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Proquest Dissertations OH detection by near-infrared fluorescence quenching of a polymethine dye Item Type text; Dissertation-Reproduction (electronic) Authors Gast, Karl Frederick, 1961- Publisher The University of Arizona. Rights Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author. Download date 30/09/2021 14:51:22 Link to Item http://hdl.handle.net/10150/282404 INFORMATION TO USERS This manuscript has been reproduced from the microfilm master. UMI films the text direct^ fix>m the orighial or copy submitted. Thus, some thesis and dissertation copies are in typewriter fiic^ while others may be fi'om any type of computer printer. The quality of this rcprodnction is dependent upon the quality of the copy submitted. Broken or indistinct print, colored or poor quality illustrations and photographs, print bleedthrough, substandard margins, and improper alignment can adversely affect reproduction. In the unlikely event that the author did not send UMI a complete manuscript and there are missmg pages, these will be noted. Also, if unauthorized copyright material had to be removed, a note will indicate the deletion. Oversize materials (e.g., maps, drawings, charts) are reproduced by sectioning the origfaial, b^inning at the upper left-hand comer and continuing from left to right in equal sections with small overiaps. Each original is also photographed in one exposure and is included in reduced form at the back of the book. Photographs included in the original manuscript have been reproduced xerographically in this copy. Higher quality 6" x 9" black and white photographic prints are available for any photographs or illustrations appearing in this copy for an additional charge. Contact UMI directly to order. UMI A BeU & Howell bfiimiation Con^ai^ 300 NoithZM Road, Ann Aibor MI 48106-1346 USA 313/761-4700 800/S21-0600 OH DETECTION BY NEAR-INFRARED FLUORESCENCE QUENCHING OF A POLYMETHINE DYE by Karl Frederick Cast A Dissertation Submitted to the Faculty of the DEPARTMENT OF ATMOSPHERIC SCIENCES In Partial Fulfillment of the Requirements For the Degree of DOCTOR OF PHILOSOPHY In the Graduate College of THE UNIVERSITY OF ARIZONA 1997 DMI Number: 980S778 UMI Microform 9806778 Copyriglit 1997, by UMI Company. All rigiits reserved. This microform edition is protected against unautiiorized copying under Title 17, United States Code. UMI 300 North Zeeb Road Ann Arbor, MI 48103 2 THE UNIVERSITY OF ARIZONA ® GRADUATE COLLEGE As members of the Final Examination Committee > we certify that we have read the dissertation prepared by Karl F. Cast entitled OH Detection by Near-Infrared Fluorescence Quenching of a Polymethine Dye and recommend that it be accepted as fulfilling the dissertation requirement for the Degree of Doctor of Philosophy ,Eic A. Better^n . Robe~ ^ ^ ^ Date Jack^. Gaskill Date William D. Sellers . Date I^t'Vvw^ ^- U)/u7 Date ^ames C. Wyant Final approval and acceptance of this dissertation is contingent upon the candidate's submission of the final copy of the dissertation to the Graduate College. I hereby certify that I have read this dissertation prepared under my direction and recommend that it be accepted as fulfilling the dissertation requirement. Dissertation Director GRIC A. Betterton Date 3 STATEMENT BY AUTHOR This dissertation has been submitted in partial fiilfillment of requirements for an advanced d^ee at The University of Arizona, and is deposited in the University Library to be made available to borrowers under rules of the Library. Brief quotations from this dissertation are allowable without special permission, provided that accurate acknowledgement of source is made. Requests for permission for extended quotation from or reproduction of this manuscript in whole or in part may be granted by the head of the major department or the Dean of the Graduate College when in his or her judgement the proposal use of the material is in the interest of scholarship. In all other instances, however, permission must be obtained from the author. Signed; 4 ACKNOWLEDGEMENTS There is no doubt that \vithout the support of many others, this work would not have been completed. The financial supporters, previous teachers and advisors, the Acuity here at The University of Arizona, fellow students, and my &mily have all contributed to the completion of this dissertation. I am grateful for the support fi-om the Electric Power Research Institute (contract number RP8004-11) for providing the funds to purchase the equipment necessary to begin and conduct this research. I am espedally grateful for The University of Arizona, Department of Atmospheric Sciences and the Institute of Atmospheric Physics, under the leadership