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Development of Aqueous Phase Hydroxyl Radical Reaction Rate DEVELOPMENT OF AQUEOUS PHASE HYDROXYL RADICAL REACTION RATE CONSTANTS PREDICTORS FOR ADVANCED OXIDATION PROCESSES A Dissertation Presented to The Academic Faculty by Daisuke Minakata In Partial Fulfillment of the Requirements for the Degree of Engineering in the School of Civil and Environmental Engineering Georgia Institute of Technology December, 2010 COPYRIGHT 2010 BY DAISUKE MINAKATA DEVELOPMENT OF AQUEOUS PHASE HYDROXYL RADICAL REACTION RATE CONSTANTS PREDICTORS FOR ADVANCED OXIDATION PROCESSES Approved by: Dr. John C. Crittenden, Advisor Dr. James Mulholland School of Civil and Environmental School of Civil and Environmental Engineering Engineering Georgia Institute of Technology Georgia Institute of Technology Dr. Jae-Hong Kim Dr. David Sherrill School of Civil and Environmental School of Chemistry and Biochemistry Engineering Georgia Institute of Technology Georgia Institute of Technology Dr. Ching-Hua Huang School of Civil and Environmental Engineering Georgia Institute of Technology Date Approved: July 16th, 2010 To my mother and deceased father ACKNOWLEDGEMENTS First of all, I would like to thank my adviser, Dr. John Crittenden, very much for his tremendous supports and advices to me. He has been my coach over the course of my doctorate study years who told me to be a super-athlete. Though I may not be a super- athlete just yet, I could not have made any progresses without his support. I would also like to thank other committee members at Georgia Tech: Dr. Jae-Hong Kim for his continuous encouragement, Dr. David Sherrill for his technical advices in quantum mechanical calculations, Dr. Ching Hua-Huang and Dr. James Mulhold for their constructive advices. My appreciation extends to my former committee members at Arizona State University: Dr. Ke Li who is now at the University of Georgia for his mentor and advisement in research as well as in carrier, and Dr. Paul Westerhoff from ASU for his technical advices and collaborations in research. I would like to include following names in appreciation for providing high performance computing resources: Drs. Karsten Schwan, Mattew Wolf and Chad Huneycutt from College of Computing at Georgia Tech; Drs. Ron Huchinsons and Neil Bright from Georgia Tech Office of Information Technology; Drs. Dan Stantione and Doug Fuller from ASU HPC. I also appreciate the IT support from CEE IT services from Georgia Tech: James Martino and Mike Anderson. Following individuals helped me with experiments: Ryan Ravenelle from Georgia Tech for his technical advices and support, and his friendship; Dr. Weihua Song from University of California, Irvine for his tremendous assistance for arranging experiments and overcoming experimental difficulties; Ryan Lisk from Environmental Health Service iv at Georgia Tech for shipment of hazardous chemical materials. Thank you so much, folks. I also appreciate others in research group at Georgia Tech as well as at ASU. Faculty and Staff at Brook Bayer Institute for Sustainable Systems encouraged me and helped me with business prospect: Dr. Michael Chang, Dr. Ming Xu, Martha Lindsay, Christy Shannon, and Brent Verrill. Thank you. I would like to acknowledge the following foundations, institutes and assistantships for their funding supports: National Science Foundation; Brook Bayer Institute for Sustainable Systems; High Tower Chair and Georgia Research Alliance at Georgia Tech; University of Notre Dame Radiation Center and Department of Energy; Richard Snell Chair at ASU. My deepest gratitude goes to my family; my mother, sister, brother, uncle, aunt, and grandparents. My mother, Chiaki, always supports my decision and encourages me to move forward. Reminiscence of my deceased father still influences me in many ways to live everyday strong as well. Finally, I appreciate the continuous support with tremendous love from my favorite person, Ayako. v TABLE OF CONTENTS Page ACKNOWLEDGEMENTS iv LIST OF TABLES ix LIST OF FIGURES xi SUMMARY xiv CHAPTER 1 ....................................................................................................................... 1 INTRODUCTION 1.1 SIGNIFICANCE AND OBJECTIVES .............................................................................. 1 1.2 STRUCTURE OF THIS DISSERTATION ...................................................................... 10 1.3 LITERATURE CITED ................................................................................................ 11 CHAPTER 2 ..................................................................................................................... 16 DEVELOPMENT OF A GROUP CONTRIBUTION METHOD TO PREDICT AQUEOUS PHASE HYDROXYL RADICAL REACTION RATE CONSTANTS 2.1 ABSTRACT ............................................................................................................. 