/cbs 0.8 2010CSO/ROL [41] Quantum CC/cbs 3.4 1998RUS/MIC [40] Thermo network 5 1975CHE/ROD [43] Review 1.7 1983KOL/PAP [44] Combustion calorimetry 5 1976WU/ROD [45] Equilibrium, CF3CF2I + HI = CF3CHF2 + I2 8 1996MIY/OZA [46] Kinetics CH3CH2F + Br 0.7 2011BUR/RUS [34] Thermo network 1.6 2011BUR/RUS [34] Thermo network 0.9 2011BUR/RUS [34] Thermo network 5.3 This work G3MP2B3. Rel ethane, CH3CF3, propene 8.9 This work G3MP2B3. Rel ethane, CH3CF3, propen-1-yl 9.7 This work G3MP2B3. Rel ethane, CH3CF3, propen-2-yl 5.7 This work G3MP2B3. Rel ethane, propyne, CH3CF3 2.1 2008FEL/PET [47] Quantum CC/cbs 2.1 1998DIX/FEL [48] Quantum CC/cbs 7 1996ASH/APP [49] Review 3 1998CUR/RAG [50] Quantum CBS-Q 2 2000VIS/BER [51] Quantum ab initio (various) 4.4 This work G3MP2B3. Rel ethane, CH3CF3, propanone Continued International Journal of Chemical Kinetics DOI 10.1002/kin.20923 550 BURGESS ET AL. Table AII Continued Formula Species fHo(298 K) Unc Reference Method C1Br1F3 C1H3Br1 C1H2Br1 C2H5Br1 C2H3Br1 C3H2Br1F3 C3H1Br1F3 C3H3Br1F3 Legend Method Ab initio CBS-Q CC/cbs G3MP2B3 Rel PEPICO Photodissocation Photoionization Equilibrium Heat hydrog Kinetics Review Thermo network CF3Br CH3Br CH2Br C2H5Br C2H3Br BTP (CF3CBr=CH2) CF3CBrCH CF3CHBrCH2 -649.8 -36.4 172.8 -62.9 74.1 -590.9 -331.3 -525.0 2.1 1998RUS/MIC [40] Thermo network 1.0 2001SON/QIA [52] PEPICO 2.6 2003SEE [53] Kinetics 2nd law BDE CH2Br+HBr = CH3Br+Br 1.5 2010BOR/SZT [54] PEPICO 3.1 2006LAG/BAR [55] PEPICO 2008LAG/BAE [56] 8.0 This work G3MP2B3, Rel ethane, br-ethene, tf-propene 10.2 This work G3MP2B3, Rel ethane, br-ethene, CF3CHCH 6.2 This work G3MP2B3, Rel 1-propyl, CH3CF3, br-ethane Description Composite value based on ab initio quantum chemical calculations CBS-Q quantum chemical model Coupled cluster calculations using complete basis sets G3MP2B3 quantum chemical model. Value derived relative to indicated reference species Photoelectron photoion coincidence spectroscopy. Use of photodissociation methods to determine thermochemistry Use of photoionization methods to determine thermochemistry Measurement of equilibrium constants via different methods to determine thermochemistry Determination of an enthalpy of formation from a heat of hydrogenation method Determination of an enthalpy of formation using a kinetic method to determine heats of reaction A recommendation based on review of available values in the literature Enthalpies of formation determined using heats of reactions for a series of coupled reactions Sheng et al. [192], and Krasnoperov et al. [193] also confirm the positive temperature dependence of the rate constants at high temperatures. The rate constants from our fitted rate expression with A = 2.10 107 cm3/mol/s, b = 1.57, and E = -6.0 kJ/mol agree with the low-temperature data to within 6% (roughly the experimental uncertainties). This recommended rate expression provides rate constants at 1000 and 1500 K that are roughly 1.5 and 2.2 times faster, respectively, than those from the rate expression given by Seetula [125], which reflects only the negative temperature dependence at low temperatures. C2H5 + HBr C2H6 + Br To provide a rate expression valid at flame temperatures, we fitted the low temperature (259-677 K) data of Seetula [128], Seakins et al. [71], and Nicovich et al. [197], while constraining the rate constants