Automatic Generation of Detailed Kinetic Models for Complex Chemical Systems

A Dissertation Presented

Fariba Seyedzadeh Khanshan

The Department of Chemical Engineering

In partial fulﬁllment of the requirements For the degree of

Doctor of Philosophy

In the ﬁeld of

Chemical Engineering

Northeastern University Boston, Massachusetts

January 29 2016 Acknowledgements

I would like to thank to my PhD advisor, Professor Richard H. West, for supporting me during this journey. He’s the nicest advisor and one of the smartest people I know. He has been supportive and I’m very grateful for his advice, guidance, patience, and friendship over the past four years. He has provided insightful discussions about my research and I am thankful for having his scientiﬁc suggestions. My sincere thanks and appreciation also go to my PhD committee members, Profes- sor Sunho Choi from the Department of Chemical Engineering, and Professors Hamed Metghalchi and Yiannis Levendis from the Department of Mechanical and Industrial En- gineering for their helpful inputs and insightful comments. I would also like to thank Dr. Robert Low, Dr. Clive Giddis, and Dr. Andrew Sharratt, from Mexichem Fluor Ltd, for providing scientiﬁc suggestions and discussions during my chlorination modeling research. IwouldliketoshowmyappreciationtoallthepresentmembersoftheCoMoChEng group. I am grateful to Pierre Bhoorasingh and Belinda Slakman who have been my good friends during these four years. I know I will miss your company. IwouldliketoacknowledgealloftheRMGdevelopersandGreengroupmembersatMIT. I’m glad I had this opportunity to work with them. Their comments and discussions always have been a great help to me in RMG development. Iamdeeplythankfultomyparents,brother,andsisterfortheirunconditionallove,care, and encouragement. I love them so much, and I would not have made it this far without them. My father, to whom this dissertation is dedicated to, has been my best friend all my life and I love him dearly and thank him for all his advice and support. I would also like to thank the Department of Chemical Engineering of Northeastern Uni- versity for funding and supporting my research.

i I dedicate this thesis to the memory of my beloved father Yaghoub Seyedzadeh Khanshan I miss you every day and thank you for everything I love you dearly forever

ii Abstract

Detailed chemical kinetic mechanisms represent molecular interactions that occur when chemical bonds are broken and reformed into new chemical compounds. Many natural and industrial processes such as combustion of hydrocarbons, biomass conversion into renewable fuels, and synthesis of halogenated-hydrocarbon through halogenation reactions, include reaction network with hundred of species and thousands of reactions. Recently, the potential of such processes is leading to rapid industrial expansion and facing some technical drawbacks. Among various tools, detailed kinetic modeling is a reliable way to improve the scientific understanding of such systems and therefore optimize process conditions for desired production plans. Detailed chemical kinetic modeling is sensitive to the system chemistry, and sometimes too complex to model by hand. For example, utilizing predictive theoretical models by hand for biomass thermal conversion, which include a wide variety of heavy cyclic oxygenated molecules, alcohols, aldehydes, ketones, ethers, esters, etc., is tedious. It is preferable to teach our chemistry knowledge to computers, and generate detailed chemical models automatically. To generate comprehensive detailed models, an extensive set of reaction classes, which would define how species can react with each other, should be implemented in mechanism generators. In this thesis, Reaction Mechanism Genera- tor (RMG), an open-source software, has been used to build detailed kinetic models for complex chemical systems. This thesis presents several significant contributions in the area of predictive automatic kinetic mechanism generation for biofuels thermal conversion and reactions of many chlorinated hydrocarbons. The first section of this thesis describes significant contributions in detailed kinetic modeling of bio-oil gasification for syngas production using RMG. The major challenge in modeling bio-oil gasification is the presence of a wide range of cyclic

iii oxygenated species and several progress has been made in RMG to improve the automated chemical modeling of this process. RMG-built models were evaluated by comparison to available published data and to improve the understanding of such detailed models, different types of analysis such as sensitivity analysis were performed. The second section of this thesis presents a theoretical study of the gas-phase unimolecular thermal decomposition of heterocyclic compounds via single step exo and endo ring opening reaction classes. Quantum chemical calculations were performed for a smaller set of reactants belonging to the endo and exo reaction classes and data were used to inspect the ’rate calculation rules’ method. To study the e↵ect of the direct ring opening reactions in the automated detailed kinetic model generation, the bio-oil gasification mechanism, from Chapter 1, was updated after updating RMGs kinetic database with these new single step ring opening reaction classes and associated rate rules. The third section of this thesis provides significant contributions toward facilitating the automatic generation of predictive detailed kinetic models for 1,1,2,3- tetrachloropropene (1230xa) production and other hydrocarbon chlorination processes. In order to enable RMG to model chlorinated hydrocarbon conversions, the chlorine (Cl) chemistry has been added into the the Python version of the software. A model has been generated in RMG for 1230xa production with known associated thermodynamic and kinetic parameters. For model evaluation, reaction flux analysis and sensitivity analysis were performed to reveal the important reaction channels in the RMG-built model and several improvements to thermodynamic estimates were discussed. The ability to automatically generate these models for such complex chemical systems demonstrates the predictive capability of detailed chemical modeling. The impact of such models significantly improves the scientific understanding of two industrial chemical processes, bio-oil gasification and chlorination.

iv Contents

1 Developing Detailed Kinetic Models of Syngas Production From Bio-Oil Gasification Using Reaction Mechanism Generator (RMG) 1 1.1 Introduction ...... 1 1.2 Critical Literature Review ...... 3 1.2.1 Bio-oil gasification experiments ...... 3 1.2.1.1 Low temperature bio-oil gasification ...... 4 1.2.1.2 Hightemperaturebio-oilgasification ...... 5 1.2.2 Chemical modeling of bio-oil gasification ...... 7 1.2.2.1 Cellulose kinetic modeling ...... 8 1.2.2.2 Lignin kinetic modeling ...... 9 1.2.2.3 HemicelluloseKineticmodeling ...... 11 1.3 Computational Method ...... 12 1.3.1 ReactionMechanismGenerator ...... 13 1.3.1.1 Molecular Representations ...... 14 1.3.1.2 DataHierarchyinRMG ...... 14 1.3.1.2.1 Thermodynamic Database ...... 15 1.3.1.2.2 Thermochemistry Estimation ...... 16 1.3.1.2.3 Kinetic Database ...... 19 1.3.1.3 Rate-Based Model Enlarger ...... 22 1.3.1.4 Pressure Dependence in RMG ...... 23 1.3.1.5 Output from RMG ...... 24 1.3.2 Cantera ...... 25 1.3.3 Model Verification and Validation ...... 26 1.3.4 Bio-oil gasification modeling ...... 27 1.3.4.1 Bio-oilComposition ...... 27 1.3.4.2 Simulating syngas production ...... 29 1.3.5 Optimization ...... 30 1.4 ResultsandDiscussions ...... 30 1.4.1 Influenceofmodelsize ...... 30 1.4.2 Influence of pressure and pressure-dependent kinetics ...... 32 1.4.3 Comparison with experiments ...... 34 1.4.4 SensitivityAnalysis...... 36 1.4.5 Poor Thermochemistry For Cyclic Molecules ...... 38

v 1.4.6 Missing Pathways in RMG Generated Mechanisms ...... 40 1.5 Summary ...... 42 1.6 Recommendations for future work ...... 45 1.6.1 ImproveRMGthermochemistryestimation ...... 45 1.6.2 Add more reaction families to the RMG database ...... 46 1.6.3 ImprovememorymanagementinRMG ...... 46 1.7 Supporting material ...... 46

2 Rate calculation Rules for Automated Generation of Detailed Kinetic Models for Heterocyclic Compounds 47 2.1 Introduction ...... 47 2.2 Critical literature review ...... 49 2.2.1 Specific reaction classes for acyclic components of biofuels . . . . . 49 2.2.1.1 Unimolecularinitiations ...... 50 2.2.1.2 Bimolecular initiations and H-abstractions ...... 51 2.2.1.3 Radicals decomposition by -scission ...... 52 2.2.1.4 Intramolecular isomerizations ...... 53 2.2.2 Specific reaction classes for cyclic components of biofuels ...... 54 2.2.2.1 Unimolecularinitiations ...... 55 2.2.2.2 Endocyclic and exocyclic ring-opening in cyclic radicals . . 56 2.2.3 Reaction rate calculation for biofuel compounds ...... 57 2.2.3.1 Quantum chemistry ...... 57 2.2.3.2 Statistical mechanics ...... 58 2.2.3.3 Transition State Theory ...... 59 2.2.4 Reaction rate estimation methods ...... 61 2.2.4.1 Linear Free Energy Relationship (LFER) ...... 61 2.2.4.2 Evans-Polanyi correlation ...... 62 2.2.4.3 Reaction Class Transition State Theory (RC-TST) . . . . 62 2.2.4.4 Rate calculation rules ...... 63 2.3 Computational Method ...... 64 2.4 ResultsandDiscussions ...... 67 2.4.1 Case study: E↵ect of new reaction families on Bio-oil gasification . 78 2.5 Summary ...... 80 2.6 Supporting material ...... 81 2.7 Recommendations for future work ...... 82 2.7.1 Expand the e↵ect of the functional groups ...... 82 2.7.2 Add more reaction families with associated data to the RMG database 82

3 Automatic Reaction Mechanism Generation for Producing 1,1,2,3- tetrachloropropane 84 3.1 Introduction ...... 84 3.2 Critical Literature Review ...... 85 3.2.1 Proposed pathways from published patents ...... 86 3.2.2 Thermodynamics of chlorinated hydrocarbons ...... 91

vi 3.2.3 Kineticsofchlorinatedhydrocarbons ...... 93 3.2.3.1 Initiation steps ...... 94 3.2.3.2 Propagation steps ...... 94 3.2.3.3 Termination steps ...... 99 3.3 Computational Method ...... 99 3.3.1 Chlorine (Cl) atom type in RMG ...... 101 3.3.2 Thermodynamics of chlorinated hydrocarbons in RMG ...... 101 3.3.2.1 Species thermochemistry libraries ...... 101 3.3.2.2 Group-based methods ...... 102 3.3.2.3 Quantum chemistry calculation ...... 104 3.3.3 Chlorination reaction families in RMG ...... 105 3.3.4 Kinetics estimation for chlorinated hydrocarbons in RMG . . . . . 106 3.3.4.1 Training Set ...... 106 3.3.4.2 Quantum chemistry ...... 108 3.3.4.3 Rate rules ...... 108 3.3.5 Model evaluation ...... 109 3.4 ResultsandDiscussions ...... 109 3.4.1 Thermodynamics evaluation ...... 111 3.4.2 Reaction ﬂux analysis ...... 114 3.4.3 Sensitivity analysis ...... 116 3.5 Summary ...... 118 3.6 Supporting material ...... 119 3.7 Recommendations for future work ...... 120 3.7.1 Improveaccuracyofkineticsestimates ...... 120 3.7.2 Liquid-phase chlorination modeling ...... 120 3.7.3 Investigating the concerted E2 elimination reaction vs. Sn2 substitution ...... 121 3.7.4 Expand 1230xa modeling to ﬂuorination reactions ...... 122

4 References 123

Appendices 134

A The largest mechanism for bio-oil gasiﬁcation generated in RMG-Java 135

B Transition State Geometries of Heterocyclic Compounds Reactions 136

C RMG-Py generated mechanism for 1230xa 149

vii List of Figures

1.1 Syngas production from bio-oil gasification at di↵erent temperatures, reproduced from Zhang et al. [1]...... 5 1.2 E↵ect of temperature on composition of gas products in bio-oil gasification experiment, reproduced from Chhiti [2]...... 6 1.3 Three proposed main pathways for LG thermal decomposition, reproduced from Zhang et al. [3]...... 9 1.4 Model for the lignin -O-4 linkage [4] ...... 9 1.5 Proposed reaction pathways for initial decomposition of PPE from di↵erent studies [4–7] ...... 10 1.6 Proposed thermal decomposition pathways for xylopyranose [8]...... 12 1.7 Molecules are represented as 2-dimensional graphs in RMG ...... 14 1.8 Groups tree structure for H-abstraction family, reproduced from RMG documentation [10]. Indented text and schematics show the used syntax in RMG to represent the parent and children nodes...... 15 1.9 Group additivity approach to estimate isobutylbenzene standard enthalpy of formation and comparison with the NIST reported value...... 17 1.10 On-the-fly Quantum-chemical (QMTP) calculation steps (reproduced from RMG documentation [10]) toward thermochemical properties calculations in RMG. .. 18 1.11 General template and reaction recipe for H-abstraction reaction family in RMG. 20 1.12 Reactants kinetic trees (reproduced from RMG documentation [10]) for H- abstraction reaction and reaction matched template...... 21 1.13 Falling up to the more general parent nodes from the exact match nodes to find data, reproduced from RMG documentation [10]...... 21 1.14 RMG explores paths with high reaction rates and will move them into the model ’core’...... 23 1.15 The Chemkin file showing the list of species, thermochemistry, and reaction information as RMG’s output...... 25 1.16 Steps toward building reliable detailed kinetic models using RMG...... 27 1.17 Work-flow of the reaction mechanism modeling for bio-oil gasification using RMG and Cantera...... 29 1.18 Syngas production varying with incomplete model size from a CSTR with residence time 5 sec...... 31

viii 1.19 Mole fraction of four major gases at exit of a CSTR with residence time 5 seconds at a range of temperatures and pressures, according to kinetic models built by RMG- Java. (a) without pressure-dependence calculations (b) with pressure- dependent reaction networks calculated by modiﬁed strong collision approximation. 33 1.20 Distribution between four major gas components as a function of temperature, (a) from experimental work by Zhang et al.[1] at 100 C intervals from 600 to 1000 C, (b) from Chhili et al.[2] at 100 C intervals from 1000 to 1400 C, (c) from Cantera simulations (this work) at 100 C intervals from 600 to 1400 C ..... 34 1.21 Distribution between four major gas components as a function of temperature from high acid model...... 36

1.22 Sensitivity analysis for (a) CO2 at T=700C, (b) CO2 at T=1400C,, (c) CO at T=700C,, (d) CO at T=140C,. See text for model details...... 37

2.1 Calculated bond dissociation energies (in kcal/mol) in ester, ether, and alcohol molecules by Tran et al. [9]...... 50 2.2 Rate of the initiation and radical recombination reaction of butanol in RMG [10]. 51 2.3 General reaction template of H-abstraction reaction family...... 51 2.4 The general template of the -scission reaction and formation of free radical upon this reaction class...... 53 2.5 The general template of intramolecular H and OH migration reaction families and formation of free radical upon these reaction classes...... 54 2.6 Proposed detailed mechanism of (a) ethylene,(b) 1-pentene, and (c) 1-hexene formation by Sirlean et al. [11] from the primary decomposition of the cyclobutane, cyclopentane, and cyclohexane and by considering di↵erent conformers of C4, C5, and C6 biradicals, respectively...... 55 2.7 Exo and endo ring-opening reactions for Cyclobutylcarbinyl radical and Cy- clobutyl radical...... 56 2.8 The general template of the exocyclic tautomerization ring-opening reaction family. The example is shown for the primary ring-opening reaction of xylose, a type of sugar from wood...... 64 2.9 The general template of the endocyclic tautomerization ring-opening reaction family. The example is shown for the endocyclic ring-opening reaction of levoglucosan, a derivative of cellulose pyrolysis...... 65 2.10 Hierarchical tree for (a) exocyclic and (b) endocyclic ring-opening reaction families. 66 2.11 High pressure limit rate coecients within the temperature range of 300-2000 K for exocyclic ring opening test set reactions to investigate the rate calculation rules. (a) results for the ﬁve, six, and seven membered carbon rings (b) results for the ﬁve, six, and seven membered oxygen rings...... 69 2.13 Rate coecient of the four, six, and seven membered rings across the C, N, and O heteroatoms in exocyclic test set reaction at T= 1100 K...... 71 2.14 Potential energy diagram for bicyclo-octane isomerization to 3-ethylcyclohexene calculated at the CBS-QB3 level through single step-endo ring-opening vs. two- steps pathway with a diradical intermediate...... 73

ix 2.15 High pressure limit rate coecients within the temperature range of 300-2000 K for endocyclic ring opening test set reactions to investigate the rate calculation rules. (a) results for the ﬁve, six, and seven membered carbon rings (b) results for the ﬁve, six, and seven membered oxygen rings...... 75 2.18 Rate coecient of the four, six, and seven membered rings across the C, N, and O heteroatoms in endocyclic test set reaction at T= 1100 K...... 77 2.19 Distribution between four major gas components as a function of temperature, (a) from experimental work by Zhang et al.[1] at 100C intervals from 600 to 1000 C, (b) from Chhili et al.[2] at 100C intervals from 1000 to 1400 C, (c) RMG-built model at 100C intervals from 600 to 1400 C before updating RMG’s kinetic database (d) after updating RMG’s kinetic database with new reaction families...... 80 2.20 The general template of ene reaction with an example...... 83

3.1 Reaction and products from 1,2,3-trichloropropane liquid phase chlorination in the presence of azobisisobutyronitrile catalyst proposed by Smith [12]...... 87 3.2 1230xa formation reaction channels via 1,1,1,2,3- and 1,1,2,2,3- pentachloropropanes dehydrochlorination and 2,3,3,3-tetrachloropropane isomerization to 1230xa proposed by Smith [12]...... 88 3.3 1230xa formation reaction channels by reacting ethylene with carbon tetrachloride from the work of Woodard [13, 14]...... 89 3.4 1230xa formation reaction channels from 1,2,3 trichloropropane proposed by Mukhopadhyay et al. [15] and Wilson et al. [16]...... 90 3.5 Non-catalytic gas phase reaction channels proposed by Nose et al. [17] for 1230xa formation...... 91 3.6 The correction in the enthalpies of formation for accounting the e↵ect of interaction as function of number of chlorine atoms for multichloro alkanes and alkenes, reproduced from [18]...... 93 3.7 Initiation, propagation and termination free radical reaction steps in methyl chloride production via methane chlorination...... 94 3.8 The general template of the H-abstraction reaction via chlorine atom...... 95 3.9 Evans-Polanyi plot for H-abstractions from C1 and C2 chlorinated hydrocarbons by Senkan et al. [19]...... 96 3.10 Comparison of SAR predictions with experimental data fro H-abstraction of chlorinated hydrocarbons by chlorine radical by Senkan et al. [19]...... 97 3.11 The general template of the Cl-abstraction reaction family...... 97 3.12 Obtained correlation by Bryukov et al. [20] between activation energies and enthalpies of reactions for (Cl,H)-abstraction from chlorinated methanes by H atom attacks. ... 98 3.13 Predicted Evans-Polanyi plot by Louis et al. [21] for (H,Cl,F)-abstraction reactions via H radical attacks for chlorinated methanes...... 99 3.14 Radical recombination reaction family general reaction template ...... 99 3.15 Main proposed reaction channels to produce 1,1,2,3-tetrachloropropene (1230xa) [12, 14–17] ...... 100

x 3.16 RMG’s thermochemistry database was updated with new chlorinated functional groups. As an example, comparison between the chloroethene thermochemistry estimation via GA approach and NIST reported value shows a good agreement. 103 3.17 Hydrogen Bond Increment (HBI) calculations for chlorinated species...... 104 3.18 More HBI calculation to consider the e↵ect of the chlorine atom on its adjacent C-H bond...... 104 3.19 The general template of the (a) H-abstraction reaction, (b) radical recombination reaction family...... 105 3.20 The general template of the (a) Cl-abstraction reaction, (b) Cl2/HCl addition into the double bond reaction family...... 106 3.21 Batch reactor simulation of 1230xa (product) and 240db (feedstock) concentration profiles from RMG-built model...... 110 3.22 Batch reactor simulation of 1230xa (product) and 240db (feedstock) concentration profiles from RMG-built model after including HBI corrections for thermochemistry estimation of chlorinated radical species...... 114 3.23 Reaction flux analysis result to reveal the important reaction channels in the RMG-built model for 1230xa production...... 115 3.24 The published patent confirms the reaction flux analysis fom RMG-built model for 1230xa production...... 116 3.25 Sensitive reaction channels for 1230xa production in RMG-built model at (a) T=550 C and (b) T=350 C...... 117 3.26 Reaction phath for concerted E2 elimination vs. Sn2 substitution...... 121 3.27 One step closer to understanding the production of fluorocarbons refrigerants from chlorinated feedstocks...... 122

xi List of Tables

I Elemental composition and physicochemical properties of Chhiti’s bio-oil (wt.%) [2]...... 5 II Supported quantum chemistry packages and levels of theory in the QMTP, reproduced from RMG documentation [10]...... 18 III Composition of surrogate bio-oil used in modeling...... 28 IV Elemental composition of bio-oil from experiment II (ref [2]) and RMG model . 29 V RMG-built model sizes in core and edge ...... 31 VI Comparison of RMG estimated thermochemistry from both Group Additivity (GA) approach and Quantum Mechanics (QM) calculations of some species to Ranzi’s biomass model [22] and other published literature where available. ... 39 VII Some missed reactions in RMG for bio-oil primary thermal decomposition. ... 41

I Example of -scission reaction’s barrier heights for oxygenated compounds. ... 53 II Arrhenius rate constant parameters for exocyclic ring-opening reactions from CBS-QB3 calculations...... 68 III Arrhenius rate constant parameters for endocyclic ring-opening reactions from CBS-QB3 calculations...... 74

I The results obtained from the reactor outlet for 1230xa production in non catalytic gas-phase reaction according to the Nose et al. [17] method...... 91 II Used activation energy (cal/mol) and pre-exponential factor (l/mol.sec) as a training set reactions in RMG from the work of Goldﬁnger et al. [23] for the H-abstraction reaction by chlorine atom for chlorinated C1 and C2 hydrocarbons.107 III 240db conversion (%) for 1230xa production from Nose et al. [17] patent and RMG-built model...... 111 IV RMG estimated thermodynamics for some chlorinated stable species...... 111 V RMG estimated thermodynamics for some chlorinated radical species...... 112 VI Group Additivity estimates improved when using HBI corrections for chlorinated radical compounds thermochemistry...... 113 VII 240db conversion (%) for 1230xa production from Nose et al. [17] patent and RMG-built models before and after adding HBI corrections...... 114

xii Chapter 1

Developing Detailed Kinetic Models of Syngas Production From Bio-Oil Gasiﬁcation Using Reaction Mechanism Generator (RMG)

1.1 Introduction

Bio-oil composition is mostly carbon, oxygen, and hydrogen. Gasiﬁcation of bio-oil is a desirable process to produce syngas as a renewable resource with no net greenhouse gas emissions. Production of syngas from bio-oil is usually a high pressure and high temperature process. Optimizing the process conditions (temperature, pressure, residence time, etc.) requires an improved understanding of the chemical kinetics of the thermal cracking reactions involved in bio- oil gasiﬁcation. However, thermal conversion of bio- oil is very sensitive to the fuel chemistry, and sometimes too complex to model by hand, especially for heavy cyclic oxygenated molecules. It is preferable to teach fuel chemistry to computers, and generate detailed chemical models automatically. In this study, Reaction

1 Mechanism Generator (RMG), an open-source software, has been used to build detailed kinetic models for bio-oil gasification. The influence of the operational conditions and RMG parameters on the model generation has been investigated. Also, as the size of the model is important, the performance of RMG-generated models with di↵erent sizes were compared. To provide more realistic simulations of bio-oil gasification, RMG-built kinetic models have been simulated with Cantera in zero-dimensional batch reactor assuming constant volume and adiabatic condition, and simulation results are compared with literature. There are some agreements and disagreements between RMG-built models and literature, showing the importance of the detailed chemical modeling for such systems, also revealing the importance of the kinetics and thermodynamics accuracy in detailed chemical model generation. Further, to generate a comprehensive mechanism, it is important to have all reaction classes for bio-oil thermal decomposition, and the major challenge is the presence of wide range of cyclic oxygenated species in the model. In particular, more attention should be paid in looking at specific reaction classes for decomposition of levogucosan, xylopyronase, and lignin that are crucial steps during bio-oil gasification. Three reactions classes for bio-oil gasification that have been missing in RMG’s kinetic database, were investigated. In this thesis chapter, the challenges involved in using RMG to build a comprehensive model for bio-oil gasification, and how they may be overcome are introduced. Fur- thermore, several ideas for next work in order to improve RMG for bio-oil gasification modeling are explained. These ideas include some thoughts on updating RMG’s current reaction families and reaction rates, as well as improving thermochemistry estimations particularity for cyclic molecules.

2 1.2 Critical Literature Review

Global warming due to greenhouse gas emissions, increasing energy demands, and decreasing fossil fuel resources have increased interest in renewable fuels. Bio-oil, a carbon neutral and renewable fuel, results from the fast pyrolysis of biomass in the absence of oxygen. Biomass can be found as forest residue, animal waste, wood chips, and municipal solid waste [24]. The major products of biomass fast pyrolysis under high temperature and pressure are liquid bio-oil, hydrogen, carbon monoxide, carbon dioxide, light hydrocarbons, and solid bio-char [25, 26]. The major components of bio-oil are organic acids, ketones, furans, levoglucosan, phenolic, and cyclic oxygenate molecules [27–29]. Bio-oil contains di↵erent amounts of these components depending on the initial source of the biomass [30, 31]. Bio-oil can be either used directly as a fuel supply or further converted to syngas. The expense of transporting biomass, a low density, bulky, polluting material, and problems with direct conversion of biomass to syngas, makes processing of biomass to bio-oil, followed by bio-oil high temperature gasiﬁcation, a suitable alternative [32]. A literature review that discusses published information regarding bio-oil gasiﬁcation experimentally and theoretically, is presented in the current section.

1.2.1 Bio-oil gasiﬁcation experiments

There is no complete detailed chemical model for bio-oil gasification to date but there are several experimental studies in the bio-oil gasification field. Lotfi et al.[32] investigated syngas production from bio-oil gasification through thermal and catalytic reactions in a pilot plant bubbling fluidized bed at moderate temperature and atmospheric pressure. Catalytic gasification of bio-oils in their micro reactor revealed that a syngas with desired yield can be produced from bio-oil gasification with a suitable catalyst and optimal operating conditions. Van Rossum et al.[33] also studied the bio-oil gasification in a fluidized

3 bed reactor over a wide temperature range (523–914 C) with and without the use of nickel-based catalysts. For both cases, initial activity of syngas (H2 and CO) production had been shown at T > 700C. Further, Adjaye et al.[34] worked on kinetic modeling of non- catalytic conversion of bio-oil in a ﬁxed-bed reactor. They calculated yields of products as a function of temperature based on their proposed lumped kinetic model from previous biomass studies and they did not provide a complete kinetic model for the process. Two non-catalytic experiments, one at lower temperature and one at higher temperature range, were chosen to evaluate RMG-built model for bio-oil gasiﬁcation, which will be explained in further detail in the following section.

1.2.1.1 Low temperature bio-oil gasiﬁcation

Zhang et al. [1] investigated the influence of the temperature and N2 flow rate on syngas production in a fixed bed reactor at atmospheric pressure and temperature from 600Cto

1000C. Thermochemical conversion of bio-oil leads to partially decomposition to other forms of oxygenated molecules (CmHnOk)andsomepermanentgasesandcoke.The overall bio-oil decomposition can be expressed as: C H O C H O +gases(H , H O, CO , CO, CH ,...)+coke n m k ! x y z 2 2 2 4 They analyzed the gas products using a micro gas chromatograph and because of the high content of the element oxygen in bio-oil, the gasiﬁcation was carried out in the absence of oxygen. They observed that by increasing temperature the content of CO decreased until

850C but then increased with increasing temperature. CO2 increased with temperature which they say is mainly because bio-oil contained a large amount of carboxylic acid and carboxylic decomposition is the main source of CO2, although they didn’t mention their primary bio-oil composition or the carboxylic content of the sample. Figure 1.1 shows the four major syngas production at di↵erent temperatures.

PEER-REVIEWED ARTICLE bioresources.com

Effect of Temperature in Fixed Bed The properties of gaseous products from bio-oil gasification at 600, 700, 800, 900 and 1000°C are shown in Fig. 6. The syngas mainly contained CO, H2, CO2, CH4, and the C2 fractions in gas phase were a very minor proportion. It can be seen that the content of syngas changed with increasing temperature. With increasing pyrolysis temperature from 800 to 900°C, the content of hydrogen reached a maximum at about 25% (In syngas). But the H2 content decreased as the temperature increased to 1000°C. This result was expected, since it could be seen that bio-oil at high temperature would lead to complete decomposition. Hydrogen reacted with oxygen-containing groups, leading to the formation of water. With increasing temperature, the content of CO decreased, it reached a minimum at 850°C, and then it increased with further increase in temperature. The carbon dioxide increased with increasing temperature. This was mainly because the bio-oil contained a lot of organic carboxylic acids, in which carboxyl decomposition was a main source of CO2. The content of CH4 increased, and at 700°C it reached a maximum, and then decreased with increasing in temperature.

H CH 2 4 40 CO CO 2 35

15 Component of gas product (vol.%) product gas of Component 10 600 700 800 900 1000 Temperature (oC)

Fig. 6.Figure Properties 1.1: of Syngasgas product production from bio-oil from gasification bio-oil at gasification different temperatures at di↵erent temperatures, reproduced from Zhang et al. [1]. Yields of the main gaseous products are shown in Table 2. In this table a nitrogen balance method was introduced and used to calculate the absolute gas yield and the Theygasification suggested efficiency. that the It optimumcan be seen temperature that increasing for temperature this process favored in improving a fixed bed the reactor yield of syngas. When the temperature was 600°C, the efficiency of gasification was is 1073about K and 20%. the The higher highest residence gasification time efficiency did not was increase 80% when the temperature syngas yield. was from 600 to 1000°C. However, the evolution of H2 and CO was mainly associated with high grade fuel through biomass, CO2 was not utilizable, and CH4 required reforming to produce 1.2.1.2moreHigh H2 and temperature CO. When considering bio-oil these gasification results with respect to maximum H2 and CO

Chhiti [2]Zhang studied et al. (2010). the influence“Bio-oil pyrolysis/gasification,” of high temperature BioResources on non-catalytic 5(1), 135-146. bio-oil gasification142 process over a wide temperature range from 1200 K to 1700 K in a laboratory scale High Temperature Entrained Flow Reactor (HT-EFR). The objectives were to determine the syngas yield and composition as a function of the temperature. The feedstock used in their experiments was bio-oil produced from a mixture of hardwood (oak, maple, ash) in an industerial-scale fluidized bed reactor. Table I summarized the elemental composition and physicochemical properties of their used bio-oil.

Table I: Elemental composition and physicochemical properties of Chhiti’s bio-oil (wt.%) [2].

CH O NH2O Ash Solids 42.97.150.58 0.1260.057 2.344 

They observed that in the operating temperature between 1000Cand1300C, bio-oil mostly decomposed to H2, CO, CO2, and CH4. Figure 1.2 shows the mole fraction of the

5 1000°C and 1300°C, bio-oil is mainly decomposed to H2, CO, CO2, CH4 and C2H2. Above

1300°C C2H2 disappears, while CH4 disappears above 1400°C. As the temperature rises, the

fraction of H2 increases monotonically at the expense of carbon monoxide, methane and acetylene. Above 1300°C the hydrogen content remains almost stable. At 1400°C hydrogen gas products from the gasiﬁcation process in their experiment. mole fraction reaches the maximum value of 64 mol% of the syngas.

Figure 3.Composition of the produced syngas (dry basis and without N2) - effect of Figure 1.2: E↵ect of temperature on composition of gas products in bio-oil gasiﬁcation experiment,temperature, reproduced at S/F=4.5 from Chhiti [2].

The reactions that may explain the increase of hydrogen with temperature are :

They also The reported steam reforming that H of2 CHincreased4 and C2H2 with into H increasing2 and CO temperature in the (2) experiment, which is due The to twowater reactions: gas shift reaction CO + H2O ↔ CO2 + H2 (3) The water gas shift reaction can also explain the increase of carbon dioxide and the decrease of carbon monoxide between 1000 and 1200°C. Above 1200°C, carbon monoxide slightly 1. The steam reforming of CH4 and C2H2 into H2 and CO increases. This may be explained by steam gasification of the solid carbon residue resulting from the pyrolysis of oil droplets to yield carbon monoxide and hydrogen following the 2. The water gas shift reaction CO + H2O=CO2 +H2 reaction:

C + H2O ↔CO + H2 (4)

They reportedand potentially that following the water the gasBoudouard shift reactionreaction which can would explain explain the the increase slight decrease of carbon of dioxide

CO2: and the decrease of carbon monoxide between 1000 and 1200C. Above 1200C, carbon C + CO2 → 2CO (5) monoxide slightly increases. This may be explained by steam gasiﬁcation of the solid carbon residue. They also concluded that the increase in the reaction temperature results in higher hydrogen concentration and higher bio-oil conversion.

6 1.2.2 Chemical modeling of bio-oil gasiﬁcation

The eciency of bio-oil conversion to syngas, through the high temperature and pressure gasification process, is highly dependent on the operation conditions of the process. Op- timization of the process conditions requires an improved understanding of the chemical kinetics of the thermal cracking reactions involved in bio-oil gasification [35]. One of the key diculties in building detailed chemical models for such systems is the complexity and varieties of biomass components. Considering only three major biomass constituents (lignin, cellulose, and hemicellulose) as major components of the bio-oil, is not defining the system composition well enough. Each of these constituents are macropolymers with ill-defined components and the composition may vary from di↵erent biomass sources. Furthermore, each component of biomass is pyrolyzed at di↵erent rates by di↵erent mechanisms and reaction pathways [2] which makes building detailed kinetic models for such systems even more challenging. To date, most of the proposed models for biomass thermal decomposition are in gas phase and the three major constituents are used as a model components [22, 36, 37]. For example, Ranzi et al. [22, 38, 39] built a detailed kinetic model for biomass pyrolysis and validated their model against existing experimental data. In their modeling work, they characterized biomass in terms of cellulose, hemicellulose, and lignin with elemental composition of C, H, and O. They also defined lumped chemical reactions for decomposition of each major component of the biomass with associated reaction rate and stoichiometry parameters. The overall biomass model includes the combination of all lumped chemical reactions of each biomass reference component. In this section of thesis, a brief literature review of proposed kinetic models for biomass major components is provided. Later in Section 1.4.6, these models and proposed pathways were compared with RMG-built models for bio-oil gasification.

7 1.2.2.1 Cellulose kinetic modeling

Cellulose is one of the main components of biomass. During biomass thermal conversion, cellulose decomposed to levoglucosan (LG) with the yield varying from 20 to 60% [3, 40], depending on the initial source of the biomass. Levoglucosan can be used as the ﬁnal product or an intermediate to decompose to lower-molecular-weight (LMW) products. Kawamoto et al. [41, 42] investigated the cellulose decomposition reaction mechanism and observed that the levoglucosan (LG) is the primary product of the cellulose decomposition and LMW products form later. Banyasz et al. [43, 44] proposed that cellulose can decompose to either levoglucosan (tar) or hydroxyacetaldehyde, formaldehyde, and CO via LMW intermediates. In their proposed kinetic model, they calculated the activation energy of the levoglucosan and formaldehyde as 151 kJ/mol and 196 kJ/mol , respectively. Zhang et al.[45] studied the mechanism for levoglucosan (LG) formation and proposed an energy barrier of 93 kJ/mol. They concluded that from woody biomass resources, the LG is one of the main components of tar and bio-oil [46, 47]. Furthermore, they performed density functional theory (DFT) calculations to propose a detailed chemical reaction mechanism for levoglucosan thermal decomposition. They divided the LG decomposition into three pathways: direct C-C bond breaking, direct C-O bond breaking and LG dehydration. They concluded that the products from direct C-O bond breaking have a large contribution in the CO and H2Oproduction,themaincomponentsof the syngas. Figure 1.3 illustrates Zhang et al. three main proposed LG decomposition chemical pathways.

8 Figure 1.3: Three proposed main pathways for LG thermal decomposition, reproduced from Zhang et al. [3].

In their theoretical study, they concluded that there are two possible pathways for direct C-O bond breaking, one is exothermic and the other one endothermic. Furthermore, the C-C bond breaking pathway is endothermic and the dehydration pathway is the more feasible reaction channel for LG decoposition due to the lower barrier height. They also came to the conclusion that the C-O bond breaking has lower barrier than the C-C bond breaking reactions.

1.2.2.2 Lignin kinetic modeling

Lignin, another main component of biomass, is a valuable natural resource for biofuel processing. Lignin chemical structure is complex and includes a variety of linkages such as -O-4 linkages, demonstrated in Figure 1.4.

Figure 1.4: Model for the lignin -O-4 linkage [4]

The simplest proposed model for the -O-4 linkage lignin is the phenethyl phenyl ether

9 (PPE) [5] and the thermal decomposition of the PPE has been studied by di↵erent research groups. Britt et al. [5–7] conducted both fast and slow pyrolysis techniques such as Flash Vacuum Pyrolysis (FVP) to study PPE primary unimolecular thermal decomposition pathways such as bond scissions and intramolecular rearrangements pathways. Beste et al. [4] used density function theories (DFT) to calculate bond dissociation enthalpies (BDEs) of the O-C and C-C bonds in PPEs that were not experimentally available. They concluded that the primary decomposition pathways for PPEs are mostly C-O bond breakage and to some extent C-C bond breaking reactions. The reaction rate for both C- O and C-C bond pathways depends on the BDE energies and are sensitive to the location of the substituents. In their theoretical investigation, they showed that the C-O BDE in PPE is 7.6 kcal/mol lower than the C-C BDE that conﬁrms the lower percentage of the products from C-C bond breaking experimentally. Four main primary decomposition pathways for PPE were proposed, summarized in Figure 1.5.

Reaction 1:

Reaction 2:

Reaction 3:

Reaction 4:

Figure 1.5: Proposed reaction pathways for initial decomposition of PPE from di↵erent studies [4–7]

Jarvis et al. [48] conducted an experimental investigation of the pyrolysis of PPE in ahyperthermalnozzleinthetemperaturerangeof300to1350Ctoobserveproductsfor reactions 1–4. They detected both radical and stable species such as phenoxy radical, cyclopentadienyl radical, benzyl radical, styrene, and benzene which are the products of the direct C-O and C-C bond breaking reactions (reactions 1 and 2). Furthermore, detection of phenol and styrene species in their experiments, suggested pyrolysis through

10 the concerted reactions (reactions 3 and 4). They also performed quantum chemistry calculations to support the experimental observations. They concluded that the C-O bond breaking reaction (reaction 1) is significant at high temperatures (>1000 C), whereas the concerted reactions 3 and 4 are significant at lower temperatures. They had a similar observation as previous studies regarding the minor influence of the C-C bond breakage at both low and high temperature ranges.

1.2.2.3 Hemicellulose Kinetic modeling

Hemicellulose is a heteropolysaccharide constitute of monosaccharide such as xylose, glu- cose, mannose, galactose, and arabinose [49] and the type and structure of the hemicellulose depends on biomass sources. Bio-oil, syngas, and coke are the main products of the hemicellulose pyrolysis . Hemicellulose thermal decomposition was the subject of many experimental [50–52] and theoretical [8, 53] studies over the past decades. For example, Shen et al. [52] conducted sets of experiments with TGAFTIR (thermo- gravimetric analysis coupled to Fourier transform infrared spectrometer) and PyGCFTIR (pyrolysisgas chromatograph Fourier transform infrared spectrometer) to investigate the inﬂuence of the temperature on the yields of the main gaseous products, CO, CO2, CH4,andH2 of the hemicellulose pyrolysis. They concluded that the yield of CO is increased at higher temperature, while the yield of CO2 was decreased. They also proposed that the feasible pathways for formation of the bio-oil and gaseous products from hemicellulose pyrolysis, were due to the xylan, O-acetylxylan, and 4-O-methylglucuronic acid primary decomposition and other secondary reactions of the fragments. Huang et al. [8] applied density functional theory methods to identify the main chemical pathways for the formation of key products during xylose pyrolysis, as the most relevant constituent of the hemicellulose. They proposed ﬁve main primary xylose decomposition pathways with the calculated kinetic parameters, illustrated in Figure 1.6.

11 Ring-opening tautomerization reaction:

Reaction 1:

Reaction 2:

Reaction 3,4:

Reaction 5:

Figure 1.6: Proposed thermal decomposition pathways for xylopyranose [8].