17 2.2 INTRODUCTION ...................................................................................................... 18 2.3 DEVELOPMENT OF THE GROUP CONTRIBUTION METHOD ...................................... 22 2.3.1 Hydrogen-atom Abstraction.......................................................................... 23 2.3.2 HO• Addition to Alkenes .............................................................................. 26 2.3.3 HO• Addition to Aromatic Compounds ........................................................ 29 2.3.4 HO• Interactions with Sulfur-, Nitrogen-, or Phosphorus-atom-containing Compounds ............................................................................................................... 31 2.4 RESULTS AND DISCUSSION ..................................................................................... 32 2.4.1 Calibration and Prediction ............................................................................ 32 2.4.2 Overall Results .............................................................................................. 40 2.4.3 Hydrogen-Atom Abstraction from Saturated Aliphatic Compounds ........... 43 2.4.3.1 Group Rate Constants for H-atom Abstraction ......................................... 44 2.4.3.2 Group Contribution Factors for H-atom Abstraction................................ 46 2.4.4 HO• Addition to Alkenes .............................................................................. 50 2.4.4.1 Group Rate Constants and Group Contribution Factors for HO• Addition to Alkenes. ................................................................................................................ 50 2.4.5 HO• Addition to Aromatic Compounds ........................................................ 52 2.4.5.1 Group Rate Constants for HO• Addition to Aromatic Compounds. ......... 55 vi 2.4.5.2 Group Contribution Factors for HO• Addition to Aromatic Compounds. 58 2.4.6 HO• Interactions with Sulfur-, Nitrogen-, or Phosphorus-containing- compounds ................................................................................................................ 59 2.4.6.1 Group Rate Constants for HO• Interaction ............................................... 60 2.4.6.2 S-, N-, or P-atom-Containing Group Contribution Factors ...................... 62 2.4.7 Predictabilities of GCM and Future Studies ................................................. 64 2.5 ACKNOWLEDGEMENT ............................................................................................ 68 2.6 APPENDICES ........................................................................................................... 68 2.7 LITERATURE CITED ................................................................................................ 68 CHAPETER 3 ................................................................................................................... 74 LINEAR FREE ENERGY RELATIONSHIPS BETWEEN AQUEOUS PHASE HYDROXYL RADICAL REACTION RATE CONSTANTS AND FREE ENERGY OF ACTIVATION 3.1 ABSTRACT ............................................................................................................. 75 3.2 INTRODUCTION ...................................................................................................... 75 3.3 LINEAR FREE ENERGY RELATIONSHIPS ................................................................. 87 3.4 COMPUTATIONAL METHODS .................................................................................. 89 3.5 RESULTS AND DISCUSSION ..................................................................................... 92 3.5.1 A Comparison of Ab initio Quantum Mechanical Methods for HO• + CH4 in the Gaseous Phase ..................................................................................................... 92 3.5.2 Verifications of Ab initio Quantum Mechanical Methods for the Gaseous Phase HO• Reactions ................................................................................................ 96 3.5.3 A Comparison of Implicit Solvation Models ................................................ 98 3.5.4 Linear Free Energy Relationships between Aqueous Phase Free Energy of Activation and Logarithm of HO• Reaction Rate Constant .................................... 101 3.6 ACKNOWLEDGEMENT .......................................................................................... 113 3.7 APPENDICES ......................................................................................................... 113 3.8 LITERATURE CITED .............................................................................................. 113 CHAPTER 4 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