at 1000-1500 K to be consistent with the relative temperature dependence calculated in the computational work of Golden et al. [199]. Our fitted rate expression agrees with the low-temperature data to within 8% (roughly the experimental uncertainties). This recommended rate expression with A = 2.15 109 cm3/mol/s, b = 0.88, and E = -6.9 kJ/mol provides rate constants at 1000 and 1500 K that are roughly 1.2 and 1.5 times faster, respectively, than the rate expression given by Seetula [128] that reflects only the negative temperature dependence at low temperatures. We note that Leplat et al. [200] claim their recent measurements of C2H5 + HBr (HI) reactions show only a positive temperature dependence. This is at odds with other experimental determinations and quantum calculations that show weak adducts formation and tunneling responsible for the negative temperature dependence at low temperatures. Please note that the rate expression given by Sheng et al. [126] is invalid. It International Journal of Chemical Kinetics DOI 10.1002/kin.20923 CHEMICAL KINETIC MECHANISM FOR 2-BTP FLAME INHIBITION 551 Table AIII Formula Br1O1 C3H7 C3H7 C2H4O1 C2H1O1 C1H2F1 C1H1F2 Some Reevaluated Enthalpies of Formation for Species Contained in the 2-BTP Mechanism Species fHo(298 K) Unc Reference Method BrO 123.4 0.4 2006KIM/DOO [28] (Selected) photodissoc D0 = 233.9(0.4) kJ/mol 125.5 2.1 2004FLE/HAR [57] Photodissoc D0 = 231.8(2.1) kJ/mol 126.4 1.7 1999WIL/HAN [58] Photodissoc D0 = 231.0(1.71) kJ/mol 119.7 5.9 1997BED/LEB [59] Kinetic/equil third law IO + Br = BrO + I 125.9 2.5 1958DUR/RAM [60] Photodissoc D0 = 231.4(2.5) 128.0 2010GRA/GAR [61] Quantum MRCI/cbs 123.8 1.3 2008FEL/PET Quantum CCSD(T)/cbs 123.8 2.5 2006PET/SHE [62] Quantum, CCSD(T)/cbs nC3H7 101.3 100.8 103.3 101.9 100 100 100.5 105.0 103.6 1.0 2006BOD/KER [32] (Selected) PEPICO, thermo network 2.1 1997SEE/SLA [63] Kinetics, R+HBr = RH+Br 1971PAP/LAI [64,65] Kinetics nC3H7 = C2H4+CH3 1964BAC/TAK [66] Kinetics nC3H7 = C2H4+CH3 1966LIN/LAI [67] Kinetics nC3H7 = C2H4+CH3 1961KER/CLA [68] Kinetics nC3H7 = C2H4+CH3 2.1 1985TSA [69] Review 5.4 2002ESP/GAR [70] Quantum CCSD(T)/6-311+G(d,p)/iso This work Quantum, G3MP2B3 iC3H7 88.5 1.0 2006BOD/KER [32] (Selected) PEPICO, thermo network 86.6 2.0 1997SEE/SLA [63] Kinetics R + HBr = RH + Br 90.0 1.7 1992SEA/PIL [71] Kinetics R + HBr = RH + Br 87.9 2.1 1989TSC/CHE [72] Kinetics iC3H7 = C3H6 + H 92.5 1975BUL/MAR [73] Kinetics iC3H7 = C2H4 + CH3 92.3 1975CAM/MAR [74] Kinetics iC3H7 = C2H4 + CH3 94.8 1971PAP/LAI [64,65] Kinetics iC3H7 = C2H4 + CH3 94.6 1964BAC/TAK [66] Kinetics iC3H7 = C2H4 + CH3 93.2 1959KER/TRO [75] Kinetics iC3H7 = C3H6 + H 91.5 2.4 1996TRA/KOM [76] Review 88 2 1996TSA [77] Review 90.4 This work Quantum G3MP2B3 CH3CHO -165.4 -166.2 -166.1 -170.7 -164.7 165.7 -166.7 0.3 2011BUR/RUS [34] 0.7 2006DAS/BOZ [78] 0.5 1994PED [79] 1.5 1991WIB/CRO [80] 0.6 1938DOL/GRE [81] 0.8 2006DAS/BOZ [77] This work (Selected) thermo network Review Review Heat hydrogenation Heat hydrogenation Quantum ab initio (various) Quantum G3MP2B3 HCCO 176.6 175.5 177. 