The ﬁrst decomposition pathway is ring-opening reaction through the tautomerization with an energy barrier of 170.4 kJ/mol. In this primary ring-opening reaction C-O bond is breaking, double bond is forming and hydrogen is transferring all at once as a single step elementary reaction. The acylic molecule, can go through the further pyrolytic reactions and form other small molecules (reactions 1-5). Huang et al. [8] based on their DFT calculations for both kinetics and thermodynamics, concluded that reaction pathways (2) and (5) are the major reaction channels in the xylopyranose pyrolysis which was in agreement the observed experimental results.

1.3 Computational Method

As already mentioned, Bio-oil is a mixture of hundreds of chemicals derived from fast pyrolysis of biomass. Production of syngas from bio-oil is usually a high pressure and high temperature process and optimizing the process conditions (temperature, pressure, residence time, etc.) requires an improved understanding of the chemical kinetics of the thermal cracking reactions involved in bio-oil gasiﬁcation. In this study, detailed ki-

12 netic models for bio-oil gasiﬁcation were generated using Reaction Mechanism Generator (RMG), an open source software tool that can build detailed kinetic models for hydrocarbon pyrolysis and combustion. Starting with a surrogate bio- oil consisting of ten known species, and reaction conditions (temperature, pressure, reaction time) from the literature, RMG builds a detailed kinetic model consisting of thousands of elementary reactions and hundreds of intermediate species. In this section, an introduction to RMG, Cantera, an open source software package for modeling chemical kinetics models, and steps for bio-oil gasiﬁcation model generation using RMG are provided.

1.3.1 Reaction Mechanism Generator

Since manually calculating the thousands of parameters in an extensive detailed kinetic model is e↵ortful and error-prone, it is preferable to use computers instead. In recent years, several computational algorithms to build large kinetic models have been developed [54, 55]. RMG, Reaction Mechanism Generator, is an open-source automatic reaction mechanism generator for building large kinetics models [56]. Like other reaction network generators, RMG has to store chemical species in memory and identify duplicates, create reactions and new species in the network, and estimate the thermochemistry of each species and the rate coecient of each reaction. There are currently two versions of the RMG software: the original, which is mostly written in Java with some Fortran, RMG- Java [57], and a more recently developed version in Python, RMG-Py [10]. In this work, we used both RMG-Java and RMG-Py versions to build models with similar speciﬁcations for bio-oil gasiﬁcation. The version of RMG-Java used was a pre-release of version 4.0, and the RMG-Py was an early beta pre-release version.

13 1.3.1.1 Molecular Representations

In RMG, molecules represent as graphs [58], with atoms as nodes and bonds as edges connecting the nodes, demonstrated in Figure 1.7; standard graph-theory methods use to identify equivalent graphs and ensure uniqueness.

Type of bonds Charge Lone pair electrons Unpaired electrons Element Atom index

3 5 1 C u0 p0 c0 {2,D} {3,S} {4,S} H 1 2 H 2 C u0 p0 c0 {1,D} {5,S} {6,S} C C 3 H u0 p0 c0 {1,S} 4 H u0 p0 c0 {1,S} H H 5 H u0 p0 c0 {2,S} 4 6 6 H u0 p0 c0 {2,S}

Figure 1.7: Molecules are represented as 2-dimensional graphs in RMG

1.3.1.2 Data Hierarchy in RMG

Groups are the most important part in all RMG’s databases. Generally, groups describe the structures around the reaction atoms. Data that are needed to compute both thermodynamic and kinetic parameters are associated with groups. In order to use estimation approaches during mechanism generation, a robust and reliable method for rapidly identifying which group values should be used for any given molecule, is required. RMG’s thermodynamics and kinetics databases are stored all the group definitions and the corresponding group values in a hierarchical tree structure. The root nodes in the tree are more general groups and children nodes, descending from the root nodes, are the most specific groups. For example, Figure 1.8 demonstrates the trees of the H-abstraction with the specified parent and children nodes for the given family.

14 H-abstraction reaction: X_H + Y_rad X_rad + Y_H

Figure 1.8: Groups tree structure for H-abstraction family, reproduced from RMG documentation [10]. Indented text and schematics show the used syntax in RMG to represent the parent and children nodes.

In the following section a brief introduction to RMG’s thermodynamics and kinetics databases is provided.

1.3.1.2.1 Thermodynamic Database RMG’s thermodynamics database reports three thermochemical quantities: 1) standard heat capacity data Cp(T )asafunction of temperature T, 2) standard enthalpy of formation f (H)(298K)and3)standarden- tropy S(298K)at298K.RMG’sthermodynamicsdatabasehastwomainfolders:

Species thermochemistry libraries: In this folder the species with known thermo- • chemistry parameters are stored, the value of the thermo properties are from either available experimental data or high-level quantum chemistry calculations.

Species thermochemistry groups: In this folder species group additive values, ring • strain corrections, Hydrogen Bond Increments (HBI), and non-nearest neighbor interactions groups are stored in a hierarchical tree fashion.

– Group additive values (GAV): In this ﬁle the the group additivity values for di↵erent functional groups are stored in a hierarchical tree.

15 – Ring Strain Corrections (RSC): RMG separates monocyclic and polycyclic ring correction databases.Monocyclic RSCs are used for molecules that contain one single ring; for a molecule with two or more fused rings RMG uses a polycyclic ring strain correction.

– Hydrogen Bond Increments (HBI): RMG has the HBI groups to consider the inﬂuence of the loss of a hydrogen atom on enthalpy of formation, entropy and heat capacity of the radical species.

– Non-nearest neighbor interactions: RMG also has a database with NNIs be- side the group additivity values, to consider the interactions between atoms separated by at least 2 atoms, such as alkane 1,4-gauche, alkane 1,5, alkene 1,4-gauche, alkene single and double cis, ene-yne cis, and ortho interactions.

1.3.1.2.2 Thermochemistry Estimation RMG estimates the thermochemistry of species via three ways:

1. Species thermochemistry libraries: these databases include thermochemical parameters of the species. Data in these libraries come from either published experimental values or high-level quantum chemistry calculations. When RMG looks for the thermochemistry of a specie, values in these libraries always have the highest priority for themo estimations in RMG.

2. Group contribution methods: RMG uses libraries of known values wherever possible to ﬁnd thermochemical data for species, but usually the data are unknown and it estimates parameters. Thermochemistry data more commonly are estimated based on Benson’s group additivity method [59]. In this method, the molecule breaks down to functional groups and the total thermochemistry property of the molecule will be the summation of the contribution of each functional group. Figure 1.9 shows an example of standard enthalpy of formation estimation for isobutylbenzene

16 using group additivity approach. The comparison between the enthalpy of formation from group additivity approach and NIST reported value for isobutylbenzene, demonstrates that the group additivity is a reliable method to estimate the thermodynamics when functional groups are adequate.

NIST value: ΔfH°= -5.138 kcal/mol

Figure 1.9: Group additivity approach to estimate isobutylbenzene standard enthalpy of formation and comparison with the NIST reported value.

3. On-the-ﬂy Quantum-chemical calculation of Thermochemical Properties: Quantum mechanical calculations are recommended to improve the thermochemistry estimates of molecules that are not available in one of the species thermochemistry databases, and also cannot be estimated with good accuracy using the group additivity method such as cyclic and oxygenated species. Quantum mechanics uses a variety of math- ematical transformation and approximation techniques to ﬁnd molecular geometries, vibrational frequencies, and bond energies to compute the thermochemical properties accurately enough. The QMTP interface steps toward thermodynamics estimation are illustrated in the Figure 1.10.

17 Figure 1.10: On-the-ﬂy Quantum-chemical (QMTP) calculation steps (reproduced from RMG documentation [10]) toward thermochemical properties calculations in RMG.

First the molecular connectivity structure of the molecule is converted into a 3-D representation using a distance geometry method, followed by a optimization using the UFF force field in RDKit [60]. Next, an input file containing the 3D atomic geometries along with a number of keywords will be generated. The generated input file will be sent to a computational chemistry package, either OpenMopac [61] or Gaussian [62], that calculates the thermochemistry of the given molecule on-the-fly. The keywords specify the type of calculation, and the level-of-theory. In the end the calculated thermochemistry data will be sent back to RMG. Table II demonstrates the computational chemistry packages and levels of theory that are currently available in the QMTP.

Table II: Supported quantum chemistry packages and levels of theory in the QMTP, reproduced from RMG documentation [10].

QM Package Supported Levels of Theory OpenMopac semi-empirical (PM3, PM6, PM7) Gaussian03 semi-empirical (PM3) MM4 molecular mechanics (MM4)

18 Although using QMTP method reduces the errors for thermodynamics estimation of some species, they are more expensive than the GA method in terms of memory and computation cost. In cases of memory limitations or failures occurring for the QM methods, RMG falls back to the group additivity approach.

1.3.1.2.3 Kinetic Database

The key step in generating a reliable chemical mechanism, is being able to accurately estimate Arrhenius rate parameters. For each reversible elementary reaction A+B C+D,bothforwardandreversereactionratesshouldbespeciﬁedinthe ! mechanism. The forward reaction rate (kf (T )) can be expressed as pressure independent modiﬁed Arrhenius rate equation:

E k (T )=AT n exp( a )(1.1) f RT

Where A is the pre-exponential factor, T is the temperature, Ea is the activation energy, and R is the universal gas constant. The reverse reaction rate (kr(T )), can be calculated from reaction’s equilibrium constant (Keq(T ))from thermodynamic properties:

kf (T ) (G) Keq(T )= =exp( )(1.2) kr(T ) RT (G)=(H) T (S)(1.3)

Where (G)istheGibbsfreeenergyandhasarelationshipwithenthalpyandentropy of formation of the species. RMG’s kinetics database has the following main folders to estimate the reaction kinetic parameters from multiple ways:

19 Libraries: kinetic libraries contain kinetic parameters for speciﬁc reactions that are • extracted from published literature or high-level quantum chemistry calculations. RMG always pick kinetics from libraries over other methods. In case of availability of data for a single reaction in multiple libraries, the priority of the data depends on how libraries are listed.

Families: RMG uses reaction families to generate all the possible reactions that a • species can undergo in the presence of the other species in the chemical mechanism; every reaction family represents a particular type of elementary chemical reaction, such as bond-breaking, or radical addition to a double bond. Each reaction family has a recipe for mutating the graph, and a library of rate expressions for di↵erent reacting sites [63, 64]. As an example, general reaction template and recipe of the H-abstraction reaction family is illustrated in Figure 1.11.

H-abstraction reaction template: *2 *2 *1 H *3. *1. H *3 R1 + R2 R1 + R2

H-abstraction reaction recipe: Break bond {*1, S, *2} Form bond {*2, S, *3} Gain radical {*1, 1} Lose radical {*3, 1}

Figure 1.11: General template and reaction recipe for H-abstraction reaction family in RMG.

So far, there are 45 reaction families in RMG’s kinetic database. When RMG generates a reaction, for example the following H-abstraction illustrated in Figure 1.12, first the reacting atom will be specified based on the reaction template. Next, RMG will search within the corresponding reaction family, in this case H-abstraction reaction family, to find the groups that mach the reaction.

20 C_sec O_pri_rad C_pri C_pri

Figure 1.12: Reactants kinetic trees (reproduced from RMG documentation [10]) for H-abstraction reaction and reaction matched template.

Desired templates for the example reaction are C-sec and O-pri-rad. After ﬁnding the matched groups, the algorithm will search for data and rate parameters in the database for the template. If there are no data available for the C-sec and O-pri-rad templates in the database, RMG using rules will fall up to more general nodes, Cs-H and O-rad, demonstrated in Figure 1.13:

Figure 1.13: Falling up to the more general parent nodes from the exact match nodes to ﬁnd data, reproduced from RMG documentation [10].

If there are still no kinetic data in the Cs-H and O-rad in the database, the entire set of children for Cs-H and O-rad will be checked. For this example, this set would include every combination of C-pri, C-sec, C-ter with O-pri-rad, O-sec-rad. If any these templates have kinetics, an average of their parameters will be returned as an estimated rate parameters for the mentioned reaction.

The training set and rules: both contain trusted kinetics that are used to ﬁll in • templates in a family.

21 – The training set contains kinetics for speciﬁc reactions, which are then matched to a template.

– A similar group contributions method is used to estimate the rate coecients for the reactions: functional groups are identiﬁed using graph matching and the rates are estimated from a database of rules [55]. The kinetic rules contain kinetic parameters that do not necessarily correspond to a speciﬁc reaction, but have been generalized for a template.

When determining the kinetics for a reaction, a match for the template is searched for in the kinetic database. The three cases in order of decreasing reliability are:

1. Reaction match from training set. he reaction match from training set is accurate within the documented uncertainty for that reaction.

2. Node template exact match using either training set or rules. A template exact match is usually accurate within about one order of magni- tude.

3. Node template estimate averaged from children nodes. When there are no kinetics available for for the template in either the training set or rules, the kinetics are averaged from the children nodes as an estimate.

1.3.1.3 Rate-Based Model Enlarger

RMG chooses species to include in the model according to reaction ﬂux. It gradually expands a ‘core’ model by adding species from the edge [65], an example is illustrated in Figure 1.14. The core begins with a trusted seed mechanism of small-molecule chemistry and the initial reactant species (in this case 10 components of bio-oil). All reactions between core species are identiﬁed and their rates estimated; any new products are added

22 to the edge.

Figure 1.14: RMG explores paths with high reaction rates and will move them into the model ’core’.

User-defined tolerances control the allowed flux (relative to the root-mean-squared flux of reactions in the core) for moving a reaction to the core or keeping the reaction on the edge. There are possibilities in RMG to set additional tolerances for the di↵erential equations solver accuracy and the pruning (deletion) of minor edge species. The core is then expanded iteratively, repeatedly adding the edge species with the largest rate of creation until the user-specified tolerance is reached and the core model is designated complete (for the given tolerance). A tight tolerance (small number) will generate a large model with a long calculation time, whereas with a looser tolerance (larger value) RMG will stop sooner and the final model will be smaller.

1.3.1.4 Pressure Dependence in RMG

Two conditions can cause pressure dependence: low pressures and high temperatures. Most discussions on the subject of pressure dependence focus on unimolecular reactions at low pressures. The collision frequency is directly proportional to the pressure, so as the pressure is decreased, the rate of collisional energy transfer decreases. Eventually the pressure becomes low enough that the rate of chemical reaction becomes faster than

23 the collision rate. RMG is able to calculate pressure-dependent rate constants k(T,P) for unimolecular reaction networks by solving master equation. A unimolecular reaction network is defined as a set of chemically reactive molecular configurations divided into unimolecular isomers and bimolecular reactants or products. Reactants can associate to form an isomer, while such association is neglected for products. These configurations are connected by chemical reactions to form a network; these are referred to as path reactions. The system also consists of an excess of inert gas, representing a thermal bath; this allows for neglecting all collisions other than those between an isomer and the bath gas. An isomer molecule at suciently high internal energy can be transformed by a number of possible events:

The isomer molecule can collide with any other molecule, resulting in an increase • or decrease in energy

The isomer molecule can isomerize to an adjacent isomer at the same energy •

The isomer molecule can dissociate into any directly connected bimolecular reactant • or product channel

It is this competition between collision and reaction events that gives rise to pressure- dependent kinetics.

1.3.1.5 Output from RMG

RMG’s output, a detailed reaction network with associated thermodynamic and kinetics parameters, is printed out in the ‘Chemkin format‘ and will be saved in a ’Chemkin file’. The information in the Chemkin file is a list of all species in the model with their associated chemical formula and thermochemistry information, standard heat and entropy of formation and heat capacity. Also the file contains a list of reactions with known kinetic parameters. An example of a chemkin file is presented in Figure 1.15.

24 Figure 1.15: The Chemkin ﬁle showing the list of species, thermochemistry, and reaction information as RMG’s output.

Many research groups have been publishing their models in Chemkin format for a long time and this format is readable for further simulations by other chemical packages such as Cantera [66] and Chemkin [67] to solve complex chemical kinetics problems. In this research, Cantera has been used for further simulations of RMG-generated models such as simulations of Plug Flow Reactors (PFR) with known operational conditions.

1.3.2 Cantera

Further simulations to determine the characteristics of biofuel processes in batch, CSTR reactors, and shock tube under di↵erent operating conditions is done using Cantera [66]. Cantera is an open source object-oriented software for modeling chemical kinetics, thermodynamics, and transport processes. Furthermore di↵erent classes (objects) are provided in Cantera to represent the phase of matter, interface between phases, time-dependent reactor network and steady one-dimensional reacting ﬂows. Here is some useful objects which are currently used in biofuel simulations:

25 Importing Phase Objects: This object is importing one phase from an input ﬁle. In • this study the phase object is the RMG-built gas phase kinetic network.

Chemical Kinetics: This the Cantera’s kinetics manager object and is responsible for • evaluating reaction rates of progress, species production rates, and other quantities pertaining to a reaction mechanism.

Thermodynamic and Transport Properties: This class is responsible to describe the • thermodynamic state of the system.

Zero-Dimensional Reactors Simulation: Cantera is conducting zero- dimentional ki- • netics simulations using this class. The type of ﬂuid the reactor containing should be speciﬁed through the associated object. Then this object will be used to compute all required thermodynamic properties and species production rates, and must implement the reaction mechanism and equation of state desired for the reactor.

1.3.3 Model Veriﬁcation and Validation

After model generation, the most important step is the mechanism evaluation. There are several methods toward mechanism evaluation; comparison to available experimental data, reaction ﬂux analysis to determine the dominant reaction channels, and sensitivity analysis to reveal the sensitive parameters to reduce the uncertainty. After the mechanism evaluation, from learned lessons, the model might need to be improved with new data. New data can be provided either from theoretical calculations or from experiments. After updating the RMG’s databases with new data and ﬁxing bugs, RMG will generate a new improved model with the best accessible chemical data. As a summary, Figure 1.16 illustrates model evaluation steps.

26 Figure 1.16: Steps toward building reliable detailed kinetic models using RMG.

1.3.4 Bio-oil gasiﬁcation modeling

In the present study, RMG was used to build bio-oil gasification models for syngas production and models were evaluated against Chhiti et al. [2] and Zhang et al. [1] experiments covering the range of temperatures and pressures. Sensitivity analysis was used to identify what information would be most valuable to obtain in order to improve mechanism predictions. Furthermore, the e↵ect of RMG parameters on the model predictions were investigated, as well as the influences of pyrolysis temperature, residence time, and pressure on the syngas yields. Model evaluations showed that RMG missed some reaction families in generating bio-oil gasification mechanisms, and several improvements are needed for thermodynamic and kinetic parameters estimations. Finally, several ideas for future work in order to improve RMG for bio-oil gasification modeling are discussed. These ideas include some thoughts on updating RMG’s current reaction families and rates, as well as improving thermochemistry estimations for some cyclic molecules.

1.3.4.1 Bio-oil Composition

Branca et al. [69] experimentally categorized bio-oil composition into several chemical groups including water (20-30)%, aldehydes (10-20)%, lignin fragments (15-30)%, car-

27 boxylic acid, carbohydrates (5-10)%, and phenols (2-5)% using GC/MS, and quantiﬁed the mass fraction of 40 components of bio-oil. Based on these measurements, Zhang et al. [70] modeled bio-oil as the mixture of 10 major components, by keeping the mass fraction of the water the same as the experiment and scaling up the mass fraction of the other nine components in order to account for the neglected components. In the current work, RMG-built kinetic models are started from the Zhang et al. [70] 10-component surrogate bio-oil mixture. The species and their mass fractions are listed as Model 1 in Table III.

Table III: Composition of surrogate bio-oil used in modeling.

Component % by mass Model 1 Model 2 (Normal) (High Acid) Water 21.10 12.0 Hydroxyacetaldehyde 21.77 12.5 Acetic Acid 9.48 19.5 Hydroxypropanone 15.06 8.6 Levoglucosan 17.27 9.9 PropanoicAcid 1.25 29.3 (5H)-furan-2-one 2.37 1.36 Isoeugenol 10.79 6.2 Phenol 0.37 0.21 Syringol 0.54 0.31

However, in order to investigate the e↵ect of a higher initial fraction of carboxylic acids on the ﬁnal simulation results, another model was generated in RMG with a much higher acid content. The ratios of species were ﬁxed except the amounts of the two carboxylic acids (acetic acid and propionic acid) were increased so that the overall elemental composition closely matched that given by Chhiti et al.[2] (Table IV). The composition of this “High Acid” Model 2 is also shown in Table III.

28 Table IV: Elemental composition of bio-oil from experiment II (ref [2]) and RMG model

Feedstocks C (wt.%) H (wt.%) O (wt.%) N (wt.%) Experiment I (ref [1]) 49.7 7.4 42.3 0.6 Experiment II (ref [2]) 42.9 7.1 50.6 <0.1 RMG Model 1 (Normal) 37.7 7.8 54.5 No Nitrogen RMG Model 2 (High Acid) 41.4 7.7 50.9 No Nitrogen

1.3.4.2 Simulating syngas production

The Python interface to Cantera 2.0 is used to create simulations of both Plug Flow Reac- tor (PFR) and Continuous Stirred Tank Reactor (CSTR) conditions for bio-oil pyrolysis, with initial mass fractions taken from Table III, and with residence times, temperatures, and pressures either corresponding to experimental data [1], or varied as part of an optimization study. The mole fractions of the major gases H2, CO, CH4 and CO2 at the end of the simulation were recorded, as these are the parameters reported by Zhang et al. [1]. As a summary, Figure 1.17 demonstrates the complete work-ﬂow of the bio-oil gasiﬁcation chemical kinetic modeling using RMG to generate the model and Cantera for performing further simulations with corresponding input and output parameters.

Input: Output: Cantera Input: Temperature Reaction mechanism with Temperature Pressure known thermochemistry Pressure Seed mechanism RMG and kinetic parameters in Initial mole fraction Initial mole fraction chemkin format. ⇌ Termination time Inert bath gas Termination time Tolerance Output: • Bio-oil gasiﬁcation • Syngas mole fraction

Figure 1.17: Work-ﬂow of the reaction mechanism modeling for bio-oil gasiﬁcation using RMG and Cantera.

Many simulations were performed to investigate the e↵ects of varying temperature, residence time, and pressure; of simulating CSTR versus PFR; of constructing models with or without pressure-dependent reactions; and of the inﬂuence of model size from a

29 series of incomplete (interrupted) RMG jobs.

1.3.5 Optimization

The optimization of the bio-oil gasiﬁcation process involves looking for the optimal temperature, pressure, and residence time within given constraints to maximize some objective function. As the pyrolysis of bio-oil is a complex process, there are many possible objective functions. In this work, primarily as proof of concept, we used a very simple objective function to represent syngas yield: the sum of the hydrogen and carbon monoxide mole fractions exiting the reactor. Also, the constraints range for temperature, pressure and time are chosen from experiments. The optimization model is therefore:

Maximize f(T,P,t)=yH + yCO T,P,t 2

subject to 800 K

0.5atm

0.5sec

The Constrained Optimization by Linear Approximation (COBYLA) method from the SciPy toolkit [71] was used to solve the optimization, with the objective function being evaluated by Cantera [66].

1.4 Results and Discussions

1.4.1 Inﬂuence of model size

To investigate the inﬂuence of model size, a large RMG-Java model was interrupted at three stages of its generation, resulting in incomplete models containing 103 species, 202 species, and 307 species in the core. Full model sizes (core and edge) are listed in Table

30 V.

Table V: RMG-built model sizes in core and edge

Model Coresize Edgesize Species Reactions Species Reactions Model I 103 1,711 10,500 27,725 Model II 202 3,765 19,322 251,781 Model III 307 7,161 22,404 428,714

The PFR and CSTR reactors produced similar results for all three models; the CSTR results are shown here. It can be seen from Figure 1.18 that predicted syngas yield, specially H2 and CO, increases with the model size. The models are quantitatively and qualitatively di↵erent, which shows the importance of having a large kinetic model.

0.5 103 Species 202 Species H 0.4 2 307 Species CO

0.3

0.2

CH4 0.1

Outlet Mole Fraction Fraction Mole Outlet CO2

0 600 800 1000 1200 1400 Temperature (C)

Figure 1.18: Syngas production varying with incomplete model size from a CSTR with residence time 5 sec.

The RMG models were built on nodes of a linux cluster with 4 or 8 GB of RAM each. As bio-oil contains several large and complex molecules, unfortunately RMG ran out of memory and all the RMG-built models for bio-oil are currently incomplete in both RMG-Java and RMG-Python. Several attempts were made to build a complete model with looser tolerances, between 1 and 5. RMG-Py completed a model with a very

31 high tolerance, 5, and reaction time 0.5 sec. The model core had only 37 species and 186 reactions, missing a lot of important pathways and species. Results from Cantera simulations showed that the completed model with the high tolerance is not useful for predicting syngas formation.

1.4.2 Inﬂuence of pressure and pressure-dependent kinetics

Figure 1.19 shows that there is an e↵ect of reactor pressure on the predicted mole fractions at the reactor exit. However, for this system (unlike small molecule combustion), there doesn’t seem to be much di↵erence between results from models without pressure-dependent calculations and with pressure-dependent reactions calculated by RMG (Figure 1.19). In both models, increasing the pressure will increase the syngas yield. The biggest di↵erence is in H2 and CH4 yield below 3 atm and from 600 to 1400 C.

32 0.5 P= 1 atm H P= 3 atm 2 P= 5 atm 0.4 P= 10 atm

0.3 CO

0.2 Outlet Mole Fraction Fraction Mole Outlet

0.1 CH4

CO2

0 600 800 1000 1200 1400 Temperature (C) (a)

0.5 P=1 atm P=3 atm P=5 atm H2 P=10 atm 0.4

0.3 CO

0.2 Outlet Mole Fraction Fraction Mole Outlet CH4 0.1

CO2 0 600 800 1000 1200 1400 Temperature (C) (b)

Figure 1.19: Mole fraction of four major gases at exit of a CSTR with residence time 5 seconds at a range of temperatures and pressures, according to kinetic models built by RMG- Java. (a) without pressure-dependence calculations (b) with pressure-dependent reaction networks calculated by modiﬁed strong collision approximation.

33 1.4.3 Comparison with experiments

The simulated syngas species concentrations at the reactor outlet were compared with measurements from two bio-oil gasiﬁcation experimentals described in the literature [1, 2] (Figure 1.20). Although the simulations give actual amounts of these and hundreds of minor species, because the only published data are the relative amounts (fractions sum to 1.0) of the four major gas products (H2, CO, CH4, and CO2)atvarioustemperatures, those are the only data compared.

(a) Experiment I (b) Experiment II 1.00 CH4

0.75 H2

0.50 CO

Syngas Fraction Syngas 0.25 CO2 0 600 700 800 900 1000 1100 1200 1300 1400

Temperature (C)

0.75 H2

0.50 CO

Syngas Fraction Syngas 0.25

CO2 0 600 700 800 900 1000 1100 1200 1300 1400 Temperature (C)

Figure 1.20: Distribution between four major gas components as a function of temperature, (a) from experimental work by Zhang et al.[1] at 100 C intervals from 600 to 1000 C, (b) from Chhili et al.[2] at 100 C intervals from 1000 to 1400 C, (c) from Cantera simulations (this work) at 100 C intervals from 600 to 1400 C

Besides the discrepancies between the experiments, it is obvious from Figure 1.20

34 that there is a di↵erence in CO2 and CO yields between the experimental and modeling results. Despite this, H2 and CH4 predictions are reasonably compatible with both experiments. Also, it is observed that by increasing process temperature the CH4 production is decreased. The thermodynamics of the water-gas shift reaction would lead the ratio of [CO2][H2] to [CO][H2O] at equilibrium to decrease with increasing temperature. The simulation reaches and is limited by the equilibrium position at about 1200 C, but at lower temperatures there is less H2 and CO2 than there would be at equilibrium. Shen et al. [52] have explained that due to the presence of a large number of cyclic oxygenated compounds such as xylan in bio-oil, CO formation is highly a↵ected by ring- opening decomposition reactions of these components and is increasing at higher temperature. On the other hand, CO2 is mainly contributed by decarboxylation reactions and is simultaneously decreasing with increasing temperature. Additionally, Zhang et al. discussed that the increase of CO2 concentration with temperature (600 – 1000 C) in their experiment was mainly because the high carboxylic acids content in their bio-oil feedstock (carboxylic acids decomposition was a major source of CO2) but they did not state their feedstock composition, only elemental composition, so the initial amount of carboxylic acids is unknown. To investigate the e↵ect of a higher initial fraction of carboxylic acids on the ﬁnal simulation results, another model was generated in RMG with a much higher initial acid content (Table IV). Simulation results for syngas production from the RMG-built ”high acid” model, Figure 1.21, shows that an increase in the carboxylic acid content doesn’t make big di↵erences in CO and CO2 levels, but at low temperature the model still underestimates CO2 and overestimates CO compared to Experiment I[1].

35 RMG High Acid Model 1.00 CH4

0.75 H2

0.50 CO

Syngas Fraction Syngas 0.25

CO2 0 600 700 800 900 1000 1100 1200 1300 1400 Temperature (C)

Figure 1.21: Distribution between four major gas components as a function of temperature from high acid model.

1.4.4 Sensitivity Analysis

A sensitivity analysis was carried out on models to identify the important channels of reactions for carboxylic acid decomposition to CO and CO2 under simulation conditions. The analysis is from the pressure-independent (high pressure limit) model and the small chemistry reactions are from Glarborg seed mechanism [72]. The sensitivity analysis can be explained by consideration of two domains: low temperature and high temperature. At both low (700C) and high (1400C) temperatures the productions of CO and CO2 are most sensitive to the decomposition of acetic and propanoic acids and several radical reactions. The results for both domains are brieﬂy summarized in Figure 1.22.

36 CO2 + CH4 ⇌ Aa C2H2 + OH ⇌ CH2CO + H Ppa + H ⇌ C[CH]C(=O)O + H2 C2H2 + OH ⇌ CO + CH3 Ppa + OH C H O + H O ⇌ 3 5 2 2 Ppa + H ⇌ C[CH]C(=O)O + H2 CH3 + [CH2]C(=O)O ⇌ Ppa H2O + O=C=CH2⇌ Aa

CO2 + C2H6 ⇌ Ppa CO2 + C2H6 ⇌ Ppa

CH2CH=CHC(=O)O ⇌ Hf2O CO2 + CH4 ⇌ Aa 0.0 -0.393 0.426 -0.252 0. 0

(a) CO2 Sensitivity at T=700 C , P= 1atm and t=4 sec (b) CO2 Sensitivity at T=1400 C , P= 1atm and t=4 sec

C2H2 + OH CH2CO + H Ppa + H ⇌ C[CH]C(=O)O + H2 ⇌ C2H2 + OH CO + CH3 Aa + H ⇌ [CH2]C(=O)O+ H2 ⇌ C2H5+ O=COH Ppa CH3CO + HCO ⇌ CH3C(=O)CH=O ⇌ OH + HCCCH2⇌ C2H2 + H2C=O CO + OH ⇌ HOCO C2H2 + C3H4 ⇌ C2H + C3H5 CO2 + C2H6 ⇌ Ppa CO2 + CH4 ⇌ Aa Ppa + OH ⇌ C[CH]C(=O)O + H2O

-0.00037 0.0962 -0.378 0.0 0.187

(c) CO Sensitivity at T=700 C , P= 1atm and t=4 sec (d) CO Sensitivity at T=1400 C , P= 1atm and t=4 sec * Ppa: Propanoic acid * Aa: Acetic acid * Hf2O: 5H-furan-2-one

Figure 1.22: Sensitivity analysis for (a) CO2 at T=700C, (b) CO2 at T=1400C,, (c) CO at T=700C,, (d) CO at T=140C,. See text for model details.

The result of sensitivity analysis showed that free radical reactions are greatly dominant at low temperature. Also predicting more methane than CO2 may indicate that the unimolecular decomposition of acetic and propanoic acids are not taking place sig- niﬁcantly at lower temperature, which is in agreement with the observation of Doolan et al. [73] in their kinetics study of acetic and propanoic acids decomposition. However, Frey [74] and Kistiakowsky [75] suggested high amounts of CO at low temperature are signiﬁcantly coming from ketene decomposition. Decomposition of acetic and propanoic acids to water and ketene are observed in models at both low and high temperature, and these ketene molecules will eventually decompose into the CO and other radicals in the model.

37 1.4.5 Poor Thermochemistry For Cyclic Molecules

In the literature there are no reports about complete detailed kinetic model of bio-oil gasification to date but there are several studies of detailed chemical modeling of biomass pyrolysis and gasification as a main source of the bio-oil. Several gas phase detailed chemical models [37, 69, 76–79] were recently developed based on the reactions involved in thermal decomposition of three major constituents of biomass: cellulose, hemicellulose, and lignin. Due to the similarity between classes of hydrocarbons in the biomass and bio-oil, bio-oil models were compered with proposed biomass models. One of the proposed models of biomass pyrolysis from Ranzi et al. [22, 80, 81], focused on studying the main kinetic features of biomass pyrolysis in the gas phase and proposed the detailed kinetic model with associated thermochemistry and kinetic data from previous experimental studies and modeling e↵orts. RMG-built models were compared with Ranzi’s biomass mechanism and a few published data for thermochemistry of heterocyclic molecules. Com- parison shows that thermodynamic parameters of some cyclic and oxygenated species from primary decomposition of cellulose, hemicellulose, and lignin fragments in RMG may not be estimated accurately using the Group Additivity approach; for example, the enthalpy of formation for xylofuranose is around 60 kcal/mol lower from that in reference [22], although it is not clear how the latter was estimated. However, other estimates place it 40 kcal/mol lower still[82], so the range in estimates is remarkably large. Species thermochemistry in RMG can be estimated based on two approaches: group additivity [59] and on-the-fly quantum mechanics (QM) methods [83] using Gaussian or OpenMopac [61]. This automatic QM approach was implemented specifically for cyclic compounds, where group additivity often performs poorly [83]. Switching from group additivity to QM methods for thermochemistry calculations of cyclic species shows significant improvement in species’ thermochemistry. Table VI shows the di↵erences of thermodynamic data between Ranzi’s biomass model and RMG estimated thermochemistry

38 from both group additivity and QM approaches for some cyclic and oxygenated species.

Table VI: Comparison of RMG estimated thermochemistry from both Group Additivity (GA) approach and Quantum Mechanics (QM) calculations of some species to Ranzi’s biomass model [22] and other published literature where available.

Species Quantity Ranzi model RMG (GA) RMG (QM) Literature

O Hf (kcal/mol) –8.3 4.9 –4.1 –6.6 [84]

Furan S(cal/mol/K) 63.9 65.2 64.3 — OH O Hf (kcal/mol) –151.5 –213.7 –226.2 –252.8 [82]

HO OH

HO S (cal/mol/K) 104.9 117.0 104.1 40.4 [82] Xylofuranose H OH Hf (kcal/mol) –200.9 –212.5 -204.2 –199.7 [85] O OH O

OH H S (cal/mol/K) 113.7 58.3 98.3 — Levoglucosan

Hf (kcal/mol) –113.5 –80.6 –92.6 –91.22 [86] O O

OH S (cal/mol/K) 134.4 99.0 105.6 — 2,6-dimethoxy phenol

HO Hf (kcal/mol) –116.0 –102.6 –112.3 —

O O S(cal/mol/K) 136.8 123.1 128.1 — 3-(4-hydroxy-3,5-dimethoxy-phenyl)acryl-aldehyde

Cyclic and oxygenated species are important intermediates in bio-oil gasiﬁcation and comparison indicates that the accuracy of thermochemical data for some oxygenated and cyclic species in RMG-built models should be improved. Many bio-oil molecules, containing sugars, cellulose, and lignin fragments, include cyclic ethers and bicyclic oxygenated groups. Thermodynamic properties of these intermediates are the controlling parameters in bio-oil gasiﬁcation modeling and can a↵ect the overall rates of subsequent reactions leading to formation of products such as CO2 and H2O. Furthermore, ring corrections to account the ring strain are required for cyclic species since group additivity approach is not able to predict the thermochemistry of the cyclic molecules accurately enough. Ring corrections, once obtained by subtracting the experimental value from group additivity value, allow estimation of the thermochemical properties for cyclic species, but the prob- lem is only very few ring corrections are available for bio-oil molecules. Using quantum

39 mechanics calculations instead of the group additivity approach to calculate the thermochemistry for cyclic and oxygenated species improved the model. Nevertheless, since there are remarkable discrepancies in thermodynamic properties of the heterocyclic compounds in literature, still additional e↵orts are needed to improve estimations and identify other factors such as ring strain and resonance e↵ects in these species.

1.4.6 Missing Pathways in RMG Generated Mechanisms

As it’s already discussed in Section 1.2.2, there are several detailed kinetic models available for primary decomposition reactions of cellulose, hemicellulose, and lignin. Comparison between the bio-oil mechanisms generated by RMG and Zahng et al. [3], Section 1.2.2.1, decomposition pathways of cellulose reveals that RMG missed one-step levoglucosan C- O bond breaking decomposition pathways. Furthermore, Carstensen and Anthony [36] developed a detailed kinetic model for biomass pyrolysis in the gas phase. They performed electronic structure and transition state calculations to determine the rate constants of primary decomposition reactions of major biomass components. Comparison between the bio-oil mechanisms generated by RMG and the Carstensen and Anthony [36] model shows that RMG missed some decomposition pathways. Another comparison between RMG-built models for bio-oil gasiﬁcation and proposed reaction mechanism for lignin thermal decomposition from the work of Beste et al. [4], Section 1.2.2.2, shows that RMG-built models missed Phenethyl Phenyl Ether thermal decomposition through the concerted reactions. Furthermore, from the comparison with Huang et al. [8] proposed model for hemicellulose thermal decomposition reaction channels, Section 1.2.2.3, RMG missed Xylose primary ring-opening reaction through the tautomerization and corresponding reaction family. Table VII shows some of these reaction pathways missing from the RMG-generated mechanisms for bio-oil gasiﬁcation with associated reaction families and references.

40 Table VII: Some missed reactions in RMG for bio-oil primary thermal decomposition.

Missed reaction Associated reaction family and reference H OH OH

O OH O OH Tautomerization ring-opening [3] O OH

OH OH H Levoglucosan Tetrahydro-2H-pyran-3,4,5-triol H OH

OH O 2 H H O OH + O O Water Celloluse decomposition [36] O hydroxylmethyl-furfural OH H Levoglucosan OH

O OH

HO O + HO OH Retro Diels-Alder reaction [36] HO OH 1-propene-1,3-diol 2,3-dihydroxy-2-propenal OH

2-(hydroxymethyl)-3,4-dihydro-2H-pyran-3,4,5-triol OH

OH O OH O OH + OH HO Retro Diels-Alder reactions [36] buta-1,3-diene-1,2,4-triol 2-hydroxyethanal HO OH

6-(hydroxymethyl)-5,6-dihydro-2H-pyran-2,3,5-triol OH O OH

O OH HO OH Tautomerization ring-opening [8] OH OH

OH Xylose 2,3,4,5-tetrahydroxypentanal OH

+ 1,3- sigmatropic H shift reaction [4]

O vinylbenzene phenethyl phenyl ether phenol O

+ 1,5- sigmatropic H shift reaction [4] O phenethyl phenyl ether cyclohexa-2,4-dien-1-one vinylbenzene

RMG generates kinetic models by predicting reactions according to a set of reaction families, which each contain a recipe and a set of rules to estimate the kinetics. When pathways are missing, either the template for an existing reaction family needs to be made more general, or a new reaction family must be created. As an example of the

41 former, the reaction of phenol and vinylbenzene (reaction 6 in table VII) should match RMG’s existing “1,3 Insertion ROR” reaction family, if the template were general enough to allow aromatic alcohols to react instead of just aliphatic alcohols. This change has now been implemented and the most recent versions of RMG can predict this reaction. The other cases will require new reaction families to be created. Kinetic models generated by RMG can be significantly improved by adding missing reaction families into the kinetics database, and ensuring they have a sucient number of accurate rate rules. Adding new reaction families starts with identifying the reaction recipe to define how the reacting species interact with each other, then proceeds with specifying rules for the reaction rates. Since the number of reactions in each reaction family is massive, and applying high-level electronic structure calculations for all of them is not feasible, rate calculations can be performed for a smaller set of reactants belonging to the particular reaction class and, if transferable, applied to the whole reaction class. The first important step, undertaken here, is to identify the missing pathways. Calculation of the rates and full specification of the new reaction family rules is dissuaded in Chapter 2.

