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Kelly A. Hislop Graduate Program in Chemistry / Environmental Science

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Kelly A. Hislop Graduate Program in Chemistry / Environmental Science Kelly A. Hislop Graduate Program in Chemistry / Environmental Science Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy FacuIty of Graduate Studies The University of Western Ontario London, Ontario March, 1999 O Kelly A. Hisiop 1999 National library Bibliothèque nationale I*m of Canada du Canada Acquisitions and Acquisitions et Bibliographie Services services bibliographiques 395 Wellington Street 395. rue Wellington OttawaON K1AON4 Ottawa ON K1A ON4 Canada canada Your @a Votre reference Ow ma Notre reference The author has granted a non- L'auteur a accordé une licence non exclusive licence allowing the exclusive permettant à la National Librq of Canada to Bibliothèque nationale du Canada de reproduce, loan, distribute or sell reproduire, prêter, distribuer ou copies of this thesis in microform, vendre des copies de cette thèse sous paper or elecîronic formats. la forme de microfiche/fïlm, de reproduction sur papier ou sur format élecîronique. The author retains ownership of the L'auteur conserve la propriété du copyright in this thesis. Neither the droit d'auteur qui protège cette thèse. thesis nor substantial extracts fiom it Ni la thèse ni des extraits substantiels may be printed or otherwise de celle-ci ne doivent être imprimés reproduced without the author's ou autrement reproduits sans son permission. autorisation. The W-Vis / ferrioxalate / hydrogen peroxide sysîern (or " femoxalate" sys rem) couples two weil known reactions to generate a photochernical method of generating hydroxyl radicals for the purpose of mineraking organic contarninants in water. The first is the photochernical reduction of femoxalate [Fe(III) coordinated with between one and three oxalate ligands] to Fe(I1) by light in the ultraviolet and/or visible. The second is the Fenton reaction, between Fe(l1) and hydrogen peroxide. which produces a hydroxyl radical. a very strong oxidizing agent. Kinetics experiments were conducted using a mode1 organic compound (Zpropanol) as a hydroxyl radical scavenger. The eEect of different reagent concentrations on the oxidation of 2-propanol oxidation to '-propanone was investigated using the initial quantum yield of organic compound oxidation as a measure of efficiency. An important aspect of the reaction mechanism is the cornpetition between oxygen and ferrioxalate for the alkyl radical formed from 2-propanol. In both cases. oxidation to 2-propanone occurs, but oxygen is a chain terminator with respect to hydroxyl radical ceneration. whereas the reaction between the alkyl radical and ferrioxalate generates C Fe(I1). This may Iead to the formation of more hydroxyl radicals, via the Fenton reaction. Evidence for this chain reaction was found in the relatively high experirnental quantum yields, which were ofien between 2 and 5. High ferrioxalate concentrations increased the quantum yields, but eventually this effect was attenuated by the reaction between ferrioxalate (or oxalate) and the hydroxyl radical. Under this condition, 2-propanol was not able to react with al1 of the hydroxyl radicals generated and a lower quantum yield was observed. A kinetic modelling prograrn was written to simulate the behaviour of the femoxalate system. A vanety of reactions. most of which are reported in the literature. were incorporated in the mode1 and theoretical quantum yields generated. Ln this way. a reaction set was developed to describe the femoxalate systern. Reasonable agreement was obtained between the expenmental and the theoretical quantum yields. providing validation for the important role of iron cycling between Fe(I1) and Fe(I1I) for high quantum yields. Keywords: femoxalate, hydrogen peroxide. Fenton reaction. Fenton reagent. hydroxyl radical, quantum yield, 2-propanol TO Elizabeth (Betty) Wilson 1 would first like to express my thanks to Dr. Bolton, for his guidance and support throughout this work. His dedication to research and the interest he shows in his comunity is inspiring. 1 am gratefûl to Dr. Mihaela Stefan, who critically reviewed this thesis. Her enthusiastic approach to scientific research and problem solving has. by exampie. taught me a great deal. Dr. Aitken Hoy. whose time in Our group overlapped several of my years here. \vas an invaluable help, especially with the debugging of early versions of the kinetic modelling program, written in Turbo Pascal. A very sincere thanlc you goes to Dr. Truis Srnitli-Palmer, Saint Francis Xavier University. without whose encouragement. 