5 173 178.3 177.9 171.1 3.0 1997OSB/MOR [82] 3 1996MOR/OSB [83] 8.8 1983OAK/JON [84] 9.6 1994BER/ELL [33] 1.5 2005SZA/TAJ [85] 1.9 2001PAR/MAR [86] This work (Selected) photoionization Photofragment spectros Photoelectron spectros Review Quantum CC/cbs Quantum W1 Quantum G3MP2B3 CH2F -31.2 -30.1 -32.6 -32.2 -28.0 -32.6 1.6 2010CSO/ROL [41] 4.6 1983PIC/ROD [87] 8.4 1971KER/TIM [88] 2000HAW/SMI [89] 2003FEL/PET [90] This work (Selected) quantum CC/cbs Equilibrium CH3F + I2 = CH2FI + HI (recalc) Kinetic CH2FCH2F = CH2F + CH2F Quantum G3 Quantum CC/cbs Quantum G3MP2B3 CHF2 -243.0 -238.9 -237.2 -245.8 3.6 2010CSO/ROL [41] 4.2 1983PIC/ROD [87] 4.4 1983PIC/ROD [87] This work (Selected) quantum CC/cbs Equilibrium CH3F + I2 = CH2FI + HI D(CHF2-H) = 431.8, DfH(CH2F2) = -451.0 Quantum G3MP2B3 Continued International Journal of Chemical Kinetics DOI 10.1002/kin.20923 552 BURGESS ET AL. Table AIII Continued Formula Species fHo(298 K) Unc Reference Method C1F2 CF2 C1F1 CF C2H3F3 CH3CF3 C1F2O1 CF2O C1F1O1 CFO C2F4O1 C2F3O1 CF3COF CF3CO -193.2 -184.1 -205 -184.5 -194.1 -192 -184.1 -177 -179.9 -190 -193.4 -193.3 -194.1 -195 -183.2 -201.7 247.0 253.6 261.5 246.9 246.4 246.6 252.9 242.7 243.5 -745.6 -748.8 -746.0 -746.9 -607.1 -606.7 -605.4 -607.5 -609.2 -608.5 -184.1 -182.8 -179.9 -445.6 -605 -608.7 1.2 2010CSO/ROL [41] 8.4 1997POU/PAU [91] 12.6 1985LIA/KAR [92] 8.4 1978SCH/WAG [93] 10.1 1974OKA/WHI [94] 10 1971COX/SIM [95] 5.4 1971CAR [96] 5 1969EHL [97] 5 1966MOD/LAG [98] 5 1965MOD/LAG [99] 0.4 2011BUR/RUS [34] 2009BAK [100] 1.3 2008FEL/PET [47] 2000HAW/SMI [89] 2002LAZ/PAP [101] 1997POU/PAU [91] (Selected) quantum CC/cbs Appearance energies Proton affinity CHF2+ Equilibrium C2F4 Quantum CHF2Br Kinetics CHF2Br = CF2 + HBr Shock decomposition C2F4 Equilibrium C2F4 Shock decomposition C2F4 Shock decomposition C2F4 Thermochemical network Quantum ATOMIC Quantum CC/cbs Quantum G3 Quantum CC/cbs Quantum G2 iso 0.8 2010CSO/ROL [41] 14.2 1999JES/SQU [102] 4.6 1997ASH/RUS [103] 0.7 2011BUR/RUS [34] 0.8 2008FEL/PET [47] 0.6 2004TAJ/SZA [104] 2002LAZ/PAP [101] 1.3 2000HAW/SMI [89] 2.1 1998DIX/FEL [48] (Selected) quantum CC/cbs Appearance energies Appearance potentials Thermochemical network Quantum CC/cbs Quantum HEAT Quantum CC/cbs Quantum G3 Quantum CC/cbs 1.7 1983KOL/PAP [44] (Selected) combustion calorimetry 3.2 1974WU/ROD [105] Equilibrium CF3CH3 + I2 = CF3CH2I + HI 1.7 1967COO/WHI1 [106] Kinetics C2F6 = CF3+CF3 1994BER/ELL [33] Quantum CBS-Q BAC 2.1 2008FEL/PET [47] 2009BAK [100] 2008MAT/NGU [107] 3.3 1998DIX/FEL [48] 4.2 1994MON/MIC [108] This work (Selected) quantum CC/cbs Quantum ATOMIC Quantum CC/cbs Quantum CC/cbs Quantum CBS-Q/APNO Quantum G3MP2B3 2.1 1998DIX/FEL [48] 9.6 1996ASH/APP [49] This work (Selected) quantum CC/cbs Review Quantum G3MP2B3 3 1998CUR/RAG [50] 2 2000VIS/BER [51] This work Quantum CBS-Q (Selected) quantum Ab initio (various) Quantum G3MP2B3 does not reflect the rate constants provided in their paper. CF3CHCH2 + H C2H4 + CF3 The rate expression provided in Table IV is based on the recent shock tube measurements by Awan and Manion [158]. CF3CBrCH2 + H C2H3Br + CF3 The rate expression provided in Table IV is based on analogy to the rate expression for CF3CHCH2 + H C2H4 + CF3 measured by Awan and Manion [158] with the preexponential A reduced by a factor of 6 to account for the preferred Br elimination channel. International Journal of Chemical Kinetics DOI 10.1002/kin.20923 CHEMICAL KINETIC MECHANISM FOR 2-BTP FLAME INHIBITION 553 Table AIV Reactions Relevant to 2-BTP Inhibition (Used in Modeling Work) PRI Reactants Products