Florida International University FIU Digital Commons FIU Electronic Theses and Dissertations University Graduate School 5-15-2018 Pyrolysis of Jet Propellants and Oxidation of Polycyclic Aromatic Radicals with Molecular Oxygen: Theoretical Study of Potential Energy Surfaces, Mechanisms, and Kinetics Daniel E. Belisario-Lara [email protected] DOI: 10.25148/etd.FIDC006814 Follow this and additional works at: https://digitalcommons.fiu.edu/etd Part of the Physical Chemistry Commons Recommended Citation Belisario-Lara, Daniel E., "Pyrolysis of Jet Propellants and Oxidation of Polycyclic Aromatic Radicals with Molecular Oxygen: Theoretical Study of Potential Energy Surfaces, Mechanisms, and Kinetics" (2018). FIU Electronic Theses and Dissertations. 3819. https://digitalcommons.fiu.edu/etd/3819 This work is brought to you for free and open access by the University Graduate School at FIU Digital Commons. It has been accepted for inclusion in FIU Electronic Theses and Dissertations by an authorized administrator of FIU Digital Commons. For more information, please contact [email protected]. FLORIDA INTERNATIONAL UNIVERSITY Miami, Florida PYROLYSIS OF JET PROPELLANTS AND OXIDATION OF POLYCYCLIC AROMATIC RADICALS WITH MOLECULAR OXYGEN: THEORETICAL STUDY OF POTENTIAL ENERGY SURFACES, MECHANISMS, AND KINETICS A dissertation submitted in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY in CHEMISTRY by Daniel Belisario-Lara 2018 To: Dean Michael R. Heithaus College of Arts, Sciences and Education This dissertation, written by Daniel Belisario-Lara, and entitled Pyrolysis of Jet Propellants and Oxidation of Polycyclic Aromatic Radicals with Molecular Oxygen: Theoretical Study of Potential Energy Surfaces, Mechanisms, and Kinetics, having been approved in respect to style and intellectual content, is referred to you for judgment. We have read this dissertation and recommend that it be approved. _______________________________________ Joong Ho Moon _______________________________________ Wenzhi Li _______________________________________ Jeffrey Joens _______________________________________ David C. Chatfield _______________________________________ Alexander M. Mebel, Major Professor Date of Defense: May 15, 2018 The dissertation of Daniel Belisario-Lara is approved. _______________________________________ Dean MDeanDeandddiD Dean Michael R. Heithaus Col College of Arts, Sciences and Education _______________________________________ Andrés G. Gil Vice President for Research and Economic Development and Dean of the University Graduate School Florida International University, 2018 ii ACKNOWLEDGMENTS I am eternally grateful to everyone who over the course of my studies supported and believed in me. My committee was especially helpful and understanding. Dr. Li showed interest in my progress and provide valuable feedback. Dr. Moon asked insightful questions that made me consider the importance of my work. Dr. Chaftield took time from his busy schedule to teach me an important class and gave helpful insight in group meetings. Dr. Joens took time from his schedule to teach a class of just me, and I am very grateful for that. Most of all Dr. Alexander Mebel, my mentor, since without his guidance I would not have been able to complete this work. Dr. Mebel is the best advisor I could have hoped for as he was always available and willing to help. I truly cannot thank him enough for all the the effort he put into my education. I also need to thank friends and family. Specifically, David Kreiger who from day one provided immense support. Thank you to my brother, to the Armstrongs, Gomezs, and Tia Ana for supporting my education. Most of all my parents Neuman and Esperanza Belisario who have given me more love and support than I can express in words. Without my parents I could not have accomplished any of this, thank you with all my heart. iii ABSTRACT OF THE DISSERTATION PYROLYSIS OF JET PROPELLANTS AND OXIDATION OF POLYCYLIC AROMATIC RADICALS WITH MOLECULAR OXYGEN: THEORETICAL STUDY OF POTENIAL ENERGY SURFACES, MECHANISMS, AND KINETICS by Daniel Belisario-Lara Florida International University, 2018 Miami, Florida Professor Alexander M. Mebel, Major Professor Two reaction classes have been studied computationally including the pyrolysis of various components of airplane fuels, such as decane, dodecane, butylbenzene isomers, and JP-10 (exo-tetrahydrodicyclopentadiene), and oxidation of a group of molecules belonging to the class of Polycyclic Aromatic Hydrocarbons (PAHs). Investigation of both reaction classes has been performed using ab initio quantum chemistry methods with the Gaussian 09 and MOLPRO programs at various levels of theory. Initially, Potential Energy Surfaces (PES) were generated at the G3(MP2,CC)/B3LYP/6-311G** level of theory for various radicals involved in the reactions as reactants, intermediates, transition states, and products. The next step was to perform Rice-Ramsperger-Kassel-Marcus (RRKM) / Master Equation calculations in order to calculate rate constants and branching ratios of different products at various temperatures and pressures characteristic for combustion flames. All calculations were then compared with previous works on similar systems available in the literature. The results of these simulations along with previous data were then used to formulate iv guidelines for the pyrolysis and oxidation patterns of larger and more complex systems, in order to achieve a better understanding of the pathways to the end products in airplane jet engines. v TABLE OF CONTENTS CHAPTER PAGE I. Introduction ................................................................................................................... 1 II. Theoretical Approach and Methodology .................................................................... 14 III. Combined Experimental and Computational Study on the Unimolecular Decomposition of JP-8 Jet Fuel Surrogates. I. n-Decane (n-C10H22) ….. ....................... 23 Introduction ........................................................................................................ 23 Methods ............................................................................................................. 27 Results and Discussion ...................................................................................... 29 References ........................................................................................................ 37 IV. Combined Experimental and Computational Study on the Unimolecular Decomposition of JP-8 Jet Fuel Surrogates. II: n-Dodecane (n-C12H26) ......................... 48 Introduction ........................................................................................................ 49 Methods ............................................................................................................. 51 Results and Discussion ...................................................................................... 53 References ........................................................................................................ 61 V. A Theoretical Study on Pyrolysis of Jet Propellant 8 Components: The Behavior of Aliphatic and Non-Aliphatic Alkyl Rings ....................................................................... 71 Introduction ........................................................................................................ 72 Methods ............................................................................................................. 76 Results and Discussion ...................................................................................... 81 References ........................................................................................................ 96 VI. A Combined Experimental Vacuum Ultraviolet Photoionization and Theoretical Study on High-Temperature Decomposition of JP-10 (exo-Tetrahydrodicyclopentadiene) ........... 129 Introduction ...................................................................................................... 130 Methods ........................................................................................................... 136 Results and Discussion .................................................................................... 138 References ...................................................................................................... 147 VII. Reaction Mechanism of Acenaphthyl Radicals with Molecular Oxygen ................. 160 Introduction ...................................................................................................... 161 Methods ........................................................................................................... 162 Results and Discussion .................................................................................... 164 References ...................................................................................................... 166 VIII. An Experimental and Theoretical Investigation of the Formation of C7H7 Isomers in the Bimolecular Reaction of Dicarbon Molecules with 1,3-Pentadiene .................... 175 Introduction ...................................................................................................... 176 Methods ........................................................................................................... 178 Results and Discussion .................................................................................... 180 References .....................................................................................................