1.5 Summary

This study made significant contributions toward automatically generating detailed kinetics models for bio-oil gasification using Reaction Mechanism Generator (RMG). Sim- ulations suggested that there are not significant di↵erences between kinetic models from RMG-Py and RMG-Java, and that inclusion of pressure dependent reactions doesn’t make aremarkabledi↵erence in these conditions. The importance of having large and complete models is demonstrated by comparing a series of incomplete models at di↵erent sizes: they are significantly di↵erent from each other and the larger kinetic models have higher syngas conversion.

42 Unfortunately this poses problems for the current single-threaded implementation of RMG, which frequently runs out of memory when simulating mixtures of large complex molecules. One option would be to use shared-memory computers with very large amounts of RAM. An alternative would be to restructure the RMG algorithm so that the entire ‘edge’ need not be held in memory at once, and ideally to allow a mechanism generation job to run on several networked computers simultaneously; if communication requirements were minimized then this parallelization would also o↵er run-time improvements. For the purpose of validating kinetic models, RMG generated models are compared with two experiments in low and high temperature range and comparison shows that there are some disagreements between experiments and RMG generated models; however, there are also discrepancies between experiments. Zhang argued the large amount of CO2 in their experiment was mainly because the bio-oil contained a lot of organic carboxylic acids from which carboxyl decomposition was a main source of CO2, but they didn’t specify their bio-oil feedstock composition. However, rebuilding RMG models with very high carboxylic acid content still doesn’t signiﬁcantly improve the model predictions for

CO2. Comparison with experimental data is further hampered by the limitation that both experiments reported gas compositions as only the relative ratios of four component mole fractions. Absolute concentrations would enable a more rigorous comparison, and a significant number of other gaseous products should be considered. Comparison of RMG’s thermochemistry for some species with literature shows that thermochemistry estimation of some bio-oil cyclic and oxygenated species is currently erroneous when using a group additivity approach without sucient ring corrections. However, using on-the-fly quantum mechanics (QM) calculations for estimating thermodynamic parameters shows remarkable improvement for some species thermochemistry. Discrepancies between literature values show that some of these heterocyclic compounds would merit further study. Finally, some reaction pathways in bio-oil gasification were found to be missing from

43 RMG, so new reaction families need to be added to RMG’s kinetic database with associated data calculated, estimated, or taken from literature, to generate more predictive mechanisms. The largest model we could build using RMG had not converged with respect to model size, so a full comparison will require improvements to the memory management and increased computing power. The complicated chemistry of oxygenated and cyclic reactants in bio-oil, and having only few models and experiments available for these systems, makes the modeling task more challenging. Despite these diculties, there is enough overlap between RMG-built models and experimental and modeling e↵orts to encourage the use of RMG to build predictive kinetic models for bio-oil gasiﬁcation.

44 1.6 Recommendations for future work

This thesis has made significant contributions toward building predictive and reliable detailed kinetic models for bio-oil gasification. Nevertheless, further kinetic analysis and experimental activities are required to fully understand the kinetics of the bio-oil thermal conversion. Three major challenges were identified in RMG while building detailed kinetic models for bio-oil gasification and particular attention should be given to improve the understanding of these challenges. Identified challenges in building detailed kinetic models for bio-oil gasification using RMG for future work are addressed in this section.

1.6.1 Improve RMG thermochemistry estimation

Thermochemistry of bio-oil’s cyclic and oxygenated species are not estimated accurately enough in RMG. Quantum chemistry calculations can be used for thermochemistry predictions instead of group additivity approach. The current version of RMG-Py uses on-the-ﬂy quantum calculations at semi-empirical level of theory such as PM7 to estimate the thermochemistry of cyclic and oxygenated molecules. However, as the calculated enthalpy of species from semi-empirical calculations had an error greater than 10 kcal/mol, high level ab-initio calculations, i.e at CBS-QB3, should be performed. Furthermore, another approach to overcome this limitation, can be keep updating RMG’s thermodynamic libraries with newly published or calculated data and reading associated parameters from libraries during mechanism generation. Error canceling reactions such as isodesmic approach or more accurate approaches such as homodesmotic and hyperhomodesmotic also should be implemented in RMG to provide reliable thermodynamic estimates for biofuel species.

45 1.6.2 Add more reaction families to the RMG database

As highlighted in the Chapter, RMG missed some primary decomposition reaction pathways of bio-oil major constituents. New reaction families need to be added to RMGs kinetic database with associated kinetic data taken either from published literature or direct quantum chemistry calculations. Chapter 2 presents a framework for updating RMG’s kinetic database with two-missing reaction families in bio-oil gasiﬁcation and automatic estimation of associated rate coecients using reaction rate rules approach.

1.6.3 Improve memory management in RMG

As mentioned, no complete mechanisms are available for bio-oil gasification modeling due to RMGs memory constraints. To overcome this limitation, parallelizing of RMG algorithm will help to improve the software memory management. For eciently parallelization, tasks that are independent from each other in RMG’s algorithm and require little communication between processes should be identified first.For example, the calculation of species thermochemistry is entirely independent job and could be done in parallel, but parallelizing thermochemistry calculations alone doesn’t save lot of time and memory in RMG-Py. Furthermore, increasing computing power by using larger shared memory clusters could always be a reliable way for better memory management

1.7 Supporting material

The largest mechanism for bio-oil gasiﬁcation generated in RMG-Java is provided in Appendix A, including Chemkin, transport, and species dictionary ﬁles.

46 Chapter 2

Rate calculation Rules for Automated Generation of Detailed Kinetic Models for Heterocyclic Compounds

2.1 Introduction

Bio-oil composition is mostly carbon, oxygen, and hydrogen. However, thermal conversion of bio-oil is very sensitive to the fuel chemistry, and sometimes too complex to model by hand, especially for heavy cyclic oxygenated molecules. In order to generate complete detailed models, an extensive set of reaction classes, which would deﬁne how fuel species can react with each other, should be implemented in mechanism generators. In chapter 1, Reaction Mechanism Generator (RMG), an open-source software, has been used to build detailed kinetic models for bio-oil gasiﬁcation. In order to propose a comprehensive mechanism, it is important to have all reaction classes for bio-oil thermal decomposition, and the major challenge is the presence of

47 wide range of cyclic oxygenated species in the model. In particular, more attention should be paid in looking at specific reaction classes for decomposition of levogucosan, xylopyronase, and lignin that are crucial steps during bio-oil gasification. In chapter 1, it’s been investigated that some specific reactions classes for bio-oil gasification are missing in RMG-built models for bio-oil gasification. Two of these missed reaction classes are primary ring-opening isomerization reactions that can take place through direct C-C or C-O bond breaking and H-migration reactions at the same time. Products from C-O bond breaking reactions are mostly H2OandCO2 that are the main gaseous products of bio-oil gasification, and would have significant impact on model prediction. However, bond dissociation energies are determining either C-C or C-O bond breaking is more feasible. RMGs kinetics database now updated with reaction recipes for these two new reaction families. Furthermore, rules to predict Arrhenius rate parameters for the new reaction classes were specified. However, the number of possible reactions in each reaction family is massive, and applying high-level electronic structure calculations for each would be prohibitively expensive. Instead, rate calculations were performed for a smaller set of reactants belonging to the particular reaction class, then the rules of the di↵erent functional groups were deliberated, and group-based rate rules were derived to estimate Arrhenius parameters for any reaction in the new reaction classes. To provide more realistic detailed kinetic model for syngas production from bio-oil gasification, RMG-built kinetic models have been simulated with Cantera in zero-dimensional batch reactor assuming constant volume and adiabatic condition, and simulation results were compared with literature. There are some significant di↵erences in simulation results between RMG-built models before and after updating the database with new reaction families, specifically in CO and CO2 predictions. Discrepancies in the models show the important role of specific reaction families when studying biofuels thermal conversion, motivating further studies in complexities like the kinetic of heterocyclic molecules. This chapter addresses all taken steps in updating RMG’s kinetic database with two

48 new reaction families and ab initio calculation details to extract reaction rate rules for new families.

2.2 Critical literature review

One of the major diculties in the detailed kinetic modeling of biofuels is defining system composition. Biomass composition as cellulose, hemicellulose and lignin, can not describe the system well, as constituents are not well-defined molecules. One possible solution is to used a set of model compounds for each biomass constituent. To generate complete and reliable detailed kinetic models for biomass model compounds, the type of reaction classes that can be used for such modeling should be specified as well. However, both cyclic and acyclic compounds are presented in the biomass composition and each class of compounds need their own specific reaction families. This section of thesis briefly addresses previous studies on biofuels both specific acyclic and cyclic reaction families and missing ones in RMG’s kinetic database.

2.2.1 Speciﬁc reaction classes for acyclic components of biofuels

Generally, there are three main types of acyclic saturated molecules in biofuels [9]: ethers [87], alcohols [88] and methyl esters [89]. Molecule’s Bond Dissociation Energies (BDE) can determine which reaction channels are most feasible in the primary thermal decomposition of the acyclic molecules. Tran et al. [9] calculated the Bond Dissociation Energy (BDE) in acyclic oxygenated molecules and concluded that the presence of the oxygen atom in the molecule makes the BDE di↵erent from hydrocarbon molecules, illustated in Figure 2.1.

49 An example of BDE in an ester molecule:

An example of BDE in an ether molecule: An example of BDE in an alcohol molecule:

Figure 2.1: Calculated bond dissociation energies (in kcal/mol) in ester, ether, and alcohol molecules by Tran et al. [9].

Ethers, alcohols and ethyl esters can go through types of reaction classes such as unimolecular initiations, bimolecular initiations, and H-abstractions, decomposition of radicals by -scission and intramolecular isomerizations.

2.2.1.1 Unimolecular initiations

Unimolecular initiation reaction involves the unimolecular decomposition of an energized reactant molecule into the radical products and is the ﬁrst step of the chain initiation mechanism. The activation energy of the primary initiation reactions depend on the strength and BDE of the C-C, C-O bonds, and also the position of the carbon atom as primary, secondary, and tertiary. However, the reverse reaction of the unimolecular decomposition is the radical recombination and the rate of the unimolecular initiation can be calculated from the reverse rate by having the thermochemical data [90, 91]. Moreover, the activation energies of radical recombination reactions are set to be zero as barrier-less reactions and the modiﬁed Arrhenius pre-exponential factors (A) can be estimated from an improved collision theory [91]. RMG’s kinetic database includes these unimolecular initiation steps for acyclic molecules in biofuels modeling. As an example, Figure 2.2 illustrates the initiation reaction rate of the butanol and its reverse rate estimated in RMG.

50 Radical-Recombination: (reverse reaction)

Barrier less reaction rate 3 7 ✕ ✕ from collision theory: k(T) (m )/(mol s) = 1.15 10

Unimolecular-initiation: (forward reaction)

Reaction rate from reverse rate -1 ✕ 21 ✕ -1.4 ✕ and thermochemistry properties: k(T) (s ) = 5.4 10 T exp( - 374.7( kJ/mol) / RT )

Figure 2.2: Rate of the initiation and radical recombination reaction of butanol in RMG [10].

2.2.1.2 Bimolecular initiations and H-abstractions

Bimolecular initiation reactions such as H-abstraction involve the collision of the two energized molecules and are the most common reaction classes in the fuels thermal decomposition. The general reaction template of H-abstraction reaction family is illustrated in Figure 2.3.

1R 2H + 3R 1R + 2H 3R

Figure 2.3: General reaction template of H-abstraction reaction family.

For hydrocarbons with no heteroatoms, the rate constants of bimolecular reactions depend on the type of alkyl H-atoms which can be abstracted: primary –CH3, secondary –CH2, or tertiary –CH [9]. However, the abstraction of H atom from a primary carbon is the most dicult one due to the high BDE and abstracting the H from a tertiary one is the easiest. In the case of oxygenated molecules, the BDEs are di↵erent from hydrocarbons and it’s been observed that the C-H bonds next to the oxygen atoms are weaker [9] (Figure 2.1). From previous studies for alkanes [92] and experimentally reported values [93], the Arrhenius pre-exponential factors (A) for H-abstraction are set to A = 7.0 1012 ⇥ (cm3/mol s) per abstractable H atom and the barrier height to the enthalpy of reaction ⇥ [94]. For ethers, the barrier for the H-abstraction from a carbon atom in the ↵-position of the oxygen atom reduced about 4 kcal/mol in comparison to the case of alkanes, proposed by Buda et al. [94].

51 Moreover, for H-abstraction from ↵-position carbon of the alcohols, the reaction rate can be expressed as an Evans-Polanyi type correlation [95]. The Evans-Polanyi correlations describes the relationship between barrier height of the reaction (E) and enthalpy of the reaction H, in which for a similar reactions belong to a particular reaction family EisproportionaltoH:

E = E f(H H)(2.1) ref ref

Thus: E f(H H) k(T )=n AT n exp( ref ref )(2.2) H RT

where nH is the number of abstractable H-atoms and R is the gas constant; A, n, and E0 are the Arrhenius rate expression parameters; ’ref’ refers to the reaction in the set chosen as a reference. For H-abstraction reaction family Dean and Bozzelli [95] chose ethane as the reference molecule and Href is the enthalpy of the reaction by the radical from ethane. H is the enthalpy of the reaction by the radical from the reacting molecule; fisacorrelationfactorandforeachradicalthefvaluesaregivenbyDeanandBozzelli [95]. Luo in his handbook [96] reported the BDE of the O-H bond in alcohols as 102 and 106 kcal/mol and the value is close to the C-H bond in an alkylic primary H-atom. Thus several research groups such as [94] used similar reaction rate parameters for H- abstraction from alcohol function to those for the abstraction from an alkylic primary H-atom. RMG’s kinetic database is rich in kinetic data for alcohols, esters, and ethers H- abstraction reactions estimated from either published literature or rate rules.

2.2.1.3 Radicals decomposition by -scission

-scission is an important reaction to form reactive free radicals in fuels thermal decomposition processes. The general template of the reaction is illustrated in Figure 2.4.

52 2R 1R 3R 2R 1R + 3R

Figure 2.4: The general template of the -scission reaction and formation of free radical upon this reaction class.

Glaude et al. [87] proposed some reaction rate parameters and barrier height values for the ethers. Later on, Glaude et al [89] in a new modeling study, obtained some reaction rate parameters for esters from quantum chemical calculations in CBS-QB3 level of theory. Table I summerizes some example of the barrier height of -scission reactions for oxygenated species. Buda et al. [94] proposed that the barrier heights for C-C bond breaking in saturated hydrocarbons are usually between 26 and 31 kcal/mol, however, values in Table I shows that how presence of the oxygen can a↵ect the reaction barrier.

Table I: Example of -scission reaction’s barrier heights for oxygenated compounds.

Reaction Barrier height (kcal/mol) Reference

5.1 CBS-QB3[9]

49.0 DFT [97]

15.0 From reverse reaction [59]

15.6 DFT[97]

2.2.1.4 Intramolecular isomerizations

In this type of isomerization reactions an H atom or OH function can transfer in the molecule through a cyclic transition state. The general reaction template for both reaction families is illustrated in Figure 2.5.

53 Intra H migration: 3H 2R 1R 2R 1R 3H

Intra OH migration: 1R 2O 3OH 3HO 1R 2O

Figure 2.5: The general template of intramolecular H and OH migration reaction families and formation of free radical upon these reaction classes.

The ring strain of the transition state structure can inﬂuence the kinetics of these families. In case of esters, Wiberg et al [98] studied the enthalpies of formation and the strain energies of monocyclic lactones with 5-14-membered rings via isodesmic reactions. They concluded that ring strain energies are equal to 9, 11, 11.2, and 12.5 kcal/mol for lactones and 6.3, 1, 6.4, and, 9.9 kcal/mol for alkyl radicals for 5, 6, 7, and 8 membered ring, respectively, and the larger ring molecules have smaller strain energies. From the literature review of biofuels speciﬁc acyclic reaction families, it is concluded that RMG handles kinetics of acyclic compounds well and all reaction families with associated data are available for alcohols, esters, and ethers.

2.2.2 Speciﬁc reaction classes for cyclic components of biofuels

Recently, many studies have been conducted for modeling the oxidation of cyclic alkanes [99–102]. Buda et al. [99] modeled oxidation of the cyclohexane in both low and medium temperature range (650-1050 K). They developed their model using computer- aided generation with 513 species and 2446 reactions and did some evaluations for the kinetics of the cyclic ether. Cavallotti et al. [100] performed ab initio calculations and reactor simulations to estimate the kinetics of the oxygen attack to the cyclohexane radical. They observed that the because ring strain energy the activation energies of cyclic alkanes slightly increased in comparison with the equivalent data for linear alkanes. Cyclic alkanes can go through speciﬁc types of reaction classes in thermal decomposition processes, such as unimolecular initiations, endo/exo tautomerizations, and isomerization of peroxy radicals. In the following sections, a brief introduction to each reaction family is provided:

54 2.2.2.1 Unimolecular initiations

Unimolecular decomposition of the cyclic compounds leads to the biradical intermediates formation. Sirjean et al. [11] conducted a theoretical study of the unimolecular decomposition of cyclobutane, cyclopentane, and cyclohexane in gas phase using quantum chemistry calculations. They investigated feasible reaction channels for biradical decomposition and validated their calculations with available experimental data. They proposed that the main reaction channels in the cyclobutane case are the decomposition to two ethylene molecules, Figure 2.6 (a), and internal disproportionation of the biradicals producing 1-pentene and 1-hexene in the case of cyclopentene and cyclohexane, Figure 2.6 (b, c), respectively.

(a) (b)

(c)

Figure 2.6: Proposed detailed mechanism of (a) ethylene,(b) 1-pentene, and (c) 1-hexene formation by Sirlean et al. [11] from the primary decomposition of the cyclobutane, cyclopentane, and cyclohexane and by considering di↵erent conformers of C4, C5, and C6 biradicals, respectively.

55 2.2.2.2 Endocyclic and exocyclic ring-opening in cyclic radicals

Sirjean et al.[103] in another study showed that for the cyclic alkyl radicals in the presence of a lateral alkyl group, ’exo’, and ’endo’ ring opening reactions are another feasible reaction channels. If the cyclic compound does not have any functional groups, then any radical created from the parent compound can go through the endo ring openings. However, in case of exo ring opening reaction, presence of the functional groups on the parent molecule causes the formation of radicals on the functional group and the double bond outside the cyclic part, Figure 2.7.

Exo ring opening:

Endo ring opening:

Figure 2.7: Exo and endo ring-opening reactions for Cyclobutylcarbinyl radical and Cyclobutyl radical.

From quantum chemistry calculations in CBS-QB3 level of theory, Sirjean et al. [103] concluded that the in the endo ring-opening reaction there is an increase of the activation energy as the ⇡ bond is being formed in contrast to the exo ring-opening reaction in which the ⇡ bond is formed on the side chain. Detail investigation on the speciﬁc reaction classes for cyclic components of biofuels must be performed, since still not adequate studies are available. In this Chapter of thesis, one-step endocyclic and exocyclic ring-opening concerted reactions were studied in further detail for bio-oil oxygenated cyclic compounds and results were compared with two-steps unimolecular decomposition pathway through diradical intermediates in section 2.4.

56 2.2.3 Reaction rate calculation for biofuel compounds

Recently, theoretical methods and quantum chemistry calculations are remarkably improved for accurate reaction rate calculations [104–106]. At the same time, the increase of CPU power allows the wide use of computers to deal with the complexity of the chemical reaction systems and cto alculate the reaction rates fast and accurately enough. These type of calculations typically use quantum chemistry methods such as Density Functional Theory, statistical mechanics methods for calculating partition functions, frequencies, optimized geometries, etc. and reaction rate theory such as Transition State Theory to obtain accurate reaction rate estimates. This section of thesis explains the general work ﬂow to directly calculate modiﬁed Arrhenius rate coecient parameters for reactions, A, n, and Ea.

2.2.3.1 Quantum chemistry

Lately, there is a big improvement in quantum chemistry calculations thanks to the development of accurate but a↵ordable quantum chemistry methods. Examples of popular methods include the G family (G1 [107, 108], G2 [109], G2MP2 [110], G3 [111], G3MP2 [112], G3MP2B3 [113], G3B3 [113], G3S [114]), the complete-basis-set family (CBS-Q [115], CBS-APNO [116], CBS-RAD [117], CBS-QB3 [116]), and hybrid density functional theory (DFT)/HartreeFock (HF) methods [118]. Furthermore, more expensive methods that are using more complicated treatment for some orbitals or conﬁgurations include CCSD(T) [119], CAS-PT2 [120], MR-CI [121, 122], and Martins W family [123]. To accurately compute the thermochemical quantities the use of both static and dynamic electron correlation e↵ects in the quantum chemistry methods are required [124]. However, the use of these type of methods is very costly and only applicable for small systems. Instead, composite methods such as CBS can be applied with lower cost for larger systems. CBS is based on the use of one determinantal wavefunctions and applies

57 an infinitely large basis set by combining energies from lower level theories. The most accurate CBS method is CBS-APNO (Atomic Pair Natural Orbital) and CBS-QB3 is about two times less accurate than CBS-APNO but significantly faster. Basic di↵erence between Gaussian methods such as G1, G2, G2MP2, G3, etc. is that Gaussian increases accuracy by adding in more empirical terms to correct for known issues with the models being used, while CBS corrects the energy by trying to extrapolate the basis set to the infinite basis set [125].

2.2.3.2 Statistical mechanics

In statistical thermodynamics, the state of a molecule is described by the partition function. The molar partition function, Q, represents the product of the partition functions of each degree of freedom of the molecule:

Q = Q Q Q Q Q Q (2.3) trans ⇥ extrot ⇥ introt ⇥ vib ⇥ elec ⇥ sym

The electronic partition function, Qelec, only considered when the molecule contains an odd electron. The standard entropy is related to the molar partition function according to:

@ ln(Q) S = k ln(Q)+k( ) (2.4) @ln(T ) V

By combining Equation 2.3 and 2.4, standard entropy can be expressed as:

S = Strans + Sextrot + Sintrot + Svib + Selec + Ssym (2.5)

Moreover, the contribution of the molecule’s symmetry in the standard entropy would be:

58 S = S Rln()(2.6) intr

Where is the symmetry number. Frequency factors, A factor, for unimolecular and bimolecular reactions can be calcu-

# lated from Equation 2.12 when the standard activation entropy, S , of the reaction

# is known. S can be calculated from the di↵erence in standard entropy between the transition state complex, Sts , and the reactants, Sreactant :

# S = S ⌃S (2.7) ts reactants

And to consider the symmetry contribution:

# ts S = Sts ⌃Sreactants + Rln( )(2.8) ⇡[reactant]

Therefore, by combining Equation 2.5 and 2.8, the standard activation entropy would be:

# # # # # # S = S + S + S + S + S trans extrot introt vib elec ts ⌃S(reactants)+Rln( )(2.9) ⇡[reactant]

# The calculation of S in Equation 2.9 will be di↵erent for every speciﬁc reaction family.

2.2.3.3 Transition State Theory

Eyring et al. [126] were the ﬁrst that presented a quantitative formulation of Transition State Theory (TST), and they called it activated complex theory in their paper. To date,

59 many research groups started using this theory to apply to practical cases. For example, Benson [59] discussed the application of the theory to various types of gas-phase reactions in his book and Cohen [127] used the theory to extrapolate experimental rate constants to higher temperatures. Based on the transition-state theory, the rate constant of a reaction can be written as:

kT k c)=( )K# (2.10) ( h c

# Where k(c), is the reaction rate constant, Kc is the equilibrium constant for the formation of the transition state complex from the reactants, T is the absolute temperature

23 (K), k is the Boltzmann constant, 1.38 10 J/K, and h is the Planck constant, 6.62 ⇥ 34 10 J.s. This equation is valid both for unimolecular and bimolecular reactions and ⇥ # the only di↵erence between both types of reactions is in the equilibrium constant, Kc . While a reaction is happening, one of the internal vibrations of the activated complex is converted into the reaction coordinate and the partition function corresponding to this

# degree of freedom is removed from the equilibrium constant. Thus, Kc , is a modiﬁed equilibrium constant [128, 129]. Moreover, by combining the the Arrhenius rate expression with the rate constant expression from TST, equation 2.10, the activation energy, E, and the frequency factor, A of the reaction cane be expressed as [128]:

# # E = H +(1 v )RT (2.11)

# # kT (S v Rln(RT) A = exp(1 v#)exp( )(2.12) h R

# # Where H and S are the standard enthalpy and the standard entropy of activation. v# is the change in number of moles in the transition from the reactants to

60 the transition state complex, which is 0 for unimolecular reactions and -1 for bimolecular reactions. The calculated standard activation entropy and enthalpy for the transition state complex, can be used in the reaction rate expression via TST:

# kBT n 1 G k(T )=(T ) V exp( )(2.13) h m RT

Where, (T )isthetunnelingfactor,Vm the molar volume, n the molarity of the reaction, n=1 for unimolecular, n=2 for bimolecular, and G# the di↵erence in free energy between the transition-state geometry and the reactant(s). G# calculates from H# and S# by the following thermodynamic expression:

G# = H# T S# Hreac + T Sreac (2.14)

2.2.4 Reaction rate estimation methods

As the number of reactions in each family is massive and applying quantum chemistry calculation for every reaction is expensive, rate estimation methods can be used instead. This section brieﬂy highlights some recent-developed estimation methods such as Evans- Polani correlations or rate calculation rules [106, 130].

2.2.4.1 Linear Free Energy Relationship (LFER)

Linear Free Energy Relationship (LFER) describes the relationship between reactions rate coecient and Gibbs free energy of the reaction. This relationship is expressed in transition-state theory (TST), Equation 2.13, which in the case of no tunneling factor is:

G# G#,ref ln(k(T )) = ln(kref (T )) (2.15) RT

61 The well-know expression of the mentioned equations is as [131] Hammett equation:

ln(k(T )) = ln(kref (T )) + ⇢ (2.16)

where is the weight of the substituent on the reaction rate as the Hammett parameter and ⇢ is a reaction class speciﬁc constant. Hammett and later Taft [132] listed resonance, hyperconjugation, induction, and steric e↵ects as stabilizing or destabilizing factors for transition states.

2.2.4.2 Evans-Polanyi correlation

Another well-known correlation for reaction rate estimation is Evans-Polani [95] relationship and it’s based on the linear correlation between reaction exothermicity and changes of the barrier height:

# H = Ea + mHR (2.17)

Which will give:

E = Eref + m(H Href )=constant + mH (2.18) a a R R R

The Evans-Polanyi correlation assumes that the pre-exponential A factor of the Arrhe- nius rate expression and the position of the transition state along the reaction coordinate are the same for all reactions belonging to a speciﬁc reaction family.

2.2.4.3 Reaction Class Transition State Theory (RC-TST)

Truong et al. [133, 134] introduced class transition state theory (RC-TST) for estimations of reaction rate constants for a large number of reactions in a given class. RC-TST method is based on the fact that as all the reactions belonging to a speciﬁc reaction family, have

62 the same reacting centers, therefore their potential energy surfaces along the reaction coordinate are very similar and can be extrapolated. This method uses the Evans-Polanyi relationship to estimate reaction barrier heights and Arrhenius pre-exponential factor by performing low level of electronic structure calculations such as DFT. In this approach, contribution of the di↵erent internal modes, symmetry, and tunneling to the partition functions, can be evaluated separately.

2.2.4.4 Rate calculation rules

Carstensen et al. [130] have shown that the rate parameters of many elementary reactions belonging to a speciﬁc reaction family can be generalized and expressed as rate rules. In their proposed rate rules approach, the temperature dependence of rate expressions of a reaction family is expressed in terms of a temperature exponent (n) and a barrier height (E) that is related to the exothermicity of a reaction by the Evans-Polanyi relationship. The pre-exponential factor (A) can be determined by averaging rate constants of a test set reactants. Even though this type of method has been available for long time, but it’s application is limited as there are not enough rate rule expressions available. One of the biggest concerns in the rate rules application, is about it’s transferability and how similar areactionshouldbetothereferencereaction,orhowmanyraterulesarerequiredto estimate the kinetics of the whole family. Most reaction rate rules which originate from literature were covered in the RMG’s kinetic database. Nevertheless, for some reaction families like exo/endocyclic ring opening reactions, new rate rules were determined from quantum calculations as explained in further detail in section 2.4.

63 2.3 Computational Method

As we saw in Chapter 1, Reaction Mechanism Generator (RMG) generates kinetic models by predicting reactions according to a set of reaction families, which each contain a recipe and a set of rules to estimate the kinetics. When pathways are missing, either the template for an existing reaction family needs to be made more general, or a new reaction family must be created. In Chapter 1, it was shown that RMG’s kinetic database was missing speciﬁc reaction classes for tautomerization ring-opening reactions [135]. Generally, ring-opening tautomerization reactions occurs in two structural fashions: 1) exocyclic and 2) endocyclic. As shown in Figure 2.8, exocyclic ring-opening reaction happens through direct R1-R2 bond breaking and H-migration at the same time. During this single-step isomerization reaction, the cyclic component will go through the unimolecular decomposition to the acyclic component. As an example, primary ring opening reaction of xylose, a type of sugar in biomass composition, is demonstrated in Figure 2.8.

1R 2R 3R H H 1R 2R 3R OH O OH

O OH

HO OH OH OH

Figure 2.8: The general template of the exocyclic tautomerization ring- opening reaction family. The example is shown for the primary ring- opening reaction of xylose, a type of sugar from wood.

Endocylic tautomerization, similar to the exocyclic family, can occur through the direct R2-R3 bond breaking and H-migration reactions inside the ring, as shown in Fig- ure 2.9.

64 H

1R 2R 3R H 1R 2R 3R

OH OH

O OH O OH O OH

OH OH

Figure 2.9: The general template of the endocyclic tautomerization ring-opening reaction family. The example is shown for the endocyclic ring-opening reaction of levoglucosan, a derivative of cellulose pyrolysis.

After updating RMG’s kinetics database with reaction recipes for two new reaction families, rules to predict Arrhenius rate parameters for the given reactions must be specified as well. RMG’s kinetic database is structured as trees and the hierarchy of the tree is an important factor in rate rule calculations. To apply the rate rules for new reaction families, hierarchical trees are constructed based on the two facts; first, the root of the tree is the most general group in the family. Second, children nodes at the very base of the tree are the most specific groups and they are di↵erent from each other based on the di↵erent functional groups around the reactive center and the atom types. When kinetics are determined for a reaction, the rules will search for the corresponding groups. If an exact match for an appropriate rule can’t be found in the database, RMG will average rules with similar groups. To generalize a specific reaction kinetic parameters to other similar reactions in the exo/endocyclic ring-opening reaction families, test set reactions on which to perform the quantum chemistry calculations are constructed based on the three factors: atom type, ring size, and functional groups (Figure 2.10). Kinetic groups for these reaction families are designed for Carbon, Oxygen, and Nitrogen heteroatoms and four ring sizes, 4-membered, 5-membered, 6-membered, and 7-membered rings, have been chosen to test the e↵ect of the ring size in the rate calculation rules.

65 4-membered ring

5-membered ring C 6-membered ring

7-membered ring

HN 4-membered ring H2N

NH 5-membered ring H2N

N NH 6-membered ring H2N

7-membered ring NH2

Exo ring opening O 4-membered ring OH

5-membered ring OH O

6-membered ring OH

O 7-membered ring OH

O OH 4-membered ring O OH

O OH OH HO

5-membered ring O

OH OH OH

O OH OH 6-membered ring O OH HO OH OH OH OH OH OH O OH OH O 7-membered ring HO OH OH OH

HO OH

(a)

4-membered ring

5-membered ring C 6-membered ring

7-membered ring

NH2 4-membered ring HN

5-membered ring NH N H N NH H 6-membered ring N

Endo ring opening NH H 7-membered ring N

4-membered ring OH O 5-membered ring O

O 6-membered ring O

O 7-membered ring O

OH OH O 6-membered ring O HO HO OH OH OH OH OH O OH OH 6-membered ring O OH HO OH OH OH OH H O OH OH

7-membered fused ring O OH HO OH O OH OH H H OH OH O

7-membered fused ring O OH HO O OH

OH OH H (b)

Figure 2.10: Hierarchical tree for (a) exocyclic and (b) endocyclic ring- opening reaction families. 66 All the quantum chemistry calculations were performed in Gaussian09 [62] and consist of three major steps. First, optimized geometries and frequencies for reactant and product species are calculated by using density function theory methods at B3LYP [136] level of theory with the 6-31G(d) basis set. Then the geometries obtained in the first step are used to find statistical molecular properties of each species in the reaction using CBS-QB3 [116] level of theory. Finally, transition state theory has been used to determine the Arrhenius rate parameters using calculated statistical thermodynamic properties in the CanTherm [137] package. Transition state searches for the four-membered rings single-step tautomerization reactions are skipped in both endocyclic and exocyclic reaction families due to the high ring strain energies. Moreover, it’s been observed that the boat conformations work for the transition states searches in these families after trying di↵erent conformers. For the vibrational partition function, the harmonic oscillator approximation has been assumed and hindered rotor calculations are skipped due to the floppy transition states. All the obtained frequencies from CBS-QB3 are scaled by a factor of 0.99 [138]. In spite of this, Arrhenius pre-exponential factor (A) is influenced by any errors in the frequency calculations more than the reaction barrier height (E), and as the di↵erences in reaction rate coecients are mostly associated with the barrier height (E) [139], the harmonic oscillator approximation should be reasonably valid for these calculations. Finally, Intrinsic Reaction Coordinate (IRC) [140] calculations have been performed to track the minimum energy path from a transition state to the corresponding reactant and product species.

2.4 Results and Discussions

Arrhenius rate parameters from CBS-QB3 calculations for the exocyclic reactions in the test set are presented in Table II. Also, the calculated rate coecients within the temperature range of 300-2000 K for the exocyclic ring-opening reactions are plotted in Figure 2.11 and 2.12.

67 Table II: Arrhenius rate constant parameters for exocyclic ring-opening reactions from CBS-QB3 calculations.

1 Reaction A (S ) n E (kJ/mol) 9.08 1010 0.97 106.0 ⇥ 1739.33 3.52 381.54

1.71 109 1.67 483.07 ⇥

9 H2N 8.13 10 1.12 335.97 HN ⇥ NH 2.28 1011 1.03 300.095 H2N ⇥

NH 10 NH2 1.11 10 0.95 314.09 ⇥ 9 OH 6.29 10 0.91 289.0 O ⇥ O 1.23 1010 1.01 351.92 OH ⇥

O 11 OH 1.19 10 0.02 360.29

⇥

O OH HO

OH 14 O 6.77 10 -0.41 192.58

⇥ OH OH OH

O OH OH

8 O OH 2.00 10 1.24 151.47 HO OH OH OH ⇥ OH OH OH O OH OH O HO 13 OH 6.11 10 0.73 176.24 OH OH ⇥

HO OH

68 20

0 0 0.5 1 1.5 2 2.5 3 3.5

-20

-40

log (k)(m3/mol.s) log -60

-80

-100 1000 K / T

(a)

OH 0 O 0 0.5 1 1.5 2 2.5 3 3.5 O

-20 O OH

-40

log (k)(m3/mol.s) log -60

-80

-100 1000 K / T

(b)

Figure 2.11: High pressure limit rate coecients within the temperature range of 300-2000 K for exocyclic ring opening test set reactions to investigate the rate calculation rules. (a) results for the ﬁve, six, and seven membered carbon rings (b) results for the ﬁve, six, and seven membered oxygen rings.

69 20

H2N

0 NH 0 0.5 1 1.5 2 2.5 3 3.5 NH2

NH -20 H2N

-40

log (k)(m3/mol.s) log -60

-80

-100 1000 K / T

(a)

O OH OH

O OH HO OH 0 OH OH OH OH OH O OH 0 0.5 1 1.5 2 2.5 3 3.5 OH O HO OH OH OH

HO OH O OH

-20 HO OH

OH OH OH -40

log (k)(m3/mol.s) log -60

-80

-100 1000 K / T

(b)

Figure 2.12: High pressure limit rate coecients within the temperature range of 300-2000 K for exocyclic ring opening test set reactions to investigate the rate calculation rules. (a) results for the ﬁve, six, and seven membered nitrogen rings (b) results for the ﬁve, six, and seven membered oxygen rings with additional ’OH’ groups

Figure 2.13 shows the comparison between the rate coecients of the ﬁve, six, and seven-membered rings across the carbon, oxygen, and nitrogen heteroatoms at T= 1100 K.

70 10$ ' 5$

R5$ 0$ R6$

R7$

log(k)'at'T=1100K'(m3/mol.s) !5$

!10$ C$ N$ O$

Figure 2.13: Rate coecient of the four, six, and seven membered rings across the C, N, and O heteroatoms in exocyclic test set reaction at T= 1100 K.

Results show that the rate calculation rules for the test set reactions including nitrogen and oxygen heteroatoms in five, six, and seven-membered rings are promising , Figures 2.11 (b) and 2.12 (a). It should be taken into account that rings with nitrogen and oxygen heteroatoms are simple rings including no additional functional groups, and calculations show that the rate calculation rules are transferable for additional similar reactions. In the most cases, the oxygenated-ring reactions, occurring in the biomass thermal conversion, have additional ’OH’ functional groups. To investigate the e↵ect of the ’OH’ functional groups, the rate rule calculations are extended for the five, six and seven membered rings with oxygen as the heteroatom. As illustrated in 2.12 (b) rate calculation rules can still be applied to this family for the reactions with additional ’OH’ functional groups. Nevertheless, the rate calculation results for carbon rings, shown in Figures 2.11 and 2.13, are di↵erent from nitrogen and oxygen rings and five membered carbon ring is not well-grouped with six and seven membered rings. In this test set, reaction rates are different based on the ring size particularly at lower temperatures; the rate constants for the six and seven membered rings are lower than the five-membered ring. Part of the

71 reason can be related to the conformation of the methylcyclopentane. Flat confirma- tion of cyclopentane with planar bond angle of 108, has very high torsional strain. The planer cyclopentane can, however, pucker in half-chair or envelope conformers with less torsional strain [141]. Furthermore, cyclopentane conformation is sensitive to the nature of functional groups, hence, di↵erent substituents, such as methyl group in the methylcyclopentane, can significantly a↵ect puckering of the ring. In spite of the di↵erent behavior of the five-membered carbon ring in the current calculations, for the purpose of automatic detailed mechanism generation, which needs a large number of rate parameters to be calculated quickly on the fly, rate rules can stay reasonably valid. Meanwhile, kinetic analysis tools such as a sensitivity analysis or flux analysis can be used to identify the important reaction channels in the detailed kinetic model and from there, further attention can be paid to those particular reactions by applying high-level quantum chemistry calculations. Sirjean and Klippenstein [11, 142] in their cyclohexane decomposition study have shown that the isomerization of cyclohexane to 1-hexene through a single step endocylic ring-opening reaction, avoiding formation of the diradical intermediate, is not favorable because of its lower entropy of activation even though the single-step reaction has the lower barrier. To investigate the rate rule application for endocyclic ring-opening reaction family, bicyclo-octane single-step ring opening reaction rate was compared versus the two- steps reaction pathways.

72 TS1 451 kJ/mol

TS2 TS3 273 kJ/mol 261 kJ/mol

240 kJ/mol

Single step: -0.8 kJ/mol

Two steps: -21 kJ/mol

• • CH H2C

Figure 2.14: Potential energy diagram for bicyclo-octane isomerization to 3-ethylcyclohexene calculated at the CBS-QB3 level through single step-endo ring-opening vs. two-steps pathway with a diradical intermediate.

Calculation shows that the single-step reaction is more favorable and has a lower barrier height compared with the two-step reaction channel as shown in Figure 2.14. Generalizing a conclusion for the entire reaction family from this single evidence is dicult and requires further investigation. Nevertheless, for the automatic mechanism generation, which needs a large number of rate coecients to be calculated reasonably cheaply, the single-step ring-opening as the favorable reaction channel can remain relevant. Rate constant calculation results within the temperature range of 300-2000 K for the single-step endocyclic ring opening reactions are plotted in Figures 2.15, 2.16 , and 2.17

73 and also rate parameters are presented in Table III. Further, the comparison between the reaction rate coecients of the ﬁve, six, and seven-membered ring containing carbon, oxygen, and nitrogen heteroatoms at T=1000 K is illustrated in Figure 2.18.

Table III: Arrhenius rate constant parameters for endocyclic ring- opening reactions from CBS-QB3 calculations.