A, b, E (mol, s-1, kJ) Reference 1 BR + BR + M = BR2 + M 1 BR2 + H = HBR + BR 1 HBR + H = BR + H2 1 HBR + F = BR + HF BR + H (+M) = HBR (+M) BR2 + H2 = HBR + HBR 1.48E14 2.28E11 1.3E10 2.7E13 1.9E21 6.52E14 HBr Chemistry 0 -7.11 1.0 1.8 1.05 0.7 0 0.7 -1.87 0 0 170 1981BAU/DUX [109] 1981BAU/D UX [109] 1991SEA/PIL [110] 2004KOR/PER [111] 1981BAU/DUX [109] 1958LEV [112] 2 HBR + O = BR + OH 1 HBR + OH = BR + H2O 1 BR + HO2 = HBR + O2 HBR + HO2 = BR + H2O2 7.73E05 4.0E12 2.05E11 4.0E12 8.6E09 4.2E02 HBr/Oxygen 2.26 6.4 0 6.8 0.58 -1.4 0 -1.3 1.0 2.0 2.93 32.1 This Work (a) 1983NAV/BOS [113] (b) This Work (a) 2007ATK/BAU [114] (b) 2012DIX/MAR [115] 2012DIX/MAR [115] BrO Chemistry 1 BRO + OH = BR + HO2 1.1E13 0 -2.1 2007ATK/BAU [114] 2 BRO + H = BR + OH 3.0E13 0 0 1996BAB/NOT [19] 2 BR2 + O = BRO + BR 1.06E13 0 -0.3 1990NIC/WIN [116] BR + O + M = BRO + M 3.0E13 0 0 1996BAB/NOT [19] BRO + H = HBR + O 1.0E12 0 0 1996BAB/NOT [19] BRO + O = BR + O2 1.15E13 0 -1.9 1996BAB/NOT [19] BRO + BRO = BR + BR + O2 1.6E12 0 0 2007ATK/BAU [114] BRO + BRO = BR2 + O2 1.5E10 0 -7.0 2007ATK/BAU [114] 1 CO + BRO = CO2 + BR 6.00E11 0 31.0 1996BAB/NOT [19] 2 CH4 + BRO = CH3 + BROH 7.83E03 2.71 46.0 2001LOU/ALL [117] 2 C2H4 + BRO = CH2BR + 5.00E12 0 12.6 1996BAB/NOT [19] CH2O 3 CH3 + BRO = CH2O + HBR 1.00E13 0 0 2002SZI/IMR [134] CH3BR + O = CH3 + BRO 1.00E13 0 56.5 1996BAB/NOT [19] BrOH Chemistry 1 BRO + HBR = BROH + BR 1.60E12 0 15.1 1999HAN/LI [118] 1 BROH + H = BRO + H2 2.00E07 1.91 33.5 2012DIX/MAR [115] 2 BROH + OH = BRO + H2O 1.90E02 3.12 -5.2 2004WAN/LI [119] 1 BR2 + OH = BROH + BR 1.1E15 -0.66 0 2006BRY/DEL [120] 1 BROH (+M) = Br + OH (+M) 1.00E15 0 203.9 2012DIX/MAR [115] BRO + HO2 = BROH + O2 3.70E12 0 -4.14 2001DEM/SAN [121] BROH + H = BR + H2O 3.00E13 0 0 2012DIX/MAR [115] BROH + H = HBR + OH 3.00E13 0 0 2012DIX/MAR [115] BROH + O = BRO + OH 7.20E13 0 3.6 2007ATK/BAU [114] BROH + HO2 = BRO + H2O2 1.00E00 3.55 54.8 2012DIX/MAR [115] 2 CH3BR + OH = CH3 + BROH 1.00E13 0 CH3BR + BRO = CH2BR + 3.00E11 0 BROH CH3O + BRO = CH2O + BROH 1.00E13 0 CH2O + BRO = HCO + BROH 1.4E13 0 HCO + BRO = CO + BROH 5.00E12 0 56.5 1996BAB/NOT [19] 44.8 1996BAB/NOT [19] 0 2002SZI/IMR [134] 27.3 2006TIA/WEI [122] 0 2002SZI/IMR [134] Br + O2 + M = BrOO + M BrOO + H = BrO + OH BrOO + O = BrO + O2 BrOO + OH = BrO + HO2 BrOO + Br = Br2 + O2 2.30E24 3.0E13 3.0E13 2.0E12 1.0E14 BrOO Chemistry -3.90 0.0 0 0.0 0 0.0 0 0.0 0 0.0 2007ATK/BAU [114] 1981BAU/DUX [109] 1971BAS/DOG [123] 2012DIX/MAR [115] 1978ASH/BAS [124] Method Review Review Review Quantum Review Flow tube Evaluated Flash photolysis Evaluated Review Review Quantum Review Estimated Flash photolysis Estimated Estimated Flash photolysis Review Review Est rel ClO Quantum Estimated Est rel CH3O Estimated Quantum Review Quantum Flash photolysis Review (c) Review Review Review Review Review Estimated Estimated Est rel Br Est rel ClO (d) Est rel CH3O Est rel Cl Est rel ClOO Est rel ClOO Review Est rel ClOO Continued International Journal of Chemical Kinetics DOI 10.1002/kin.20923 554 BURGESS ET AL. Table AIV Continued PRI Reactants Products A, b, E (mol, s-1, kJ) Reference 1 CH3 + HBR = CH4 + BR 1 C2H5 + HBR = C2H6 + BR 3 C2H3 + HBR = C2H4 + BR C2H5 + HBR = C2H6 + BR C3H8 + BR = nC3H7 + HBR C3H8 + BR = iC3H7 + HBR CH3 + BR = CH2 + HBR CH2 + BR = CH + HBR Hydrocarbons/Bromine 2.10E07 