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Measurement and Modeling of Isocyanic Acid (Hnco) in the Troposphere

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Measurement and Modeling of Isocyanic Acid (Hnco) in the Troposphere North Carolina Agricultural and Technical State University Aggie Digital Collections and Scholarship Dissertations Electronic Theses and Dissertations 2012 Measurement And Modeling Of Isocyanic Acid (Hnco) In The Troposphere Anthony Kozeque Cochran North Carolina Agricultural and Technical State University Follow this and additional works at: https://digital.library.ncat.edu/dissertations Recommended Citation Cochran, Anthony Kozeque, "Measurement And Modeling Of Isocyanic Acid (Hnco) In The Troposphere" (2012). Dissertations. 33. https://digital.library.ncat.edu/dissertations/33 This Dissertation is brought to you for free and open access by the Electronic Theses and Dissertations at Aggie Digital Collections and Scholarship. It has been accepted for inclusion in Dissertations by an authorized administrator of Aggie Digital Collections and Scholarship. For more information, please contact [email protected]. Measurement and Modeling of Isocyanic Acid (HNCO) in the Troposphere Anthony Kozeque Cochran North Carolina A&T State University A dissertation submitted to the graduate faculty in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY Department: Energy & Environmental Systems Major: Energy and Environmental Systems Major Professor: Dr. Solomon Bililign Greensboro, North Carolina 2012 i School of Graduate Studies North Carolina Agricultural and Technical State University This is to certify that the Doctoral Dissertation of Anthony Kozeque Cochran has met the thesis requirements of North Carolina Agricultural and Technical State University Greensboro, North Carolina 2012 Approved by: Solomon Bililign, Ph.D. James Roberts, Ph.D. Major Professor Committee Member Zerihun Assefa, Ph.D. Keith A. Schimmel, Ph.D. Committee Member Committee Member and Department Chairperson Sanjiv Sarin, Ph.D. Associate Vice Chancellor for Research and Dean of Graduate Studies ii Copyright by ANTHONY KOZEQUE COCHRAN 2012 iii Dedication To my grandmother Ionia Webb Smith and my grandfather L. C. Cochran, for the energy and gifts you left me with after you left this earth. iv Biographical Sketch Anthony Cochran earned his B.S. degree at Chicago State University in 1996 and then moved on to Baton Rouge, LA to work on the M.S. degree in particle physics at Southern University to search for evidence of neutrino oscillations at Los Alamos National Laboratory’s linear accelerator. After finishing the M.S. degree in 1998, he moved on to Hampton University to work on a Ph.D. in nuclear physics. He was privileged to have collaborated on several experiments in Halls A and C at the Jefferson Lab accelerator before completing his experiment on quasi-elastic electron scattering from He-4. Taking a break from his Ph.D. efforts in 2001- 2003, he accepted two research fellowships at the New Brunswick Laboratory for nuclear standards and Argonne National Laboratory, both in Argonne Illinois. He continued his Ph.D. pursuit in systems science at Clark Atlanta University where he worked in surface physics research. He was awarded a research fellowship to work at one of the NSF’s STCs. He chose to work at the Nanobiotechnology Center at Cornell University from 2004-2005 using microfabrication techniques to develop an optical nanobiosensor. Finally, after a 2006 decision to start his career as patent examiner in X-ray CT systems with the US Patent and Trademark Office, he joined Dr. Solomon Bililign’s group at North Carolina A&T State University to complete his Ph.D. in Energy and Environmental Systems. His current work involves the study and characterization of trace gases emitted by biomass burning in the atmosphere. v Acknowledgments Thanking first my parents Margaret A. and Willie L. Cochran for bringing me here. They did what they could to build a solid and well-rounded foundation in a child amidst the struggles of the big city of Chicago. Thanks to my sister LaMonica Cochran-Ray, for having such perfect timing, to join our family when we really needed her the most, and some 30 or so years later, being the person that I needed to talk to in order to take my mind off of science and distractions just long enough to get back to work. Thanks also to my sister for making me the one and only “Uncle Hoss” to Jeremiah Anthony Ray. Thanks to Dr. Elliott Treadwell for recognizing some of the gifts that I had in physics as an undergraduate and showing me the path to real research. Thanks to Dr. Ali R. Fazely and Dr. Larry Henry and Diola Bagayoko for helping me carve a way to the master’s degree. Thanks to my mentor Dr. Margaret E. M. Tolbert for the relentless support in my endeavors, motivation in the face of the seemingly impossible and her general advice which shaped me into a true professional. Thanks also to my spiritual mentor and brother RoAnne for the powerful insight, wisdom, and knowing that so few are just gifted with. Thanks to my current advisor Dr. Solomon Bililign for all of the financial support and experimental opportunities coordinated that allowed me to put together a solid dissertation and for the opportunities to travel abroad which were most rewarding and helped me to put life into a global perspective. Also thanks to my co-advisor Dr. James Roberts and (graduate student at the time) Dr. Patrick Veres, for welcoming me into their laboratory at NOAA ESRL CSD in order to conduct portions of my doctoral research and sharing techniques of conducting chemical ionization mass spectrometry. Thanks also to the rest of the CSD scientists for making the work and my stays in Boulder so much fun. vi It is impossible to describe and no one would comprehend how many people kept me on the path, motivated, and striving throughout this process through conversation, opinion, good advice, advice, bad advice, or just plain old encouragement when needed . so this goes out to you. I will not be able to name all of the friends and associates, but there are a few that are special for reasons that they will know so I list them individually in no special order: Auntie Helen, Dora Ann Dyson, Br. Dejuan Hood, Tamiko James, Melva Smith, Pamela Bivens-Pippen, Dr. Mark Harvey, Alisha Williams, Dr. Tara Wade, Carmen Jones (rest peacefully), Dakia Jones, Dina George, Br. Willie Harrington, Cedric Moore (“hey big guy”), Karen Davis, Babette Stevens (for the name “Dr. Southside”). vii Table of Contents List of Figures ................................................................................................................................. x List of Tables ................................................................................................................................. xv Abstract ........................................................................................................................................... 2 CHAPTER 1. Scope of the Work ................................................................................................... 3 1.1 Background ...................................................................................................................... 3 1.2 Experimental Goals .......................................................................................................... 5 1.3 Modeling Goals ................................................................................................................ 6 CHAPTER 2. Experimental Characterization of Isocyanic Acid: A Product of Biomass Burning ................................................................................................. 8 2.1 Overview .......................................................................................................................... 8 2.2 Biomass Burning .............................................................................................................. 9 2.3 Organic Acids in the Troposphere ................................................................................. 13 2.3.1 Introduction ........................................................................................................ 13 2.3.2 Carboxylic acids: An important subgroup of organic acids ............................... 13 2.3.3 Isocyanic acid (HNCO): A unique organic acid from biomass burning ................................................................................................. 16 2.4 Gas Phase Kinetics ......................................................................................................... 18 2.5 Heterogeneous Chemical Kinetics: Gas Uptake ............................................................ 20 2.5.1 Resistance model of gas uptake ......................................................................... 20 2.5.2 Gas stripping and extracting equilibrium constants ........................................... 25 2.5.3 pH dependence of H ........................................................................................... 28 2.6 Experimental Techniques: Mass Spectrometry in Biomass Burning ............................. 29 viii 2.6.1 Background ........................................................................................................ 29 2.6.2 Equipment and methods ..................................................................................... 35 2.6.3 NCAT time-of-flight system .............................................................................. 36 2.6.3.1 Chemical ionization............................................................................. 39 2.6.3.2 Soft ionization ....................................................................................
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