Doctoral Dissertation Template

UNIVERSITY OF OKLAHOMA GRADUATE COLLEGE THERMOGRAVIMETRY-MASS SPECTROMETRY AND VARIABLE TEMPERATURE INFRARED SPECTROSCOPY INVESTIGATIONS OF AROMATIC ACID INTERACTIONS WITH MONTMORILLONITE CLAYS AND ACID/BASE PROPERTIES OF DIIRON COORDINATION COMPLEXES A DISSERTATION SUBMITTED TO THE GRADUATE FACULTY in partial fulfillment of the requirements for the Degree of DOCTOR OF PHILOSOPHY By AUDREY LYNN INGRAM Norman, Oklahoma 2015 THERMOGRAVIMETRY-MASS SPECTROMETRY AND VARIABLE TEMPERATURE INFRARED SPECTROSCOPY INVESTIGATIONS OF AROMATIC ACID INTERACTIONS WITH MONTMORILLONITE CLAYS AND ACID/BASE PROPERTIES OF DIIRON COORDINATION COMPLEXES A DISSERTATION APPROVED FOR THE DEPARTMENT OF CHEMISTRY AND BIOCHEMISTRY BY ______________________________ Dr. Robert L. White, Chair ______________________________ Dr. Mark A. Nanny ______________________________ Dr. Kenneth M. Nicholas ______________________________ Dr. Wai Tak Yip ______________________________ Dr. Zhibo Yang © Copyright by AUDREY LYNN INGRAM 2015 All Rights Reserved. For my wonderful husband, Dr. Kyle Ingram, and for my family: Dr. Dwight Myers, Nancy Myers, and Karen Myers. My achievements would not have been possible without them. Acknowledgements First and foremost, I would like to thank my mentor, Dr. Robert White, for all of his guidance and support. He is a brilliant chemist and teacher, and his enthusiasm for research and for helping his students to succeed are truly inspiring. I appreciate that he is always happy to take time to talk about the “why” instead of just caring about results. I would also like to thank my former research advisor, Dr. Robert Houser, for his guidance and patience as I learned how to perform research in the graduate setting. I appreciated that he always made time to talk about my project, even when he was busy with his departmental duties as Assistant Chair. I am grateful for the enthusiasm and constructive feedback provided by my committee members, Dr. Mark Nanny, Dr. Kenneth Nicholas, Dr. Wai Tak Yip, and Dr. Zhibo Yang. I am also especially grateful for help with pKa calculations provided by my former committee member, Dr. Richard Taylor. My research group members, Dalia Maraoulaite and Dr. Tara Nickels, have been wonderful colleagues and friends to me. Our brainstorming sessions have been invaluable to our research and writing progress. I am also grateful for the help and friendship provided by my former research group members: Dr. Anna Jozwiuk, Dr. Mike McClain, Dr. Zhaodang Wang, Dr. Rajendra Shakya, and Adam Campbell. Additionally, my friend Dr. Katie Branscum Foster started the Ph.D. program in this department at the same time that I did, and now she defended her dissertation the same week that I defended mine. It has been so helpful to have a close friend whose career is on a parallel track with mine. Katie’s friendship and support have been indispensable, and I’m very grateful for her. iv I wish to thank my dad, Dr. Dwight Myers, who was also my undergraduate research advisor. He provided a great deal of advice and guidance, especially during my college years, but all throughout my life as well. His pride in my achievements has been a huge source of encouragement over the years. My mom, Nancy Myers, was my very first teacher, and she taught me everything at home, starting in kindergarten and continuing all the way through my senior year of high school. She was an extremely well-rounded person and a very enthusiastic teacher. She inspired me to do my best at everything, especially science. She was also my confidant for personal matters; I could always trust her advice. Without her unconditional love and support I would not be the person that I am today. I am eternally grateful that I got to spend so much time with her during my school years, and that I lived at home while I went to college, because she passed away shortly after I started graduate school in 2008. Even though she isn’t here with me now, I know that she would be bursting with pride to see me graduating with my Ph.D. To have had two such loving parents that were also incredible role-models is rare, but it doesn’t end there. My sister, Karen Myers, has been a great friend and support to me over the years. I cannot imagine a better sister, mother, or father than mine. I also can’t say enough about my husband, Dr. Kyle Ingram. He is so much more than I ever imagined that I would find in a husband. He is one of the smartest people I know, and he has an incredible work ethic and a great sense of humor. His support for me has been phenomenal. He celebrates my achievements with me, he comforts me when times are hard, and he always makes me laugh. I am so grateful to have him, and I look forward to spending the rest of my life with him. v Table of Contents Acknowledgements ......................................................................................................... iv Table of Contents ............................................................................................................ vi List of Tables ................................................................................................................... xi List of Figures ................................................................................................................ xiv Abstract ........................................................................................................................ xxvi Chapter 1 : Introduction .................................................................................................... 1 1.1 Pharmaceuticals and Personal Care Products ....................................................... 1 1.1.1 Use and Environmental Release of Pharmaceuticals and Personal Care Products .................................................................................................... 1 1.1.2 Investigations of PPCPs in the Environment ............................................... 2 1.1.3 Overview of Research Goals ....................................................................... 4 1.2 Salicylic Acid and Acetylsalicylic Acid ............................................................... 6 1.2.1 Structure and Properties of Salicylic Acid and Acetylsalicylic Acid .......... 6 1.2.2 History and Use of Salicylic Acid and Acetylsalicylic Acid ...................... 7 1.2.3 Salicylic Acid and Acetylsalicylic Acid in the Environment ...................... 9 1.2.4 Retention of Salicylic Acid by Soils and Clays ......................................... 10 1.3 Montmorillonite .................................................................................................. 11 1.3.1 Classification and Structure of Montmorillonite ....................................... 11 1.3.2 Cation Exchange and its Effect on Interlayer Water ................................. 13 1.4 Interactions of Aromatic Acids with Montmorillonite ....................................... 14 1.4.1 Benzoic Acid ............................................................................................. 14 1.4.2 Salicylic Acid and Acetylsalicylic Acid .................................................... 16 vi 1.5 Research Goals ................................................................................................... 18 1.5.1 Thermogravimetry-Mass Spectrometry Studies ........................................ 18 1.5.2 Diffuse Reflection Infrared Fourier Transform Spectroscopy Studies ...... 19 1.5.3 Summary of Research Goals ..................................................................... 25 Chapter 2 : Experimental ................................................................................................ 26 2.1 Materials and Reagents ....................................................................................... 26 2.2 Sample Preparation ............................................................................................. 26 2.2.1 Preparation of Montmorillonite Samples by Cation Exchange ................. 26 2.2.2 Loading of Clay Samples with Adsorbates ............................................... 27 2.2.3 Dilution of Samples in Silver Powder for VT-DRIFTS Analysis ............. 27 2.3 Instrumentation ................................................................................................... 29 2.3.1 General ...................................................................................................... 29 2.3.2 Thermogravimetry-Mass Spectrometry ..................................................... 29 2.3.3 Variable Temperature Diffuse Reflection Infrared Fourier Transform Spectroscopy ........................................................................................... 30 2.4 Data Manipulation .............................................................................................. 33 2.4.1 Thermogravimetry-Mass Spectrometry Data ............................................ 33 2.4.2 VT-DRIFTS Data ...................................................................................... 34 Chapter 3 : Thermogravimetry – Mass Spectrometry Investigations of Montmorillonite Interlayer Water Molecule Environment Perturbations caused by Aromatic Acid Adsorbates .......................................................................................................... 36 3.1 Introduction ........................................................................................................ 36 3.2 Results ................................................................................................................ 36 vii 3.3 Discussion

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