1.57 -6.0 This Work 1.39E12 0 -0.6 2002SEE [125] 2.15E09 0.88 -6.9 This work 4.4E08 1.49 -11.8 2004SHE/LI [126] 5.00E12 0 0 1989RUS/SEN [127] 1.13E12 0 -3.7 1998SEE [128] 7.00E13 0 46.0 1992SEA/PIL [71] 5.30E13 0 36.0 1992SEA/PIL [71] 1.10E14 0 96.4 1990GOL/TEM [129] 1.10E14 0 96.4 2005YU/KEN [130] Oxidized Hydrocarbons/Bromine 1 CH2O + BR = HCO + HBR 1.02E13 0 6.7 1989ATK/BAU1 [131] 1 HCO + BR = CO + HBR 1.70E14 0 0 1984POU/LAV [132] CH2OH + HBR = CH3OH + BR 1.20E12 0 -3.7 1998JOD/RAY [133] CH3O + BR = CH2O + HBR 3.00E13 0 0 2002SZI/IMR [134] CH3O + HBR = CH3OH + BR 4.85E05 1.9 10.8 1998JOD/RAY [133] C2H5OH + BR = CH3CHOH + 5.00E13 0 59 This work HBR CH3CHO + BR = CH3CO + HBR 7.8E12 0 3.0 1992ATK/BAU2 [135] 1 CF3 + HBR = CHF3 + BR CH3F + BR = CH2F + HBR CH2F2 + BR = CHF2 + HBR CHF2-CF3 + BR = CF3-CF2 + HBR 2.63E11 5.45E13 2.38E13 1.10E13 Fluoroalkanes 0 10.7 1983WEE/WHI [136] 0 67.4 1968AMP/WHI [137] 0 69.3 1968AMP/WHI [137] 0 80.7 1968AMP/WHI [137] Fluoropropene 1 CF3CHCH2 + H = CF3CCH2 + 4.0E14 0 50 1992TSA [138] H2 1 CF3CHCH2 + H = C2H4 + CF3 9.2E13 0 25.4 2015AWA/MAN [158] 5.0E13 0 20 1990MAN/LOU [139] 1 CF3CHCH2 + O = CH3CO + CF3 2.0E14 0 10 This work 1 CF3CHCH2 + OH = CH3CHO + 1.0E13 0 0 This work CF3 CF3CHCH2 + OH = CF3COCH3 1.0E12 0 20 This work +H CF3CHCH2 + CH3 = C3H6 + 5.0E12 0 50 This work CF3 3 BTP + H = CF3CHBRCH2 2.0E13 0 40 This work 3 CF3CHCH2 + BR = CF3CHBRCH2 8.00E12 0 11 This work Fluoropropenyl 2 CF3CCH2 = C2H2 + CF3 2.00E13 0 155 This work CF3CCH2 + O2 = CF3CCH + 2.00E13 0 100 This work HO2 CF3CCH2 + H = C2H3 + CF3 4.00E13 0 20 This work CF3CCH2 + H = CF3CCH + H2 2.00E13 0 0 1988HEI/HOF [140] CF3CCH2 + O = CH2CO + CF3 5.00E13 0 0 This work CF3CCH2 + O = CF3CCH + OH 5.00E13 0 10 This work CF3CCH2 + OH = CH2CO + CF3 5.00E13 0 40 This work +H Method Evaluated (a) Flow tube (b) Evaluated (a) Quantum (b) Flash photolysis (d) Flow tube Est rel iC3H7 Flash photolysis Flow tube Est rel CH3 Review Discharge flow Quantum Discharge flow Quantum Est rel C2H6 Review Flash photolysis Flash photolysis Flash photolysis Flash photolysis Est rel propene Shock tube (a) Est rel toluene (b) Estimated (E=10) Estimated (E=0) Estimated (E=20) Estimated (H+13) Quantum (G3MP2B3) Quantum (G3MP2B3) Estimated (H+24) Est Rel propenyl Estimated (E=20) Est rel ethenyl Estimated (E=0) Estimated (E=10) Estimated (E=40) Continued International Journal of Chemical Kinetics DOI 10.1002/kin.20923 CHEMICAL KINETIC MECHANISM FOR 2-BTP FLAME INHIBITION 555 Table AIV Continued PRI Reactants Products CF3CCH2 + OH = CF3CCH + H2O CF3CCH2 + CH3 = CH3CCH2 + CF3 CF3CCH2 + CH3 = CF3CCH + CH4 CF3CCH2 + C2H3 = CF3CCH + CF3 1 CF3CCH + H = CF3CCH2 A, b, E (mol, s-1, kJ) 5.00E13 0 20 4.00E13 0 20 1.00E13 0 0 4.00E13 0 20 Reference This work This work 200STO/KNY [141] This work 6.00E14 Fluoropropyne 0 20 This work 2 CF3CCH + H = C2H2 + CF3 2.00E14 0 40 This work 2 CF3CCH + F = CF3 + C2HF 5.00E13 0 46 This work 1 CF3CCH + OH = CH2CO + CF3 2.00E14 0 20 This work 1 CF3CCH + CH3 = pC3H4 + CF3 2.00E14 0 40 This work CF3CCH + O = HCCO + CF3 1.00E13 0 10 This work CF3CCH + F = C2HF + CF3 1.00E13 0 10 Estimated CF3CCH + OH = CH2CO + CF3 2.00E14 0 20 This work CF3CCH + C2H3 = CH2CHCCH 1.00E13 0 10 + CF3 Fluoropropanone (CF3COCH3) 1 CH3CO + CF3 = CF3COCH3 4.00E13 0 0 This work CF3COCH3 + H = CH2CO + H2 6.00E14 0 100 This