development of aqueous phase hydroxyl radical - SMARTech

395 Pages·2010·11.56 MB·English

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
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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.
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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
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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 ................................................................................................................... 126
QUANTITATIVE UNDERSTANDING OF AQUEOUS PHASE HYDROXYL
RADICAL REACTIONS WITH HALOACETATE IONS:
EXPERIMENTAL AND THEORETICAL STUDIES
4.1 ABSTRACT ........................................................................................................... 127
4.2 INTRODUCTION .................................................................................................... 128
4.3 METHODS ............................................................................................................ 133
4.3.1 Experimental ............................................................................................... 133
4.3.1.1 Linear Accelerator (LINAC) .................................................................... 133
4.3.1.2 Flow Cell .................................................................................................. 135
4.3.1.3 Radiolysis of Water .................................................................................. 136
4.3.1.4 Competition Kinetics ............................................................................... 138
4.3.1.5 Procedures ................................................................................................ 139
4.3.1.6 Thermochemical Properties ..................................................................... 140
4.3.2 Group Contribution Method ....................................................................... 142
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4.3.3 Theoretical Basis ......................................................................................... 143
4.3.4 Linear Free Energy Relationships ............................................................... 145
4.4 RESULTS AND DISCUSSION ................................................................................... 147
4.4.1 Experimental Section .................................................................................. 147
4.4.1.1 Hydroxyl Radical Reaction Rate Constants ............................................ 147
4.4.1.2 Arrhenius Parameters .............................................................................. 150
4.4.1.3 Thermochemical Properties of Reactions ............................................... 152
4.4.2 Update of Group Contribution Method....................................................... 154
4.4.3 THEORETICAL .............................................................................................. 156
4.4.3.1 Ab initio Quantum Mechanical Approach .............................................. 156
4.4.3.2 Optimized Structure of Stationary, Pre-reactive Complex and Transition
States ................................................................................................................. 161
4.4.3.3 Linear Free Energy Relationships ........................................................... 164
4.4.3.4 Entropy Contribution .............................................................................. 165
4.4.3.5 Charge Distribution and Reaction Mechanisms ..................................... 170
4.4.3.6 Addition of Explicit Water Molecules .................................................... 175
4.5 CONCLUSIONS ...................................................................................................... 179
4.6 ACKNOWLEDGEMENT .......................................................................................... 180
4.7 APPENDICES ......................................................................................................... 180
4.8 LITERATURE CITED .............................................................................................. 180
CHAPTER 5 ................................................................................................................... 188
IMPLICATIONS AND FUTURE STUDIES
APPENDIX A………………………………………………………………………… 196
APPENDIX B………………………………………………………………………… 203
APPENDIX C………………………………………………………………………… 242
APPENDIX D………………………………………………………………………… 254
APPENDIX E………………………………………………………………………… 260
APPENDIX F………………………………………………………………………… 316
APPENDIX G………………………………………………………………………… 344
VITA………………………………………………………………………………….. 379  

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LIST OF TABLES
Table 2.1: Calculated HO• reaction rate constants (Normal: calculated, Italic: predicted,
Bold: error is out of the EG) as compared to literature-reported experimental values….34

Table 2.2: Summary of experimental data and statistical results for calibration………..42

Table 2.3: Summary of experimental data and statistical results for prediction…………43

Table 2.4: Group rate constants and group contribution factors for H-atom abstraction..48

Table 2.5: Summary of the structural configurations in equation (2.13) based on the
experimental rate constants………………………………………………………………50

Table 2.6: Group rate constants and group contribution factors for HO• addition to
alkenes……………………………………………………………………………………52

Table 2.7: Summary of structural configurations in equation (2.17) based on the
experimental rate constants with aromatic compounds………………………………….54

Table 2.8: Group rate constants and group contribution factors for HO• addition to
aromatic compounds that include benzene rings………………………………………...56

Table 2.9: Group rate constants and group contribution factors for HO• addition to
aromatic compounds that include pyridine………………………………………………57

Table 2.10: Group rate constants and group contribution factors for HO• addition to
aromatic compounds that include furan………………………………………………….57

Table 2.11: Group rate constants and group contribution factors for HO• addition to
aromatic compounds that include imidazole……………………………………………..58

Table 2.12: Group rate constants and group contribution factors for HO• addition to
aromatic compounds that include triazine……………………………………………….59

Table 2.13: Group rate constants and group contribution factors for S, N, and P-atom
containing compounds…………………………………………………………………...61

Table 2.14: Predicted HO• reaction rate constants for emerging contaminants…………67

Table 3.1: Number of available experimental rate constants in the aqueous phase AOPs
on the basis of the extensive literature review…………………………………………...77

Table 3.2: Summary of theoretical studies of gaseous phase HO• reactions…………….81

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Table 3.3: A comparison of Ab initio quantum mechanical methods for the gaseous phase
reaction of HO• with CH ………………………………………………………………..93
4

Table 3.4: Calculated energy barrier for the gaseous phase reactions of HO• with CH OH,
3
CH CHO, CH OCH , CH COCH , CH COOH, CH F, CH Cl and CH Br, and the
3 3 3 3 3 3 3 3 3
literature-reported values………………………………………………………………...97

Table 3.5: Calculated ∆G≠ , tunneling factor and literature reported HO• reaction rate
rxn,aq
constants for the H-atom……………………………………………………………..…102

Table 3.6: Calculated ∆G≠ , tunneling factor and literature reported HO• reaction rate
rxn,aq
constants for the HO• addition to alkenes………………………………………………103

Table 3.7: Calculated diffusion coefficients, radius of molecule and diffusion rate
constants………………………………………………………………………………...109

Table 4.1: Experimentally obtained temperature-dependent HO• rate constants and
thermochemical properties, and theoretically calculated free energies of activation…..148 
Table 4.2: Calibrated group rate constants and group contribution factors…………….155

Table 4.3: Molecules and rate constants that were used for the calibration……………156

Table 4.4: Calculated gaseous and aqueous phase barrier height and free energy of
activation………………………………………………………………………………..160

Table 4.5: Geometry of HO• and H O………………………………………………….162
2

Table 4.6: Geometry of acetate and halogenated acetate……………………………….162

Table 4.7: Geometry of transition states for the reaction of HO• with halogenated
acetate…………………………………………………………………………………..163

Table 4.8: Calculated cavitation entropy of activation, change in cavity volume,
nonelectrostatic energy of activation and experimentally obtained entropy of
activation………………………………………………………………………………..167

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