of Phil Krider and Ben Herman, for providing financial support through teaching and research assistantships for the duration of my studies. I wish to thank the faculty of the Physics Departments at The Colorado College and The University of Denver, especially my advisors at those institutions, Dick Hilt and Dave Murcray, for motivating me to continue my education as well as providing me with the basic skills to do so. Thanks are also due the members of The University of Arizona Departments of Atmospheric Sciences and Optical Sciences who were always available with advice and equipment, in particular to my committee members. Bob Dickinson, Jack Gaskill, Bill Sellers, and Jim Wyant. I am also grateful for the advice and discussions with Don Huffinan and Sean Twomey, and Chuck Weidman. Their insight into the pitfalls of experimental science are always helpful and eye opening. My fellow students have also provided assistance and support. I have benefitted fi'om discussions with many, including Darcy Anderson, Brian Barbaris Tom Caudill, David Craig, Jun Du, Luis Farfan, Dave Flittner, Mike Leuthold, and Joel Mozer. The patience and support of my family, especially of my wife, Miriam, and my parents, Jim and Thea, has been of immeasurable value in enabling me to continue my studies and complete this work. For their love and encouragement I will always be grate&l. Above all, I am indebted to my advisor, Eric Betterton, whose encouragement, insight, and guidance kept me fi'om straying too far fi-om the path, and provided me with the perseverance to complete the research presented here. I am fortunate to have studied with him, and hope to have the opportunity to work with him in the future. Thank you. 5 TABLE OF CONTENTS LISTOFnOURES J LIST OF TABLES 8 ABSTRACT 9 1. INTRODUCTION 10 2. TROPOSPHERIC OH CHEMISTRY. 14 2.1 Daytime OH Production. 16 2.2 >nghttime OH Production 17 2.3 Oxidation of Carbon Species 18 2.4 Oxidation of Mtrogen Species .22 2.5 Oxidation of Other Species 23 3. CURRENT TECHNIQUES FOR TROPOSPHERIC OH MEASUREMENT 27 3.1 Laser Induced Fluorescence 28 3.2 Long Path Absorption 30 3.3 Isotopically Labeled "CO Titration. 32 3.4 Ion-Assisted Mass Spectroscopy. 34 3.5 Methyl Chloroform Mass Balance Calculation 36 3.6 Summary 38 4. PRINCIPLES OF THE FLUORESCENT QUENCHING TECHNIQUE 41 4.1 Basis of Technique 42 4.2 Oudine of Method Development 44 5. MATERL^-S 46 5.1 Chemical Supplies 46 5.2 Solvents 46 5.3 Compressed Gas Supplies 47 5.4 Instrumentation 48 6. PHYSICOCHEMICAL PROPERTIES OF IR125 54 6.1 Physical Data 54 6.2 IR125 pK, Verification 59 6.3 Reaction of IR125 with Species other than OH 60 6.4 Reaction of IR125 with OH. 66 6.4.1 Fenton System 66 6.4.2 N-Hydroxy-2-Thiopyridone System 68 6.5 Summary 76 7. FLUORIMETER DESCRIPTION 54 7.1 Hardware Description 94 7.2 Software Description 101 7.3 Operation 102 7.4 Output Analysis 106 6 TABLE OF CONTENTS - continued 8. CALBRATION. 114 8.1 Hydroxyl Source Description. 115 8.2 Computer Model of the Photolysis Cell Chemistry. 117 8.2.1 Nitrous Acid as the Hydroxyl Radical Precursor. 121 8.2.2 Hydrogen Peroxide as the Hydroxyl Radical Precursor. 125 8.3 Determination of the Photolysis Rate Constants 126 8.4 Calibration of Sampling Methods 133 8.5 Summary 133 9. SAMPLING OF THE AMBIENT AIR. 146 9.1 Method Description. 146 9.2 IRl 25 Response Calculation 154 9.3 Alternative Sampling Techniques 155 10. RESULTS 163 10.1 Overview 163 10.2 A Case Study: Sampling Results From 6-7 July 1996 164 10.3 Photodecomposition 166 10.4 Non-OH Reactions 167 10.5 Possible Measurement Errors .168 10.6 Additional Tests 171 11. SUMMATION: CONCLUSIONS AND FUTURE WORK 180 11.1 Conclusions 181 11.2 Recommended Future Work 183 11.2.1 Fluorimeter Improvement 183 11.2.2 Calibration Source Development 184 11.2.3 Further Studies 185 APPENDIX A: Reactions and Rates Included in the Photolysis Cell Model 187 APPENDIX B: Data Acquisition Software 189 APPENDIX C: Photolysis Cell Computer Model 195 REFERENCES 206 7 UST OF FIGURES 6.1 Structure of IR125 78 6.2 Absorption Spectra of IR125 in Water, Methanol, and DMSO 79 6.3 Fluorescence Spectra of IR125 in Water, Methanol, and DMSO 80 6.4 HPLC Separation of IR125 Solution 81 6.5 Decay of IR125 in Water. 82 6.6 Spectrophotometric Determination of the pK, of IR125 53 6.7 Photosensitization Suspected Effect on IR12S Fluorescence 84 6.8 Decay of IR125 Fluorescence in the Fenton SystenL .85 6.9 Decay of IR125 Fluorescence in the N-HT System 86 6.10 Absorption Spectrum of IR125 in the N-HT System 87 6.11 HPLC Separation of the Reaction Products in Flask 3 88 6.12 HPLC Separation of Reaction Products in N-HT Photolysis System 89 6.13 Mass Spectrum of
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