work + CF3 CF3COCH3 + F = CH2CO + HF 1.00E13 0 42 This work + CF3 CF3COCH3 + OH = CH2CO + 5.00E13 0 15 This work H2O + CF3 CF3COCH3 + CF3 = CH2CO + 2.0E13 0 90 This work CHF3 + CF3 CH3CO + CF3 = CH2CO + CHF3 1.00E13 0 0 This work CH3CO + F = CH2CO + HF 1.00E13 0 0 This work CH3CO + CF3 = CO + CH3 + 2.0E13 0 40 This work CF3 CH3Br Chemistry 1 CH3BR = CH3 + BR 1.58E13 0 300 1988TAK/INO [142] 1 CH3BR + H = CH3 + HBR 5.11E13 0 24.4 1981BAU/DUX [109] 2 CH2BR + H2 = CH3BR + H 2.00E12 0 54.8 1996BAB/NOT [19] 3 CH3BR + O = CH2BR + OH 1.70E05 2.33 17.6 2002ZHA/WAN [143] 3 CH3BR + F = CH2BR + HF 6.00E13 0 3.5 2005WAN/LI [144] 1 CH3 + BR2 = CH3BR + BR 1.21E13 0 -1.6 1986TIM/RUS [145] 1 CH2BR + HBR = CH3BR + BR 3.50E12 0 7.3 2006ZHA/LIU [146] 2 CH3BR + OH = CH2BR + H2O 7.60E07 1.3 2.1 1991COH/WES [147] 3 CH3BR + CH3 = CH2BR + CH4 1.26E12 0 42.3 1972KON [148] CH2BR + HO2 = CH3BR + O2 2.00E12 0 0 1996BAB/NOT [19] CH3BR + HO2 = CH2BR + H2O2 1.00E13 0 69.9 1996BAB/NOT [19] CH2BR + CHF3 = CH3BR + CF3 5.00E11 0 50.2 1996BAB/NOT [19] C2H3BR + CH3 = CH3BR + 1.00E13 0 46.0 1996BAB/NOT [19] C2H3 CH2BR + C2H6 = CH3BR + 1.00E12 0 35.6 1996BAB/NOT [19] C2H5 CH2BR + CH2O = CH3BR + 3.60E11 0 25.9 1996BAB/NOT [19] HCO International Journal of Chemical Kinetics DOI 10.1002/kin.20923 Method Estimated (E=20) (d) Estimated (H+9) Est rel ethenyl Estimated (H+9) Quantum (G3MP2B3) Analogy (E=40) Estimated (E=46) Estimated (E=20) Estimated (E=40) Estimated (E=10) Estimated (E=10) Estimated (E=20) Estimated (E=10) Estimated (E=0) Estimated (H+7) Estimated (E=42) (d) Estimated (E=15) Estimated (H+3) Estimated (E=0) Estimated (E=0) Estimated (H+0) Shock tube Review Estimated Quantum Quantum Flash photolysis Quantum Review Review rel CH3 Analogy Estimated Estimated Estimated Estimated Continued 556 BURGESS ET AL. Table AIV Continued PRI Reactants Products A, b, E (mol, s-1, kJ) Reference CH2BR Chemistry 1 CH2 + HBR = CH2BR + H 1.00E13 0 CH2BR + O = CH2O + BR 7.00E12 0 CH2BR + OH = CH2O + HBR 2.00E10 0 CH2BR + HO2 = CH2O + OH + 1.00E13 0 46.0 1996BAB/NOT [19] 0 1996BAB/NOT [19] 41.8 1996BAB/NOT [19] 0 1996BAB/NOT [19] BR CH2BR + BR = CH2 + BR2 5.00E09 0 42.7 1972KON [148] Bromoethane (CH3CH2Br) 1 C2H5BR = C2H4 + HBR 2.34E13 0 224.0 1987JUN/KAN [149] 1 C2H5 + BR = C2H5BR 2.00E13 0 0 1996BAB/NOT [19] 1 CH2BR + CH3 = C2H5BR 3.10E11 0 -18.0 1996BAB/NOT [19] 2 CH2BR + CH3 = C2H4 + HBR 5.40E12 0 5.9 1996BAB/NOT [19] 3 CH2BR + CH3 = C2H5 + BR 1.00E13 0 29.3 1996BAB/NOT [19] C2H5 + BR = C2H4 + HBR 7.11E12 0 0 1997DOB/BEN [150] C2H5BR + H = C2H5 + BR 1.00E14 0 20.9 1996BAB/NOT [19] C2H5BR + O = C2H5 + BRO 2.00E13 0 59 This work C2H5 + BR2 = C2H5BR + BR 1.57E13 0 -3.4 1990TIM/SEE [151] C2H5BR + OH = C2H5 + BROH 2.00E13 0 63 This work C2H5BR + CH3 = CH3BR + 1.00E13 0 25.1 1996BAB/NOT [19] C2H5 Bromoethene (C2H3Br, CH2=CHBr) 1 C2H3BR + M = C2H2 + HBR + 8.0E18 0 250 2001LAW/HAY [152] M 1 C2H3 + BR = C2H3BR 3.00E13 0 0 1996BAB/NOT [19] 1 C2H3BR + OH = CH3CHO + BR 3.00E13 0 10 Hrxn = -159 kJ/mol C2H3BR + H = C2H3 + HBR 3.00E14 0 50 Estimated C2H3BR + O = CH3CO + BR 1.00E13 0 10 Est Hrxn = -217 kJ/mol C2H3 + BR2 = C2H3BR + BR 2.40E13 0 -2.4 1993TIM/SEE [153] C2H3BR + OH = C2H3 + BROH 3.00E12 0 109 Estimated C2H3BR + CH3 = CH3BR + 5.00E12 0 50 Hrxn = 43 C2H3 CF3BR chemistry (Halon 1301) 1 CF3BR = CF3 + BR 2.00E13 0 263 1986TSA [154] 