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Hydrogen Atom Addition Reactions with Alkenes, Oxidation of Cyclopentadienone, Trifluoroethene and Transport Properties

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Hydrogen Atom Addition Reactions with Alkenes, Oxidation of Cyclopentadienone, Trifluoroethene and Transport Properties New Jersey Institute of Technology Digital Commons @ NJIT Dissertations Electronic Theses and Dissertations Summer 8-31-2015 Thermochemistry and kinetics: hydrogen atom addition reactions with alkenes, oxidation of cyclopentadienone, trifluoroethene and transport properties Suriyakit Yommee New Jersey Institute of Technology Follow this and additional works at: https://digitalcommons.njit.edu/dissertations Part of the Environmental Sciences Commons Recommended Citation Yommee, Suriyakit, "Thermochemistry and kinetics: hydrogen atom addition reactions with alkenes, oxidation of cyclopentadienone, trifluoroethene and transport properties" (2015). Dissertations. 127. https://digitalcommons.njit.edu/dissertations/127 This Dissertation is brought to you for free and open access by the Electronic Theses and Dissertations at Digital Commons @ NJIT. It has been accepted for inclusion in Dissertations by an authorized administrator of Digital Commons @ NJIT. For more information, please contact [email protected]. Copyright Warning & Restrictions The copyright law of the United States (Title 17, United States Code) governs the making of photocopies or other reproductions of copyrighted material. Under certain conditions specified in the law, libraries and archives are authorized to furnish a photocopy or other reproduction. One of these specified conditions is that the photocopy or reproduction is not to be “used for any purpose other than private study, scholarship, or research.” If a, user makes a request for, or later uses, a photocopy or reproduction for purposes in excess of “fair use” that user may be liable for copyright infringement, This institution reserves the right to refuse to accept a copying order if, in its judgment, fulfillment of the order would involve violation of copyright law. Please Note: The author retains the copyright while the New Jersey Institute of Technology reserves the right to distribute this thesis or dissertation Printing note: If you do not wish to print this page, then select “Pages from: first page # to: last page #” on the print dialog screen The Van Houten library has removed some of the personal information and all signatures from the approval page and biographical sketches of theses and dissertations in order to protect the identity of NJIT graduates and faculty. ABSTRACT THERMOCHEMISTRY AND KINETICS: HYDROGEN ATOM ADDITION REACTIONS WITH ALKENES, OXIDATION OF CYCLOPENTADIENONE, TRIFLUOROETHENE AND TRANSPORT PROPERTIES by Suriyakit Yommee Thermochemical and transport properties and reaction kinetic parameters are important to understand and to model atmospheric chemistry, combustion and other thermal systems. These processes are all important to the environment. Thermochemical properties kinetic parameters and models for several atmospheric and combustion related chemical systems are determined using computational chemistry coupled with fundamentals of thermodynamics and statistical mechanics. Transport properties of hydrocarbon and oxygenated hydrocarbons which are important to the calculation of fluid dynamics of gas phase flow reactions and mixing needed for evaluation in the combustion and thermal (flow) fluid dynamic modeling. Transport properties of radicals cannot be measured so computational chemistry is method of choice. The dissertation determine dipole moment, polarizability and molecular diameters of hydrocarbon and oxygenated hydrocarbons needed for calculation of multicomponent viscosities, thermal conductivities, and thermal diffusion coefficients. Cyclopentadienone with cyclic five-member ring aromatic structure is an important intermediate in combustion systems. Thermochemical and kinetic parameters for the initial reactions of cyclopentadienone radicals with O2 and the thermochemical properties for cyclopentadienone - hydroperoxides, alcohols, alkenyl , alkoxy and peroxy radicals are determined by use of computational chemistry via Density Functional Theory (DFT) and the composite, Complete Basis Set (CBS) methods. Enthalpies of formation o (ΔfH 298) with the isodesmic reaction schemes with several work reactions for each o o species are used for standard enthalpies. Entropy and heat capacity, S (T) and CP (T) (50 K ≤ T ≤ 5000 K) are also determined. Chemical activation kinetics using quantum RRK analysis for k(E) and master equation for fall-off are used for kinetic parameters and to show significance of chain branching as a function of temperature and pressure. The cyclopentadienone vinylic carbon radicals of with molecular oxygen appear to undergo chain branching via reaction with O2, to a higher extent