1 Reaction A (S ) n E (kJ/mol)

1135 4.65 442.01

188727 3.21 441.09

24055.2 3.42 411.63

NH 5.62 108 2.30 486.85 N H ⇥ NH H N 6.05 1010 1.31 494.00 ⇥

NH H 10 N 5.41 10 1.20 470.52

⇥ O

1.35 107 2.80 399.99 O ⇥ O O 6.21 1010 1.40 495.61 ⇥

O 9 O 2.05 10 2.24 466.71 ⇥ OH OH O 10 HO HO OH 4.21 10 1.27 389.95 OH OH OH ⇥ OH O OH OH

8 O OH 7.35 10 2.07 468.60 HO OH OH OH ⇥ OH H OH OH O 10 O OH HO 4.61 10 0.97 249.00 O OH ⇥ OH OH H H O OH OH

8 O OH HO OH 6.19 10 2.22 298.70 O ⇥ OH OH H

74 30

0 0" 0.5" 1" 1.5" 2" 2.5" 3" 3.5" -30

-60

log$(k)$(m3/mol.s)$ -90

-120

-150 1000$K$/$T$ (a)

0 O O 0" 0.5" 1" 1.5" 2" 2.5" 3" 3.5" O

O -30

-60

log$(k)$(m3/mol.s)$ -90

-120

-150 1000$K$/$T$

(b)

Figure 2.15: High pressure limit rate coecients within the temperature range of 300-2000 K for endocyclic ring opening test set reactions to investigate the rate calculation rules. (a) results for the ﬁve, six, and seven membered carbon rings (b) results for the ﬁve, six, and seven membered oxygen rings.

75 30

NH N 0 H NH H 0" 0.5" 1" 1.5" 2" 2.5" 3" 3.5" N

NH H -30 N

-60

log$(k)$(m3/mol.s)$ -90

-120

-150 1000$K$/$T$ (a)

H OH OH O

O OH HO 0 O OH OH OH H

H O OH 0" 0.5" 1" 1.5" 2" 2.5" 3" 3.5" OH

O OH HO OH O OH -30 OH H

-60

log$(k)$(m3/mol.s)$ -90

-120

-150 1000$K$/$T$

(b)

Figure 2.16: High pressure limit rate coecients within the temperature range of 300- 2000 K for endocyclic ring opening test set reactions to investigate the rate calculation rules. (a) results for the ﬁve, six, and seven membered nitrogen rings (b) results for the six membered rings with additional ’OH’ functional groups.

76 30

OH OH O

HO HO OH 0 OH OH OH OH 0" 0.5" 1" 1.5" 2" 2.5" 3" 3.5" O OH OH

O OH HO OH OH OH -30 OH

-60

log$(k)$(m3/mol.s)$ -90

-120

-150 1000$K$/$T$

Figure 2.17: High pressure limit rate coecients within the temperature range of 300-2000 K for endocyclic ring opening test set reactions to investigate the rate calculation rules for the seven membered fused rings.

0$ ' !5$

R5$ !10$ R6$

R7$

!15$ log(k)'at'T=1100K'(m3/mol.s)

!20$ C$ N$ O$

Figure 2.18: Rate coecient of the four, six, and seven membered rings across the C, N, and O heteroatoms in endocyclic test set reaction at T= 1100 K.

Results show that the rate coecients for ﬁve, six, and seven membered carbon and

77 oxygen and nitrogen rings are grouped well together and rate rules are transferable in this family to similar reactions for quick and accurate rate estimation Figures 2.15 and 2.16. The calculations are extended for the six-membered oxygenated ring with additional ’OH’ groups to study the impact of the functional groups, and as shown in Figure 2.16 (b), the rate rules application is evenly valid in these cases as well. Primary fused ring- opening of levoglucosan, as an important cellulose derivative, through endocyclic single step tautomerization reaction, appears as an important step in studying biomass thermal conversion. Rate constants for levoglucosan’s initiation steps, have been calculated to investigate the rate rules relevance, Figure 2.17. Though, there are slight di↵erences in the reaction rates at lower temperatures, still the rates can be represented from rate rules for similar reactions in the family for quick and cheap on the ﬂy automatic estimation.

2.4.1 Case study: E↵ect of new reaction families on Bio-oil gasi-

ﬁcation

As described in detail in chapter 1, Bio-oil composition is defined in terms of three reference elements: carbon, oxygen, and hydrogen and its thermal conversion is very sensitive to the fuel chemistry. Depending on the initial source of the biomass, bio-oil contains di↵erent amounts of organic acids, ketones, furans, levoglucosan, and other phenolic and cyclic oxygenated molecules [27–31]. Gasification of bio-oil at the high temperature and pressure is a desirable process for syngas production. A detailed kinetic model for bio-oil gasification at high temperature was previously built in RMG [135]. To provide more realistic detailed kinetic model for syngas production from bio-oil gasification, RMG-built kinetic models have been simulated with Cantera [66] in a zero-dimensional batch reactor, assuming constant volume and adiabatic conditions, and simulated synagas species concentrations were compared with the literature [1, 2]. As shown in Figure 2.19 (a, b, c), the previously RMG-generated model couldn’t pre-

78 dict CO and CO2 formation properly. After performing flux analysis, it has been identified that RMG-built model was missing ring-opening initiation reactions [135]. Since products from primary ring opening reactions through CO bond breaking have major contributors to CO and CO2 formation, the bio-oil gasification mechanism has been updated after adding these new reaction classes and associated kinetic parameters from rate calculation rules. There are some significant di↵erences in simulation results between the RMG-built models before and after updating RMG’s kinetic database shown in Figure 2.19 (c, d), which demonstrates the importance of these reaction families and their kinetic features when studying the thermal conversion of biofuels.

79 (a) Experiment I (b) Experiment II 1.00 CH4

0.75 H2

0.50 CO

Syngas Fraction Syngas 0.25 CO2 0 600 700 800 900 1000 1100 1200 1300 1400

Temperature (C)

0.50 CO

Syngas Fraction Syngas 0.25

0 CO2 600 700 800 900 1000 1100 1200 1300 1400 Temperature (C)

(d) RMG model after updating reaction classes 1.00 CH4 0.75 H2

0.50 CO

Syngas Fraction Syngas 0.25

0 CO2 600 700 800 900 1000 1100 1200 1300 1400 Temperature (C)

Figure 2.19: Distribution between four major gas components as a function of temperature, (a) from experimental work by Zhang et al.[1] at 100C intervals from 600 to 1000 C, (b) from Chhili et al.[2] at 100C intervals from 1000 to 1400 C , (c) RMG-built model at 100C intervals from 600 to 1400 C before updating RMG’s kinetic database (d) after updating RMG’s kinetic database with new reaction families.

2.5 Summary

Developing predictive detailed chemical models for heterocyclic compounds, that are important intermediates in di↵erent complex chemical systems, is challenging. To propose

80 acomprehensivemechanism,moreattentionshouldbepaidinlookingatspecificreac- tion classes that are specific to heterocyclic species and their associated rate parameters. In the present study, a mechanistic study of the tautomerization reactions as important initiation ring-opening steps in heterocyclic molecules, is presented. Reaction Mechanism Generator (RMG) is used to build detailed kinetic models for chemical systems including large number of heterocyclic compounds. To test the e↵ect of the new families after updating the RMG’s database with two new reaction families, a previously generated bio-oil gasification model has been re-built. After adding reaction recipes for two families, electronic structure methods have been used to study the kinetics and relevance of the rate rules. As the rate estimates are based on the local structure of the reacting sites, the e↵ects of the ring size, atom type and functional groups in the rate calculation rules have been investigated for the two new reaction families. In spite of the fact that some rate constants, such as five-membered carbon ring belonging to the exocyclic ring-opening family, is not well grouped with the six and seven membered rings, still generalized rate calculation rules have sucient accuracy for calculating the large number of possible reactions quickly with a low computational cost. After generating the detailed reaction network with known kinetic parameters, sensitivity analysis or reaction flux analysis can be performed to identify the crucial reactions channels in the model. Then high-level quantum chemistry calculations can be applied to study these reactions in further details with sucient accuracy. Lastly, new families have impacted the bio-oil detailed kinetic modeling significantly and as there are only few kinetic models concerning alargenumberofheterocyclicderivatives,continuouskineticstudiesofthedecomposition these compounds are required.

2.6 Supporting material

Cartesian coordinates of all transition states are provided in Appendix A.

81 2.7 Recommendations for future work

This study has made signiﬁcant contributions toward generating automatic detailed detailed kinetics models for biofuels. Particular attention has been given to the accurate and computationally a↵ordable estimation of reaction rate coecients for bio-oil’s cyclic and oxygenated compounds using rate calculation rules approach. The success of this method, was demonstrated by comparing RMG-build models for bio-oil gasiﬁcation process before and after updating RMG’s kinetic database with new rate rules. However, still there are several challenges towards building predictive detailed chemical kinetics for biofuels using RMG. In the current section, several such challenges for future work are addressed.

2.7.1 Expand the e↵ect of the functional groups

To investigate the e↵ect of the functional groups, the rate rule calculations were performed for the e↵ect of the ’OH’ groups on ﬁve, six, and seven membered rings with oxygen as the heteroatom. To fully study the e↵ect of the ’OH’ functional groups, rate rule calculations should be extended to ﬁve, six, and seven membered rings with carbon and nitrogen as the heteroatoms. Therefore, still several rules are needed to be updated in RMG’s kinetic database in order to obtain reasonable estimates for type of exo/endo ring-opening reactions.

2.7.2 Add more reaction families with associated data to the

RMG database

In constructing detailed kinetics models for biofuels, as mentioned in Chapter 1, the presence of all the feasible elementary reactions in the model is necessary. For example, RMG needs new reaction family for ene reactions, such as 1,5 hydrogen shift reaction speciﬁed as a missing reaction family in Chapter 1. The ene reaction is a reaction between

82 an alkene with an allylic hydrogen (the ene) and a compound containing a multiple bond (the enophile), in order to form a new -bond with migration of the ene double bond and 1,5 hydrogen shift [143]. The ene reaction is useful CC forming tool for the many lignin derivative molecules and is a typical type of reaction that is happening in lignin pyrolysis. The general template and an example of this reaction is illustrated in Figure 2.20.

R3 R3 R 1 R4 R1 R4 + R 2 R5 R2 R5 H 6 H6

Figure 2.20: The general template of ene reaction with an example.

After updating the database with the new reaction family, it is necessary to obtain accurate kinetic parameters and reaction rate rules.

83 Chapter 3

Automatic Reaction Mechanism Generation for Producing 1,1,2,3-tetrachloropropane

3.1 Introduction

As introduced by our collaborators in Mexichem Fluor: ”The fluorochemical sector of the global chemical industry is currently gearing up to replace existing products with equivalents that o↵er the same performance characteristics but with lower global warming potential (GWP). Thus, the current generation of hydrofluorocarbon (HFC) products will be replaced with hydrofluoroolefins (HFOs). Key to the timely commercialisation of HFOs will be the availability of chlorinated feedstocks from which they can be con- veniently prepared. 2,3,3,3-Tetrafluoropropene (1234yf) is one of the leading low GWP HFO products identified as a possible replacement for 1,1,1,2-tetrafluoroethane (134a) in mobile air conditioning applications. The key chlorinated feedstock for 1234yf manufacture is 1,1,2,3-tetrachloropropene (1230xa), which can be prepared by two routes, one starting from ethylene and the other from tetrachloroethylene”. Both pathways include

84 several steps of dehydrochlorination and free chain radical chlorination reactions. Detailed kinetic modeling of these processes can be a helpful tool to better understand, design and optimize 1230xa production. There are several published patent applications with limited numbers of reactions and intermediates, showing the recognized value of this kinetic modeling approach. However, building a detailed chemical model with an extensive set of free radical reactions, that contains a large number of intermediates and reactions and needs many associated thermodynamic and kinetic parameters, is not easy to do by hand; it is preferable to do it automatically, using a tool that is exhaustive and scalable. In this chapter, I extend the Python version of Reaction Mechanism Generator (RMG-Py), an open source and free tool, to generate such detailed kinetic models for chlorinated hydrocarbons. RMG includes C, N, O, S, and Si chemistry; in order to add chlorine, Cl, chemistry into the software, several steps were taken that are explained in this chapter. Further- more, an RMG-generated model was validated by comparing with available data from literature. Building predictive detailed chemical models for chlorination processes using RMG can save several months of research and development time and cost for manufac- turing companies and for each new process, and the models can also be used to optimize existing processes to lower costs of production.

3.2 Critical Literature Review

Chlorinated hydrocarbons are chemical compounds composed of carbon, hydrogen, and chlorine. These compounds can be used as intermediates to produce other chemicals or can be used directly as chlorinated solvents. Chemical and pharmaceutical companies are the main chlorinated hydrocarbons customers for a variety of applications such as refrigerants, aerosol product formulation, dry cleaning detergents, pharmaceutical solvents, and paint formulation and stripping. 1,1,2,3-tetrachloropropene, 1230xa, with the

85 chemical formula CCl2=CClCH2Cl, is an important chlorinated intermediate that is used widely to produce the new generation of the refrigerants. Detailed kinetic modeling of 1230xa chlorination can be a helpful tool to better understand, design, optimize, and commission refrigerant processes. To date, there are several published patents proposing important reaction channels for 1230xa production, showing the recognized value of the kinetic modeling approach. In this section of thesis, a brief literature review regarding proposed reaction pathways for 1230xa production from published patents is provided. Moreover, few studies regarding thermodynamics of chlorinated species and exist kinetics estimation of chlorination reactions in the literature also are addressed in this section of thesis.

3.2.1 Proposed pathways from published patents

Smith [12] proposed a method to produce 1230xa from 1,2,3-trichloropropane in the liquid phase. The summary of the proposed method is as the following steps:

Chlorination of the 1,2,3-trichloropropane in the presence of azobisisobutyroni- • trile catalyst, reaction and products illustrated in Figure 3.1, and passing the chlorinator e✏uent which made up of 1,2,3-trichloropropane, 1,1,2,3- tetrachloropropane, 1,2,2,3-tetrachloropropane, 1,1,1,2,3-pentachloropropane, 1,1,2,2,3-pentachloropropane, and 1,1,2,3,3-pentachloropropane to a fractionating column.

86 Cl Cl

Cl Cl

Cl 1,1,1,2,3-pentachloropropane

Cl Cl

Cl Cl Cl 1,1,2,2,3-pentachloropropane Cl Cl + Cl Cl

1,2,3-trichloropropane Cl Cl

Cl Cl

1,2,2,3-tetrachloropropane

Cl Cl

Cl 1,1,2,3,3-pentachloropropane

Figure 3.1: Reaction and products from 1,2,3-trichloropropane liquid phase chlorination in the presence of azobisisobutyronitrile catalyst proposed by Smith [12].

Recycling the 1,2,3-trichloropropane fraction to the chlorinator and removing the • 1,2,2,3-tetrachloropropane fraction

Passing the 1,1,1,2,3- and 1,1,2,2,3-pentachloro propanes fraction from the fraction- • ating column to the second caustic dehydrochlorinator

Dehydrochlorinating the second chlorinator e✏uent and the 1,1,1,2,3- and 1,1,2,2,3- • pentachloropropanes fraction from the fractionating column.

Passing the second dehydrochlorinatore e✏uent, including 1,1,2,3- • tetrachloropropane and 2,3,3,3-tetrachloropropane to an isomerizer packed with siliceous granules with polar surface and isomerizing the 2,3,3,3-tetrachloropropane to 1,1,2,3-tetrachloropropane, summerized in Figure 3.2.

87 Cl Cl Cl

Cl Cl Cl

Cl Cl - HCl Cl 1,1,1,2,3-pentachloropropane 2,3,3,3-tetrachloroproeene

isomerization

Cl Cl

- HCl Cl Cl Cl Cl

Cl Cl Cl 1,1,2,2,3-pentachloropropane 1,1,2,3-tetrachloropropene

Figure 3.2: 1230xa formation reaction channels via 1,1,1,2,3- and 1,1,2,2,3-pentachloropropanes dehydrochlorination and 2,3,3,3- tetrachloropropane isomerization to 1230xa proposed by Smith [12].

Later, Woodard [13, 14] proposed a process to 1230xa production by dehydrochlorination of 1,1,1,2,3-pentachloropropane in the presence of a ferric chloride catalyst. Their process includes these steps and the complete mechanism is summarized in Figure 3.3:

Preparing 1,1,1,3-tetrachloropropane by reacting ethylene with carbon tetrachloride • in the presence of of metallic iron and a promoter for the reaction, phosphorus (V) compounds containing a phosphoryl group

Dehydrochlorination of 1,1,1,3-tetrachloropropane to produce 1,1,3- and 3,3,3- • trichloropropenes

Chlorinating of the 1,1,3- or 3,3,3-trichloropropenes to produce 1,1,1,2,3- • pentachloropropane, 240db.

Dehydrochlorinating the 1,1,1,2,3-pentachloropropane, 240db, to produce a mixture • of 1,1,2,3- and 2,3,3,3-tetrachloropropenes

Isomerization of 2,3,3,3-tetrachloropropene to 1,1,2,3-tetrachloropropene by con- • tancting the tetrachloropropenes mixture with a rearrangement catalyst

88 Cl Cl Cl

+ Cl Cl Cl Cl ethene 1,1,1,3-tetrachloropropane Cl carbon tetrachloride

-HCl

Cl Cl Cl and Cl Cl Cl 1,1,3-trichloropropene 3,3,3-trichloropropene

+Cl2

Cl Cl Cl Cl Cl -HCl Cl Cl 2,3,3,3-tetrachloroproeene Cl 1,1,1,2,3-pentachloropropane -HCl isomerization 240db

Cl Cl

Cl 1,1,2,3-tetrachloropropene 1230xa

Figure 3.3: 1230xa formation reaction channels by reacting ethylene with carbon tetrachloride from the work of Woodard [13, 14].

These two proposed processes for 1230xa production were in solvent phase that required a long reaction time and had high cost due to use of catalysts. To overcome these diculties associated with the proposed methods, Mukhopadhyay et al. [15], and Wilson et al. [16] introduced a method for 1230xa production as illustrated in Figure 3.4:

Dehydrochlorination of 1,2,3 trichloropropane with an alkali (NaOH) •

Two rounds of chlorination reaction with chlorine, (Cl ), and repeating these reac- • 2 tions to produce 1,1,2,2,3-pentachloropropane, 240aa

Removing HCl from 1,1,2,2,3-pentachloropropane to produce l,1,2,3- • tetrachloropropene

89 Cl Cl

Cl Cl -HCl Cl

1,2,3-trichloropropane 2,3-dichloropropene

+Cl2

Cl Cl

-HCl Cl Cl Cl Cl

Cl Cl Cl 1,1,2,2,3-pentachloropropane 1,1,2,3-tetrachloropropene 240aa 1230xa

Figure 3.4: 1230xa formation reaction channels from 1,2,3 trichloropropane proposed by Mukhopadhyay et al. [15] and Wilson et al. [16].

Nevertheless, this proposed method still had a lower yield and generated too much waste because of using alkali. Furthermore, Nose et al. [17] introduced a method for 1230xa production from heating 1,1,1,2,3-pentachloropropane,240db, in the gas-phase for non-catalytic dehdrochlorination reaction. They reported the process as, Figure 3.5:

Heating 1,1,1,2,3-pentachloropropane, 240db, to 200-550 n absence of catalyst •

Dehydrochlorination of 1,1,1,2,3-pentachloropropane,240db, by simultaneously pro- •

viding inert gas, N2, in an amount of 0.5 to 100 mol per mol of 1,1,1,2,3- pentachloropropane

Returning unreacted 1,1,1,2,3-pentachloropropane and 2,3,3,3- • tetrachloropropene,1230xf, if it’s in the product, to the reactor for further conversion

90 Cl Cl Cl Cl -HCl Cl Cl Cl Cl Cl 2,3,3,3-tetrachloroproeene 1,1,1,2,3-pentachloropropane -HCl 1230xf 240db isomerization

Cl Cl

Cl 1,1,2,3-tetrachloropropene 1230xa

Figure 3.5: Non-catalytic gas phase reaction channels proposed by Nose et al. [17] for 1230xa formation.

They concluded that the operating in such method can produce 1230xa with a high selectivity. They also highlighted the importance of the process temperature; lowering the process temperature from the mentioned range, would decrease the 1230 conversion ratio and increasing the temperature would cause the formation of cyclic dimers, dechlorinated 3,3,3-trichloropropene, etc. as by products and lower the selectivity. Their results, showing the reactor outlet from their method in 4 di↵erent examples, summarized in Table I.

Table I: The results obtained from the reactor outlet for 1230xa production in non catalytic gas-phase reaction according to the Nose et al. [17] method.

Condition Example 1 Example 2 Example 3 Example 4 Reaction temperature (C) 350 400 285 350 Contact time (sec) 10.2 47 22 24.9 240db Conversion ratio (%) 75.4 73.4 48.8 77.6 1230xa selectivity 97.9 90.3 96.8 88.3 1230xf selectivity 1.6 1.5 2.3 2

3.2.2 Thermodynamics of chlorinated hydrocarbons

Thermodynamic properties of the chlorinated hydrocarbons are important in the detailed chemical modeling of chlorocarbon systems and to study their thermodynamic equilib-

91 rium. There are two methods available to estimate the thermochemistry of chlorinated hydrocarbons; performing electronic structure calculations and using group-based estimates such as Benson Group Additivity (GA) approach [59]. Quantum chemistry calculations at at higher level of theory and also for larger systems, to obtain a good estimate, are computationally expensive. Even though using cheaper methods are faster, they don’t have the sucient accuracy for Hfsofchlorocarbons[18].Dewaretal.[144]intheir

AM1 quantum mechanical calculations reported that the error in Hf for more than 60 chlorocarbons were larger than 5kcal/mol.Furthermore,LiZhuetal.[145]calculated ±

Hf298, S298 and CP (T ), 300 < T < 1500 K, for all C1 and C2 and eight C3-C6 chlorocarbons using MOPAC6 PM3 [61] and compared with the literature. In their theoretical study, they concluded that PM3 derived S298 and CP (T ), are in good agreement with the literature, but for H , there were 5 kcal/mol error, similar to the Dewar et al. [144] f298 ± observations. Using the Benson’s GA approach to estimate the thermochemistry of the chlorinated hydrocarbons is a valuable method [146, 147]. However, the Benson GA approach does not fully consider the steric e↵ect, termed as non-next-nearest-neighbor interactions, of the adjacent functional groups such as chlorine or methyl on the thermodynamic properties. Chen et al. [18] developed chlorinated groups while considering the e↵ect of the non-next- nearest-neighbor interaction for use in thermodynamic estimation of the chlorocarbons using Benson GA approach. They derived the Benson groups for chlorinated alkanes and alkenes from molecules where no chlorines were on the carbon next to the carbon atom bonded to chlorine(s). They also used gauche interactions [59] to consider the non-next- nearest-neighbor e↵ects in their previous studies [148, 149]. In conclusion, they illustrated that the interactions increased in highly chlorinated hydrocarbons and the correction to account the interaction term should be increased as well, as shown in Figure 3.6.

92 Figure 3.6: The correction in the enthalpies of formation for accounting the e↵ect of interaction as function of number of chlorine atoms for multichloro alkanes and alkenes, reproduced from [18].

Furthermore, they compared their results with literature and showed good agreement between their calculations and literature data with the error H = 0.29 kcal/mol, f298 ± S = 0.68 cal/mol.K and C (T )= 0.23 cal/mol.K. 298 ± P ±

3.2.3 Kinetics of chlorinated hydrocarbons

As mentioned earlier, many natural and industrial processes to manufacture chlorinated products such as 1230xa, include detailed reaction mechanism networks. In order to propose a comprehensive mechanism for each process, speciﬁc reaction classes, which deﬁne how chlorinated hydrocarbon species could react with each other, are required. Like other free radical reactions, chlorination mechanism includes three steps: initiation steps, propagation steps, and termination steps. For example, methyl chloride production through a complete detailed mechanism of methane chlorination is illustrated in Figure 3.7.

93 Figure 3.7: Initiation, propagation and termination free radical reaction steps in methyl chloride production via methane chlorination.

3.2.3.1 Initiation steps

Free radical reaction mechanism starts with initiation step to initiates the reaction, which in the chlorination case, is the separation of the Cl2 into two Cl radicals with single unpaired electrons via the equal splitting of a Cl-Cl bond. Therefore, the reaction rate depends on the the strength and bond dissociation energy (BDE) of the Cl-Cl bond. Moreover, the reverse reaction of the initiation reaction is the radical recombination, already exists in RMG, and the rate of the initiation can be calculated from the reverse rate by knowing the thermochemical data [90, 91]. The activation energies of radical recombination reactions are set to be zero as barrier-less reactions and the modiﬁed Arrhenius pre-exponential factors (A) can be estimated from an improved collision theory [91].

3.2.3.2 Propagation steps

Propagation step is the reaction of one reactive radical species with a non-radical stable molecule to produce two new molecules: radical and stable molecules. Hydrogen abstraction and chlorine abstraction families are the most common reaction classes during the propagation step.

94 H-abstraction: The H abstraction from a chlorinated molecule via chlorine atom to • form a reactive molecule and a chlorinated stable molecule, is a common reaction. The general template of the reaction is demonstrated in Figure 3.8.

1R 2H + 3Cl 1R + 2H 3Cl

Figure 3.8: The general template of the H-abstraction reaction via chlorine atom.

Goldﬁnger et al. [23] investigated the H-abstraction reaction kinetics from chlorinated ethanes via chlorine atom in the gas phase experimentally, to study the non bonding interactions between the attacking chlorine atom and the chlorine atoms in the molecule. They observed that there is a decrease in the pre-exponential A factors in the highly chlorinated ethanes, on the other hand, activation energy increased with the number of chlorine atoms on the attacked carbon and the adjacent carbon atom. Furthermore, they calculated the bond dissociation energy D(C-H) and concluded that the D(C-H) decreases from CH H to CCl H. 3 3 Seetula [150] studied the e↵ect of the chlorine atom on the structure and bond dissociation energy of some chlorinated ethanes and propanes both theoretically and experimentally. He performed MP2 and MP4 calculations to investigate the e↵ect of di↵erent substituents on the C-H bond energies and also the e↵ect of the Cl atom on its adjacent C-H bond. He concluded that the ↵-C-H bond is weaker than the -C-H bond in chlorinated hydrocarbons and furthermore, the C-Cl bond becomes

weaker in the following order ( kJ/mol): 351.0 (CH3Cl) > 334.1 (CH2Cl2) > 315.1

(CHCl3) > 288.3 (CCl4), which is in great agreement with previous observations [151, 152].

Senkan et al. [19] studied the kinetics of the H-abstraction reaction of hydrocarbons and chlorinated hydrocarbons by chlorine atom and analyzed their result using Evans-Polanyi and structure-activity relationships (SAR). In their investigation,

95 they’ve shown that even the Evans-Polanyi correlation is valid for C1 chlorinated hydrocarbons, but they couldn’t ﬁnd such correlation for C2 chlorinated hydrocarbons (Figure 3.9).

Figure 3.9: Evans-Polanyi plot for H-abstractions from C1 and C2 chlorinated hydrocarbons by Senkan et al. [19].

To establish the SAR correlation Senkan et al. used Atkins [153, 154] approach by assuming the total rate of H-abstraction reaction by chlorine radicals can be expressed as a linear combination of the abstraction rates of primary, secondary, and tertiary H atoms. They showed promising success of the SAR analysis in kinetic modeling of chlorinated hydrocarbons by plotting the SAR predictions versus experimental data, Figure 3.10.

96 Figure 3.10: Comparison of SAR predictions with experimental data fro H- abstraction of chlorinated hydrocarbons by chlorine radical by Senkan et al. [19].

Cl-abstraction: The general template of the Cl-abstraction reaction is illustrated in • Figure 3.11.

1R 2Cl + 3R 1R +2Cl 3R

Figure 3.11: The general template of the Cl-abstraction reaction family.

Bryukov et al. [20] conducted an experimental study for the kinetics of the (Cl,H)-abstraction from chlorinated methanes by H atom using the discharge ﬂow/resonance ﬂuorescence technique over wide ranges of temperatures. They also used transition state theory and performed quantum chemistry calculations to obtain a correlation between the activation energies and enthalpies of the reactions, illustrated in Figure 3.12

97 H+ CH4 = H2 +CH3 H+CHCl3 = H2 +CCl3 H abstraction H+CH3Cl = H2 +CH2Cl (Open symbols) H+CH2Cl2 = H2+CHCl2} Cl-abstraction H-abstraction H+CCl4 = HCl+CCl3 H+CHCl3 = HCl+CHCl2 Cl abstraction H+CH2Cl2 = HCl+CH2Cl (Filled symbols) H+CH3Cl = HCl+CH3 }

Figure 3.12: Obtained correlation by Bryukov et al. [20] between activation energies and enthalpies of reactions for (Cl,H)-abstraction from chlorinated methanes by H atom attacks.

Furthermore, Louis et al. [21] investigated the (H,Cl,F)-abstraction kinetics of chlorinated methanes via H radical attacks theoretically. They performed the geometry optimization and frequency calculations at MP2 level of theory and single point energy calculations at CCSD(T) level. Furthermore, they used transition state theory to estimate the rate constants as a function of temperature, 700-2500 K. For the reactivity trend analysis, they correlated barriers with Evans-Polanyi relations to correlate barriers with heats of reactions. In this study, they’ve shown that the Evans-Polanyi correlation is valid for (H,Cl,F)-abstraction reactions via H radical attacks, and their results are illustrated in Figure 3.13.

98 Figure 3.13: Predicted Evans-Polanyi plot by Louis et al. [21] for (H,Cl,F)-abstraction reactions via H radical attacks for chlorinated methanes.

3.2.3.3 Termination steps

Free radical chlorination reaction will be terminated by loss of the free-radical intermediates and decreases in reactants concentration. The most common termination reaction, is radical recombination when two radicals couple to form a stable molecule. The general template of the radical recombination reaction class is illustrated in Figure 3.14. Once again, the activation energies of this family are barrier-less and the modiﬁed Arrhenius pre-exponential factors (A) can be estimated from collision theory [91].

1R + 2R 1R 2R

Figure 3.14: Radical recombination reaction family general reaction template

3.3 Computational Method

Between proposed reaction pathways for 1230xa production in Section 3.2.1, there are two main reaction channels to produce 1,1,2,3-tetrachloropropene (1230xa), as illustrated in Figure 3.15; one starting from 1,1,1,3-tetrachloropropane, red pathway in Figure 3.15, and the other from 1,1,1,2,2-pentachloropropane,blue pathway in Figure 3.15.

99 Figure 3.15: Main proposed reaction channels to produce 1,1,2,3- tetrachloropropene (1230xa) [12, 14–17]

Both pathways include several steps of dehydrochlorination and free chain radical chlorination reactions. Detailed kinetic modeling of these processes can be a helpful tool to better understand, design, and optimize 1230xa production. However, building a detailed chemical model with an extensive set of free radical reactions, that contains a large number of intermediates and reactions and needs many associated thermodynamic and kinetic parameters, is not easy to do by hand; it is preferable to do it automatically, using RMG. In order to propose a comprehensive mechanism for 1230xa production using RMG, four speciﬁc reaction classes, which deﬁne how chlorinated hydrocarbon species could react with each other, were used. Two of these reaction classes were new: the chlorine addition into the double bond and chlorine abstraction reactions that can take place through free radical chain mechanism. Two existing reaction families in RMGs kinetic database were updated with new chlorinated functional groups. Furthermore, thermodynamic data for these chlorinated species were estimated via Bensons group additivity approach and QM calculations. In the following sections, technical and computational aspects of detailed

100 kinetic model generation for 1230xa will be explained in further detail.

3.3.1 Chlorine (Cl) atom type in RMG

Before this work, RMG was able to model systems with only C, H, O, N, S, and Si atoms. To include chlorine chemistry, RMG’s molecule module was updated with Cl atom type. The atom type module of an atom in RMG describes the atom itself and some information about the local bond structure around that atom, for example, whether the atom is able to have single or double bond types with another atom. Chlorine belongs to the halogen group in the periodic table with seven valence electrons and by gaining only one electron can satisfy the octet rule [155], eight electrons in its valence shell. Thus, the current atom type for chlorine in RMG was deﬁned as chlorine atom with one single bond.

3.3.2 Thermodynamics of chlorinated hydrocarbons in RMG

Thermochemistry of chlorinated species in RMG can be estimated via three methods:

Species thermochemistry libraries •

Group based methods •

Quantum-chemical calculation • This section gives some detail descriptions of each method to determine the thermochemistry of the chlorinated species in 1230xa detailed kinetic modeling.

3.3.2.1 Species thermochemistry libraries

These libraries have known thermochemical parameters for both radical and stable species. Values for the thermochemistry of the species are from experimental data or high level quantum chemistry calculations. RMG’s thermo database was updated with a new thermochemistry library for chlorinated hydrocarbon, and standard heat capacity, standard

101 enthalpy of formation at 298K and standard entropy at 298K data, from direct quantum chemistry calculations and published literature [156, 157], were reported for every species in the library.

3.3.2.2 Group-based methods

RMG’s thermodynamic database includes functional groups for fast thermo estimates via the group additivity approach. For stable species, RMG mainly estimates the thermochemistry from the Benson Group Additivity (GA) [158] method, by dividing a molecule into functional groups and summing the contribution of each functional group to the overall thermodynamics. The accuracy of the using group additivity approach in the prediction of thermochemical parameters depends on two factors; 1) whether group values derived from other compounds can be used and, 2) accuracy of the group values. In order to enable RMG to estimate the thermodynamic of chlorinated species from GA method, the thermochemistry database of the RMG was updated with chlorinated functional groups. The values for these chlorinated groups were taken from the Chen et al. [18] study. Figure 3.16 shows the new implemented chlorinated functional groups in RMGs thermochemistry database with an example of calculated thermochemistry of chloroethene. As illustrated in Figure 3.16, comparison with NIST reported value for chloroethene [157] shows that the Benson group contribution approach is an accurate and fast method when functional groups are adequate.

102 Figure 3.16: RMG’s thermochemistry database was updated with new chlorinated functional groups. As an example, comparison between the chloroethene thermochemistry estimation via GA approach and NIST reported value shows a good agreement.

Furthermore, for radical species, RMG has Hydrogen Bond Increments (HBI) [159] groups that describe the inﬂuence of the loss of a hydrogen atom on enthalpy of formation, entropy, and heat capacity of the radical species. HBI correction groups can be coupled with Bensons Group Additivity method to estimate the thermochemistry of the radical molecules. Therefore, based on Lay et al. [159], the thermochemistry of the radical molecule, R⇤, can be calculated from the corresponding parent molecule by adding a HBI to account for the loss of a hydrogen atom using following equations:

H (R⇤)=HBI( H )+ H (R H)(3.1) f 298 f 298 f 298

C (R⇤)=HBI(C )+C (R H)(3.2) P P P

S (R⇤)=HBI(S )+S (R H)(3.3) 298 298 298

For the group-based thermochemistry estimation of the chlorinated radical molecules, RMG’s HBI database was updated with chlorinated groups, illustrated in Figure 3.17.

103 Radical HBI (ΔfHo298) HBI (So298) HBI (Cop 298) Parent molecule molecule (kcal/mol) (cal/mol*K) (cal/mol*K)

98.2 3.0 0.55

95.7 1.2 -0.31

109.9 1.5 -0.51

96.7 3.8 0.12

Figure 3.17: Hydrogen Bond Increment (HBI) calculations for chlorinated species.

Further, in order to consider the e↵ect of the Cl atom on its adjacent C-H bond, more HBI calculations were performed for the chlorinated hydrocarbons including two chlorine atoms next to the radical carbon. Calculation results were demonstrated in Figure 3.18 and RMG’s HBI database was updated with new calculated values.

o o o Parent molecule Radical molecule HBI(ΔfH 298) HBI(S 298) HBI(C p 298) (kcal/mol) (cal/mol*K) (cal/mol*K) 94.9 3.6 -0.16

99.5 3.2 0.42

111.9 2.0 -0.61

95.8 5.1 0.19

Figure 3.18: More HBI calculation to consider the e↵ect of the chlorine atom on its adjacent C-H bond.

3.3.2.3 Quantum chemistry calculation

As the computational cost increases exponentially with the number of heavy atoms, most of the quantum chemistry calculations for chlorinated compounds were performed at the CBS-QB3 [116] level of theory in the Gaussian09 package [62]. Geometry optimization and frequency calculations of all chlorinated radical and stable species were ﬁrst performed at B3LYP [136] level of theory with the 6-31G(d) basis set. The calculated geometries were then used to ﬁnd improved geometries, electronic energies, and frequencies at the CBS- QB3 [116] level of theory. The CanTherm [137] package was used to calculate the entropy and heat capacities as a function of temperature from those data. For the vibrational partition function, the harmonic oscillator approximation has been assumed and all the

104 obtained frequencies from CBS-QB3 calculations were scaled by a factor of 0.99 [138]. Furthermore, bond additivity corrections for CBS-QB3 standard enthalpies of formation were added from the work of Petersson et al. [160] for a C-H, C-C, C=C, and C-Cl bond as -0.11, -0.3, -0.08, and 1.29 kJ/mol, respectively.

3.3.3 Chlorination reaction families in RMG

RMG uses a database of reaction families to generate all the possible reactions that a species can undergo in the presence of the other species in the chemical mechanism; every reaction family represents a particular type of elementary chemical reaction, such as bond-breaking, or radical addition to a double bond. For generating free radical reaction mechanism for 1230xa production through several steps of free radical dehydrochlorination and chlorination process, two existing reaction families in RMG, hydrogen abstraction and radical recombination, were updated with chlorinated groups to make RMG able to build such models. Figure 3.19 (a) shows the general template of the H-abstraction reaction family, and to enable RMG to generate H-abstraction reactions for chlorinated species, R1, and R3 groups were updated to include chlorine atom and chlorinated functional groups Figure 3.19 (b) is related to radical-recombination reaction family and R1 and R2 groups were updated with chlorinated groups.

1R 2H + 3R 1R + 2H 3R (a)

1R + 2R 1R 2R (b)

Figure 3.19: The general template of the (a) H-abstraction reaction, (b) radical recombination reaction family.

Furthermore, two new reaction families for Cl-Cl/H-Cl addition into the double bond and chlorine abstraction reactions (Cl-Abstraction) were added into the RMG’s database,

105 reaction general templates were illustrated in Figure 3.20.

(a)

(b)

Figure 3.20: The general template of the (a) Cl-abstraction reaction, (b) Cl2/HCl addition into the double bond reaction family.

3.3.4 Kinetics estimation for chlorinated hydrocarbons in RMG

After updating RMG’s kinetic database with new reaction families and also updating the existing ones, the next step is filling the database with accurate kinetic parameters. For the radical recombination reaction family, as mentioned earlier, the activation energies were set to be zero and the modified Arrhenius pre-exponential factors (A) were estimated from an improved collision theory. Quantum chemistry calculations can be used to estimate Arrhenius rate parameters and fill the kinetics database for each reaction family. However, the number of reactions in each reaction family is massive, and applying high- level electronic structure calculations, would be prohibitively computationally expensive. Alternatively, the kinetic parameters can be taken from available data in literature and rate rule estimation.

3.3.4.1 Training Set

Each reaction family in RMG’s kinetic database includes three specific files; 1) groups that contain reaction recipe, definition of groups and reacting centers, 2) training set that contains a set of training reaction with known kinetic parameters and 3) rules that specify

106 kinetic parameters by averaging rate parameters from children nodes. There are several published kinetics data available for the H-abstraction by chlorine atom, Cl-abstraction and HCl insertion into double bond reaction families. Reported data from literature were used to fill in training and rules templates of the associated reaction families in RMG. In the training sets, each reported reaction was matched to a specific template with known kinetic parameters. Some of references uses as training sets in the three mentioned reaction families are briefly presented in the following section. Published reaction rates from the work of Goldfinger et al. [23] for primary, secondary, and tertiary hydrogen atom abstraction from chlorinated C1 and C2 hydrocarbons by chlorine radical, summarized in Table II, were used in the training set of the RMG’s H-abstraction family.

Table II: Used activation energy (cal/mol) and pre-exponential factor (l/mol.sec) as a training set reactions in RMG from the work of Goldﬁnger et al. [23] for the H-abstraction reaction by chlorine atom for chlorinated C1 and C2 hydrocarbons.

