Sift-Ms: Development of Instrumentation and Applications
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SIFT-MS: DEVELOPMENT OF INSTRUMENTATION AND APPLICATIONS Gregory James Francis Department of Chemistry A thesis presented for the Degree of Doctor of Philosophy at the University of Canterbury, Christchurch, New Zealand. December 2007 “I decorated it myself. Thank you, you’re too much. Honestly, it was nothing.” -Keith Buckley Dedicated to Esmé Margaret Colville who sadly passed away while this thesis was in preparation. A generous, wise and loving grandmother who was guiding light in my life and proved that the world through an artists eyes is a beautiful place. TABLE OF CONTENTS Title Page.....................................................................................................................................i Table of Contents.......................................................................................................................iii Acknowledgements.....................................................................................................................v List of Tables.............................................................................................................................vii List of Figures............................................................................................................................ix Publications...............................................................................................................................xii Abstract....................................................................................................................................xiii 1. Gas-Phase Ion-Molecule Kinetics Meets Analytical Chemistry 1 1.1 A Common Thread......................................................................................................1 1.2 Historical Review........................................................................................................2 1.3 Theory of SIFT-MS Operation.................................................................................10 1.4 Gas-Phase Ionic Reactions........................................................................................19 1.5 Introduction to the Current Research........................................................................24 2. Experimental 27 2.1 The Flowing Afterglow – Selected Ion Flow Tube Mass Spectrometer...................27 2.2 The Voice100 Selected Ion Flow Tube Mass Spectrometer......................................33 2.3 Data Acquisition and Analysis..................................................................................46 2.4 Voice100 Standard Operating Conditions and Currents...........................................48 2.5 Ancillary Systems.....................................................................................................49 2.6 Methods of Measuring Rate Coefficients.................................................................52 2.7 Carrier Gases and Reagents......................................................................................54 2.8 Ab Initio and Density Functional Theory Calculations............................................54 3. Instrumental Verification 57 3.1 Mixing Carrier Gases – Addition of Argon...............................................................58 3.2 Flow Tube Performance............................................................................................63 3.3 Ionic Diffusion in Carrier Gas Mixtures...................................................................70 3.4 Determining Rate Coefficients for Hydronium Ion Water Cluster Reactions..........92 4. GeoVOC: Geochemical Volatile Organic Compounds 101 4.1 An Introduction to Oil and Gas Exploration...........................................................101 4.2 Measurement of Kinetic Parameters.......................................................................106 4.3 Analytical Method...................................................................................................117 4.4 Case Study: The Depth-Dependant Composition of an Oil/Gas Well....................131 4.5 Case Study: Hydrocarbon Micro-seep Detection Using Water Samples................138 4.6 Concluding Remarks...............................................................................................141 5. Reactions and Rearrangements of Alkyl Esters 143 5.1 Introduction.............................................................................................................143 5.2 Measurement of Kinetic Parameters.......................................................................145 5.3 Discussion of Reaction Pathways...........................................................................152 5.4 Computational Mechanistic Studies of Gas-Phase Cyclo-Reversion.....................162 5.5 Detection of Alkyl Esters by SIFT-MS...................................................................174 5.6 Conclusions.............................................................................................................178 6. Chemical Warfare Agents 179 6.1 Introduction.............................................................................................................179 6.2 Measurement of Kinetic Parameters – Precursors and Surrogates.........................183 6.3 Semi-Quantitative Detection of Native Schedule I CWAs.....................................196 6.4 Conclusions.............................................................................................................202 7. Hazardous Air Pollutants 205 7.1 Introduction.............................................................................................................205 7.2 Experimental...........................................................................................................207 7.3 Results and Discussion............................................................................................209 7.4 Quantitative Detection of Toxic Air Pollutants.......................................................219 7.5 Conclusions.............................................................................................................220 8. Concluding Remarks and Suggestions for Future Work 223 8.1 A Summary of the Preceding Research...................................................................223 8.2 Suggestions for Further Research...........................................................................229 Appendix A.............................................................................................................................233 Appendix B.............................................................................................................................237 References...............................................................................................................................239 - v - ACKNOWLEDGEMENTS I wish to extent my gratitude to my academic supervisor Prof. Murray McEwan, for without whom, this thesis would not be possible. In early 2003, Murray was gracious enough to accept me into his research group as a BSc(Hons) student, even though I had recently neglected to hand-in an undergraduate assignment he had set. To this day I am still reminded about that assignment on a regular occasion! Murray's wisdom and sharp wit have helped me resolve many issues during the course of this research and made the process very enjoyable; to him I am forever indebted. Furthermore, many thanks to my assistant supervisors Dr. Daniel Milligan, Dr. Barry Prince, Dr. Vaughan Langford and Dr. Paul Wilson. Each has had a large role in the day-to-day supervision of the research presented herein and without their expert input, many research avenues would not have been pursued or explored to their full potential. Gratitude is extended to the employees of Syft Technologies, where the majority of the research presented herein was undertaken. I could not ask for a more pleasant group of people to spend 40-50 hours per week (and sometimes a few hours in the weekend) with. All of the 61 employees who I have encountered in the previous three and a half years have had some part to play in this thesis and for that I am very thankful. Particular gratitude is reserved for CEO Geoff Peck, who has provided me many tremendous opportunities that few Ph.D. students even dream of, let alone accomplish. Because of Syft Technologies and Geoff, I have learned to see science from both an academic and commercial point-of-view, as well as being able to travel the world. I also wish to thank staff and students at the University of Canterbury Chemistry Department. Particular thanks go to Dr. Robert Maclagan for advice on computational studies, Dr. Colin Freeman for general advice on gas-phase ion-molecule chemistry and Robert McGregor for blowing the glassware discussed herein (and then repairing that glassware when I had broken it). Also thanks are given to the University of Canterbury based SIFT group, Sam Edwards and Dr. Brett Davis, for allowing me to share laboratory and office space, and a few good laughs. I wish to acknowledge the researchers involved in the chemical warfare program at the Defence Science and Technology Organisation in Melbourne, Australia for their time and involvement in work presented herein. - vi - Special thanks go to Prof. Diethard Bohme for welcoming me into his research group at York University (Toronto, ON, Canada) in 2003 and for his guidance and support during the six months I spent in Toronto as a research assistant. I would also like to extent thanks to the remainder of the Bohme group