to that of vinyl and phenyl radicals. Reaction kinetics of hydrogen atom addition to primary (P), secondary (S), tertiary (T) vinylic (olefin) carbons to form an alkyl radical is investigated using Density Functional Theory (DFT) and ab initio composite level methods. Results from calculations at different levels are compared with the experimental literature data for hydrogen atom addition to Ethylene, Propene, 1-Butene, E-2-Butene, Z-2-Butene, and Isobutene. Activation energy and rate constants for forward and reverse paths are investigated and compared with available experimental data. One goal of the study is to determine accurate calculation method for use on large molecules. Chlorofluorocarbons are widely present in the environment. Thermochemical and kinetic properties work will aid in the understanding the chlorofluorocarbons reactions in combustion and atmospheric environments. Trifluoroethene (CF2=CHF) reaction in atmospheric and combustion environment initiated via OH radical system is investigated. The HF generated channel is currently not reported in any kinetic study. It is important as the toxic gas that can cause severe respiratory damage in humans. THERMOCHEMISTRY AND KINETICS: HYDROGEN ATOM ADDITION REACTIONS WITH ALKENES, OXIDATION OF CYCLOPENTADIENONE, TRIFLUOROETHENE AND TRANSPORT PROPERTIES by Suriyakit Yommee A Dissertation Submitted to the Faculty of New Jersey Institute of Technology in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy in Environmental Science Department of Chemistry and Environmental Science August 2015 Copyright © 2015 by Suriyakit Yommee ALL RIGHTS RESERVED . APPROVAL PAGE THERMOCHEMISTRY AND KINETICS: HYDROGEN ATOM ADDITION REACTIONS WITH ALKENES, OXIDATION OF CYCLOPENTADIENONE, TRIFLUOROETHENE AND TRANSPORT PROPERTIES Suriyakit Yommee Dr. Joseph W. Bozzelli, Dissertation Advisor Date Distinguished Professor of Chemistry and Environmental Science, NJIT Dr. Tamara Gund, Committee Member Date Professor of Chemistry and Environmental Science, NJIT Dr. Nancy L. Jackson, Committee Member Date Professor of Chemistry and Environmental Science, NJIT Dr. Alexei Khalizov, Committee Member Date Assistant Professor of Chemistry and Environmental Science, NJIT Dr. Yogesh V. Joshi, Committee Member Date Senior Researcher, Exxon Mobile, NJ BIOGRAPHICAL SKETCH Author: Suriyakit Yommee Degree: Doctor of Philosophy Date: May 2015 Undergraduate and Graduate Education: • Doctor of Philosophy in Environmental Science, New Jersey Institute of Technology, Newark, NJ, 2015 • Master of Science in Environmental Technology, King Mongut’s University of Technology Thonburi, Bangkok, Thailand, 2003 • Bachelor of Science in Environmental Science, Thammasat University, Bangkok, Thailand, 1997 Major: Environmental Science Publications: Yommee, S.; Bozzelli, J.W. Cyclopentadienone Oxidation Reaction Kinetics and Thermochemistry for the Alcohols, Hydroperoxides, Vinylic, Alkoxy and Alkylperoxy Radicals, submitted. Oral Presentations: Suriyakit Yommee and Joseph W. Bozzelli, “Reaction Kinetics of Hydrogen addition Reaction with Ethelene, Propene, 1-Butene, E-2-Butene,nd Z-2-Butene, and Isobutene: Comparison with Experiment,” 32 Regional Meeting on Kinetics and Dynamics, Hartford, CT, January 2014. Suriyakit Yommee and Joseph W. Bozzelli, “Thermochemical Properties for Cyclopentadienone Alcohols, Hydroperoxides,rd Alkenyl, Alkoxy and Alkylperoxy Radicals R • + O2 Kinetics,” 33 Regional Meeting on Kinetics and Dynamics, Amherst, MA, January 2015. iv Poster Presentation: Suriyakit Yommee and Joseph W. Bozzelli, “Calculation of Reaction Kinetic Parameters for Hydrogen Addition to Olefin Primary, Secondary and Tertiary Sites, and Reverse Elimination: Comparison with Experiments,” 23rd International Symposium on Gas Kinetics and Related Phenomena, Hungary, July 2014. v Mom, Dad, Brother, My Love (Namoun) and her mom I Love You!!! Life Can Live, Because of You ขอบคณุ ทุกความห่วงใยและกา ลงั ใจที่มีให้กนั ตลอดมา vi ACKNOWLEDGMENT I would like to express my sincerely grateful to my advisor, Prof. Joseph W. Bozzelli, for his advice, patience, and ethical point of view on academic and also his kindness for all of students in research group. My sincerely expression extended to Prof. Tamara Gund, Prof. Nancy L. Jacson, Asst. Prof. Alexei Khalizov, and Dr. Yogesh V. Joshi for serving on my committee. I would like to gratefully thank the Ministry of Science and Technology (Thailand) and Thammasat University (Thailand) for funding my studies at New Jersey Institute of Technology. I would also thank all the members in the Computational Chemistry Research Group: Suarwee Snitsiriwat, Itasaso Auzmendi Murua, Heng Wang, Jason Hudzik and Dr. Alvaro Castillo for all their help and friendship during several years at New Jersey Institute of Technology. vii TABLE OF CONTENTS Chapter Page 1 INTRODUCTIO N……............................……………..…………….…………….
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