Type of H-atom attacked Reactant (RH) Ea (cal/mol) log10A (l/mol.sec) Primary C2H6 1050 10.95 Primary C2H5Cl 1500 10.05 Primary 1,1-C2H4Cl2 3400 10.00 Primary 1,1,1-C2H3Cl3 3600 9.40 Secondary C2H5C1 1500 10.55 Secondary 1,2-C2H4Cl2 3100 10.80 Secondary 1,1,2-C2H3C13 3700 10.15 Secondary 1,1,1,2-C2H2C14 2450 9.15 Tertiary 1,l-C2H4Cl2 1900 9.95 Tertiary 1,1,2-C2H3C13 3100 9.95 Tertiary 1,1,2,2-C2H2Cl4, 2450 9.95 Tertiary C2HCl5 3550 9.65

Furthermore, Senkan et al. [19] gathered reaction rate parameters of the chlorinated hydrocarbons hydrogen abstraction reaction by Cl radical from previous published literature to study the Evans-Polanyi and structure-activity relationships (SAR), and these data were used in the RMG’s H-abstraction family’s training set.

107 3.3.4.2 Quantum chemistry

All the quantum chemistry calculations were performed in Gaussian09 [62]. Density function theory methods at B3LYP [136] level of theory with the 6-31G(d) basis set were used to optimize geometries and frequencies for reactants and products. Then the obtained optimized geometries were used to ﬁnd statistical molecular properties of each species in the reaction using CBS-QB3 [116] level of theory. Transition state theory was applied to determine the Arrehnius rate parameters using calculated statistical thermodynamic properties in the CanTherm [137] package. For the vibrational partition function, the harmonic oscillator approximation was assumed and hindered rotor calculations were not included. All the obtained frequencies from CBS-QB3 are scaled by a factor of 0.99 [138]. Furthermore, Intrinsic Reaction Coordinate (IRC) [140] calculations have been performed to track the minimum energy path from a transition state to the corresponding reactant and product species.

3.3.4.3 Rate rules

For those reaction rates in the model that are not either reported in the literature (training set) or calculated via quantum chemistry calculations, RMG’s rate rules were applied to ﬁll the database and kinetics were averaged from the children nodes as an estimate. Though in these cases the kinetics estimation are less reliable than direct calculation, but previous studies showed the promising success of using these type of correlations in kinetic modeling of chlorinated hydrocarbons, such as SAR analysis results by Senkan et al. [19], Bryukov et al.[20], and Louis et al. [21] Evans-Polanyi correlation results, more detail is provided in section 3.2.3.2.

108 3.3.5 Model evaluation

After model generation, reaction mechanism evaluation is required. There are several methods to evaluate the mechanism; comparison to the available experimental data, reaction ﬂux analysis to reveal the dominant reaction channels, and sensitivity analysis to identify the sensitive rate parameters to reduce the uncertainty. After the mechanism evaluation, from the comparison between the model and available data, the model might need to be improved with new data. New data can be provided either from theoretical calculations or from literature. After updating the RMG’s databases with new data and ﬁxing bugs, a new model was built with the best chemical data.

3.4 Results and Discussions

A ﬁrst model was generated in Reaction Mechanism generator (RMG) for 1,1,2,3- tetrachloropropene (1230xa) production with 74 species and 936 reactions. Every species in the model has known thermodynamic properties and 936 reactions were based on the four implemented reaction families: H-abstraction, radical recombination, Cl abstraction, and HCl/Cl2 insertion into double bond, with associated reaction rate parameters. The output of the RMGs generated model in Chemkin format was used for the further simulation of 1230xa in batch reactor in Cantera [66]. Simulations were performed at atmospheric pressure, reaction temperature between 350 to 400 Cand25to30seconds residence time; these experimental operation condition were taken from the published patent by Nose et al. [17] for 1230xa production under non catalytic gas-phase conditions. The result from the batch reactor simulation for the concentration proﬁles of 1,1,2,3-tetrachloropropene (1230xa) ( product) and 1,1,1,2,3-pentachloropropane (240db) (feedstock) versus time is presented in Figure 3.21.

109 Figure 3.21: Batch reactor simulation of 1230xa (product) and 240db (feedstock) concentration proﬁles from RMG-built model.

To date, there is no complete reaction mechanism for 1,1,1,2,3-pentachloropropane (1230xa) production, and published patents only proposed a small number of reactions, as a mechanism for 1230xa. Therefore, validating the yield of the 1230xa production from the RMG-built model by comparing it with experimental data, has remained a challenge. The only relevant published data are from the work of Nose et al. [17], that looked at afewreactionsfrom1,1,1,2,3-pentachloropropane(240db)to1,1,2,3-tetrachloropropene (1230xa) and reported the conversion of 240db to 1230xa (more detail is discussed in Section 3.2.1). A comparison is provided for 1230xa conversion in Table III between RMG-built model and Nose et al. [17] patent, though this comparison is not ideal as the RMG-built model is more detailed than the patent.

110 Table III: 240db conversion (%) for 1230xa production from Nose et al. [17] patent and RMG- built model.

Model vs. experiment 240db conversion (%) Noseetal.[17]patent 78 RMG-built model 40

From the comparison, no absolute conclusion could be taken, but the low conversion of 1230xa from RMG-built model was a concern. In order to evaluate the model further, thermochemistry of the main species in the RMG-generated model was compared with available published data.

3.4.1 Thermodynamics evaluation

RMG estimated thermodynamics for both chlorinated stable and radical species were compared with NIST reported values for stable species and with CBS-QB3 quantum chemistry calculations for radical species. Comparison shows that thermodynamic parameters of stable molecules, calculated from the group additivity approach have a good agreement with NIST values, as illustrated in Table IV.

Table IV: RMG estimated thermodynamics for some chlorinated stable species.

Hf298 (kcal/mol) RMG GA estimate NIST -49.25 -45.40

-7.36 -9.6

-18.64 -20.6

-56.04 -53.1

111 But thermochemistry of chlorinated radical species in RMG may not be estimated accurately enough using the group additivity approach, Table V.

Table V: RMG estimated thermodynamics for some chlorinated radical species.

Hf298 (kcal/mol) RMG GA estimate CBS-QB3 6.64 -12.85

-4.24 -10.05

9.45 -8.76

3.86 -10.10

As mentioned in Section 3.3.2.2, to improve group additivity estimates in RMG, Hy- dogen Bond Increments (HBI) corrections were calculated to consider the e↵ect of the loss of a hydrogen atom on enthalpy of formation, entropy, and heat capacity of the chlorinated radical species. Using HBI corrections for estimating thermodynamic parameters via group additivity shows remarkable improvement thermochemistry of chlorinated radical compounds, as the comparison shown in Table VI.

112 Table VI: Group Additivity estimates improved when using HBI corrections for chlorinated radical compounds thermochemistry.

Hf298 (kcal/mol) GA estimate GA estimate with HBI CBS-QB3 6.64 -10.84 -12.85

-4.24 -9.62 -10.05

9.45 -6.11 -8.76

3.86 -13.64 -10.10

After improving thermochemistry estimation for chlorinated radical species, a new model was generated for 1230xa in RMG and batch reactor simulations were performed to demonstrate the 1230xa concentration proﬁle in the new model. There is a di↵erence between batch reactor simulation results with and without HBI corrections, illustrated in Figure 3.22, showing the important inﬂuence of the thermodynamic properties on the free radical chlorination chemical modeling.

113 Figure 3.22: Batch reactor simulation of 1230xa (product) and 240db (feedstock) concentration proﬁles from RMG-built model after including HBI corrections for thermochemistry estimation of chlorinated radical species.

Moreover, 240db conversion was increased in the new RMG-built model when using HBI corrections, illustrated in Table VII.

Table VII: 240db conversion (%) for 1230xa production from Nose et al. [17] patent and RMG- built models before and after adding HBI corrections.

Model vs. experiment 240db conversion (%) Noseetal.[17]patent 78 RMG-builtmodelwithnoHBIcorrections 40 RMG-builtmodelwithHBIcorrections 55

3.4.2 Reaction ﬂux analysis

Reaction ﬂux analysis was performed to reveal the important reaction channels for 1230xa production under the simulation conditions as shown in Figure 3.23. The main purpose of this analysis was comparing these important reaction channels with available proposed pathways in published patents.

114 250fb

240db

1230xa

Figure 3.23: Reaction ﬂux analysis result to reveal the important reaction channels in the RMG-built model for 1230xa production.

Published patents [16, 17], illustrated in Figure 3.24, conﬁrm the reaction ﬂux analysis result, Figure 3.23, which shows that the non-catalytic production of 1230xa in gas-phase from 1,1,1,2,3-pentachloropropane (240db), has a high yield as a single step reaction.

115 250fb

240db

1230xa

Figure 3.24: The published patent conﬁrms the reaction ﬂux analysis fom RMG-built model for 1230xa production.

3.4.3 Sensitivity analysis

A sensitivity analysis was carried out on a RMG-built model to identify the important reaction channels for 1230xa production under simulation conditions. The results for this analysis are summarized in Figure 3.25:

116 at T= 550 C

(a)

at T= 350 C

(b)

Figure 3.25: Sensitive reaction channels for 1230xa production in RMG-built model at (a) T=550 C and (b) T=350 C.

Sensitivity analysis shows that free radical reactions are greatly dominant in 1230xa production and some important reaction channels are not present in the patents. More- over, high sensitivity to the 240db and 250fb dehydrochlorination reactions shows a great agreement with the observation in the published patents. Furthermore, both sensitivity analysis and reaction ﬂux analysis show that the RMG- built model provides more detailed data for 123xa production as all competing chemical pathways and intermediates for the process are proposed in the model.

117 3.5 Summary

Due to the high contribution of chlorinated refrigerants to the global climate change and ozone depletion, refrigerant manufacturers are developing a new generation of refrigerants, each requiring di↵erent intermediates and feedstocks. The key chlorinated feedstock for new generation of refrigerants manufacture with lower Global Warming Potential (GWP) is 1,1,2,3-tetrachloropropene (1230xa). Detailed kinetic models are helpful to improve the understanding of chlorinated hydrocarbons conversion and address the knowledge gap in such systems. However, building predictive detailed kinetic models has high level of complexity due to the presence of large number of thermodynamic and kinetic parameters that must be estimated accurately. In this study, the Python version of the Reaction Mechanism Generator (RMG), was extended to build a detailed kinetic model for 1230xa production. RMG already has a good success in detailed chemical modeling of hydrocarbons in both gas and liquid phase that contain carbon, oxygen, nitrogen, sulfur, and silicon chemistry. To make RMG a capable tool to model chlorinated hydrocarbons, the software was modiﬁed with additional features. To ensure that RMG was not missing any pathways for chlorination processes, two speciﬁc reaction classes were implemented in RMG. These reaction classes were related to the Cl2/HCl insertion into the double bond and chlorine abstraction reactions that can take place through free radical chain mechanism. Furthermore, two existing reaction families, hydrogen abstraction and radical recombination, in RMG’s kinetic database were updated with new chlorinated groups. RMG mainly estimates the thermochemistry of the species from Benson Group Additivity (GA) method, by dividing a molecule into functional groups and summing the contribution of each functional group to the overall thermodynamics. To enable RMG to estimate the thermodynamic of chlorinated species from GA method, the thermochemistry database of the RMG was updated with chlori-

118 nated functional groups. A detailed kinetic model was built for 1230xa production using RMG and simulation results were compared with experimental data from the patent literature. To validate the thermochemistry of the both stable and radical chlorinated species, RMGs estimates from the GA approach were compared with NIST reported values for stable species and with CBS-QB3 quantum chemistry calculations for radical species. Comparison of the data shows that thermodynamic parameters of radical species in RMG may not be estimated accurately using the GA approach. To improve GA estimates, Hydrogen Bond Incre- ments (HBI) corrections were calculated to consider the e↵ect of loss a hydrogen atom on enthalpy of formation, entropy, and heat capacity of the chlorinated radical species. Using HBI corrections for estimating thermodynamic parameters via Group Additivity approach showed remarkable improvement for chlorinated radical compounds thermochemistry. Furthermore, sensitivity analysis and reaction ﬂux analysis were performed to reveal important reaction channels in the 1230xa production. Both analyses not only show a great agreement between RMG-built model and proposed pathways from published patents but also highlight that the RMG-built model provides more detailed data by proposing all competing chemical pathways and intermediates in the process.

3.6 Supporting material

The Chemkin ﬁle of the RMG-built model for 1230xa production is provided in Appendix B.

119 3.7 Recommendations for future work

This study has made several signiﬁcant contributions in building detailed kinetic models for chlorinated hydrocarbons, speciﬁcally for 1,1,2,3-tetrachloropropene (1230xa) production. Particular attention has been given to improve the understanding of the free radical chlorination process and kinetics and thermodynamics of such systems. However, there are still a number of challenges that need to be addressed in order to improve our detailed kinetic model generation capabilities for 1230xa production. In this section, several such challenges as recommendations for future work are discussed.

3.7.1 Improve accuracy of kinetics estimates

To move toward predictive chemical kinetics, a version of RMG-Py is under development that uses on-the-ﬂy quantum calculations to estimate rate coecients [165]. This tool can be used not only for automatically determining the kinetic parameters for hydrogen abstraction, chlorine abstraction and HCl addition into double bond reaction families, but also to improve accuracy of kinetics estimates in chlorination modeling. This tool has the ability to automatically determine transition state structures using quantum chemistry calculations and use Transition State Theory (TST) to calculate the rate parameters. Nevertheless, still part of the challenge will be the computational cost, as conducting quantum chemistry calculations for the transition state of all reactions is expensive. Another challenge is identifying the appropriate level of theory for chlorination reactions.

3.7.2 Liquid-phase chlorination modeling

The primary detailed model for 1230xa production is generated in gas-phase. The next step after estimating all the thermochemistry and kinetic parameters accurately in the

120 gas-phase, will be modelling 1230xa production in the liquid-phase as there are several published patents proposing 1230xa production in solvent phase. Furthermore, there some experimental data available for 1230xa production in liquid-phase for model evaluation purpose. In order to extend this project from gas-phase to liquid-phase such steps need to be taken:

RMG’s thermodynamic database must be modiﬁed with solvation thermochemistry • predictions to cover chlorinated hydrocarbons and relevant solvents [166].

Kinetic solvent e↵ects database for existing gas phase chlorination reactions families • is required to be developed [167].

Kinetic database should be updated with a library of known liquid phase reaction • rates.

3.7.3 Investigating the concerted E2 elimination reaction vs.

Sn2 substitution

Under homogeneous conditions, there are two competing pathways for dehydrochlorination reaction (HCl/Cl2 insertion into double bond) in the solvent phase, as illustrated in Figure 3.26:

Concerted E2 elimination reaction that are favorable for solution phase processes • Sn2 substitution reaction, one bond is broken and one bond is formed •

Figure 3.26: Reaction phath for concerted E2 elimination vs. Sn2 substitution.

121 The rate of the reaction for these two competing pathways depends upon the strength of the base. Generally, relatively strong bases are required for concerted E2 elimination reactions. The solvent for these type of reaction is often an alcohol, like ethanol, and water. The base resulting from deprotonation of the solvent better promotes elimination reactions. However, despite the solvent e↵ects, it is useful to ﬁnd the branching ratio between these two competing pathways in 1230xa reaction mechanism and their e↵ect in the ﬁnal model yield and selectivity.

3.7.4 Expand 1230xa modeling to ﬂuorination reactions

Fluorocarbons are manufactured by the controlled fluorination of chlorinated organic compounds. 1230xa is an intermediate in processing new low global warming potential refrigerants. After building a reliable and predictive model for 1230xa production and introducing the factors that can influence the selectivity and yield of 1230xa, the next interest will be performing similar modeling procedure for the fluorination and dehydroflu- orination of 1230xa. Figure 3.27 provides the overview for the next step of the project; building fluorination model based on the 1230xa detailed reaction mechanism.

CH =CH 2 2 CCl3CH2CH2Cl + CCl4 250fb -HCl

CCl2=CHCH2Cl 1240za

+Cl2

CCl3CHClCH2Cl 240db -HCl

CF3CCl=CH2 1233xf +HF CF CF=CH CCl2=CClCH2Cl -HCl 3 2 CCl =CCl 1230xa +HF CF3CFClCH3 1234yf 2 2 CH CCl Cl + CH Cl 3 2 3 244bb Used as 3 240ab refrigerant -HCl -HCl

CH2ClCCl2CHCl2 240aa CH2ClCH=CH2 Allyl chloride +Cl2

CH2ClCHClCH2Cl CH2ClCCl=CHCl +Cl 1,2,3-TCP 2 -HCl 1240xd -HCl CH3CH=CH2 CH ClCCl CH Cl -HCl 2 2 2 +Cl2 250aa ! CH2ClCH2ClCH3 CH =CClCH Cl ! CCl CH=CHCl +Cl2 2 2 CHCl CH=CCl 3 1,2-DCP 1250xf 2 2 1230zd 1230za -HCl -HCl

CCl3CH2CHCl2 CH2=CHCl + 240fa CCl4

Figure 3.27: One step closer to understanding the production of ﬂuorocar- bons refrigerants from chlorinated feedstocks.

122 Chapter 4

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133 Appendices

134 Appendix A

The largest mechanism for bio-oil gasiﬁcation generated in RMG-Java

The largest mechanism for bio-oil gasiﬁcation generated in RMG-Java is attached as a text ﬁle in supplementary material.

135 Appendix B

Transition State Geometries of Heterocyclic Compounds Reactions

Reaction Transition state geometry C"""""""""""1.02896"""""""""0.66996""""""""*0.27695" C""""""""""*0.22112"""""""""1.23646"""""""""0.23816" C""""""""""*1.34150"""""""""0.12500""""""""*0.08746" C""""""""""*0.68723""""""""*1.21933""""""""*0.07065" C"""""""""""1.34563""""""""*0.63637"""""""""0.21690" H"""""""""""0.53159""""""""*0.55685""""""""*0.70576" H"""""""""""1.66294"""""""""1.15857""""""""*1.00250" H""""""""""*0.47511"""""""""2.19746""""""""*0.21175" H""""""""""*0.22464"""""""""1.36484"""""""""1.32978" H""""""""""*2.13680"""""""""0.19807"""""""""0.65401" H""""""""""*1.76767"""""""""0.35961""""""""*1.06413" H""""""""""*0.83466""""""""*1.80540"""""""""0.83617" H""""""""""*0.84529""""""""*1.84944""""""""*0.94835" H"""""""""""1.19457""""""""*0.92699"""""""""1.25852" H"""""""""""2.14666""""""""*1.19417""""""""*0.26599" C"""""""""""1.06510"""""""""0.56867""""""""*0.18975" C""""""""""*1.31535"""""""""0.21473"""""""""0.17994" C""""""""""*0.88237""""""""*1.09158""""""""*0.28027" C"""""""""""1.29328""""""""*0.75932"""""""""0.29298" H"""""""""""0.77818""""""""*0.58369""""""""*0.83453" H"""""""""""1.83000"""""""""1.10005""""""""*0.74136"

NH H""""""""""*1.69625"""""""""0.21368"""""""""1.20200" N H""""""""""*2.04086"""""""""0.71978""""""""*0.46362" H H""""""""""*1.23870""""""""*1.96088"""""""""0.26423" H""""""""""*0.87564""""""""*1.25924""""""""*1.36003" H"""""""""""0.94717""""""""*1.14549"""""""""1.24605" H"""""""""""2.22847""""""""*1.21049""""""""*0.03800" N""""""""""*0.08995"""""""""1.21704"""""""""0.16485" H""""""""""*0.26671"""""""""2.01199""""""""*0.44607"

136 C"""""""""""1.15582""""""""(0.69726"""""""""0.37174" C"""""""""""1.55170"""""""""0.71994""""""""(0.01420" C""""""""""(0.53242"""""""""1.49685""""""""(0.32007" C""""""""""(1.30867"""""""""0.52392"""""""""0.40961" C""""""""""(1.19479""""""""(0.90582""""""""(0.05523" H""""""""""(0.57317"""""""""2.53450""""""""(0.01030"

O H"""""""""""2.23683"""""""""1.21220"""""""""0.67942"

O H"""""""""""1.86224"""""""""0.81043""""""""(1.05212" H"""""""""""0.78260""""""""(0.72896"""""""""1.41161" H"""""""""""0.01679"""""""""0.88280"""""""""0.61501" H""""""""""(1.89218"""""""""0.81257"""""""""1.27151" H""""""""""(1.82447""""""""(1.13651""""""""(0.92515" H""""""""""(1.48072""""""""(1.59345"""""""""0.75437" H"""""""""""1.99785""""""""(1.39740"""""""""0.33695" H""""""""""(0.30516"""""""""1.33676""""""""(1.36592" O"""""""""""0.14369""""""""(1.19484""""""""(0.50831" C""""""""""#1.12932"""""""""0.30087"""""""""0.22054" C"""""""""""1.66232"""""""""0.31836""""""""#0.21648" C"""""""""""1.18672""""""""#0.78091"""""""""0.37221" C""""""""""#1.14304""""""""#0.98842""""""""#0.40690" H""""""""""#0.77594""""""""#0.40679"""""""""1.10946"

O H""""""""""#2.08795"""""""""0.44944"""""""""0.79431" H"""""""""""1.88307"""""""""0.34661""""""""#1.27744" O H"""""""""""1.83382"""""""""1.23293"""""""""0.33200" H"""""""""""1.20888""""""""#1.75687""""""""#0.10187" H"""""""""""1.01508""""""""#0.81244"""""""""1.44505" H""""""""""#0.61115""""""""#1.24529""""""""#1.31377" H""""""""""#1.80013""""""""#1.73688"""""""""0.02543" O""""""""""#0.51572"""""""""1.35373""""""""#0.10368" C""""""""""#1.17593""""""""#0.66657""""""""#0.45797" C""""""""""#1.60089"""""""""0.69189"""""""""0.07585" C"""""""""""0.49071"""""""""1.55055"""""""""0.33764" C"""""""""""1.26360"""""""""0.60241""""""""#0.42042" C"""""""""""1.31988""""""""#0.82949"""""""""0.04463" C""""""""""#0.10027""""""""#1.33833"""""""""0.42006" H"""""""""""0.49000"""""""""2.58718"""""""""0.02113" H""""""""""#2.31524"""""""""1.23712""""""""#0.54240" H""""""""""#1.87160"""""""""0.69528"""""""""1.12988" H""""""""""#0.31732""""""""#1.13016"""""""""1.47308" H""""""""""#0.75760""""""""#0.55594""""""""#1.47500" H""""""""""#0.07610"""""""""0.91723""""""""#0.56598" H"""""""""""1.82782"""""""""0.95006""""""""#1.27446" H"""""""""""2.00237""""""""#0.97052"""""""""0.89809" H"""""""""""1.71536""""""""#1.44635""""""""#0.76849" H""""""""""#0.13473""""""""#2.42537"""""""""0.31022" H""""""""""#2.04354""""""""#1.32377""""""""#0.59778" H"""""""""""0.29792"""""""""1.40256"""""""""1.39303"

137 C"""""""""""1.11255""""""""'0.76238"""""""""0.38086" C"""""""""""1.62137"""""""""0.62351""""""""'0.00626" C""""""""""'0.39916"""""""""1.53458""""""""'0.36362" C""""""""""'1.24529"""""""""0.65418"""""""""0.40055" C""""""""""'1.30546""""""""'0.79641""""""""'0.00583" H""""""""""'0.36283"""""""""2.58221""""""""'0.08835" H"""""""""""2.32001"""""""""1.07159"""""""""0.70413" NH H"""""""""""1.96473"""""""""0.68203""""""""'1.03631" H N H"""""""""""0.77545""""""""'0.75882"""""""""1.43623" H"""""""""""0.10706"""""""""0.91237"""""""""0.59283" H""""""""""'1.82180"""""""""1.03930"""""""""1.22875" H""""""""""'2.03969""""""""'0.98908""""""""'0.80537" H""""""""""'1.61887""""""""'1.39661"""""""""0.86711" H"""""""""""1.92261""""""""'1.50067"""""""""0.34716" H""""""""""'0.17452"""""""""1.31711""""""""'1.39871" N"""""""""""0.02416""""""""'1.18508""""""""'0.51601" H"""""""""""0.05468""""""""'2.18482""""""""'0.66957" O""""""""""#3.53855""""""""#0.48759""""""""#0.64939" C""""""""""#2.18101""""""""#0.36251""""""""#0.44168" C""""""""""#1.57714"""""""""0.86694""""""""#0.17325" O""""""""""#0.47182""""""""#1.25200"""""""""1.16641" C"""""""""""0.31937""""""""#1.65795"""""""""0.30010" O"""""""""""2.61011""""""""#1.42527""""""""#0.44800" C"""""""""""1.03936"""""""""0.42812""""""""#0.61238" O"""""""""""2.15884"""""""""1.29609""""""""#0.78826" C""""""""""#0.12838"""""""""1.26745""""""""#0.03084" OH OH O O"""""""""""0.15804"""""""""1.61044"""""""""1.33582" HO HO OH H""""""""""#1.60356""""""""#1.10985""""""""#1.03762" OH OH OH OH H""""""""""#1.72808""""""""#1.02425"""""""""0.58068" H""""""""""#2.24108"""""""""1.68682"""""""""0.10148" H"""""""""""3.20207""""""""#0.71794""""""""#0.73352" H"""""""""""0.78912"""""""""0.05834""""""""#1.60861" H"""""""""""2.28753"""""""""1.74683"""""""""0.05752" H""""""""""#0.04334"""""""""2.22504""""""""#0.55930" H""""""""""#0.05055"""""""""0.81584"""""""""1.85070" C"""""""""""1.55523""""""""#0.79700"""""""""0.23137" H"""""""""""1.86752""""""""#0.43098"""""""""1.22343" H""""""""""#3.97719"""""""""0.34643""""""""#0.44731"

138 C"""""""""""1.62601""""""""(2.38050""""""""(0.17079" C"""""""""""0.85049""""""""(1.29795""""""""(0.02287" O""""""""""(0.52033""""""""(1.52779"""""""""0.13549" C""""""""""(1.49950""""""""(0.55931""""""""(0.26982" O""""""""""(2.76447""""""""(1.13634""""""""(0.10070" C""""""""""(1.29882"""""""""0.72599"""""""""0.49833" O""""""""""(2.04708"""""""""1.79881"""""""""0.01301" C"""""""""""0.66215"""""""""1.21846""""""""(0.42880"

O OH OH O"""""""""""1.20738"""""""""2.41301""""""""(0.18444" C"""""""""""1.37048"""""""""0.06548"""""""""0.13595" O OH O"""""""""""2.74412"""""""""0.26112"""""""""0.34518" HO OH OH OH H"""""""""""1.18217""""""""(3.36551""""""""(0.20320" OH H"""""""""""2.70269""""""""(2.29393""""""""(0.17933" H""""""""""(1.42377""""""""(0.37264""""""""(1.34962" H""""""""""(2.83746""""""""(1.39708"""""""""0.82650" H""""""""""(1.38346"""""""""0.57838"""""""""1.58864" H""""""""""(2.94056"""""""""1.48270""""""""(0.17813" H"""""""""""0.01837"""""""""1.27875""""""""(1.30826" H"""""""""""1.98740"""""""""2.26429"""""""""0.38034" H"""""""""""3.21867"""""""""0.05363""""""""(0.47492" H"""""""""""0.25401"""""""""0.66797"""""""""0.77766" C""""""""""#0.60479""""""""#1.30847"""""""""0.46489" C""""""""""#1.84878""""""""#0.65873""""""""#0.12234" C""""""""""#1.25616"""""""""1.39838"""""""""0.08427" C"""""""""""0.65566""""""""#1.35471""""""""#0.44465" C"""""""""""0.10160"""""""""1.50911""""""""#0.37840" C"""""""""""1.79046""""""""#0.40006""""""""#0.02522" C"""""""""""1.27839"""""""""0.99928"""""""""0.40321" H""""""""""#0.35865""""""""#0.81968"""""""""1.41546" H""""""""""#2.10393""""""""#0.99599""""""""#1.13127" H""""""""""#1.44473"""""""""1.25449"""""""""1.14452" H""""""""""#0.84694"""""""""0.48345""""""""#0.62457" H"""""""""""0.36620""""""""#1.13850""""""""#1.47878" H"""""""""""2.49169""""""""#0.30335""""""""#0.86193" H""""""""""#0.84689""""""""#2.34015"""""""""0.75327" H""""""""""#2.72023""""""""#0.67690"""""""""0.53189" H""""""""""#2.02697"""""""""1.94201""""""""#0.44919" H"""""""""""1.05003""""""""#2.37504""""""""#0.46427" H"""""""""""0.26019"""""""""2.01666""""""""#1.32227" H"""""""""""2.36091""""""""#0.83766"""""""""0.80283" H"""""""""""2.10672"""""""""1.71346"""""""""0.32525" H"""""""""""1.01429"""""""""0.96838"""""""""1.46852"

139 C""""""""""#0.61218""""""""#1.31239"""""""""0.44095" C""""""""""#1.84024""""""""#0.61008""""""""#0.11418" C""""""""""#1.20898"""""""""1.41885"""""""""0.08213" C"""""""""""0.66323""""""""#1.32314""""""""#0.44222" C"""""""""""0.15404"""""""""1.49382""""""""#0.38788" C"""""""""""1.29283"""""""""0.93234"""""""""0.40383" H""""""""""#0.35185""""""""#0.89889"""""""""1.42136" H""""""""""#2.12324""""""""#0.91626""""""""#1.12527" H""""""""""#1.38572"""""""""1.29648"""""""""1.14681" NH H H""""""""""#0.82530"""""""""0.48881""""""""#0.61529" N H"""""""""""0.38114""""""""#1.07911""""""""#1.48157" H""""""""""#0.87310""""""""#2.35753"""""""""0.65149" H""""""""""#2.70098""""""""#0.61062"""""""""0.55311" H""""""""""#1.97163"""""""""1.97609""""""""#0.44879" H"""""""""""1.06980""""""""#2.33817""""""""#0.47050" H"""""""""""0.32724"""""""""1.96346""""""""#1.34859" H"""""""""""2.17851"""""""""1.56479"""""""""0.28627" H"""""""""""1.03756"""""""""0.96879"""""""""1.47185" N"""""""""""1.72245""""""""#0.45958"""""""""0.09113" H"""""""""""2.48827""""""""#0.43723""""""""#0.57457" C""""""""""#0.64517""""""""#1.31311"""""""""0.41063" C""""""""""#1.84442""""""""#0.53728""""""""#0.10781" C""""""""""#1.14911"""""""""1.44085"""""""""0.11670" C"""""""""""0.65343""""""""#1.31452""""""""#0.44061" C"""""""""""0.20804"""""""""1.47661""""""""#0.38834" C"""""""""""1.33323"""""""""0.88183"""""""""0.36889" H""""""""""#0.38700""""""""#0.98609"""""""""1.42441" H""""""""""#2.14941""""""""#0.79827""""""""#1.12528"

O H""""""""""#1.29830"""""""""1.31712"""""""""1.18529" O H""""""""""#0.81881"""""""""0.50424""""""""#0.59493" H"""""""""""0.41395""""""""#1.09164""""""""#1.49225" H""""""""""#0.94524""""""""#2.36266"""""""""0.53008" H""""""""""#2.70018""""""""#0.51837"""""""""0.56480" H""""""""""#1.90362"""""""""2.03406""""""""#0.38640" H"""""""""""1.08590""""""""#2.31683""""""""#0.42431" H"""""""""""0.37658"""""""""1.94350""""""""#1.35002" H"""""""""""2.25158"""""""""1.44849"""""""""0.19952" H"""""""""""1.12260"""""""""0.91066"""""""""1.44895" O"""""""""""1.70199""""""""#0.48631"""""""""0.03293"

140 O"""""""""""1.64615"""""""""1.99595"""""""")0.18587" C"""""""""""0.94688"""""""""0.79597"""""""")0.54748" C"""""""""""1.42518"""""""")0.33814"""""""""0.39199" C"""""""""""1.54492"""""""")1.66884"""""""")0.36080" O"""""""""""0.27349"""""""")2.06235"""""""")0.68203" C"""""""""")0.80561"""""""")0.85379"""""""""0.94402" O"""""""""""0.38945"""""""")0.63037"""""""""1.41903" C"""""""""")1.31333"""""""")0.28492"""""""")0.28007" H OH OH C"""""""""")0.59696"""""""""1.04898"""""""")0.50592" O O"""""""""")0.90974"""""""""1.95590"""""""""0.54315" O OH HO H"""""""""""1.69376"""""""""2.56648"""""""")0.96044" O OH H"""""""""""1.22054"""""""""0.50596"""""""")1.56694" OH OH H H"""""""""""2.29966"""""""")0.02344"""""""""0.95678" H"""""""""""2.03749"""""""")2.42021"""""""""0.27855" H"""""""""""2.21385"""""""")1.49374"""""""")1.22282" H"""""""""")1.44255"""""""")1.43434"""""""""1.60701" H"""""""""")0.91465"""""""""1.47054"""""""")1.46961" H"""""""""")0.12472"""""""""2.50917"""""""""0.66066" H"""""""""")0.63221"""""""")1.14007"""""""")0.92783" O"""""""""")2.72145"""""""")0.25428"""""""")0.35505" H"""""""""")2.98081"""""""")0.77475"""""""")1.11956" O""""""""""""""""0""""0.09643435""""2.80211738""".0.08683905" "C""""""""""""""""0""""0.34416535""""1.43930638""".0.44057905" "C""""""""""""""""0""""1.35317435""""0.74667338""""0.52233295" "C""""""""""""""""0""""2.51186450""""0.49572613""".0.01101742" "O""""""""""""""""0""""1.29803431""".1.63411208""".0.36324400" "C""""""""""""""""0""""0.30415835""".1.18930262""""0.49302495" "O""""""""""""""""0""""0.66841235""".0.16662462""""1.39041995" "C""""""""""""""""0""".0.89143265""".0.77452662""".0.41330805" H O OH OH "C""""""""""""""""0""".1.04864465""""0.75704438""".0.39904805" "O""""""""""""""""0""".1.75784165""""1.13962738""""0.75814195" O OH HO OH "H""""""""""""""""0""""0.91684135""""3.29973038""".0.14574405" O OH "H""""""""""""""""0""""0.72966135""""1.39031338""".1.46765905" OH H "H""""""""""""""""0""""1.53944536""".0.73720107""""0.12642052" "H""""""""""""""""0""""3.39224550""""0.26813213""""0.59844058" "H""""""""""""""""0""""2.82999450""""0.83025913""".1.00130042" "H""""""""""""""""0""""0.08306235""".2.09171262""""1.06525195" "H""""""""""""""""0""".1.60261865""""1.06368438""".1.29719005" "H""""""""""""""""0""".1.55402565""""2.07188938""""0.89949895" "H""""""""""""""""0""".0.62863865""".1.08349962""".1.43328005" "O""""""""""""""""0""".2.12018365""".1.35248662""".0.01035305" "H""""""""""""""""0""".2.09666465""".2.28305862""".0.25227005"

141 C""""""""""#1.16300"""""""""0.75144"""""""""0.49244" H""""""""""#2.05044"""""""""1.39224"""""""""0.54140" H""""""""""#0.72202"""""""""0.72642"""""""""1.50032" C""""""""""#1.43841""""""""#0.65300"""""""""0.00663" H""""""""""#2.07929""""""""#1.25362"""""""""0.66179" H""""""""""#1.91541""""""""#0.61238""""""""#0.98269" C""""""""""#0.14319"""""""""1.22023""""""""#0.50051" H""""""""""#0.58925"""""""""1.38044""""""""#1.49487" H"""""""""""0.27805"""""""""2.21214""""""""#0.21462" C""""""""""#0.03892""""""""#1.24589""""""""#0.08395" H""""""""""#0.04293""""""""#2.12287""""""""#0.74964" H"""""""""""0.23455""""""""#1.63518"""""""""0.90254" C"""""""""""1.03690""""""""#0.34875""""""""#0.50863" H"""""""""""1.39521""""""""#0.35362""""""""#1.53900" C"""""""""""1.77868"""""""""0.11451"""""""""0.53745" H"""""""""""1.51909""""""""#0.17707"""""""""1.54815" H"""""""""""2.81035"""""""""0.43251"""""""""0.39613" H"""""""""""0.96972"""""""""0.97978""""""""#0.23009" O""""""""""#2.27925""""""""#0.33901""""""""#0.12634" C""""""""""#0.95783"""""""""0.08738""""""""#0.36232" C""""""""""#0.76741"""""""""1.54450"""""""""0.00988" O"""""""""""0.63591"""""""""1.71376"""""""""0.21825" C"""""""""""1.36377"""""""""0.00396"""""""""0.44591"

O"""""""""""1.93080""""""""#0.22727""""""""#0.72745"

O OH HO C"""""""""""0.05476""""""""#0.65216"""""""""0.53125" OH O"""""""""""0.14653""""""""#2.02637"""""""""0.16641" O

H""""""""""#2.29273""""""""#1.29406""""""""#0.26289" OH

OH OH H""""""""""#0.67085""""""""#0.08047""""""""#1.41082" H""""""""""#1.30312"""""""""1.76395"""""""""0.93878" H""""""""""#1.10530"""""""""2.23632""""""""#0.76535" H"""""""""""1.98016"""""""""0.20682"""""""""1.32247" H"""""""""""1.39073"""""""""0.98442""""""""#0.75132" H""""""""""#0.34667""""""""#0.63756"""""""""1.54969" H"""""""""""0.71618""""""""#2.05033""""""""#0.61584" C""""""""""#1.40821""""""""#0.57584""""""""#0.36366" H""""""""""#2.36471""""""""#0.99723""""""""#0.04633" H""""""""""#1.37167""""""""#0.64849""""""""#1.45454" C""""""""""#1.25999"""""""""0.91112"""""""""0.06297" H""""""""""#1.85441"""""""""1.56926""""""""#0.57879" H""""""""""#1.62920"""""""""1.02750"""""""""1.08796" C"""""""""""0.27612"""""""""1.21855"""""""""0.02070" H"""""""""""0.47093"""""""""2.12231"""""""""0.61346"

H2N H"""""""""""0.54672"""""""""1.41476""""""""#1.00562" HN C"""""""""""0.90804"""""""""0.04918"""""""""0.59949" H"""""""""""1.06148""""""""#0.04468"""""""""1.67154" C"""""""""""1.80628""""""""#0.19300""""""""#0.42603" H"""""""""""2.07315"""""""""0.55695""""""""#1.15141" H"""""""""""2.68102""""""""#0.82333""""""""#0.20390" H"""""""""""0.74177""""""""#1.25698""""""""#0.59975" N""""""""""#0.25240""""""""#1.33332"""""""""0.20320" H""""""""""#0.52166""""""""#2.04696"""""""""0.88417"

142 C"""""""""""1.35165""""""""(0.74160"""""""""0.30238" H"""""""""""2.26199""""""""(1.25323""""""""(0.03494" H"""""""""""1.29846""""""""(0.85253"""""""""1.39616" C"""""""""""1.37835"""""""""0.75683""""""""(0.06131" H"""""""""""2.06800"""""""""1.33436"""""""""0.56225" H"""""""""""1.69267"""""""""0.87019""""""""(1.10382" C""""""""""(0.08196"""""""""1.22830"""""""""0.09854" H""""""""""(0.20027"""""""""2.22294""""""""(0.35277" OH O H""""""""""(0.31816"""""""""1.32723"""""""""1.15849" C""""""""""(0.99236"""""""""0.28946""""""""(0.54038" H""""""""""(1.06039"""""""""0.20948""""""""(1.61733" C""""""""""(1.92290""""""""(0.21564"""""""""0.35211" H""""""""""(2.03291"""""""""0.26869"""""""""1.31449" H""""""""""(2.82371""""""""(0.69954""""""""(0.01782" H""""""""""(0.91798""""""""(1.14171"""""""""0.37661" O"""""""""""0.20445""""""""(1.27376""""""""(0.32367" C"""""""""""1.30195"""""""")1.04727"""""""")0.28737" C"""""""""")1.36528"""""""""0.04513"""""""")0.43507" C"""""""""")0.42755"""""""""1.16368"""""""")0.78346" C"""""""""""0.71002"""""""""1.42420"""""""""0.22499" C"""""""""""1.50781"""""""""0.15954"""""""""0.64141" H"""""""""")1.90396"""""""")0.38154"""""""")1.27416" H"""""""""")1.03267"""""""""2.07477"""""""")0.89173" H"""""""""""1.38182"""""""""2.15562"""""""")0.23348" H"""""""""""1.21275"""""""")0.14607"""""""""1.65031" O H"""""""""""1.64694"""""""")0.81178"""""""")1.30612" OH H"""""""""""1.91739"""""""")1.88761"""""""""0.06117" H"""""""""")0.82517"""""""")1.19125"""""""""0.67627" C"""""""""")1.81803"""""""")0.26967"""""""""0.87060" H"""""""""")1.55348"""""""""0.39786"""""""""1.68529" H"""""""""")2.78021"""""""")0.76176"""""""""0.96491" H"""""""""""2.57532"""""""""0.39731"""""""""0.69365" H"""""""""""0.30617"""""""""1.91048"""""""""1.11720" H"""""""""")0.00538"""""""""0.96512"""""""")1.77288" O"""""""""")0.04913"""""""")1.44686"""""""")0.34463" "