8.89E14 0 286 (high pressure) 1 CF3BR + H = CF3 + HBR 2.00E07 2.01 14 1998TRU/THE [155] 2 CF3 + BR2 = CF3BR + BR 1.21E12 0 1 1988TIM [156] 2 CF3BR + CH3 = CH3BR + CF3 2.77E05 2.05 44 1998BER/MAR [157] 3 CF3BR + CF3 = CF3-CF3 + BR 2.00E12 0 34 Estimate CF3BR + O = CF3 + BRO 9.00E12 0 57 1994DEM/SAN [121] CF3BR + OH = CF3 + BROH 1.00E13 0 75 1996BAB/NOT [19] C2H5BR + CF3 = CF3BR + C2H5 1.00E12 0 33 Estimate C2H3BR + CF3 = CF3BR + C2H3 2.00E12 0 42 Estimate 2-Bromotrifluoropropene (2-BTP, CF3CBr=CH2) 2 BTP= CF3CCH2 + BR CF3CCH2 + BR = BTP 5.00E13 0 345 Hrxn = 338 kJ/mol 2.00E14 0 0 This work 3 CF3CCH + HBR = BTP 2.00E12 0 215 This work 1 BTP + H = CF3CBRCH + H2 8.00E14 0 60 Estimate Method Estimated Estimated Estimated Estimated Review (d) Static reactor Estimated Analogy Analogy Analogy Flow tube Estimated Analogy Flash photolysis Analogy Estimated Batch reactor Estimated Analogy Est rel C2H5Br (d) Estimated Flash photolysis Estimated Estimated Shock (d) Flash photolysis Flash photolysis Quantum Est rel CF3Br+CH3 Review Analogy Est rel CF3Br+CH3 Est rel CF3Br+CH3 Bond energy Quantum (G3MP2B3) (d) Quantum (G3MP2B3) Rel ethene, propene, Cl-ethene Continued International Journal of Chemical Kinetics DOI 10.1002/kin.20923 CHEMICAL KINETIC MECHANISM FOR 2-BTP FLAME INHIBITION 557 Table AIV Continued PRI Reactants Products 1 BTP + H = CF3CHCH2 + BR 2 BTP + H = CF3CCH2 + HBR A, b, E (mol, s-1, kJ) 2.40E14 0 37.5 5.00E12 0 20 3.0E14 0 60 Reference 2015AWA/MAN [158] Est rel clbenzene, trichloroethene (b) This work 2 BTP + H = C2H3BR + CF3 1.5E13 0 25 2015AWA/MAN [158] 5.0E13 0 20 Estimate 1 BTP + OH = CF3COCH3 + BR 1.0E13 0 10 Hrxn = -160 kJ/mol 2 BTP + OH = CF3CBRCH + H2O 5.0E13 0 25 Estimate 1 BTP + CF3 = CF3CBRCH + 2.0E13 0 45 Hrxn = 31 kJ/mol CHF3 1 BTP + CF3 = CF3CCH2 + CF3BR 1.0E13 0 40 Estimate BTP + F = CF3CBRCH + HF 5.0E13 0 30 Estimate BTP + O = CH2CO + CF3 + BR 1.0E12 0 20 Hrxn = -170 kJ/mol BTP + CH3 = CH3BR + 2.0E13 0 60 Hrxn = 46 kJ/mol CF3CCH2 BTP + CH3 = CH4 + CF3CBrCH 2.0E13 0 55 Hrxn = 40 kJ/mol BTP + C2H3 = CF3CBRCH + 2.0E13 0 15 Hrxn = 3 kJ/mol C2H4 BTP + C2H3 = C2H3Br + 2.0E13 0 39 Hrxn = 16 kJ/mol CF3CCH2 1 CF3CBrCH = CF3CCH + BR 5.0E13 0 30 Hrxn = 25 kJ/mol F + F + M = F2 + M F2 + H = F + HF H2 + F2 = HF + F + H OH + F2 = HF + F + O Fluorine Chemistry 1.0E14 0 0 1971LLO [159] 2.90E09 1.4 5.6 1983COH/WES [160] 3.44E12 0 82.8 1975BOK/CHA [161] 7.00E13 0 37.7 1964NOS/LOV [162] C3H8 + F = nC3H7 + HF C3H8 + F = iC3H7 + HF CH4 + F2 = CH3 + HF + F Hydrocarbon/Fluorine Chemistry 3.50E13 0 0 1960FET/KNO [163] 4.10E13 0 0 1960FET/KNO [163] 2.00E12 0 47.0 1981SEE/ROT [164] CF2 + F2 = CF3 + F CH3 + F2 = CH3F + F CF4 + CH3 = CH3F + CF3 CF3 + F2 = CF4 + F C3H8 + CF3 = nC3H7 + CHF3 C3H8 + CF3 = iC3H7 + CHF3 C3H8 + CF3CF2 = nC3H7 + CHF2CF3 C3H8 + CF3CF2 = iC3H7 + CHF2CF3 Fluoroalkane Chemistry 1.20E12 0 12.6 1982SEE/ROT [165] 4.00E12 0 4.6 1981SEE/ROT [164] 9.64E04 2.41 109.3 1998BER/MAR [157] 2.65E12 0 10.5 1986TEI/VED [166] 5.40E11 0 35.7 1973ARI/POT [167] 1.80E11 0 27.4 1973ARI/POT [167] 3.90E11 0 32.6 1972WHY/GRA [168] 3.30E11 0 25.5 1972WHY/GRA [168] CF3-CF3 + CF3 = CF3-CF2 + CF4 CF3-CF2 + F = CF3 + CF3 C2H4 + F2 = CH2F-CH2 + F CF3-CF2 = CF2 + CF3 CF2:CF2 + F = CF3-CF2 Fluoroethanes/Fluoroethyls Chemistry 3.00E12 0 47.3 This Work 3.16E13 0 0 1999HYN/MAC [169] 4.80E10 0 19.2 1967KAP/CHA [170] 4.27E15 0 235.3 1991AIN [171] 3.15E13 0 32.5 1999HYN/MAC2 [169] Method Shock tube (a) analogy Quantum (G3MP2B3) (d) Est rel CF3CHCH2 (a) rel propene, toluene, TFMeBz (b) Analogy Rel ethene, propene, Cl-ethene Est rel H,OH,CH3 Est rel CH3 Analogy (d) Analogy Est rel CF3Br Est rel ethane Est rel OH Est rel CF3Br Analogy Review Review Static reactor (NG) NG Static reactor Static reactor Flow reactor (NG) Estimated Flow reactor Quantum Review Flash photolysis Flash photolysis Flash photolysis Flash photolysis Analogy Shock tube Flame NG Estimated Shock tube (0.5) Continued International Journal of Chemical Kinetics DOI 10.1002/kin.20923 558 BURGESS ET AL. Table AIV Continued PRI Reactants Products A, b, E (mol, s-1, kJ) Reference Method CF3 (+M) = CF2 + F (+M) CF + CF = C2F2 CF + F2 = CF2 + F C + F2 = CF + F Fluoromethylene/Fluoromethylidyne Chemistry 1.00E15 0 344.6 2010COB/CRO [172] 5.00E13 0 0 1999HYN/MAC2 [169] 9.03E12 0 3.1 2009VET/DIL [173] 1.70E12 0 6.3 1967MAY/SCH [174] Shock tube Shock tube Flash photolysis (d) Estimated 1 CF2:O + H = CF:O + HF 1 CF + O2 = CF:O + O 1 CO + F + M = CF:O + M 2 CF2 + OH = CF:O + HF CF3O + CO = CO2 + CF3 CF:O + F2 = CF2:O + F CF:O + CF2 = CF3 + CO CO + F2 = CF:O + F Carbonyl Fluoride Chemistry 1.20E10 0.83 6.62E12 0 3.09E19 -1.4 1.00E13 0 3.13E10 0 1.00E12 0 5.40E11 0 4.70E11 0 93.3 1995BUR/ZAC [13] 7.1 2009VET/DIL [173] -2.0 1998SAS/ZHU [17] 0 1978BIO/LAZ [175] 0 1999HYN/MAC2 [169] 0 1970MOD [176] 0 2007VOL/KLO [177] 56.5 1961HER/ARV [178] Recommended Flash photolysis Recommended Recommended Shock tube Estimated Estimated A*3 Static reactor C2H5OH + F = CH3CH2O + HF C2H5OH + F = CH3CHOH + HF C2H5OH + F = C2H4OH + HF C2H5OH + CF3 = CH3CHOH + CHF3 3.80E13 1.50E13 2.30E13 4.00E11 Ethanol Chemistry 0 0 1989KHA/EDE [179] 0 0 1989KHA/EDE [179] 0 0 1989KHA/EDE [179] 0 40.6 1986ARI/ART [180] Discharge flow Discharge flow Discharge flow Est rel C2H6 Fluoroacetyl Chemistry 1 CF3COF (+M) = CF:O + CF3 4.30E16 0 376.6 1998HYN/MAC [181] (+M) 1 CF3COF + H = CF3CO + HF 2.00E13 0 12.6 1998HYN/MAC [181] 2 CF3COF + CF3 = CF3CO + CF4 2.00E12 0 37.7 This work CF3COF+CF3CF2 = 3.00E11 0 58.6 This work CF3CO+CF3CF3 1 CF3CO (+M) = CF3 + CO (+M) 2.65E14 0.0 50.2 2000TOM/CAR [182] CF3CO + F = CF3 + CF:O 3.00E12 0 0 1989EBR/HAC [183] CF3CO + F = CF4 + CO 5.00E12 0 0 This work Recommended Recommended Analogy Analogy Recommended Est rel toluene Estimated Legend Method Column: (a) Recommended value (see the Discussion below). (b) Value used in modeling work. (c) pressure dependent (d) consider reevaluation Hrxn: Heat of Reaction Est rel: Estimated relative to reactions involving following species First Column: (1) indicates primary reaction pathway (most important). (2) indicates secondary reaction pathway (contributes small amount). (3) indicates minor reaction pathway (>1% of relative flux, very small but not negligible). (unlabeled) does not contribute under conditions studied (but may contribute under other conditions). Note. The ranking is qualitative, subjective, and relative. A "primary reaction pathway" means a reaction that has a high reaction flux for creating or destroying one or more species. This is not an absolute measure. For example, in the table CH3Br has three reactions that are labeled as "primary." 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