Pyrolysis of Jet Propellants and Oxidation of Polycyclic Aromatic Radicals with Molecular Oxygen: Theoretical Study of Potential Energy Surfaces, Mechanisms, and Kinetics

Authors

Daniel E. Belisario-LaraFollow

Document Type

Dissertation

Degree

Doctor of Philosophy (PhD)

Major/Program

Chemistry

First Advisor's Name

Alexander Mebel

First Advisor's Committee Title

Committee Chair

Second Advisor's Name

David Chatfield

Second Advisor's Committee Title

Committee Member

Third Advisor's Name

Jeffrey Joens

Third Advisor's Committee Title

Committee Member

Fourth Advisor's Name

Joong Ho Moon

Fourth Advisor's Committee Title

Committee Member

Fifth Advisor's Name

Wenzhi Li

Fifth Advisor's Committee Title

Committee Member

Keywords

Theoretical Chemistry, Computation, Oxidation, Combustion, Pyrolysis

Date of Defense

5-15-2018

Abstract

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 have 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 RiceRamsperger-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 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.

Identifier

FIDC006814

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