143 C""""""""""#1.26740""""""""#1.44339""""""""#0.21262" C"""""""""""1.53151""""""""#0.14725"""""""""0.67385" C""""""""""#1.87264""""""""#0.21090"""""""""0.46535" C"""""""""""0.93464"""""""""1.17921"""""""""0.56364" C""""""""""#1.55147"""""""""1.12940""""""""#0.21745" C""""""""""#0.08160"""""""""1.39377""""""""#0.59064" H""""""""""#1.53611""""""""#1.44941""""""""#1.28082" H"""""""""""0.43777"""""""""1.47675"""""""""1.49648" H""""""""""#1.51750""""""""#0.20044"""""""""1.50249" H""""""""""#1.89933"""""""""1.93835"""""""""0.43671" O H""""""""""#1.70374""""""""#2.35079"""""""""0.23273" OH H"""""""""""1.58334""""""""#0.69118"""""""""1.60504" H""""""""""#2.96225""""""""#0.32193"""""""""0.51924" H"""""""""""1.76043"""""""""1.88787"""""""""0.43638" H""""""""""#2.14484"""""""""1.21330""""""""#1.13579" H""""""""""#0.00583"""""""""2.43497""""""""#0.92006" H"""""""""""0.20449"""""""""0.78258""""""""#1.44762" C"""""""""""2.29243""""""""#0.43452""""""""#0.43928" H"""""""""""2.48971"""""""""0.36187""""""""#1.14803" H"""""""""""3.08265""""""""#1.17933""""""""#0.37281" H"""""""""""1.21311""""""""#1.11611""""""""#0.78979" O"""""""""""0.13567""""""""#1.44806""""""""#0.07391" C"""""""""""1.63393"""""""""0.72786"""""""""0.10707" C"""""""""",1.32523"""""""""0.28884"""""""""0.40951" H"""""""""",1.76950"""""""""0.94524"""""""""1.15740" H"""""""""""1.97292"""""""""0.41437"""""""""1.10605" H"""""""""""2.47619"""""""""1.28748"""""""",0.32778" C"""""""""""1.34968"""""""",0.51114"""""""",0.74172" H"""""""""""0.88322"""""""",0.18210"""""""",1.68382" H"""""""""""2.28124"""""""",1.01353"""""""",1.03051" C"""""""""""0.43473"""""""",1.51200"""""""",0.02616" H"""""""""",0.11459"""""""",2.11103"""""""",0.76407" H"""""""""""1.04501"""""""",2.22530"""""""""0.54390" C"""""""""",0.54786"""""""",0.87145"""""""""0.95820" H"""""""""",1.28988"""""""",1.62046"""""""""1.27262" H"""""""""",0.01537"""""""",0.55240"""""""""1.86323" C"""""""""",2.02768"""""""""0.19296"""""""",0.83402" H"""""""""",2.87181"""""""""0.84217"""""""",1.03234" H"""""""""",1.79165"""""""",0.60684"""""""",1.52793" C"""""""""""0.39112"""""""""1.58438"""""""""0.21163" H"""""""""",0.84088"""""""""0.98550"""""""",0.55614" H"""""""""""0.29700"""""""""2.17720"""""""""1.12662" H"""""""""""0.28594"""""""""2.26300"""""""",0.65425"

144 C"""""""""""0.33200""""""""'1.51500""""""""'0.68547" O""""""""""'1.01732""""""""'1.56252""""""""'0.23287" C""""""""""'1.62373""""""""'0.06673"""""""""0.46993" C""""""""""'0.85259"""""""""1.05204""""""""'0.18398" C"""""""""""0.67753"""""""""0.90044""""""""'0.12484" C"""""""""""1.15386""""""""'0.52021"""""""""0.12039" O""""""""""'1.36224""""""""'0.49535"""""""""1.66397" O""""""""""'1.32453"""""""""1.23559""""""""'1.49931" O OH OH O"""""""""""1.17615"""""""""1.76797"""""""""0.86011" O"""""""""""2.51372""""""""'0.54794""""""""'0.26922" O OH HO OH H""""""""""'2.65707""""""""'0.12990"""""""""0.07719" OH OH OH H""""""""""'1.09324"""""""""1.96687"""""""""0.37759" H"""""""""""1.03800"""""""""1.18477""""""""'1.13115" H"""""""""""1.03850""""""""'0.72779"""""""""1.19536" H"""""""""""0.35923""""""""'1.24135""""""""'1.75128" H"""""""""""0.75557""""""""'2.52538""""""""'0.60379" H""""""""""'1.07724""""""""'1.50803"""""""""0.96553" H""""""""""'1.44101"""""""""0.36821""""""""'1.90474" H"""""""""""2.13211"""""""""1.63862"""""""""0.88049" H"""""""""""2.93640""""""""'1.31129"""""""""0.13723" C""""""""""#1.72257"""""""""0.45059""""""""#0.32408" C""""""""""#0.48883"""""""""1.38954""""""""#0.29049" C"""""""""""0.56151"""""""""0.98410"""""""""0.76290" C"""""""""""1.19252""""""""#0.33199"""""""""0.50256" C""""""""""#1.43901""""""""#0.97736"""""""""0.17897" H"""""""""""1.34724"""""""""1.73727"""""""""0.82046" H""""""""""#0.01830"""""""""1.39668""""""""#1.27402" H""""""""""#0.81943"""""""""2.41257""""""""#0.09020" H""""""""""#1.58739""""""""#1.03679"""""""""1.26330" NH H""""""""""#2.10460"""""""""0.40518""""""""#1.34786" H2N H"""""""""""1.54870""""""""#0.87958"""""""""1.37872" H""""""""""#2.13198""""""""#1.68961""""""""#0.27805" H""""""""""#2.53053"""""""""0.86211"""""""""0.28846" H"""""""""""0.05774"""""""""1.01217"""""""""1.74348" N""""""""""#0.04814""""""""#1.36784""""""""#0.12044" H"""""""""""0.15388""""""""#2.33661"""""""""0.12637" C"""""""""""2.01181""""""""#0.10302""""""""#0.65520" H"""""""""""0.65864""""""""#0.96416""""""""#1.07812" H"""""""""""2.18233"""""""""0.92034""""""""#0.96276" H"""""""""""2.88808""""""""#0.73588""""""""#0.79469"

145 C"""""""""""1.05992"""""""""1.44322""""""""+0.38178" C""""""""""+0.37521"""""""""1.47625"""""""""0.20284" C""""""""""+1.66218"""""""""0.05037"""""""""0.53835" C"""""""""""1.95600"""""""""0.38516"""""""""0.27923" C""""""""""+0.74865""""""""+1.05480"""""""""0.71371" C"""""""""""1.69258""""""""+1.06644""""""""+0.16950" C"""""""""""0.22031""""""""+1.41542""""""""+0.43889" H"""""""""""1.01857"""""""""1.27967""""""""+1.46615" H""""""""""+0.29087"""""""""1.59661"""""""""1.28662" H""""""""""+0.17394""""""""+0.95456"""""""""1.64244" H"""""""""""1.83658"""""""""0.46478"""""""""1.36643" H"""""""""""2.10492""""""""+1.74851"""""""""0.58322" H"""""""""""1.51973"""""""""2.42960""""""""+0.24897" H""""""""""+0.91304"""""""""2.37871""""""""+0.13053" H""""""""""+2.04121"""""""""0.55966"""""""""1.42941" H"""""""""""3.00628"""""""""0.62185"""""""""0.07974" H""""""""""+1.40918""""""""+1.91742"""""""""0.89368" H"""""""""""2.24925""""""""+1.26566""""""""+1.09244" H"""""""""""0.15346""""""""+2.48777""""""""+0.64110" H""""""""""+0.11829""""""""+0.92604""""""""+1.35334" C""""""""""+2.22925"""""""""0.06459""""""""+0.70345" H""""""""""+2.36754""""""""+0.88420""""""""+1.21336" H""""""""""+3.03125"""""""""0.77427""""""""+0.89589" H""""""""""+1.02455"""""""""0.78145""""""""+0.48279" C""""""""""#1.24672"""""""""0.61106""""""""#0.19636" C""""""""""#1.63852""""""""#0.81104"""""""""0.18532" C""""""""""#0.64861""""""""#1.86555""""""""#0.30344" C"""""""""""0.09625"""""""""1.11048"""""""""0.33892" C"""""""""""1.33478"""""""""0.42441""""""""#0.30031" C"""""""""""1.92779""""""""#0.64964"""""""""0.48727" H""""""""""#1.22480"""""""""0.67447""""""""#1.29462" H""""""""""#1.71301""""""""#0.87906"""""""""1.27786" H""""""""""#0.41054""""""""#1.70134""""""""#1.36348" H"""""""""""0.12052"""""""""0.98332"""""""""1.43013" OH OH O OH H""""""""""#1.12226""""""""#2.85252""""""""#0.22876" OH O H"""""""""""1.09285"""""""""0.03908""""""""#1.29732" HO OH OH OH H"""""""""""2.02796""""""""#0.52563"""""""""1.57028"

HO OH O"""""""""""0.50002""""""""#1.88395"""""""""0.52505" O"""""""""""2.74739""""""""#1.39475""""""""#0.17871" H"""""""""""1.71894""""""""#2.12445""""""""#0.05265" O"""""""""""2.41113"""""""""1.35816""""""""#0.40312" H"""""""""""1.99957"""""""""2.23478""""""""#0.41278" O"""""""""""0.19746"""""""""2.49865"""""""""0.02581" H""""""""""#0.67686"""""""""2.88138"""""""""0.17589" O""""""""""#2.21880"""""""""1.52599"""""""""0.31352" H""""""""""#3.07895"""""""""1.18836"""""""""0.03542" O""""""""""#2.92748""""""""#0.99077""""""""#0.42028" H""""""""""#3.36098""""""""#1.74325""""""""#0.00661"

146 C"""""""""""1.16089"""""""""1.48421""""""""+0.19127" C""""""""""+1.43394"""""""""0.24286"""""""""0.59365" C"""""""""""1.88304"""""""""0.29011"""""""""0.42786" C""""""""""+0.73905""""""""+1.05505"""""""""0.68153" C"""""""""""1.65921""""""""+1.05363""""""""+0.28113" C"""""""""""0.18100""""""""+1.43242""""""""+0.50369" H"""""""""""1.48551"""""""""1.62478""""""""+1.22823" H""""""""""+0.13751""""""""+1.13494"""""""""1.59892" H"""""""""""1.58497"""""""""0.20962"""""""""1.47793" H"""""""""""2.14436""""""""+1.82953"""""""""0.32201"

NH H"""""""""""1.44064"""""""""2.38960"""""""""0.35715"

NH2 H""""""""""+1.63571"""""""""0.75325"""""""""1.53542" H"""""""""""2.95478"""""""""0.51611"""""""""0.43645" H""""""""""+1.51019""""""""+1.81944"""""""""0.79374" H"""""""""""2.17881""""""""+1.05108""""""""+1.24615" H"""""""""""0.12508""""""""+2.51204""""""""+0.66900" H""""""""""+0.19875""""""""+0.97499""""""""+1.41921" N""""""""""+0.32715"""""""""1.34785""""""""+0.21092" H""""""""""+0.74422"""""""""2.25726""""""""+0.01671" C""""""""""+2.42769"""""""""0.09299""""""""+0.43030" H""""""""""+2.62481""""""""+0.90516""""""""+0.79899" H""""""""""+3.30808"""""""""0.73245""""""""+0.40183" H""""""""""+1.16566"""""""""0.89482""""""""+1.04496" C""""""""""#0.71911"""""""""1.41541""""""""#0.37090" C"""""""""""0.46076"""""""""0.97933"""""""""0.54123" C"""""""""""1.71793"""""""""0.52503""""""""#0.22268" C""""""""""#0.41120""""""""#1.32397"""""""""0.71134" C""""""""""#1.09882""""""""#1.06200""""""""#0.54085" C""""""""""#1.78099"""""""""0.31399""""""""#0.56733" H""""""""""#0.31656"""""""""1.70749""""""""#1.34589" H"""""""""""0.76056"""""""""1.85023"""""""""1.13255" H"""""""""""2.54725"""""""""0.49757"""""""""0.51121" H"""""""""""2.00953"""""""""1.33008""""""""#0.91414" H""""""""""#0.30869""""""""#2.33024"""""""""1.09937" H""""""""""#2.30759"""""""""0.45879""""""""#1.51472" H""""""""""#0.27403""""""""#0.96489""""""""#1.35748" C"""""""""""1.72246""""""""#0.77973""""""""#0.95646" H"""""""""""1.09635""""""""#1.61222""""""""#0.68966" H"""""""""""2.71609""""""""#1.05991""""""""#1.31193" C"""""""""""0.02553""""""""#0.14875"""""""""1.51267" H""""""""""#0.79705"""""""""0.22748"""""""""2.14647" H"""""""""""0.83988""""""""#0.40645"""""""""2.19872" H""""""""""#1.73580""""""""#1.88679""""""""#0.86977" H""""""""""#2.53511"""""""""0.36528"""""""""0.22528" H""""""""""#1.19421"""""""""2.30777"""""""""0.04783"

147 C""""""""""""""""""0.35682400""""1.20125100""""0.39357500" "C""""""""""""""""""1.49926800""""0.78654600""".0.60473300" "C""""""""""""""""""0.82468716""".1.09640544""""1.10095972" "H""""""""""""""""""0.39285555""""2.28432540""""0.60609195" "H""""""""""""""""""2.47636090""""0.83059032""".0.09571882" "H""""""""""""""""""1.54399242""""1.46241427""".1.47393393" "H""""""""""""""""""1.31046824""".1.81783247""""1.78145146" "C""""""""""""""""""1.16815553""".0.56720172""".1.06085704" "H""""""""""""""""""1.98439396""".1.24267221""".0.75552463" "H""""""""""""""""""1.03755854""".0.67109657""".2.15010154" "C""""""""""""""""""0.82239141""""0.36980925""""1.55533009" • • CH H2C "H""""""""""""""""""1.75317121""""0.72463765""""2.02897964" "H""""""""""""""""""0.02288918""""0.36685598""""2.31245085" "C""""""""""""""""".0.45499360""".1.64697070""""0.47878910" "H""""""""""""""""".0.31076415""".2.11958464""".0.50742064" "H""""""""""""""""".0.79369316""".2.43841717""""1.16904762" "C""""""""""""""""".1.57660787""".0.55899932""""0.38662402" "H""""""""""""""""".1.99736044""".0.40263414""""1.39353730" "H""""""""""""""""".2.39928119""".0.92890567""".0.24896392" "C""""""""""""""""".1.06889303""""0.81693887""".0.16046181" "H""""""""""""""""".1.79867841""""1.59468766""""0.12249877" "H""""""""""""""""".1.03596020""""0.79176669""".1.26275760" C"""""""""""""""""#0.18122013""""2.01575063"""#1.54834727" "C""""""""""""""""""0.19061193""""1.34208849"""#0.19370194" "C""""""""""""""""""1.42775215""""0.43169512"""#0.28231099" "C"""""""""""""""""#1.39011552"""#0.52242277"""#0.68798542" "C"""""""""""""""""#1.27666794"""#0.21669688"""#2.03919278" "C"""""""""""""""""#1.32205924""""1.30875991"""#2.31952410" "H""""""""""""""""""0.71247496""""2.04205003"""#2.17944372" "H""""""""""""""""""0.42347145""""2.13036878""""0.52773176" "H""""""""""""""""""1.73662377""""0.19550008""""0.75529208" "H""""""""""""""""""2.26589846""""1.02672914"""#0.67495746" "H"""""""""""""""""#1.82486053"""#1.45861645"""#0.35805076"

• • CH "H"""""""""""""""""#1.23509866""""1.52074090"""#3.38888233" H2C "H"""""""""""""""""#0.02026315"""#0.96003212"""#1.29550401" "C""""""""""""""""""1.34184115"""#0.85947188"""#1.03731899" "H""""""""""""""""""1.17823755"""#1.80300136"""#0.54323179" "H""""""""""""""""""2.04105578"""#0.90544908"""#1.87469737" "C"""""""""""""""""#1.01399863""""0.51532596""""0.33931753" "H"""""""""""""""""#1.85707102""""1.20569623""""0.51933193" "H"""""""""""""""""#0.77882930""""0.07122744""""1.31293177" "H"""""""""""""""""#0.46514661""""3.05783211"""#1.37240758" "H"""""""""""""""""#2.29404960""""1.69897500"""#1.99878249" "H"""""""""""""""""#1.92521874"""#0.81030051"""#2.68667657"

148 Appendix C

RMG-Py generated mechanism for 1230xa

ELEMENTS H C O N Ne Ar He Si S Cl END

SPECIES Ar He Ne N2 xa(1) HCl(2) Cl2(3) Cl(4) xf(5) ab(6) db(7) fb(8) za(9) zf(10) rad1(11) rad2(12) rad3(13) rad4(14) rad5(15) C3Cl4H(18) S(20) S(25) C3Cl4H(26) S(30) S(31) S(32) S(35) S(36) S(38) S(40) S(44) S(45) S(47) S(48) S(52) C3Cl3H(56) S(58) S(79) S(85) S(86) S(87) C3Cl5H(93) C3Cl4H(95) C3Cl4H(96) S(98) S(100) S(101) S(102) S(103) C3Cl5(106) S(107) S(110) S(111) C3Cl5(114) S(120) S(127) C3Cl5(128) END

THERM ALL 300.000 1000.000 5000.000

Ar Ar1 G200.000 6000.000 1000.00 1 2.50000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 2 -7.45375000E+02 4.37967000E+00 2.50000000E+00 0.00000000E+00 0.00000000E+00 3 0.00000000E+00 0.00000000E+00-7.45375000E+02 4.37967000E+00 4

He He1 G200.000 6000.000 1000.00 1 2.50000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 2 -7.45375000E+02 9.28724000E-01 2.50000000E+00 0.00000000E+00 0.00000000E+00 3 0.00000000E+00 0.00000000E+00-7.45375000E+02 9.28724000E-01 4

Ne Ne1 G200.000 6000.000 1000.00 1 2.50000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 2 -7.45375000E+02 3.35532000E+00 2.50000000E+00 0.00000000E+00 0.00000000E+00 3 0.00000000E+00 0.00000000E+00-7.45375000E+02 3.35532000E+00 4

N2 N 2 G200.000 6000.000 1000.00 1

149 2.95258000E+00 1.39690000E-03-4.92632000E-07 7.86010000E-11-4.60755000E-15 2 -9.23949000E+02 5.87189000E+00 3.53101000E+00-1.23661000E-04-5.02999000E-07 3 2.43531000E-09-1.40881000E-12-1.04698000E+03 2.96747000E+00 4 xa(1) C 3 H 2 Cl4 G100.000 5000.000 651.72 1 1.08993247E+01 1.64998088E-02-8.28408659E-06 1.60440844E-09-1.11439259E-13 2 -1.64301295E+04-1.96918747E+01 1.26651083E+00 6.58475863E-02-9.93654249E-05 3 7.17607574E-08-1.81951957E-11-1.49669695E+04 2.42492586E+01 4

HCl(2) H 1 Cl1 G200.000 6000.000 1000.00 1 2.75758000E+00 1.45387000E-03-4.79647000E-07 7.77909000E-11-4.79574000E-15 2 -1.19138000E+04 6.52197000E+00 3.46376000E+00 4.76484000E-04-2.00301000E-06 3 3.31714000E-09-1.44958000E-12-1.21444000E+04 2.66428000E+00 4

Cl2(3) Cl2 G200.000 6000.000 1000.00 1 4.74728000E+00-4.88582000E-04 2.68445000E-07-2.43476000E-11-1.03683000E-15 2 -1.51102000E+03-3.44539000E-01 2.73638000E+00 7.83526000E-03-1.45105000E-05 3 1.25731000E-08-4.13247000E-12-1.05880000E+03 9.44557000E+00 4

Cl(4) Cl1 G200.000 6000.000 1000.00 1 2.94658000E+00-3.85985000E-04 1.36139000E-07-2.17033000E-11 1.28751000E-15 2 1.36970000E+04 3.11330000E+00 2.26062000E+00 1.54154000E-03-6.80284000E-07 3 -1.59973000E-09 1.15417000E-12 1.38553000E+04 6.57021000E+00 4 xf(5) C 3 H 2 Cl4 G100.000 5000.000 702.07 1 1.19197373E+01 1.59458886E-02-8.21279585E-06 1.60626658E-09-1.12188634E-13 2 -1.42407068E+04-2.68593957E+01 9.93706938E-01 7.13844639E-02-1.12105755E-04 3 8.64403414E-08-2.53996119E-11-1.25386621E+04 2.31831943E+01 4 ab(6) C 3 H 3 Cl5 G100.000 5000.000 936.20 1 1.72397189E+01 1.54384704E-02-7.38629535E-06 1.43122285E-09-1.00892825E-13 2 -3.44343251E+04-5.35045761E+01 6.66935873E-02 8.88105566E-02-1.24942672E-04 3 8.51415427E-08-2.24542664E-11-3.12187938E+04 2.82134810E+01 4 db(7) C 3 H 3 Cl5 G100.000 5000.000 1028.43 1 1.51058860E+01 1.96378541E-02-9.93544791E-06 1.99844790E-09-1.44594702E-13 2 -3.35598145E+04-4.04977805E+01 6.40881691E-01 7.58993993E-02-9.19962979E-05 3 5.51943096E-08-1.30761557E-11-3.05846192E+04 2.96927456E+01 4 fb(8) C 3 H 4 Cl4 G100.000 5000.000 1104.28 1 1.41564590E+01 1.75117196E-02-7.90979375E-06 1.52394197E-09-1.08028188E-13 2 -2.84641520E+04-3.86521194E+01 9.96593390E-01 6.51803823E-02-7.26606848E-05 3 4.06148727E-08-8.95791144E-12-2.55577216E+04 2.61419768E+01 4

150 za(9) C 3 H 3 Cl3 G100.000 5000.000 1143.99 1 1.07509764E+01 1.46445126E-02-6.46593732E-06 1.23183364E-09-8.66885039E-14 2 -1.12778503E+04-2.26894311E+01 1.88794519E+00 4.56342156E-02-4.70993985E-05 3 2.49110705E-08-5.26136083E-12-9.24999416E+03 2.12618988E+01 4 zf(10) C 3 H 3 Cl3 G100.000 5000.000 1120.36 1 1.17410069E+01 1.41451731E-02-6.42750374E-06 1.24171333E-09-8.81204273E-14 2 -9.07617631E+03-2.96867187E+01 1.69473960E+00 5.00132584E-02-5.44498005E-05 3 2.98172992E-08-6.46456554E-12-6.82509465E+03 1.99224478E+01 4 rad1(11) C 3 H 2 Cl3 G100.000 5000.000 918.97 1 1.11881100E+01 1.18049534E-02-5.51941450E-06 1.05979520E-09-7.42919842E-14 2 5.01823186E+03-2.62757512E+01 1.65922763E+00 5.32806730E-02-7.32176210E-05 3 5.01706936E-08-1.34343967E-11 6.76961024E+03 1.88905369E+01 4 rad2(12) C 3 H 1 Cl6 G100.000 5000.000 868.95 1 1.90717209E+01 1.17128480E-02-6.31840569E-06 1.24773205E-09-8.75053685E-14 2 -1.34302277E+04-5.64324828E+01-4.15457388E-01 1.01421642E-01-1.61183074E-04 3 1.20067077E-07-3.42738944E-11-1.00437136E+04 3.48435938E+01 4 rad3(13) C 3 H 2 Cl5 G100.000 5000.000 939.20 1 1.65076454E+01 1.37741627E-02-7.30239405E-06 1.48082953E-09-1.07103894E-13 2 -1.13749145E+04-4.42715342E+01 3.85100528E-01 8.24381837E-02-1.16964388E-04 3 7.93204167E-08-2.08264564E-11-8.34641194E+03 3.24993419E+01 4 rad4(14) C 3 H 2 Cl5 G100.000 5000.000 939.25 1 1.65076833E+01 1.37740895E-02-7.30234790E-06 1.48081791E-09-1.07102885E-13 2 -1.13749275E+04-4.49648880E+01 3.85114975E-01 8.24380305E-02-1.16963927E-04 3 7.93199067E-08-2.08262684E-11-8.34641259E+03 3.18061417E+01 4 rad5(15) C 3 H 4 Cl1 G100.000 5000.000 1141.50 1 7.36539273E+00 1.37132518E-02-5.54601922E-06 1.01798455E-09-7.02683914E-14 2 2.44167061E+04-1.00983885E+01 2.75462078E+00 2.36389400E-02-1.04007897E-05 3 -9.28824331E-10 1.40343730E-12 2.58753144E+04 1.45343527E+01 4

C3Cl4H(18) C 3 H 1 Cl4 G100.000 5000.000 851.31 1 1.09214351E+01 1.37848608E-02-7.25900539E-06 1.39864136E-09-9.54299429E-14 2 8.39293821E+03-1.75909608E+01 1.11609586E+00 6.92038573E-02-1.21376522E-04 3 1.03662486E-07-3.39143462E-11 9.72370573E+03 2.61463357E+01 4

S(20) C 3 H 2 Cl3 G100.000 5000.000 822.86 1 9.09394721E+00 1.49625301E-02-7.22562522E-06 1.39659353E-09-9.77397414E-14 2 1.81626249E+04-1.16503090E+01 1.85887718E+00 5.01321909E-02-7.13354941E-05 3 5.33362507E-08-1.58776503E-11 1.93533384E+04 2.18442490E+01 4

151 S(25) C 3 H 2 Cl3 G100.000 5000.000 842.87 1 1.00968542E+01 1.44449905E-02-7.17823048E-06 1.40462278E-09-9.90348561E-14 2 2.03577048E+04-1.87224104E+01 1.67210243E+00 5.44244464E-02-7.83238084E-05 3 5.76745593E-08-1.67882613E-11 2.17779631E+04 2.04823791E+01 4

C3Cl4H(26) C 3 H 1 Cl4 G100.000 5000.000 852.61 1 1.24762454E+01 1.25465749E-02-6.83970822E-06 1.32519614E-09-9.03537927E-14 2 1.55307132E+04-2.82353765E+01 7.89171764E-01 7.66472648E-02-1.35922926E-04 3 1.15010529E-07-3.71644172E-11 1.71866401E+04 2.43083116E+01 4

S(30) C 3 H 3 Cl4 G100.000 5000.000 891.28 1 1.20338739E+01 2.10774487E-02-1.09995158E-05 2.21583277E-09-1.59560938E-13 2 -6.67446557E+03-2.58114764E+01 1.00081724E+00 7.05937232E-02-9.43352646E-05 3 6.45508673E-08-1.76445085E-11-4.70778547E+03 2.61466169E+01 4

S(31) C 3 H 2 Cl5 G100.000 5000.000 884.41 1 1.70761325E+01 1.30732949E-02-6.57787446E-06 1.27932870E-09-8.95250282E-14 2 -9.54345316E+03-4.99739875E+01 6.54945248E-02 9.00058128E-02-1.37053852E-04 3 9.96280353E-08-2.78890909E-11-6.53445971E+03 3.00036798E+01 4

S(32) C 3 H 3 Cl4 G100.000 5000.000 977.65 1 1.46144556E+01 1.49520363E-02-7.45293132E-06 1.48604687E-09-1.06894361E-13 2 -7.52841933E+03-3.94823656E+01 8.46412960E-01 7.12830899E-02-9.38810015E-05 3 6.04218544E-08-1.51776466E-11-4.83634830E+03 2.66293037E+01 4

S(35) C 3 H 3 Cl4 G100.000 5000.000 943.56 1 1.13721851E+01 1.96455653E-02-9.84047977E-06 1.96199698E-09-1.40890906E-13 2 -4.07148822E+03-2.03625110E+01 1.32263745E+00 6.22493534E-02-7.75704973E-05 3 4.98174731E-08-1.28207189E-11-2.17506705E+03 2.75366553E+01 4

S(36) C 3 H 2 Cl5 G100.000 5000.000 866.40 1 1.40142169E+01 1.97468806E-02-1.07590456E-05 2.18904579E-09-1.57961045E-13 2 -1.05561260E+04-3.17815653E+01 5.13586233E-01 8.20773426E-02-1.18673074E-04 3 8.52262928E-08-2.41186471E-11-8.21676229E+03 3.14149198E+01 4

S(38) C 3 H 2 Cl5 G100.000 5000.000 951.99 1 1.46977729E+01 1.77051611E-02-9.38363846E-06 1.90845156E-09-1.38442461E-13 2 -8.57170697E+03-3.60076814E+01 6.74681782E-01 7.66255079E-02-1.02219997E-04 3 6.69196819E-08-1.72106601E-11-5.90170115E+03 3.09558767E+01 4

S(40) C 3 H 2 Cl4 G100.000 5000.000 990.57 1 1.31002656E+01 1.40385234E-02-6.87772550E-06 1.36209108E-09-9.76681106E-14 2 -1.31392330E+04-3.32836510E+01 1.25442626E+00 6.18723919E-02-7.93107197E-05 3

152 5.01098723E-08-1.24004843E-11-1.07923785E+04 2.37535807E+01 4

S(44) C 3 H 3 Cl4 G100.000 5000.000 941.60 1 1.41974249E+01 1.54036172E-02-7.38403769E-06 1.43809986E-09-1.01820102E-13 2 -4.95770933E+03-3.62780199E+01 8.15376092E-01 7.22506580E-02-9.79415287E-05 3 6.55529133E-08-1.71243322E-11-2.43755379E+03 2.74776246E+01 4

S(45) C 3 H 4 Cl3 G100.000 5000.000 1233.53 1 1.23329373E+01 1.59395197E-02-7.40095126E-06 1.44419791E-09-1.02862147E-13 2 -4.55718039E+03-2.97840090E+01 1.62339582E+00 5.06683107E-02-4.96327637E-05 3 2.42690125E-08-4.72886679E-12-1.91512405E+03 2.41308461E+01 4

S(47) C 3 H 3 Cl2 G100.000 5000.000 993.06 1 1.11994722E+01 9.69387558E-03-3.56143935E-06 6.55658844E-10-4.70214983E-14 2 1.00984679E+04-3.01844003E+01 2.20943835E+00 3.36205336E-02-2.11462594E-05 3 3.67217469E-12 3.25316522E-12 1.24897387E+04 1.61745876E+01 4

S(48) C 3 H 2 Cl3 G100.000 5000.000 997.59 1 1.01294504E+01 1.30651108E-02-6.11375169E-06 1.18826179E-09-8.43403556E-14 2 1.38031039E+04-1.69912317E+01 1.97131681E+00 4.57763306E-02-5.52988943E-05 3 3.40574222E-08-8.32144445E-12 1.54308058E+04 2.23473994E+01 4

S(52) C 3 H 2 Cl3 G100.000 5000.000 968.38 1 1.16398030E+01 1.19064526E-02-5.74213576E-06 1.12639548E-09-8.02448085E-14 2 2.09582214E+04-2.73882505E+01 1.64636937E+00 5.31862020E-02-6.96847869E-05 3 4.51475784E-08-1.14451036E-11 2.28936734E+04 2.05030065E+01 4

C3Cl3H(56) C 3 H 1 Cl3 G100.000 5000.000 822.82 1 8.92252829E+00 1.77966745E-02-8.44656302E-06 1.58378551E-09-1.07897883E-13 2 3.20324726E+04-1.26404183E+01 1.58600525E+00 5.66373695E-02-8.50419588E-05 3 6.83333267E-08-2.18136961E-11 3.31323074E+04 2.06701120E+01 4

S(58) C 3 H 3 Cl3 G100.000 5000.000 866.60 1 9.20726217E+00 1.82705537E-02-9.35335079E-06 1.87717667E-09-1.34975910E-13 2 -1.21268279E+04-1.38711026E+01 1.78896071E+00 5.25114949E-02-6.86210647E-05 3 4.74712234E-08-1.32881138E-11-1.08410876E+04 2.08557795E+01 4

S(79) C 3 H 3 Cl5 G100.000 5000.000 1019.40 1 1.58063256E+01 1.80093795E-02-9.19926463E-06 1.85960428E-09-1.34952981E-13 2 -3.10499900E+04-4.46635488E+01 5.45556289E-01 7.78891291E-02-9.73071527E-05 3 5.94787864E-08-1.42652293E-11-2.79385398E+04 2.92544803E+01 4

S(85) C 3 H 2 Cl2 G100.000 5000.000 1369.98 1 9.50552401E+00 1.47856398E-02-5.99813409E-06 1.06858280E-09-7.17074013E-14 2

153 3.68479495E+04-1.98132416E+01 2.19964937E+00 3.61170140E-02-2.93540402E-05 3 1.24341755E-08-2.14575503E-12 3.88497260E+04 1.77332271E+01 4

S(86) C 3 H 2 Cl4 G100.000 5000.000 1012.95 1 1.23454751E+01 1.52356577E-02-7.80909427E-06 1.58014402E-09-1.14660506E-13 2 -1.38402119E+04-2.83888524E+01 1.44027221E+00 5.82990874E-02-7.15788497E-05 3 4.35500860E-08-1.04730742E-11-1.16309415E+04 2.43626909E+01 4

S(87) C 3 H 3 Cl3 G100.000 5000.000 1270.27 1 1.17490332E+01 1.40456765E-02-6.67975276E-06 1.31636407E-09-9.41601392E-14 2 -1.15965658E+04-2.79551987E+01 1.87291600E+00 4.51447921E-02-4.34030030E-05 3 2.05894682E-08-3.88725313E-12-9.08748630E+03 2.20540650E+01 4

C3Cl5H(93) C 3 H 1 Cl5 G100.000 5000.000 822.31 1 1.38897975E+01 1.47634459E-02-8.02647051E-06 1.57339485E-09-1.08841103E-13 2 -1.85487953E+04-3.38707757E+01 3.76025220E-01 8.55920038E-02-1.46517105E-04 3 1.21382921E-07-3.88233717E-11-1.64984815E+04 2.76345765E+01 4

C3Cl4H(95) C 3 H 1 Cl4 G100.000 5000.000 800.11 1 1.19997385E+01 1.33919201E-02-7.07318410E-06 1.39215446E-09-9.74571025E-14 2 1.60732977E+04-2.53651072E+01 1.10942491E+00 6.78417351E-02-1.09163299E-04 3 8.64645098E-08-2.66817114E-11 1.78158039E+04 2.47446078E+01 4

C3Cl4H(96) C 3 H 1 Cl4 G100.000 5000.000 882.48 1 1.27424644E+01 1.21862129E-02-6.39029690E-06 1.27626379E-09-9.10340778E-14 2 1.62452967E+04-2.96242208E+01 1.21623525E+00 6.44326894E-02-9.51995116E-05 3 6.83691592E-08-1.90985913E-11 1.82795615E+04 2.45417844E+01 4

S(98) C 3 H 2 Cl5 G100.000 5000.000 888.74 1 1.32990278E+01 1.96815397E-02-1.08678881E-05 2.23652255E-09-1.62794792E-13 2 -6.77677916E+03-2.79401963E+01 7.83273689E-01 7.60114353E-02-1.05939780E-04 3 7.35518388E-08-2.02234334E-11-4.55211179E+03 3.09649386E+01 4

S(100) C 3 H 2 Cl5 G100.000 5000.000 934.42 1 1.56841340E+01 1.58509664E-02-8.56119146E-06 1.74946402E-09-1.27054205E-13 2 -8.83830800E+03-4.31059312E+01 4.86361109E-01 8.09056835E-02-1.12987254E-04 3 7.62495020E-08-2.00583417E-11-5.99796301E+03 2.91843498E+01 4

S(101) C 3 H 1 Cl4 G100.000 5000.000 916.11 1 1.20039765E+01 1.31890431E-02-7.19135355E-06 1.47453765E-09-1.07211517E-13 2 1.11201309E+04-2.49665610E+01 1.45650301E+00 5.92410210E-02-8.25927521E-05 3 5.63436577E-08-1.50801782E-11 1.30527158E+04 2.49950483E+01 4

S(102) C 3 H 1 Cl4 G100.000 5000.000 795.66 1

154 1.11492482E+01 1.47654396E-02-8.11231134E-06 1.63675383E-09-1.16721669E-13 2 1.54080374E+04-1.99414200E+01 1.28643559E+00 6.43441634E-02-1.01571320E-04 3 7.99372428E-08-2.47169447E-11 1.69776635E+04 2.53873359E+01 4

S(103) C 3 H 2 Cl3 G100.000 5000.000 1056.13 1 1.04668539E+01 1.37328484E-02-7.06696153E-06 1.43488578E-09-1.04335273E-13 2 1.81873885E+04-1.90701710E+01 1.99016034E+00 4.58375329E-02-5.26645207E-05 3 3.02176345E-08-6.91758339E-12 1.99778894E+04 2.22879122E+01 4

C3Cl5(106) C 3 Cl5 G100.000 5000.000 859.38 1 1.33205514E+01 1.32864479E-02-7.75068928E-06 1.52111634E-09-1.03788230E-13 2 1.19029981E+04-2.88847241E+01 3.68383124E-01 8.79486750E-02-1.63162386E-04 3 1.41548297E-07-4.65016058E-11 1.35983067E+04 2.85505516E+01 4

S(107) C 3 H 4 Cl2 G100.000 5000.000 1219.09 1 1.07812904E+01 1.35736360E-02-5.93192368E-06 1.13194208E-09-7.96912309E-14 2 -7.72829888E+03-2.66234067E+01 2.15603945E+00 3.49804684E-02-2.37892041E-05 3 6.25876735E-09-1.79831361E-13-5.11303352E+03 1.87981896E+01 4

S(110) C 3 H 1 Cl5 G100.000 5000.000 660.29 1 1.29825140E+01 1.62502861E-02-9.13834852E-06 1.83651726E-09-1.29728239E-13 2 -1.91949432E+04-2.81369464E+01 6.68082349E-01 8.04286897E-02-1.31258997E-04 3 1.01232656E-07-2.87127484E-11-1.73415384E+04 2.78819853E+01 4

S(111) C 3 H 2 Cl4 G100.000 5000.000 809.80 1 1.10735768E+01 1.72875299E-02-9.29219646E-06 1.87571132E-09-1.34351799E-13 2 -1.63983895E+04-2.03134796E+01 1.22350692E+00 6.59432354E-02-9.94201493E-05 3 7.60755088E-08-2.30418257E-11-1.48031172E+04 2.51290864E+01 4

C3Cl5(114) C 3 Cl5 G100.000 5000.000 833.30 1 1.30375485E+01 1.34766063E-02-8.07821376E-06 1.62225939E-09-1.13001269E-13 2 5.61522772E+03-2.69124761E+01 5.23944845E-01 8.36793485E-02-1.52692086E-04 3 1.31913736E-07-4.35809266E-11 7.34886336E+03 2.90650495E+01 4

S(120) C 3 H 2 Cl3 G100.000 5000.000 903.16 1 9.27911322E+00 1.57338478E-02-8.22514984E-06 1.66601765E-09-1.20505676E-13 2 1.81898518E+04-1.23320531E+01 1.96661178E+00 4.81201879E-02-6.20136019E-05 3 4.13699665E-08-1.11108077E-11 1.95107217E+04 2.22017101E+01 4

S(127) C 3 H 1 Cl5 G100.000 5000.000 885.89 1 1.47120369E+01 1.35284396E-02-7.03723615E-06 1.39857219E-09-9.94261532E-14 2 -1.58185227E+04-3.94506232E+01 6.61477906E-01 7.69706944E-02-1.14459644E-04 3 8.22390067E-08-2.29130178E-11-1.33291004E+04 2.66326456E+01 4