1 might never have returned to university to pursue graduate work. Jolm Van Stone was very helpful. providing assistance with the old Perkin-Elrner gas chromatograph, which required some work before it could be used. Firially, 1 would like to mention those from whom 1 have drawn moral support during the completion of this work: Dr. Maria Koulis. my grandparents and parents. Jan Hislop, and John Higney. CERTIFICATE OF EXAMINATION ... ABSTRACT 111 DEDICATION ACKNOWLEDGEMENTS v i TABLE OF CONTENTS vii LIST OF TABLES s LIST OF FIGURES xii LIST OF APPENDICES xv PREFACE svi INTRODUCTORY OVERVIEW 1 General Introduction..................................................................................... 1 Organisation of the Thesis ........................................ .............. ................... 2 Definitions ...................................................... ........... ......*..........*.... 3 Ferrioxalate .................................................................................................. 4 Iron and Hydrogen Peroxide ........................................................................ 6 1..1 The Fenton recrction .......................................................................... 6- 1. j . 2 The "Fenton-like " reuction ................................................................ 3 Qtrestions concerning rhe oxidnnt in the Fenton recrction ................ 8 1.4 The photo-Fenton reaciion ................... .... ............................... II I .5.5 The photo-Fenton reuction using complexed Fe ...................... 12 Advanced Oxidation Technologies ............................................................. 13 Applications of the Fenton and Fenton-like Reactions ............................ 14 1.7.1 The dnrk Fenton rectction................................................................ I-l 1. 7.2 Durk cdphotoossisted Fenton-like reuctions ............................... 16 1.7.3 The photo-Fenton reaction ............................................................. 17 I 7. 4 The photo-Fenton renction nsing ferrioxalote ................................ 18 EXPERIMENTAL 20 Chapter Introduction ....................................................... ......................... 20 Considerations behind the Experimental Design ..................................... 20 72.1 Quantr3ing *OH.......................... .. ............................................. 20 2.2.2 Calculating the qrianturn yield .................... ... ........................ 71 The PT1 Quantacount Apparatus .......................................... .................... 22 The Rayox Reactor ................................................................................ 27 Actinometry ........ .. ................................................................................... 28 2.5. l Ferr ioxalate aclinome:ry ................................................................ 28 2-52 Peroxydiszrlfilte actiinornetry ....................... .. ............................... 30 Methods and Materials ............................................................................... 31 2.6.1 Rcagents .......................................................................................... 31 vii . 2.6.2 Irrudzatron procedures .................................................................... 32 2.6.3 Ferrioxalate and Persulfare Actinometry ....................................... 33 2.6.4 Determination of the concenfrntion of 2-pr-opanone ...................... 34 2.6. 5 Determination of formaldehyde ...... ........................................... 35 26.6 Dekv-mination of Hydrogen Peroride ............................................. 36 2.6. 7 O-rygen Concentration Menszrrements ............................................ 37 VERIFICATION OF THE METHOD 38 Chapter Introduction .............................................................. .............. 38 The PT1 Quantacount Apparatus .............................. .......... ..................... 38 3-21 Discrission of possible interferencefrom strlzy light....................... 38 3.2.2 Quantacount conjgzirutionfor H20rphotolysis experirnenfs........ 41 3.2.3 Culibrution of the Qrcuntacormr lamp ............................................. 43 H202Photolysis and the Measurement of Quantum Yields .................... 47 3.3.1 The primury phorochernicul process ............................................... 4: 3.3.2 On the method by which Op is mecmrred: a literutzire revieiv ....... -18 3.3.3 On the irse of 2-propanoi cis a hydro-uyI radical scavenger ............ 54 00.1 Determination using the PT1 Quantacount Apparatus ................... 57 3-41 The reaction rnechunisrn ................................................................. 3; 3-42 Experirnentul resrilts und discussion ............................................... .j9 THE FERRTOXALATE EXPERIMENTS 64 Chapter Introduction ........................ ... .............................................. 64 Mechanistic Studies involving Iron: A Brief Literature Review
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