155 C3Cl5(128) C 3 Cl5 G100.000 5000.000 842.78 1 1.39029274E+01 1.23543339E-02-6.91456063E-06 1.35099186E-09-9.26155320E-14 2 1.32818845E+04-3.31506560E+01 4.72754060E-01 8.35515621E-02-1.46901678E-04 3 1.22581320E-07-3.91675455E-11 1.52808662E+04 2.77742208E+01 4

END REACTIONS KCAL/MOLE MOLES ab(6)+C3Cl3H(56)=rad1(11)+S(31) 2.124e-02 4.340 3.400 ab(6)+C3Cl4H(18)=S(110)+S(30) 8.420e-13 2.100 1.140 ab(6)+C3Cl4H(18)=S(110)+S(32) 1.263e-12 2.100 1.140 ab(6)+C3Cl4H(18)=S(111)+S(31) 7.242e-04 4.340 14.303 ab(6)+C3Cl4H(18)=xa(1)+S(31) 1.752e-03 4.416 12.058 ab(6)+C3Cl4H(26)=C3Cl5H(93)+S(30) 8.420e-13 2.100 1.140 ab(6)+C3Cl4H(26)=C3Cl5H(93)+S(32) 1.263e-12 2.100 1.140 ab(6)+C3Cl4H(26)=xf(5)+S(31) 2.124e-02 4.340 3.400 ab(6)+C3Cl4H(95)=C3Cl5H(93)+S(30) 8.420e-13 2.100 1.140 ab(6)+C3Cl4H(95)=C3Cl5H(93)+S(32) 1.263e-12 2.100 1.140 ab(6)+C3Cl4H(96)=S(127)+S(30) 8.420e-13 2.100 1.140 ab(6)+C3Cl4H(96)=S(127)+S(32) 1.263e-12 2.100 1.140 ab(6)+C3Cl4H(96)=S(40)+S(31) 5.592e-03 4.340 3.788 ab(6)+C3Cl5(106)=C3Cl5H(93)+S(31) 5.592e-03 4.340 3.788 ab(6)+C3Cl5(114)=S(110)+S(31) 7.242e-04 4.340 14.303 ab(6)+S(101)=S(86)+S(31) 7.242e-04 4.340 14.303 ab(6)+S(102)=S(110)+S(30) 8.420e-13 2.100 1.140 ab(6)+S(102)=S(110)+S(32) 1.263e-12 2.100 1.140 ab(6)+S(103)=S(86)+S(30) 8.420e-13 2.100 1.140 ab(6)+S(103)=S(86)+S(32) 1.263e-12 2.100 1.140 ab(6)+S(103)=S(87)+S(31) 5.592e-03 4.340 3.788 ab(6)+S(120)=S(111)+S(30) 8.420e-13 2.100 1.140 ab(6)+S(120)=S(111)+S(32) 1.263e-12 2.100 1.140 ab(6)+S(20)=xa(1)+S(30) 8.420e-13 2.100 1.140 ab(6)+S(20)=xa(1)+S(32) 1.263e-12 2.100 1.140 ab(6)+S(25)=xf(5)+S(30) 8.420e-13 2.100 1.140 ab(6)+S(25)=xf(5)+S(32) 1.263e-12 2.100 1.140 ab(6)+S(30)=ab(6)+S(32) 1.263e-12 2.100 1.140 ab(6)+S(35)=db(7)+S(30) 8.420e-13 2.100 1.140 ab(6)+S(35)=db(7)+S(32) 1.263e-12 2.100 1.140 ab(6)+S(38)=db(7)+S(31) 1.752e-03 4.416 12.058 ab(6)+S(48)=S(86)+S(30) 8.420e-13 2.100 1.140 ab(6)+S(48)=S(86)+S(32) 1.263e-12 2.100 1.140 ab(6)+S(48)=S(87)+S(31) 7.242e-04 4.340 14.303 ab(6)+S(48)=za(9)+S(31) 1.752e-03 4.416 12.058 ab(6)+S(52)=S(40)+S(30) 8.420e-13 2.100 1.140 ab(6)+S(52)=S(40)+S(32) 1.263e-12 2.100 1.140

156 ab(6)+S(52)=zf(10)+S(31) 2.124e-02 4.340 3.400 ab(6)+S(85)=S(47)+S(31) 2.124e-02 4.340 3.400 C3Cl3H(56)+C3Cl4H(26)=C3Cl3H(56)+C3Cl4H(18) 1.263e-12 2.100 1.140 C3Cl3H(56)+S(107)=rad1(11)+S(47) 5.490e+00 3.330 0.630 C3Cl3H(56)+S(110)=rad1(11)+C3Cl5(114) 5.490e+00 3.330 0.630 C3Cl3H(56)+S(111)=rad1(11)+C3Cl4H(18) 5.490e+00 3.330 0.630 C3Cl3H(56)+S(40)=rad1(11)+C3Cl4H(95) 8.420e-01 3.500 9.670 C3Cl3H(56)+S(47)=rad1(11)+S(85) 1.850e-02 4.340 6.100 C3Cl3H(56)+S(48)=S(85)+C3Cl4H(18) 4.210e-13 2.100 1.140 C3Cl3H(56)+S(52)=S(85)+C3Cl4H(18) 1.263e-12 2.100 1.140 C3Cl3H(56)+S(52)=S(85)+C3Cl4H(26) 1.263e-12 2.100 1.140 C3Cl3H(56)+S(58)=rad1(11)+rad1(11) 5.490e+00 3.330 0.630 C3Cl3H(56)+S(79)=rad1(11)+S(100) 5.490e+00 3.330 0.630 C3Cl3H(56)+S(79)=rad1(11)+S(98) 1.020e+03 3.100 8.820 C3Cl3H(56)+S(86)=rad1(11)+S(101) 5.490e+00 3.330 0.630 C3Cl3H(56)+S(86)=rad1(11)+S(102) 8.420e-01 3.500 9.670 C3Cl3H(56)+S(87)=rad1(11)+S(120) 8.420e-01 3.500 9.670 C3Cl3H(56)+S(87)=rad1(11)+S(48) 5.490e+00 3.330 0.630 C3Cl4H(18)+C3Cl4H(18)=C3Cl3H(56)+C3Cl5H(93) 4.210e-13 2.100 1.140 C3Cl4H(18)+C3Cl4H(18)=C3Cl3H(56)+S(110) 4.210e-13 2.100 1.140 C3Cl4H(18)+C3Cl4H(26)=C3Cl3H(56)+C3Cl5H(93) 1.684e-12 2.100 1.140 C3Cl4H(18)+C3Cl4H(26)=C3Cl3H(56)+S(110) 1.263e-12 2.100 1.140 C3Cl4H(18)+S(20)=xa(1)+C3Cl3H(56) 4.210e-13 2.100 1.140 C3Cl4H(18)+S(25)=xf(5)+C3Cl3H(56) 4.210e-13 2.100 1.140 C3Cl4H(18)+S(30)=ab(6)+C3Cl3H(56) 4.210e-13 2.100 1.140 C3Cl4H(18)+S(32)=ab(6)+C3Cl3H(56) 4.210e-13 2.100 1.140 C3Cl4H(26)+C3Cl4H(26)=C3Cl3H(56)+C3Cl5H(93) 1.263e-12 2.100 1.140 C3Cl4H(26)+S(30)=ab(6)+C3Cl3H(56) 1.263e-12 2.100 1.140 C3Cl4H(26)+S(32)=ab(6)+C3Cl3H(56) 1.263e-12 2.100 1.140 C3Cl4H(95)+C3Cl4H(18)=C3Cl3H(56)+C3Cl5H(93) 4.210e-13 2.100 1.140 C3Cl4H(95)+C3Cl4H(26)=C3Cl3H(56)+C3Cl5H(93) 1.263e-12 2.100 1.140 C3Cl4H(95)+S(107)=S(40)+S(47) 1.512e-03 4.340 -1.662 C3Cl4H(95)+S(110)=C3Cl5H(93)+C3Cl4H(18) 8.420e-13 2.100 1.140 C3Cl4H(95)+S(110)=C3Cl5H(93)+S(102) 4.210e-13 2.100 1.140 C3Cl4H(95)+S(110)=S(40)+C3Cl5(114) 1.512e-03 4.340 -1.662 C3Cl4H(95)+S(111)=S(40)+C3Cl4H(18) 1.512e-03 4.340 -1.662 C3Cl4H(96)+C3Cl4H(18)=S(127)+C3Cl3H(56) 4.210e-13 2.100 1.140 C3Cl4H(96)+C3Cl4H(26)=S(127)+C3Cl3H(56) 1.263e-12 2.100 1.140 C3Cl4H(96)+S(107)=S(40)+S(47) 1.512e-03 4.340 -1.662 C3Cl4H(96)+S(110)=S(127)+C3Cl4H(18) 8.420e-13 2.100 1.140 C3Cl4H(96)+S(110)=S(40)+C3Cl5(114) 1.512e-03 4.340 -1.662 C3Cl4H(96)+S(111)=S(40)+C3Cl4H(18) 1.512e-03 4.340 -1.662 C3Cl5(106)+S(107)=S(47)+C3Cl5H(93) 1.512e-03 4.340 -1.662 C3Cl5(106)+S(110)=C3Cl5H(93)+C3Cl5(114) 1.512e-03 4.340 -1.662

157 C3Cl5(106)+S(111)=C3Cl5H(93)+C3Cl4H(18) 1.512e-03 4.340 -1.662 C3Cl5(128)+S(107)=S(127)+S(47) 1.512e-03 4.340 -1.662 C3Cl5(128)+S(110)=S(127)+C3Cl5(114) 1.512e-03 4.340 -1.662 C3Cl5(128)+S(111)=S(127)+C3Cl4H(18) 1.512e-03 4.340 -1.662 C3Cl5(128)+S(58)=rad1(11)+S(127) 1.512e-03 4.340 -1.662 C3Cl5(128)+S(79)=S(127)+S(100) 1.512e-03 4.340 -1.662 C3Cl5(128)+S(86)=S(127)+S(101) 1.512e-03 4.340 -1.662 C3Cl5(128)+S(87)=S(127)+S(48) 1.512e-03 4.340 -1.662 C3Cl5H(93)+C3Cl4H(18)=S(110)+C3Cl4H(18) 1.263e-12 2.100 1.140 C3Cl5H(93)+C3Cl4H(26)=C3Cl5H(93)+C3Cl4H(18) 1.263e-12 2.100 1.140 C3Cl5H(93)+C3Cl4H(95)=C3Cl5H(93)+C3Cl4H(18) 1.263e-12 2.100 1.140 C3Cl5H(93)+C3Cl4H(95)=C3Cl5H(93)+C3Cl4H(26) 4.210e-13 2.100 1.140 C3Cl5H(93)+C3Cl4H(96)=S(127)+C3Cl4H(18) 1.263e-12 2.100 1.140 C3Cl5H(93)+C3Cl4H(96)=S(40)+C3Cl5(106) 5.781e-03 4.340 6.104 C3Cl5H(93)+S(101)=S(127)+C3Cl4H(18) 1.263e-12 2.100 1.140 C3Cl5H(93)+S(102)=S(110)+C3Cl4H(18) 1.263e-12 2.100 1.140 C3Cl5H(93)+S(102)=S(110)+C3Cl4H(26) 4.210e-13 2.100 1.140 C3Cl5H(93)+S(103)=S(86)+C3Cl4H(18) 1.263e-12 2.100 1.140 C3Cl5H(93)+S(120)=C3Cl4H(95)+S(111) 4.210e-13 2.100 1.140 C3Cl5H(93)+S(120)=S(111)+C3Cl4H(18) 1.263e-12 2.100 1.140 C3Cl5H(93)+S(120)=S(111)+C3Cl4H(26) 4.210e-13 2.100 1.140 C3Cl5H(93)+S(20)=xa(1)+C3Cl4H(18) 1.263e-12 2.100 1.140 C3Cl5H(93)+S(20)=xa(1)+C3Cl4H(26) 4.210e-13 2.100 1.140 C3Cl5H(93)+S(25)=xf(5)+C3Cl4H(18) 1.263e-12 2.100 1.140 C3Cl5H(93)+S(25)=xf(5)+C3Cl4H(26) 4.210e-13 2.100 1.140 C3Cl5H(93)+S(30)=ab(6)+C3Cl4H(18) 1.263e-12 2.100 1.140 C3Cl5H(93)+S(32)=ab(6)+C3Cl4H(18) 1.263e-12 2.100 1.140 Cl(4)+ab(6)=HCl(2)+S(31) 8.469e+04 2.483 10.027 Cl(4)+C3Cl3H(56)=C3Cl4H(18) 1.000e+13 0.000 0.000 Cl(4)+C3Cl3H(56)=C3Cl4H(26) 1.000e+13 0.000 0.000 Cl(4)+C3Cl4H(18)=C3Cl5H(93) 1.000e+13 0.000 0.000 Cl(4)+C3Cl4H(18)=S(110) 1.000e+13 0.000 0.000 Cl(4)+C3Cl4H(26)=C3Cl5H(93) 1.000e+13 0.000 0.000 Cl(4)+C3Cl4H(26)=Cl2(3)+C3Cl3H(56) 1.263e-12 2.100 2.125 Cl(4)+C3Cl4H(95)=C3Cl5H(93) 1.000e+13 0.000 0.000 Cl(4)+C3Cl4H(96)=S(127) 1.000e+13 0.000 0.000 Cl(4)+Cl(4)=Cl2(3) 1.000e+13 0.000 0.000 Cl(4)+db(7)=HCl(2)+S(36) 2.823e+04 2.483 9.977 Cl(4)+db(7)=HCl(2)+S(38) 5.646e+04 2.483 10.027 Cl(4)+fb(8)=HCl(2)+S(35) 5.646e+04 2.483 9.997 Cl(4)+fb(8)=HCl(2)+S(44) 5.646e+04 2.483 9.994 Cl(4)+rad1(11)=HCl(2)+C3Cl3H(56) 5.646e+04 2.483 10.066 Cl(4)+rad1(11)=xa(1) 1.000e+13 0.000 0.000 Cl(4)+rad1(11)=xf(5) 1.000e+13 0.000 0.000

158 Cl(4)+S(101)=S(127) 1.000e+13 0.000 0.000 Cl(4)+S(102)=S(110) 1.000e+13 0.000 0.000 Cl(4)+S(103)=S(86) 1.000e+13 0.000 0.000 Cl(4)+S(107)=HCl(2)+S(47) 2.823e+04 2.483 9.869 Cl(4)+S(110)=HCl(2)+C3Cl5(114) 2.823e+04 2.483 10.027 Cl(4)+S(111)=HCl(2)+C3Cl4H(18) 2.823e+04 2.483 10.023 Cl(4)+S(120)=S(111) 1.000e+13 0.000 0.000 Cl(4)+S(20)=xa(1) 1.000e+13 0.000 0.000 Cl(4)+S(25)=xf(5) 1.000e+13 0.000 0.000 Cl(4)+S(30)=ab(6) 1.000e+13 0.000 0.000 Cl(4)+S(32)=ab(6) 1.000e+13 0.000 0.000 Cl(4)+S(35)=db(7) 1.000e+13 0.000 0.000 Cl(4)+S(44)=S(79) 1.000e+13 0.000 0.000 Cl(4)+S(45)=fb(8) 1.000e+13 0.000 0.000 Cl(4)+S(47)=HCl(2)+S(85) 5.646e+04 2.483 10.066 Cl(4)+S(47)=za(9) 1.000e+13 0.000 0.000 Cl(4)+S(47)=zf(10) 1.000e+13 0.000 0.000 Cl(4)+S(48)=S(40) 1.000e+13 0.000 0.000 Cl(4)+S(48)=S(86) 1.000e+13 0.000 0.000 Cl(4)+S(52)=Cl2(3)+S(85) 1.263e-12 2.100 2.125 Cl(4)+S(52)=S(40) 1.000e+13 0.000 0.000 Cl(4)+S(58)=HCl(2)+rad1(11) 2.823e+04 2.483 9.869 Cl(4)+S(79)=HCl(2)+S(100) 2.823e+04 2.483 9.966 Cl(4)+S(79)=HCl(2)+S(98) 5.646e+04 2.483 9.997 Cl(4)+S(85)=S(48) 1.000e+13 0.000 0.000 Cl(4)+S(85)=S(52) 1.000e+13 0.000 0.000 Cl(4)+S(86)=HCl(2)+S(101) 2.823e+04 2.483 10.027 Cl(4)+S(87)=HCl(2)+S(48) 2.823e+04 2.483 10.023 Cl(4)+za(9)=Cl2(3)+S(47) 4.210e-13 2.100 13.705 Cl(4)+za(9)=HCl(2)+S(48) 5.646e+04 2.483 10.027 Cl2(3)+C3Cl3H(56)=Cl(4)+C3Cl4H(18) 8.420e-13 2.100 1.140 Cl2(3)+C3Cl4H(18)=Cl(4)+C3Cl5H(93) 8.420e-13 2.100 1.140 Cl2(3)+C3Cl4H(18)=Cl(4)+S(110) 8.420e-13 2.100 1.140 Cl2(3)+C3Cl4H(26)=Cl(4)+C3Cl5H(93) 8.420e-13 2.100 1.140 Cl2(3)+C3Cl4H(95)=Cl(4)+C3Cl5H(93) 8.420e-13 2.100 1.140 Cl2(3)+C3Cl4H(96)=Cl(4)+S(127) 8.420e-13 2.100 1.140 Cl2(3)+rad1(11)=Cl(4)+xf(5) 8.420e-13 2.100 1.140 Cl2(3)+S(101)=Cl(4)+S(127) 8.420e-13 2.100 1.140 Cl2(3)+S(102)=Cl(4)+S(110) 8.420e-13 2.100 1.140 Cl2(3)+S(103)=Cl(4)+S(86) 8.420e-13 2.100 1.140 Cl2(3)+S(120)=Cl(4)+S(111) 8.420e-13 2.100 1.140 Cl2(3)+S(20)=xa(1)+Cl(4) 8.420e-13 2.100 1.140 Cl2(3)+S(25)=Cl(4)+xf(5) 8.420e-13 2.100 1.140 Cl2(3)+S(30)=Cl(4)+ab(6) 8.420e-13 2.100 1.140

159 Cl2(3)+S(32)=Cl(4)+ab(6) 8.420e-13 2.100 1.140 Cl2(3)+S(35)=Cl(4)+db(7) 8.420e-13 2.100 1.140 Cl2(3)+S(44)=Cl(4)+S(79) 8.420e-13 2.100 1.140 Cl2(3)+S(45)=Cl(4)+fb(8) 8.420e-13 2.100 1.140 Cl2(3)+S(47)=Cl(4)+zf(10) 8.420e-13 2.100 1.140 Cl2(3)+S(48)=Cl(4)+S(40) 8.420e-13 2.100 1.140 Cl2(3)+S(48)=Cl(4)+S(86) 8.420e-13 2.100 1.140 Cl2(3)+S(52)=Cl(4)+S(40) 8.420e-13 2.100 1.140 Cl2(3)+S(85)=Cl(4)+S(48) 8.420e-13 2.100 1.140 Cl2(3)+za(9)=db(7) 1.600e+03 3.000 45.000 Cl2(3)+zf(10)=db(7) 1.600e+03 3.000 45.000 db(7)+C3Cl3H(56)=rad1(11)+S(36) 5.490e+00 3.330 0.630 db(7)+C3Cl3H(56)=rad1(11)+S(38) 5.200e-02 3.900 0.860 db(7)+C3Cl4H(18)=S(36)+S(111) 1.126e-04 4.331 4.596 db(7)+C3Cl4H(18)=S(38)+S(111) 3.117e-04 4.388 8.709 db(7)+C3Cl4H(18)=xa(1)+S(36) 5.842e-04 4.388 5.581 db(7)+C3Cl4H(26)=S(35)+C3Cl5H(93) 4.210e-13 2.100 1.140 db(7)+C3Cl4H(26)=xf(5)+S(36) 5.490e+00 3.330 0.630 db(7)+C3Cl4H(26)=xf(5)+S(38) 5.200e-02 3.900 0.860 db(7)+C3Cl4H(95)=S(35)+C3Cl5H(93) 4.210e-13 2.100 1.140 db(7)+C3Cl4H(95)=S(36)+S(40) 1.512e-03 4.340 -1.662 db(7)+C3Cl4H(95)=S(38)+S(40) 5.826e-03 4.305 1.115 db(7)+C3Cl4H(96)=S(127)+S(35) 4.210e-13 2.100 1.140 db(7)+C3Cl4H(96)=S(36)+S(40) 1.512e-03 4.340 -1.662 db(7)+C3Cl4H(96)=S(38)+S(40) 5.826e-03 4.305 1.115 db(7)+C3Cl5(106)=S(36)+C3Cl5H(93) 1.512e-03 4.340 -1.662 db(7)+C3Cl5(106)=S(38)+C3Cl5H(93) 5.826e-03 4.305 1.115 db(7)+C3Cl5(114)=S(38)+S(110) 3.117e-04 4.388 8.709 db(7)+C3Cl5(128)=S(127)+S(36) 1.512e-03 4.340 -1.662 db(7)+C3Cl5(128)=S(127)+S(38) 5.826e-03 4.305 1.115 db(7)+rad1(11)=S(58)+S(36) 1.126e-04 4.331 9.642 db(7)+S(101)=S(38)+S(86) 3.117e-04 4.388 8.709 db(7)+S(102)=S(35)+S(110) 4.210e-13 2.100 1.140 db(7)+S(102)=S(36)+S(86) 1.512e-03 4.340 -1.662 db(7)+S(102)=S(38)+S(86) 5.826e-03 4.305 1.115 db(7)+S(103)=S(35)+S(86) 4.210e-13 2.100 1.140 db(7)+S(103)=S(36)+S(87) 1.512e-03 4.340 -1.662 db(7)+S(103)=S(38)+S(87) 5.826e-03 4.305 1.115 db(7)+S(120)=S(35)+S(111) 4.210e-13 2.100 1.140 db(7)+S(120)=S(36)+S(87) 1.512e-03 4.340 -1.662 db(7)+S(120)=S(38)+S(87) 5.826e-03 4.305 1.115 db(7)+S(20)=xa(1)+S(35) 4.210e-13 2.100 1.140 db(7)+S(20)=za(9)+S(36) 1.512e-03 4.340 -1.662 db(7)+S(20)=za(9)+S(38) 5.826e-03 4.305 1.115

160 db(7)+S(25)=xf(5)+S(35) 4.210e-13 2.100 1.140 db(7)+S(25)=zf(10)+S(36) 1.512e-03 4.340 -1.662 db(7)+S(25)=zf(10)+S(38) 5.826e-03 4.305 1.115 db(7)+S(31)=ab(6)+S(36) 9.240e-04 4.378 5.465 db(7)+S(35)=fb(8)+S(36) 5.842e-04 4.388 5.581 db(7)+S(38)=db(7)+S(36) 5.842e-04 4.388 5.581 db(7)+S(44)=fb(8)+S(36) 5.842e-04 4.388 5.581 db(7)+S(44)=fb(8)+S(38) 2.162e-03 4.354 9.271 db(7)+S(47)=S(36)+S(107) 1.126e-04 4.331 9.642 db(7)+S(48)=S(36)+S(87) 1.126e-04 4.331 4.596 db(7)+S(48)=S(38)+S(87) 3.117e-04 4.388 8.709 db(7)+S(48)=za(9)+S(36) 5.842e-04 4.388 5.581 db(7)+S(48)=za(9)+S(38) 2.162e-03 4.354 9.271 db(7)+S(52)=S(35)+S(40) 4.210e-13 2.100 1.140 db(7)+S(52)=zf(10)+S(36) 5.490e+00 3.330 0.630 db(7)+S(52)=zf(10)+S(38) 5.200e-02 3.900 0.860 db(7)+S(85)=S(36)+S(47) 5.490e+00 3.330 0.630 db(7)+S(85)=S(38)+S(47) 5.200e-02 3.900 0.860 db(7)+S(98)=S(36)+S(79) 5.842e-04 4.388 5.581 fb(8)+C3Cl3H(56)=rad1(11)+S(35) 1.020e+03 3.100 8.820 fb(8)+C3Cl3H(56)=rad1(11)+S(44) 5.200e-02 3.900 0.860 fb(8)+C3Cl3H(56)=S(45)+C3Cl4H(18) 1.263e-12 2.100 1.140 fb(8)+C3Cl4H(18)=S(35)+S(111) 3.117e-04 4.388 8.709 fb(8)+C3Cl4H(18)=S(44)+S(111) 3.117e-04 4.388 8.709 fb(8)+C3Cl4H(18)=S(45)+C3Cl5H(93) 1.263e-12 2.100 1.140 fb(8)+C3Cl4H(18)=S(45)+S(110) 1.263e-12 2.100 1.140 fb(8)+C3Cl4H(18)=xa(1)+S(35) 2.162e-03 4.354 9.271 fb(8)+C3Cl4H(26)=S(45)+C3Cl5H(93) 1.263e-12 2.100 1.140 fb(8)+C3Cl4H(26)=xf(5)+S(35) 1.020e+03 3.100 8.820 fb(8)+C3Cl4H(26)=xf(5)+S(44) 5.200e-02 3.900 0.860 fb(8)+C3Cl4H(95)=S(40)+S(44) 5.826e-03 4.305 1.115 fb(8)+C3Cl4H(95)=S(45)+C3Cl5H(93) 1.263e-12 2.100 1.140 fb(8)+C3Cl4H(96)=S(127)+S(45) 1.263e-12 2.100 1.140 fb(8)+C3Cl4H(96)=S(35)+S(40) 5.826e-03 4.305 1.115 fb(8)+C3Cl4H(96)=S(40)+S(44) 5.826e-03 4.305 1.115 fb(8)+C3Cl5(106)=S(35)+C3Cl5H(93) 5.826e-03 4.305 1.115 fb(8)+C3Cl5(106)=S(44)+C3Cl5H(93) 5.826e-03 4.305 1.115 fb(8)+C3Cl5(114)=S(35)+S(110) 3.117e-04 4.388 8.709 fb(8)+C3Cl5(114)=S(44)+S(110) 3.117e-04 4.388 8.709 fb(8)+C3Cl5(128)=S(127)+S(44) 5.826e-03 4.305 1.115 fb(8)+S(101)=S(127)+S(45) 1.263e-12 2.100 1.140 fb(8)+S(101)=S(35)+S(86) 3.117e-04 4.388 8.709 fb(8)+S(101)=S(44)+S(86) 3.117e-04 4.388 8.709 fb(8)+S(102)=S(44)+S(86) 5.826e-03 4.305 1.115

161 fb(8)+S(102)=S(45)+S(110) 1.263e-12 2.100 1.140 fb(8)+S(103)=S(35)+S(87) 5.826e-03 4.305 1.115 fb(8)+S(103)=S(44)+S(87) 5.826e-03 4.305 1.115 fb(8)+S(103)=S(45)+S(86) 1.263e-12 2.100 1.140 fb(8)+S(120)=S(44)+S(87) 5.826e-03 4.305 1.115 fb(8)+S(120)=S(45)+S(111) 1.263e-12 2.100 1.140 fb(8)+S(20)=xa(1)+S(45) 1.263e-12 2.100 1.140 fb(8)+S(20)=za(9)+S(44) 5.826e-03 4.305 1.115 fb(8)+S(25)=xf(5)+S(45) 1.263e-12 2.100 1.140 fb(8)+S(25)=zf(10)+S(44) 5.826e-03 4.305 1.115 fb(8)+S(30)=ab(6)+S(45) 1.263e-12 2.100 1.140 fb(8)+S(31)=ab(6)+S(35) 1.840e-03 4.340 7.000 fb(8)+S(31)=ab(6)+S(44) 4.969e-03 4.304 8.942 fb(8)+S(32)=ab(6)+S(45) 1.263e-12 2.100 1.140 fb(8)+S(35)=db(7)+S(45) 1.263e-12 2.100 1.140 fb(8)+S(38)=db(7)+S(35) 2.162e-03 4.354 9.271 fb(8)+S(44)=fb(8)+S(35) 2.162e-03 4.354 9.271 fb(8)+S(44)=S(45)+S(79) 1.263e-12 2.100 1.140 fb(8)+S(48)=S(35)+S(87) 3.117e-04 4.388 8.709 fb(8)+S(48)=S(40)+S(45) 1.263e-12 2.100 1.140 fb(8)+S(48)=S(44)+S(87) 3.117e-04 4.388 8.709 fb(8)+S(48)=S(45)+S(86) 1.263e-12 2.100 1.140 fb(8)+S(48)=za(9)+S(35) 2.162e-03 4.354 9.271 fb(8)+S(52)=S(40)+S(45) 1.263e-12 2.100 1.140 fb(8)+S(52)=zf(10)+S(35) 1.020e+03 3.100 8.820 fb(8)+S(52)=zf(10)+S(44) 5.200e-02 3.900 0.860 fb(8)+S(85)=S(35)+S(47) 1.020e+03 3.100 8.820 fb(8)+S(85)=S(44)+S(47) 5.200e-02 3.900 0.860 fb(8)+S(85)=S(45)+S(48) 1.263e-12 2.100 1.140 HCl(2)+C3Cl4H(26)=Cl(4)+xf(5) 2.823e+04 2.483 9.960 HCl(2)+C3Cl4H(95)=Cl(4)+S(40) 2.823e+04 2.483 9.984 HCl(2)+C3Cl4H(96)=Cl(4)+S(40) 2.823e+04 2.483 9.975 HCl(2)+C3Cl5(106)=Cl(4)+C3Cl5H(93) 2.823e+04 2.483 9.952 HCl(2)+C3Cl5(128)=Cl(4)+S(127) 2.823e+04 2.483 9.984 HCl(2)+S(102)=Cl(4)+S(86) 2.823e+04 2.483 9.984 HCl(2)+S(103)=Cl(4)+S(87) 2.823e+04 2.483 9.975 HCl(2)+S(120)=Cl(4)+S(87) 2.823e+04 2.483 9.984 HCl(2)+S(20)=Cl(4)+za(9) 2.823e+04 2.483 9.984 HCl(2)+S(25)=Cl(4)+zf(10) 2.823e+04 2.483 9.984 HCl(2)+S(40)=db(7) 4.000e+02 3.000 45.000 HCl(2)+S(40)=S(79) 4.000e+02 3.000 45.000 HCl(2)+S(52)=Cl(4)+zf(10) 2.823e+04 2.483 9.960 HCl(2)+S(86)=S(79) 4.000e+02 3.000 45.000 HCl(2)+xf(5)=ab(6) 4.000e+02 3.000 45.000

162 HCl(2)+xf(5)=db(7) 4.000e+02 3.000 45.000 HCl(2)+za(9)=fb(8) 4.000e+02 3.000 45.000 HCl(2)+zf(10)=fb(8) 4.000e+02 3.000 45.000 rad1(11)+C3Cl4H(26)=xa(1)+C3Cl3H(56) 1.263e-12 2.100 1.140 rad1(11)+C3Cl4H(26)=xf(5)+C3Cl3H(56) 1.263e-12 2.100 1.140 rad1(11)+C3Cl4H(26)=xf(5)+C3Cl3H(56) 1.850e-02 4.340 6.100 rad1(11)+C3Cl4H(96)=C3Cl3H(56)+S(40) 2.604e-02 4.340 8.405 rad1(11)+C3Cl5(106)=C3Cl3H(56)+C3Cl5H(93) 2.604e-02 4.340 8.405 rad1(11)+S(103)=C3Cl3H(56)+S(87) 2.604e-02 4.340 8.405 rad1(11)+S(110)=S(58)+C3Cl5(114) 1.126e-04 4.331 14.080 rad1(11)+S(111)=S(58)+C3Cl4H(18) 1.126e-04 4.331 13.760 rad1(11)+S(52)=xa(1)+S(85) 1.263e-12 2.100 1.140 rad1(11)+S(52)=xf(5)+S(85) 1.263e-12 2.100 1.140 rad1(11)+S(52)=zf(10)+C3Cl3H(56) 1.850e-02 4.340 6.100 rad1(11)+S(79)=S(58)+S(100) 1.126e-04 4.331 8.700 rad1(11)+S(86)=S(58)+S(101) 1.126e-04 4.331 14.080 rad1(11)+S(87)=S(58)+S(48) 1.126e-04 4.331 13.760 S(100)+S(110)=S(79)+C3Cl5(114) 1.126e-04 4.331 5.456 S(101)+C3Cl4H(18)=S(127)+C3Cl3H(56) 4.210e-13 2.100 1.140 S(101)+C3Cl4H(26)=S(127)+C3Cl3H(56) 1.263e-12 2.100 1.140 S(101)+S(110)=S(86)+C3Cl5(114) 1.126e-04 4.331 4.596 S(102)+C3Cl4H(18)=C3Cl3H(56)+S(110) 4.210e-13 2.100 1.140 S(102)+C3Cl4H(26)=C3Cl3H(56)+S(110) 1.263e-12 2.100 1.140 S(102)+S(107)=S(47)+S(86) 1.512e-03 4.340 -1.662 S(102)+S(110)=S(110)+C3Cl4H(18) 8.420e-13 2.100 1.140 S(102)+S(110)=S(86)+C3Cl5(114) 1.512e-03 4.340 -1.662 S(102)+S(111)=S(86)+C3Cl4H(18) 1.512e-03 4.340 -1.662 S(103)+C3Cl4H(18)=C3Cl3H(56)+S(86) 4.210e-13 2.100 1.140 S(103)+C3Cl4H(26)=C3Cl3H(56)+S(86) 1.263e-12 2.100 1.140 S(103)+S(107)=S(47)+S(87) 1.512e-03 4.340 -1.662 S(103)+S(110)=S(86)+C3Cl4H(18) 8.420e-13 2.100 1.140 S(103)+S(110)=S(87)+C3Cl5(114) 1.512e-03 4.340 -1.662 S(103)+S(111)=S(87)+C3Cl4H(18) 1.512e-03 4.340 -1.662 S(107)+C3Cl4H(18)=xa(1)+S(47) 5.842e-04 4.388 5.581 S(107)+C3Cl4H(26)=xf(5)+S(47) 5.490e+00 3.330 0.630 S(107)+S(120)=S(47)+S(87) 1.512e-03 4.340 -1.662 S(107)+S(20)=za(9)+S(47) 1.512e-03 4.340 -1.662 S(107)+S(25)=zf(10)+S(47) 1.512e-03 4.340 -1.662 S(107)+S(31)=ab(6)+S(47) 9.240e-04 4.378 5.465 S(110)+C3Cl4H(18)=S(111)+C3Cl5(114) 1.126e-04 4.331 4.596 S(110)+C3Cl4H(26)=C3Cl5H(93)+C3Cl4H(18) 8.420e-13 2.100 1.140 S(110)+C3Cl4H(26)=xf(5)+C3Cl5(114) 5.490e+00 3.330 0.630 S(110)+S(120)=S(102)+S(111) 4.210e-13 2.100 1.140 S(110)+S(120)=S(111)+C3Cl4H(18) 8.420e-13 2.100 1.140

163 S(110)+S(120)=S(87)+C3Cl5(114) 1.512e-03 4.340 -1.662 S(110)+S(20)=xa(1)+C3Cl4H(18) 8.420e-13 2.100 1.140 S(110)+S(20)=za(9)+C3Cl5(114) 1.512e-03 4.340 -1.662 S(110)+S(25)=xf(5)+C3Cl4H(18) 8.420e-13 2.100 1.140 S(110)+S(25)=zf(10)+C3Cl5(114) 1.512e-03 4.340 -1.662 S(111)+C3Cl4H(26)=xf(5)+C3Cl4H(18) 5.490e+00 3.330 0.630 S(111)+S(120)=S(87)+C3Cl4H(18) 1.512e-03 4.340 -1.662 S(111)+S(20)=za(9)+C3Cl4H(18) 1.512e-03 4.340 -1.662 S(111)+S(25)=zf(10)+C3Cl4H(18) 1.512e-03 4.340 -1.662 S(120)+C3Cl4H(18)=C3Cl3H(56)+S(111) 4.210e-13 2.100 1.140 S(120)+C3Cl4H(26)=C3Cl3H(56)+S(111) 1.263e-12 2.100 1.140 S(127)+C3Cl3H(56)=rad1(11)+C3Cl5(128) 8.420e-01 3.500 9.670 S(127)+C3Cl4H(18)=S(101)+S(110) 1.263e-12 2.100 1.140 S(127)+C3Cl4H(26)=C3Cl5H(93)+C3Cl4H(96) 8.420e-13 2.100 1.140 S(127)+C3Cl4H(26)=C3Cl5H(93)+S(101) 1.263e-12 2.100 1.140 S(127)+C3Cl4H(26)=xf(5)+C3Cl5(128) 8.420e-01 3.500 9.670 S(127)+C3Cl4H(95)=C3Cl5(128)+S(40) 5.560e-03 4.340 4.500 S(127)+C3Cl4H(95)=C3Cl5H(93)+C3Cl4H(96) 8.420e-13 2.100 1.140 S(127)+C3Cl4H(95)=C3Cl5H(93)+S(101) 1.263e-12 2.100 1.140 S(127)+C3Cl4H(96)=C3Cl5(128)+S(40) 5.781e-03 4.340 6.104 S(127)+C3Cl4H(96)=S(127)+S(101) 1.263e-12 2.100 1.140 S(127)+C3Cl5(106)=C3Cl5(128)+C3Cl5H(93) 5.781e-03 4.340 6.104 S(127)+S(102)=C3Cl4H(96)+S(110) 8.420e-13 2.100 1.140 S(127)+S(102)=C3Cl5(128)+S(86) 5.560e-03 4.340 4.500 S(127)+S(102)=S(101)+S(110) 1.263e-12 2.100 1.140 S(127)+S(103)=C3Cl5(128)+S(87) 5.781e-03 4.340 6.104 S(127)+S(103)=S(86)+S(101) 1.263e-12 2.100 1.140 S(127)+S(120)=C3Cl4H(96)+S(111) 8.420e-13 2.100 1.140 S(127)+S(120)=C3Cl5(128)+S(87) 5.560e-03 4.340 4.500 S(127)+S(120)=S(101)+S(111) 1.263e-12 2.100 1.140 S(127)+S(20)=xa(1)+C3Cl4H(96) 8.420e-13 2.100 1.140 S(127)+S(20)=xa(1)+S(101) 1.263e-12 2.100 1.140 S(127)+S(20)=za(9)+C3Cl5(128) 5.560e-03 4.340 4.500 S(127)+S(25)=xf(5)+C3Cl4H(96) 8.420e-13 2.100 1.140 S(127)+S(25)=xf(5)+S(101) 1.263e-12 2.100 1.140 S(127)+S(30)=ab(6)+S(101) 1.263e-12 2.100 1.140 S(127)+S(31)=ab(6)+C3Cl5(128) 1.280e-03 4.340 9.700 S(127)+S(32)=ab(6)+S(101) 1.263e-12 2.100 1.140 S(127)+S(35)=db(7)+S(101) 1.263e-12 2.100 1.140 S(127)+S(35)=fb(8)+C3Cl5(128) 1.480e-03 4.340 10.550 S(127)+S(48)=S(86)+S(101) 1.263e-12 2.100 1.140 S(127)+S(52)=S(40)+C3Cl4H(96) 8.420e-13 2.100 1.140 S(127)+S(52)=S(40)+S(101) 1.263e-12 2.100 1.140 S(127)+S(52)=zf(10)+C3Cl5(128) 8.420e-01 3.500 9.670

164 S(127)+S(85)=C3Cl5(128)+S(47) 8.420e-01 3.500 9.670 S(127)+S(98)=C3Cl5(128)+S(79) 1.480e-03 4.340 10.550 S(20)+C3Cl4H(26)=xa(1)+C3Cl3H(56) 1.263e-12 2.100 1.140 S(25)+C3Cl4H(26)=xf(5)+C3Cl3H(56) 1.263e-12 2.100 1.140 S(35)+C3Cl4H(18)=db(7)+C3Cl3H(56) 4.210e-13 2.100 1.140 S(35)+C3Cl4H(26)=db(7)+C3Cl3H(56) 1.263e-12 2.100 1.140 S(35)+C3Cl5H(93)=db(7)+C3Cl4H(18) 1.263e-12 2.100 1.140 S(35)+S(107)=fb(8)+S(47) 5.842e-04 4.388 5.581 S(35)+S(110)=db(7)+C3Cl4H(18) 8.420e-13 2.100 1.140 S(35)+S(40)=db(7)+S(48) 1.263e-12 2.100 1.140 S(35)+S(40)=fb(8)+C3Cl4H(95) 1.480e-03 4.340 10.550 S(35)+S(48)=db(7)+S(85) 4.210e-13 2.100 1.140 S(35)+S(52)=db(7)+S(85) 1.263e-12 2.100 1.140 S(35)+S(79)=db(7)+S(44) 8.420e-13 2.100 1.140 S(35)+S(79)=fb(8)+S(100) 5.842e-04 4.388 5.581 S(35)+S(79)=fb(8)+S(98) 1.730e-03 4.340 7.500 S(35)+S(86)=db(7)+S(48) 8.420e-13 2.100 1.140 S(35)+S(86)=fb(8)+S(102) 1.480e-03 4.340 10.550 S(35)+S(87)=fb(8)+S(120) 1.480e-03 4.340 10.550 S(36)+S(110)=db(7)+C3Cl5(114) 1.126e-04 4.331 4.608 S(36)+S(79)=db(7)+S(100) 1.126e-04 4.331 4.596 S(36)+S(86)=db(7)+S(101) 1.126e-04 4.331 4.608 S(38)+S(107)=db(7)+S(47) 5.842e-04 4.388 5.581 S(38)+S(79)=db(7)+S(100) 5.842e-04 4.388 5.581 S(38)+S(79)=db(7)+S(98) 2.162e-03 4.354 9.271 S(40)+C3Cl4H(18)=S(48)+S(110) 1.263e-12 2.100 1.140 S(40)+C3Cl4H(26)=S(48)+C3Cl5H(93) 1.263e-12 2.100 1.140 S(40)+C3Cl4H(26)=S(52)+C3Cl5H(93) 4.210e-13 2.100 1.140 S(40)+C3Cl4H(26)=xf(5)+C3Cl4H(95) 8.420e-01 3.500 9.670 S(40)+C3Cl4H(26)=xf(5)+C3Cl4H(96) 1.302e-02 4.340 8.405 S(40)+C3Cl4H(95)=S(48)+C3Cl5H(93) 1.263e-12 2.100 1.140 S(40)+C3Cl4H(95)=S(52)+C3Cl5H(93) 4.210e-13 2.100 1.140 S(40)+C3Cl4H(96)=S(127)+S(48) 1.263e-12 2.100 1.140 S(40)+C3Cl4H(96)=S(40)+C3Cl4H(95) 5.781e-03 4.340 6.104 S(40)+C3Cl5(106)=C3Cl5H(93)+C3Cl4H(95) 5.781e-03 4.340 6.104 S(40)+S(101)=S(127)+S(48) 1.263e-12 2.100 1.140 S(40)+S(102)=S(48)+S(110) 1.263e-12 2.100 1.140 S(40)+S(102)=S(52)+S(110) 4.210e-13 2.100 1.140 S(40)+S(103)=S(48)+S(86) 1.263e-12 2.100 1.140 S(40)+S(103)=S(87)+C3Cl4H(95) 5.781e-03 4.340 6.104 S(40)+S(120)=S(48)+S(111) 1.263e-12 2.100 1.140 S(40)+S(120)=S(52)+S(111) 4.210e-13 2.100 1.140 S(40)+S(20)=xa(1)+S(48) 1.263e-12 2.100 1.140 S(40)+S(20)=xa(1)+S(52) 4.210e-13 2.100 1.140

165 S(40)+S(20)=za(9)+C3Cl4H(95) 5.560e-03 4.340 4.500 S(40)+S(25)=xf(5)+S(48) 1.263e-12 2.100 1.140 S(40)+S(25)=xf(5)+S(52) 4.210e-13 2.100 1.140 S(40)+S(30)=ab(6)+S(48) 1.263e-12 2.100 1.140 S(40)+S(31)=ab(6)+C3Cl4H(95) 1.280e-03 4.340 9.700 S(40)+S(32)=ab(6)+S(48) 1.263e-12 2.100 1.140 S(40)+S(48)=S(48)+S(86) 1.263e-12 2.100 1.140 S(40)+S(52)=S(40)+S(48) 1.263e-12 2.100 1.140 S(40)+S(52)=zf(10)+C3Cl4H(95) 8.420e-01 3.500 9.670 S(40)+S(52)=zf(10)+C3Cl4H(96) 1.302e-02 4.340 8.405 S(40)+S(85)=S(47)+C3Cl4H(95) 8.420e-01 3.500 9.670 S(40)+S(98)=S(79)+C3Cl4H(95) 1.480e-03 4.340 10.550 S(44)+C3Cl4H(18)=C3Cl3H(56)+S(79) 4.210e-13 2.100 1.140 S(44)+C3Cl4H(26)=C3Cl3H(56)+S(79) 1.263e-12 2.100 1.140 S(44)+S(107)=fb(8)+S(47) 5.842e-04 4.388 5.581 S(44)+S(48)=S(79)+S(85) 4.210e-13 2.100 1.140 S(44)+S(52)=S(79)+S(85) 1.263e-12 2.100 1.140 S(44)+S(79)=fb(8)+S(100) 5.842e-04 4.388 5.581 S(44)+S(79)=fb(8)+S(98) 2.162e-03 4.354 9.271 S(45)+C3Cl4H(26)=fb(8)+C3Cl3H(56) 1.263e-12 2.100 1.140 S(45)+S(52)=fb(8)+S(85) 1.263e-12 2.100 1.140 S(47)+C3Cl4H(26)=xf(5)+S(85) 1.850e-02 4.340 6.100 S(47)+C3Cl4H(26)=za(9)+C3Cl3H(56) 1.263e-12 2.100 1.140 S(47)+C3Cl4H(26)=zf(10)+C3Cl3H(56) 1.263e-12 2.100 1.140 S(47)+C3Cl4H(96)=S(40)+S(85) 2.604e-02 4.340 8.405 S(47)+C3Cl5(106)=S(85)+C3Cl5H(93) 2.604e-02 4.340 8.405 S(47)+S(103)=S(85)+S(87) 2.604e-02 4.340 8.405 S(47)+S(110)=S(107)+C3Cl5(114) 1.126e-04 4.331 14.080 S(47)+S(111)=S(107)+C3Cl4H(18) 1.126e-04 4.331 13.760 S(47)+S(52)=za(9)+S(85) 1.263e-12 2.100 1.140 S(47)+S(52)=zf(10)+S(85) 1.263e-12 2.100 1.140 S(47)+S(52)=zf(10)+S(85) 1.850e-02 4.340 6.100 S(47)+S(79)=S(100)+S(107) 1.126e-04 4.331 8.700 S(47)+S(86)=S(101)+S(107) 1.126e-04 4.331 14.080 S(47)+S(87)=S(48)+S(107) 1.126e-04 4.331 13.760 S(48)+C3Cl4H(18)=C3Cl3H(56)+S(40) 4.210e-13 2.100 1.140 S(48)+C3Cl4H(18)=C3Cl3H(56)+S(86) 4.210e-13 2.100 1.140 S(48)+C3Cl4H(18)=S(85)+C3Cl5H(93) 4.210e-13 2.100 1.140 S(48)+C3Cl4H(18)=S(85)+S(110) 4.210e-13 2.100 1.140 S(48)+C3Cl4H(26)=C3Cl3H(56)+S(40) 1.263e-12 2.100 1.140 S(48)+C3Cl4H(26)=C3Cl3H(56)+S(86) 1.263e-12 2.100 1.140 S(48)+C3Cl4H(26)=S(85)+C3Cl5H(93) 4.210e-13 2.100 1.140 S(48)+C3Cl4H(95)=S(85)+C3Cl5H(93) 4.210e-13 2.100 1.140 S(48)+C3Cl4H(96)=S(127)+S(85) 4.210e-13 2.100 1.140

166 S(48)+C3Cl5H(93)=S(40)+C3Cl4H(18) 1.263e-12 2.100 1.140 S(48)+C3Cl5H(93)=S(86)+C3Cl4H(18) 1.263e-12 2.100 1.140 S(48)+S(101)=S(127)+S(85) 4.210e-13 2.100 1.140 S(48)+S(102)=S(85)+S(110) 4.210e-13 2.100 1.140 S(48)+S(103)=S(85)+S(86) 4.210e-13 2.100 1.140 S(48)+S(107)=za(9)+S(47) 5.842e-04 4.388 5.581 S(48)+S(110)=S(86)+C3Cl4H(18) 8.420e-13 2.100 1.140 S(48)+S(110)=S(87)+C3Cl5(114) 1.126e-04 4.331 4.596 S(48)+S(120)=S(85)+S(111) 4.210e-13 2.100 1.140 S(48)+S(20)=xa(1)+S(85) 4.210e-13 2.100 1.140 S(48)+S(25)=xf(5)+S(85) 4.210e-13 2.100 1.140 S(48)+S(30)=ab(6)+S(85) 4.210e-13 2.100 1.140 S(48)+S(32)=ab(6)+S(85) 4.210e-13 2.100 1.140 S(48)+S(48)=S(40)+S(85) 4.210e-13 2.100 1.140 S(48)+S(48)=S(85)+S(86) 4.210e-13 2.100 1.140 S(48)+S(52)=S(40)+S(85) 1.684e-12 2.100 1.140 S(48)+S(52)=S(85)+S(86) 1.263e-12 2.100 1.140 S(48)+S(79)=S(40)+S(44) 8.420e-13 2.100 1.140 S(48)+S(79)=S(44)+S(86) 8.420e-13 2.100 1.140 S(48)+S(79)=S(87)+S(100) 1.126e-04 4.331 4.596 S(48)+S(79)=S(87)+S(98) 3.117e-04 4.388 8.709 S(48)+S(79)=za(9)+S(100) 5.842e-04 4.388 5.581 S(48)+S(79)=za(9)+S(98) 2.162e-03 4.354 9.271 S(48)+S(86)=S(87)+S(101) 1.126e-04 4.331 4.596 S(52)+C3Cl4H(18)=C3Cl3H(56)+S(40) 4.210e-13 2.100 1.140 S(52)+C3Cl4H(18)=S(85)+C3Cl5H(93) 1.263e-12 2.100 1.140 S(52)+C3Cl4H(18)=S(85)+S(110) 1.263e-12 2.100 1.140 S(52)+C3Cl4H(26)=C3Cl3H(56)+S(40) 1.263e-12 2.100 1.140 S(52)+C3Cl4H(26)=S(85)+C3Cl5H(93) 1.263e-12 2.100 1.140 S(52)+C3Cl4H(95)=S(85)+C3Cl5H(93) 1.263e-12 2.100 1.140 S(52)+C3Cl4H(96)=S(127)+S(85) 1.263e-12 2.100 1.140 S(52)+C3Cl5H(93)=S(40)+C3Cl4H(18) 1.263e-12 2.100 1.140 S(52)+S(101)=S(127)+S(85) 1.263e-12 2.100 1.140 S(52)+S(102)=S(85)+S(110) 1.263e-12 2.100 1.140 S(52)+S(103)=S(85)+S(86) 1.263e-12 2.100 1.140 S(52)+S(107)=zf(10)+S(47) 5.490e+00 3.330 0.630 S(52)+S(110)=S(40)+C3Cl4H(18) 8.420e-13 2.100 1.140 S(52)+S(110)=zf(10)+C3Cl5(114) 5.490e+00 3.330 0.630 S(52)+S(111)=zf(10)+C3Cl4H(18) 5.490e+00 3.330 0.630 S(52)+S(120)=S(85)+S(111) 1.263e-12 2.100 1.140 S(52)+S(20)=xa(1)+S(85) 1.263e-12 2.100 1.140 S(52)+S(25)=xf(5)+S(85) 1.263e-12 2.100 1.140 S(52)+S(30)=ab(6)+S(85) 1.263e-12 2.100 1.140 S(52)+S(32)=ab(6)+S(85) 1.263e-12 2.100 1.140

167 S(52)+S(52)=S(40)+S(85) 1.263e-12 2.100 1.140 S(52)+S(79)=S(40)+S(44) 8.420e-13 2.100 1.140 S(52)+S(79)=zf(10)+S(100) 5.490e+00 3.330 0.630 S(52)+S(79)=zf(10)+S(98) 1.020e+03 3.100 8.820 S(52)+S(85)=S(48)+S(85) 1.263e-12 2.100 1.140 S(52)+S(86)=S(40)+S(103) 8.420e-13 2.100 1.140 S(52)+S(86)=S(40)+S(48) 8.420e-13 2.100 1.140 S(52)+S(86)=zf(10)+S(101) 5.490e+00 3.330 0.630 S(52)+S(86)=zf(10)+S(102) 8.420e-01 3.500 9.670 S(52)+S(87)=zf(10)+S(103) 1.302e-02 4.340 8.405 S(52)+S(87)=zf(10)+S(120) 8.420e-01 3.500 9.670 S(52)+S(87)=zf(10)+S(48) 5.490e+00 3.330 0.630 S(58)+C3Cl4H(18)=xa(1)+rad1(11) 5.842e-04 4.388 5.581 S(58)+C3Cl4H(26)=xf(5)+rad1(11) 5.490e+00 3.330 0.630 S(58)+C3Cl4H(95)=rad1(11)+S(40) 1.512e-03 4.340 -1.662 S(58)+C3Cl4H(96)=rad1(11)+S(40) 1.512e-03 4.340 -1.662 S(58)+C3Cl5(106)=rad1(11)+C3Cl5H(93) 1.512e-03 4.340 -1.662 S(58)+S(102)=rad1(11)+S(86) 1.512e-03 4.340 -1.662 S(58)+S(103)=rad1(11)+S(87) 1.512e-03 4.340 -1.662 S(58)+S(120)=rad1(11)+S(87) 1.512e-03 4.340 -1.662 S(58)+S(20)=za(9)+rad1(11) 1.512e-03 4.340 -1.662 S(58)+S(25)=zf(10)+rad1(11) 1.512e-03 4.340 -1.662 S(58)+S(31)=ab(6)+rad1(11) 9.240e-04 4.378 5.465 S(58)+S(35)=fb(8)+rad1(11) 5.842e-04 4.388 5.581 S(58)+S(38)=db(7)+rad1(11) 5.842e-04 4.388 5.581 S(58)+S(44)=fb(8)+rad1(11) 5.842e-04 4.388 5.581 S(58)+S(47)=rad1(11)+S(107) 1.126e-04 4.331 4.596 S(58)+S(48)=za(9)+rad1(11) 5.842e-04 4.388 5.581 S(58)+S(52)=zf(10)+rad1(11) 5.490e+00 3.330 0.630 S(58)+S(85)=rad1(11)+S(47) 5.490e+00 3.330 0.630 S(58)+S(98)=rad1(11)+S(79) 5.842e-04 4.388 5.581 S(79)+C3Cl4H(18)=S(100)+S(111) 1.126e-04 4.331 4.596 S(79)+C3Cl4H(18)=S(44)+C3Cl5H(93) 8.420e-13 2.100 1.140 S(79)+C3Cl4H(18)=S(44)+S(110) 8.420e-13 2.100 1.140 S(79)+C3Cl4H(18)=S(98)+S(111) 3.117e-04 4.388 8.709 S(79)+C3Cl4H(18)=xa(1)+S(100) 5.842e-04 4.388 5.581 S(79)+C3Cl4H(18)=xa(1)+S(98) 2.162e-03 4.354 9.271 S(79)+C3Cl4H(26)=S(44)+C3Cl5H(93) 8.420e-13 2.100 1.140 S(79)+C3Cl4H(26)=xf(5)+S(100) 5.490e+00 3.330 0.630 S(79)+C3Cl4H(26)=xf(5)+S(98) 1.020e+03 3.100 8.820 S(79)+C3Cl4H(95)=S(40)+S(100) 1.512e-03 4.340 -1.662 S(79)+C3Cl4H(95)=S(44)+C3Cl5H(93) 8.420e-13 2.100 1.140 S(79)+C3Cl4H(96)=S(127)+S(44) 8.420e-13 2.100 1.140 S(79)+C3Cl4H(96)=S(40)+S(100) 1.512e-03 4.340 -1.662

168 S(79)+C3Cl4H(96)=S(40)+S(98) 5.826e-03 4.305 1.115 S(79)+C3Cl5(106)=C3Cl5H(93)+S(100) 1.512e-03 4.340 -1.662 S(79)+C3Cl5(106)=C3Cl5H(93)+S(98) 5.826e-03 4.305 1.115 S(79)+C3Cl5(114)=S(98)+S(110) 3.117e-04 4.388 8.709 S(79)+S(101)=S(127)+S(44) 8.420e-13 2.100 1.140 S(79)+S(101)=S(86)+S(100) 1.126e-04 4.331 4.596 S(79)+S(101)=S(86)+S(98) 3.117e-04 4.388 8.709 S(79)+S(102)=S(44)+S(110) 8.420e-13 2.100 1.140 S(79)+S(102)=S(86)+S(100) 1.512e-03 4.340 -1.662 S(79)+S(103)=S(44)+S(86) 8.420e-13 2.100 1.140 S(79)+S(103)=S(87)+S(100) 1.512e-03 4.340 -1.662 S(79)+S(103)=S(87)+S(98) 5.826e-03 4.305 1.115 S(79)+S(120)=S(44)+S(111) 8.420e-13 2.100 1.140 S(79)+S(120)=S(87)+S(100) 1.512e-03 4.340 -1.662 S(79)+S(20)=xa(1)+S(44) 8.420e-13 2.100 1.140 S(79)+S(20)=za(9)+S(100) 1.512e-03 4.340 -1.662 S(79)+S(25)=xf(5)+S(44) 8.420e-13 2.100 1.140 S(79)+S(25)=zf(10)+S(100) 1.512e-03 4.340 -1.662 S(79)+S(30)=ab(6)+S(44) 8.420e-13 2.100 1.140 S(79)+S(31)=ab(6)+S(100) 9.240e-04 4.378 5.465 S(79)+S(31)=ab(6)+S(98) 1.840e-03 4.340 7.000 S(79)+S(32)=ab(6)+S(44) 8.420e-13 2.100 1.140 S(79)+S(85)=S(47)+S(100) 5.490e+00 3.330 0.630 S(79)+S(85)=S(47)+S(98) 1.020e+03 3.100 8.820 S(79)+S(98)=S(79)+S(100) 5.842e-04 4.388 5.581 S(85)+C3Cl4H(26)=C3Cl3H(56)+S(48) 1.263e-12 2.100 1.140 S(85)+S(107)=S(47)+S(47) 5.490e+00 3.330 0.630 S(85)+S(110)=S(47)+C3Cl5(114) 5.490e+00 3.330 0.630 S(85)+S(111)=S(47)+C3Cl4H(18) 5.490e+00 3.330 0.630 S(85)+S(86)=S(47)+S(101) 5.490e+00 3.330 0.630 S(85)+S(86)=S(47)+S(102) 8.420e-01 3.500 9.670 S(85)+S(87)=S(47)+S(120) 8.420e-01 3.500 9.670 S(85)+S(87)=S(47)+S(48) 5.490e+00 3.330 0.630 S(86)+C3Cl4H(18)=S(101)+S(111) 1.126e-04 4.331 4.596 S(86)+C3Cl4H(26)=C3Cl5H(93)+S(103) 8.420e-13 2.100 1.140 S(86)+C3Cl4H(26)=S(48)+C3Cl5H(93) 8.420e-13 2.100 1.140 S(86)+C3Cl4H(26)=xf(5)+S(101) 5.490e+00 3.330 0.630 S(86)+C3Cl4H(26)=xf(5)+S(102) 8.420e-01 3.500 9.670 S(86)+C3Cl4H(95)=C3Cl5H(93)+S(103) 8.420e-13 2.100 1.140 S(86)+C3Cl4H(95)=S(40)+S(101) 1.512e-03 4.340 -1.662 S(86)+C3Cl4H(95)=S(40)+S(102) 5.560e-03 4.340 4.500 S(86)+C3Cl4H(95)=S(48)+C3Cl5H(93) 8.420e-13 2.100 1.140 S(86)+C3Cl4H(96)=S(127)+S(103) 8.420e-13 2.100 1.140 S(86)+C3Cl4H(96)=S(127)+S(48) 8.420e-13 2.100 1.140

169 S(86)+C3Cl4H(96)=S(40)+S(101) 1.512e-03 4.340 -1.662 S(86)+C3Cl4H(96)=S(40)+S(102) 5.781e-03 4.340 6.104 S(86)+C3Cl5(106)=C3Cl5H(93)+S(101) 1.512e-03 4.340 -1.662 S(86)+C3Cl5(106)=C3Cl5H(93)+S(102) 5.781e-03 4.340 6.104 S(86)+S(102)=S(103)+S(110) 8.420e-13 2.100 1.140 S(86)+S(102)=S(48)+S(110) 8.420e-13 2.100 1.140 S(86)+S(102)=S(86)+S(101) 1.512e-03 4.340 -1.662 S(86)+S(103)=S(48)+S(86) 8.420e-13 2.100 1.140 S(86)+S(103)=S(87)+S(101) 1.512e-03 4.340 -1.662 S(86)+S(103)=S(87)+S(102) 5.781e-03 4.340 6.104 S(86)+S(120)=S(103)+S(111) 8.420e-13 2.100 1.140 S(86)+S(120)=S(48)+S(111) 8.420e-13 2.100 1.140 S(86)+S(120)=S(87)+S(101) 1.512e-03 4.340 -1.662 S(86)+S(20)=xa(1)+S(103) 8.420e-13 2.100 1.140 S(86)+S(20)=xa(1)+S(48) 8.420e-13 2.100 1.140 S(86)+S(20)=za(9)+S(101) 1.512e-03 4.340 -1.662 S(86)+S(20)=za(9)+S(102) 5.560e-03 4.340 4.500 S(86)+S(25)=xf(5)+S(103) 8.420e-13 2.100 1.140 S(86)+S(25)=xf(5)+S(48) 8.420e-13 2.100 1.140 S(86)+S(25)=zf(10)+S(101) 1.512e-03 4.340 -1.662 S(86)+S(31)=ab(6)+S(102) 1.280e-03 4.340 9.700 S(86)+S(98)=S(79)+S(102) 1.480e-03 4.340 10.550 S(87)+C3Cl4H(18)=S(48)+S(111) 1.126e-04 4.331 4.596 S(87)+C3Cl4H(26)=xf(5)+S(103) 1.302e-02 4.340 8.405 S(87)+C3Cl4H(26)=xf(5)+S(120) 8.420e-01 3.500 9.670 S(87)+C3Cl4H(26)=xf(5)+S(48) 5.490e+00 3.330 0.630 S(87)+C3Cl4H(95)=S(40)+S(120) 5.560e-03 4.340 4.500 S(87)+C3Cl4H(95)=S(40)+S(48) 1.512e-03 4.340 -1.662 S(87)+C3Cl4H(96)=S(40)+S(103) 5.781e-03 4.340 6.104 S(87)+C3Cl4H(96)=S(40)+S(120) 5.781e-03 4.340 6.104 S(87)+C3Cl4H(96)=S(40)+S(48) 1.512e-03 4.340 -1.662 S(87)+C3Cl5(106)=C3Cl5H(93)+S(103) 5.781e-03 4.340 6.104 S(87)+C3Cl5(106)=C3Cl5H(93)+S(120) 5.781e-03 4.340 6.104 S(87)+C3Cl5(106)=S(48)+C3Cl5H(93) 1.512e-03 4.340 -1.662 S(87)+S(102)=S(48)+S(86) 1.512e-03 4.340 -1.662 S(87)+S(102)=S(86)+S(120) 5.560e-03 4.340 4.500 S(87)+S(103)=S(48)+S(87) 1.512e-03 4.340 -1.662 S(87)+S(103)=S(87)+S(120) 5.781e-03 4.340 6.104 S(87)+S(120)=S(48)+S(87) 1.512e-03 4.340 -1.662 S(87)+S(20)=za(9)+S(120) 5.560e-03 4.340 4.500 S(87)+S(20)=za(9)+S(48) 1.512e-03 4.340 -1.662 S(87)+S(25)=zf(10)+S(48) 1.512e-03 4.340 -1.662 S(87)+S(31)=ab(6)+S(120) 1.280e-03 4.340 9.700 S(87)+S(98)=S(79)+S(120) 1.480e-03 4.340 10.550

170 S(98)+S(107)=S(47)+S(79) 5.842e-04 4.388 5.581 xa(1)+C3Cl3H(56)=rad1(11)+C3Cl4H(18) 4.210e-13 2.100 1.140 xa(1)+C3Cl3H(56)=rad1(11)+C3Cl4H(18) 5.200e-02 3.900 0.860 xa(1)+C3Cl4H(18)=rad1(11)+C3Cl5H(93) 4.210e-13 2.100 1.140 xa(1)+C3Cl4H(18)=rad1(11)+S(110) 4.210e-13 2.100 1.140 xa(1)+C3Cl4H(18)=S(111)+C3Cl4H(18) 3.117e-04 4.388 8.709 xa(1)+C3Cl4H(26)=rad1(11)+C3Cl5H(93) 4.210e-13 2.100 1.140 xa(1)+C3Cl4H(26)=xf(5)+C3Cl4H(18) 5.200e-02 3.900 0.860 xa(1)+C3Cl4H(95)=C3Cl5H(93)+S(20) 4.210e-13 2.100 1.140 xa(1)+C3Cl4H(95)=rad1(11)+C3Cl5H(93) 4.210e-13 2.100 1.140 xa(1)+C3Cl4H(95)=S(40)+C3Cl4H(18) 5.826e-03 4.305 1.115 xa(1)+C3Cl4H(96)=rad1(11)+S(127) 4.210e-13 2.100 1.140 xa(1)+C3Cl4H(96)=S(40)+C3Cl4H(18) 5.826e-03 4.305 1.115 xa(1)+C3Cl5(106)=C3Cl5H(93)+C3Cl4H(18) 5.826e-03 4.305 1.115 xa(1)+C3Cl5(114)=S(110)+C3Cl4H(18) 3.117e-04 4.388 8.709 xa(1)+C3Cl5(128)=S(127)+C3Cl4H(18) 5.826e-03 4.305 1.115 xa(1)+Cl(4)=Cl2(3)+rad1(11) 4.210e-13 2.100 13.705 xa(1)+Cl(4)=HCl(2)+C3Cl4H(18) 5.646e+04 2.483 10.027 xa(1)+HCl(2)=db(7) 4.000e+02 3.000 45.000 xa(1)+S(101)=rad1(11)+S(127) 4.210e-13 2.100 1.140 xa(1)+S(101)=S(86)+C3Cl4H(18) 3.117e-04 4.388 8.709 xa(1)+S(102)=rad1(11)+S(110) 4.210e-13 2.100 1.140 xa(1)+S(102)=S(110)+S(20) 4.210e-13 2.100 1.140 xa(1)+S(102)=S(86)+C3Cl4H(18) 5.826e-03 4.305 1.115 xa(1)+S(103)=rad1(11)+S(86) 4.210e-13 2.100 1.140 xa(1)+S(103)=S(87)+C3Cl4H(18) 5.826e-03 4.305 1.115 xa(1)+S(120)=rad1(11)+S(111) 4.210e-13 2.100 1.140 xa(1)+S(120)=S(111)+S(20) 4.210e-13 2.100 1.140 xa(1)+S(120)=S(87)+C3Cl4H(18) 5.826e-03 4.305 1.115 xa(1)+S(20)=xa(1)+rad1(11) 4.210e-13 2.100 1.140 xa(1)+S(20)=za(9)+C3Cl4H(18) 5.826e-03 4.305 1.115 xa(1)+S(25)=xf(5)+rad1(11) 4.210e-13 2.100 1.140 xa(1)+S(25)=xf(5)+S(20) 4.210e-13 2.100 1.140 xa(1)+S(25)=zf(10)+C3Cl4H(18) 5.826e-03 4.305 1.115 xa(1)+S(30)=ab(6)+rad1(11) 4.210e-13 2.100 1.140 xa(1)+S(32)=ab(6)+rad1(11) 4.210e-13 2.100 1.140 xa(1)+S(35)=db(7)+rad1(11) 4.210e-13 2.100 1.140 xa(1)+S(38)=db(7)+C3Cl4H(18) 2.162e-03 4.354 9.271 xa(1)+S(44)=fb(8)+C3Cl4H(18) 2.162e-03 4.354 9.271 xa(1)+S(44)=rad1(11)+S(79) 4.210e-13 2.100 1.140 xa(1)+S(45)=fb(8)+rad1(11) 4.210e-13 2.100 1.140 xa(1)+S(47)=za(9)+rad1(11) 4.210e-13 2.100 1.140 xa(1)+S(48)=rad1(11)+S(40) 4.210e-13 2.100 1.140 xa(1)+S(48)=rad1(11)+S(86) 4.210e-13 2.100 1.140

171 xa(1)+S(48)=S(87)+C3Cl4H(18) 3.117e-04 4.388 8.709 xa(1)+S(48)=za(9)+C3Cl4H(18) 2.162e-03 4.354 9.271 xa(1)+S(52)=rad1(11)+S(40) 4.210e-13 2.100 1.140 xa(1)+S(52)=zf(10)+C3Cl4H(18) 5.200e-02 3.900 0.860 xa(1)+S(85)=rad1(11)+S(48) 4.210e-13 2.100 1.140 xa(1)+S(85)=S(47)+C3Cl4H(18) 5.200e-02 3.900 0.860 xf(5)+C3Cl3H(56)=rad1(11)+C3Cl4H(18) 1.263e-12 2.100 1.140 xf(5)+C3Cl4H(18)=rad1(11)+C3Cl5H(93) 1.263e-12 2.100 1.140 xf(5)+C3Cl4H(18)=rad1(11)+S(110) 1.263e-12 2.100 1.140 xf(5)+C3Cl4H(26)=rad1(11)+C3Cl5H(93) 1.263e-12 2.100 1.140 xf(5)+C3Cl4H(95)=C3Cl5H(93)+S(25) 4.210e-13 2.100 1.140 xf(5)+C3Cl4H(95)=rad1(11)+C3Cl5H(93) 1.263e-12 2.100 1.140 xf(5)+C3Cl4H(96)=rad1(11)+S(127) 1.263e-12 2.100 1.140 xf(5)+C3Cl5(106)=C3Cl5H(93)+C3Cl4H(26) 2.604e-02 4.340 8.405 xf(5)+rad1(11)=xa(1)+rad1(11) 1.263e-12 2.100 1.140 xf(5)+S(101)=rad1(11)+S(127) 1.263e-12 2.100 1.140 xf(5)+S(102)=rad1(11)+S(110) 1.263e-12 2.100 1.140 xf(5)+S(102)=S(110)+S(25) 4.210e-13 2.100 1.140 xf(5)+S(103)=rad1(11)+S(86) 1.263e-12 2.100 1.140 xf(5)+S(120)=rad1(11)+S(111) 1.263e-12 2.100 1.140 xf(5)+S(120)=S(111)+S(25) 4.210e-13 2.100 1.140 xf(5)+S(20)=xa(1)+rad1(11) 1.263e-12 2.100 1.140 xf(5)+S(25)=xf(5)+rad1(11) 1.263e-12 2.100 1.140 xf(5)+S(30)=ab(6)+rad1(11) 1.263e-12 2.100 1.140 xf(5)+S(32)=ab(6)+rad1(11) 1.263e-12 2.100 1.140 xf(5)+S(35)=db(7)+rad1(11) 1.263e-12 2.100 1.140 xf(5)+S(44)=rad1(11)+S(79) 1.263e-12 2.100 1.140 xf(5)+S(45)=fb(8)+rad1(11) 1.263e-12 2.100 1.140 xf(5)+S(47)=za(9)+rad1(11) 1.263e-12 2.100 1.140 xf(5)+S(47)=zf(10)+rad1(11) 1.263e-12 2.100 1.140 xf(5)+S(48)=rad1(11)+S(40) 1.263e-12 2.100 1.140 xf(5)+S(48)=rad1(11)+S(86) 1.263e-12 2.100 1.140 xf(5)+S(52)=rad1(11)+S(40) 1.263e-12 2.100 1.140 xf(5)+S(52)=zf(10)+C3Cl4H(26) 1.850e-02 4.340 6.100 xf(5)+S(85)=rad1(11)+S(48) 1.263e-12 2.100 1.140 za(9)+C3Cl3H(56)=rad1(11)+S(20) 8.420e-01 3.500 9.670 za(9)+C3Cl3H(56)=rad1(11)+S(48) 5.200e-02 3.900 0.860 za(9)+C3Cl3H(56)=S(47)+C3Cl4H(18) 4.210e-13 2.100 1.140 za(9)+C3Cl4H(18)=S(47)+C3Cl5H(93) 4.210e-13 2.100 1.140 za(9)+C3Cl4H(18)=S(47)+S(110) 4.210e-13 2.100 1.140 za(9)+C3Cl4H(18)=S(48)+S(111) 3.117e-04 4.388 8.709 za(9)+C3Cl4H(26)=S(47)+C3Cl5H(93) 4.210e-13 2.100 1.140 za(9)+C3Cl4H(26)=xf(5)+S(20) 8.420e-01 3.500 9.670 za(9)+C3Cl4H(26)=xf(5)+S(48) 5.200e-02 3.900 0.860

172 za(9)+C3Cl4H(95)=S(40)+S(48) 5.826e-03 4.305 1.115 za(9)+C3Cl4H(95)=S(47)+C3Cl5H(93) 4.210e-13 2.100 1.140 za(9)+C3Cl4H(96)=S(127)+S(47) 4.210e-13 2.100 1.140 za(9)+C3Cl4H(96)=S(40)+S(20) 5.781e-03 4.340 6.104 za(9)+C3Cl4H(96)=S(40)+S(48) 5.826e-03 4.305 1.115 za(9)+C3Cl5(106)=C3Cl5H(93)+S(20) 5.781e-03 4.340 6.104 za(9)+C3Cl5(106)=S(48)+C3Cl5H(93) 5.826e-03 4.305 1.115 za(9)+C3Cl5(114)=S(48)+S(110) 3.117e-04 4.388 8.709 za(9)+C3Cl5(128)=S(127)+S(48) 5.826e-03 4.305 1.115 za(9)+S(101)=S(127)+S(47) 4.210e-13 2.100 1.140 za(9)+S(101)=S(48)+S(86) 3.117e-04 4.388 8.709 za(9)+S(102)=S(47)+S(110) 4.210e-13 2.100 1.140 za(9)+S(102)=S(48)+S(86) 5.826e-03 4.305 1.115 za(9)+S(103)=S(47)+S(86) 4.210e-13 2.100 1.140 za(9)+S(103)=S(48)+S(87) 5.826e-03 4.305 1.115 za(9)+S(103)=S(87)+S(20) 5.781e-03 4.340 6.104 za(9)+S(120)=S(47)+S(111) 4.210e-13 2.100 1.140 za(9)+S(120)=S(48)+S(87) 5.826e-03 4.305 1.115 za(9)+S(20)=xa(1)+S(47) 4.210e-13 2.100 1.140 za(9)+S(20)=za(9)+S(48) 5.826e-03 4.305 1.115 za(9)+S(25)=xf(5)+S(47) 4.210e-13 2.100 1.140 za(9)+S(25)=zf(10)+S(48) 5.826e-03 4.305 1.115 za(9)+S(30)=ab(6)+S(47) 4.210e-13 2.100 1.140 za(9)+S(31)=ab(6)+S(20) 1.280e-03 4.340 9.700 za(9)+S(32)=ab(6)+S(47) 4.210e-13 2.100 1.140 za(9)+S(35)=db(7)+S(47) 4.210e-13 2.100 1.140 za(9)+S(35)=fb(8)+S(20) 1.480e-03 4.340 10.550 za(9)+S(44)=fb(8)+S(48) 2.162e-03 4.354 9.271 za(9)+S(44)=S(47)+S(79) 4.210e-13 2.100 1.140 za(9)+S(45)=fb(8)+S(47) 4.210e-13 2.100 1.140 za(9)+S(48)=S(40)+S(47) 4.210e-13 2.100 1.140 za(9)+S(48)=S(47)+S(86) 4.210e-13 2.100 1.140 za(9)+S(48)=S(48)+S(87) 3.117e-04 4.388 8.709 za(9)+S(52)=S(40)+S(47) 4.210e-13 2.100 1.140 za(9)+S(52)=zf(10)+S(20) 8.420e-01 3.500 9.670 za(9)+S(52)=zf(10)+S(48) 5.200e-02 3.900 0.860 za(9)+S(85)=S(47)+S(20) 8.420e-01 3.500 9.670 za(9)+S(85)=S(47)+S(48) 4.210e-13 2.100 1.140 za(9)+S(85)=S(47)+S(48) 5.200e-02 3.900 0.860 za(9)+S(98)=S(79)+S(20) 1.480e-03 4.340 10.550 zf(10)+C3Cl3H(56)=rad1(11)+S(25) 8.420e-01 3.500 9.670 zf(10)+C3Cl3H(56)=S(47)+C3Cl4H(18) 1.263e-12 2.100 1.140 zf(10)+C3Cl4H(18)=S(47)+C3Cl5H(93) 1.263e-12 2.100 1.140 zf(10)+C3Cl4H(18)=S(47)+S(110) 1.263e-12 2.100 1.140

173 zf(10)+C3Cl4H(26)=S(47)+C3Cl5H(93) 1.263e-12 2.100 1.140 zf(10)+C3Cl4H(26)=xf(5)+S(25) 8.420e-01 3.500 9.670 zf(10)+C3Cl4H(95)=S(40)+S(25) 5.560e-03 4.340 4.500 zf(10)+C3Cl4H(95)=S(47)+C3Cl5H(93) 1.263e-12 2.100 1.140 zf(10)+C3Cl4H(96)=S(127)+S(47) 1.263e-12 2.100 1.140 zf(10)+C3Cl4H(96)=S(40)+S(25) 5.781e-03 4.340 6.104 zf(10)+C3Cl5(106)=C3Cl5H(93)+S(25) 5.781e-03 4.340 6.104 zf(10)+C3Cl5(106)=S(52)+C3Cl5H(93) 2.604e-02 4.340 8.405 zf(10)+C3Cl5(128)=S(127)+S(25) 5.560e-03 4.340 4.500 zf(10)+rad1(11)=xa(1)+S(47) 1.263e-12 2.100 1.140 zf(10)+S(101)=S(127)+S(47) 1.263e-12 2.100 1.140 zf(10)+S(102)=S(47)+S(110) 1.263e-12 2.100 1.140 zf(10)+S(102)=S(86)+S(25) 5.560e-03 4.340 4.500 zf(10)+S(103)=S(47)+S(86) 1.263e-12 2.100 1.140 zf(10)+S(103)=S(87)+S(25) 5.781e-03 4.340 6.104 zf(10)+S(120)=S(47)+S(111) 1.263e-12 2.100 1.140 zf(10)+S(120)=S(87)+S(25) 5.560e-03 4.340 4.500 zf(10)+S(20)=xa(1)+S(47) 1.263e-12 2.100 1.140 zf(10)+S(20)=za(9)+S(25) 5.560e-03 4.340 4.500 zf(10)+S(25)=xf(5)+S(47) 1.263e-12 2.100 1.140 zf(10)+S(30)=ab(6)+S(47) 1.263e-12 2.100 1.140 zf(10)+S(31)=ab(6)+S(25) 1.280e-03 4.340 9.700 zf(10)+S(32)=ab(6)+S(47) 1.263e-12 2.100 1.140 zf(10)+S(35)=db(7)+S(47) 1.263e-12 2.100 1.140 zf(10)+S(35)=fb(8)+S(25) 1.480e-03 4.340 10.550 zf(10)+S(44)=S(47)+S(79) 1.263e-12 2.100 1.140 zf(10)+S(45)=fb(8)+S(47) 1.263e-12 2.100 1.140 zf(10)+S(47)=za(9)+S(47) 1.263e-12 2.100 1.140 zf(10)+S(48)=S(40)+S(47) 1.263e-12 2.100 1.140 zf(10)+S(48)=S(47)+S(86) 1.263e-12 2.100 1.140 zf(10)+S(52)=S(40)+S(47) 1.263e-12 2.100 1.140 zf(10)+S(52)=zf(10)+S(25) 8.420e-01 3.500 9.670 zf(10)+S(85)=S(47)+S(25) 8.420e-01 3.500 9.670 zf(10)+S(85)=S(47)+S(48) 1.263e-12 2.100 1.140 zf(10)+S(98)=S(79)+S(25) 1.480e-03 4.340 10.550 END

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