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The Tritium Beta-Ray Induced Reactions in Deuterium Oxide Vapor and Hydrogen Or Carbon Monoxide and the Exchange of H-Atoms with Water Molecules

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The Tritium Beta-Ray Induced Reactions in Deuterium Oxide Vapor and Hydrogen Or Carbon Monoxide and the Exchange of H-Atoms with Water Molecules This dissertation has been microfilmed exactly as received 66-6232 BIBLER, Ned Eugene, 1937- THE TRITIUM BETA-RAY INDUCED REACTIONS IN DEUTERIUM OXIDE VAPOR AND HYDROGEN OR CARBON MONOXIDE AND THE EXCHANGE OF H-ATOMS WITH WATER MOLECULES. The Ohio State University, Ph.D., 1965 Chemistry, physical University Microfilms, Inc., Ann Arbor, Michigan THE TRITIUM 3ETA-RAY INDUCED REACTIONS IN DEUTERIUM OXIDE VAPOR AND HYDROGEN OR CARBON MONOXIDE AND THE EXCHANGE OF H-ATOMS WITH WATER MOLECULES DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By Ned Eugene B ib le r , B .S ., M.S * * * * * The Ohio S ta te U n iversity 1965 Approved by Adviser Department of Chemistry ACKNOWLEDGMENTS Several groups were influential in the completion of this work and the culmination of my graduate career at the Ohio State University. I have singled out two who deserve special acknowledg­ ment. I wish to express my appreciation to the members of my family for their understanding and sympathetic guidance during this demanding period. In particular, I thank my wife, Jane, who was a source of encouragement, for her devotion, scientific advice, and unswervingly honest criticism ; and my mother in law, Mrs. Pauline Pycraft, who typed a major portion of the first draft of this thesis. I am indebted to the stimulating research group headed by Dr. R. F. Firestone for many fruitful discussions and altercations on an array of subjects, including the radiation chemistry of water vapor. Specifically, I thank Dr. Firestone for his keen interest and set of high scientific standards which, when applied to the course and completion of this study, made it a maturing and g r a tify in g experience. VITA July 25, 1937 Born - Bucyrus, Ohio 1959 .... B.S., Denison University, Granville, Ohio 1959 - 1962 . Teaching Assistant, Department of Chemistry, The Ohio State University, Columbus, Ohio 1962 .... M. S., The Ohio State University, Columbus, Ohio 1962 - 1965 . Research Fellow, Department of Chemistry, The Ohio State University, Columbus, Ohio i i i CONTENTS Page ACKNOWLEDGMENTS ................................................................................................ i i VITA................................................................................................................................i i i TABLES . .......................................................................................................v ILLUSTRATIONS ....................................................................................................... v i i Chapter I . INTRODUCTION............................................................................................ 1 I I . HISTORICAL REVIEW ........................................................................... 4 I I I . EXPERIMENTAL APPARATUS AND PROCEDURES ................................. 10 Reagents Apparatus Procedures IV. EXPERIMENTAL RESULTS ....................................................................6 8 Hydrogen:water vapor systems Carbon monoxide:water vapor systems V. DISCUSSION.............................................................................................85 VI. CONCLUSIONS............................................................................................146 BIBLIOGRAPHY . ; ....................................................................................148 TABLES T ab le Page 1. Amount of Impurities Present in the Carbon Monoxide . 11 2. Calibration of the Metering T ube.....................................................22 3. Determination of Vtotal/Vcal T°r ^1 ..... ..................... 33 4. Determination of Vtotal/^cal - Vunk for ..............................35 5. Determination of V3 ................................................................................... 37 6 . Calibration of the Gas Chromatograph Using Deuterium . 41 7. Variation of the Ratio Time .........................................46 8 . Isotopic Ratios in the Calibration Standards ...................... 49 9. Ratio of the Mass 3 Signal to the Mass 2 Signal in H2 . 50 10. Observed Signal Ratios R^ 3 and R/j.^2 an a Mixture of 2.06% HD and 6 x 10"7% D 2 ........................................................................51 11. Pressure Dependence of R2 , 3 anc* ^ 3 , 2 ............................................^ 12. Pressure Dependence of R§?2 a Mixture when the Ratio nH c/nU2 is 0 , 0 2 ...................................................................................................53 13. Dependence of the Sensitivity Ratio H on the Sample Com position ............................... ’ .2 .......................... 54 14. Variation of R^L u w ith Sample Pressure in HD 9 2 Syn thetic M ixture No. 2 . (13% H D )......................................................55 15. Determination of nHE/nH2 *n ExP®riment 49 when the values of R^^ are Pressure Dependent....................................56 16. Comparison of kD 2 pp as Determined by the Equilibrium and Synthetic Mixtures ........................................................................ 58 17. Assay of the Tritium-Water...................................................................62 v TABLES ( c o n td .) T able Page 18. Results of the Mass Spectrometric Determination o f nHD/n H2, nD2/n HD, and 70 19. Values of G(HD), G(D2), G(T) and the Separation Factor Below 245°C 72 20. E ffect o f Temperature Above 266°C on G(HD), G(D2 ), G(T), and the Separation Factor at a Vapor Density of 0.595 m g/m l..............................................................................................75 21. E ffect o f Temperature Above 297°C on G(HD), G(D2 ), G(T) and the Separation Factor a t a Vapor D ensity o f 0.319 mg/ml...................................................................................................... 76 22. Effect of Changing the Mole Fraction of H2 a t 320°C and Vapor Densities of 0.590 m g/m l..................................................78 23. Effect of Changing the Mole Fraction of H2 a t 319°C and Vapor Densities of 0.319 m g/m l..................................................78 24. E ffect o f Changing the Vapor D ensity on G(HD), G(D2 ), G(T) and the Separation F a c t o r............................... 80 25. The Results of an Experiment in which a Large Percentage of Hydrogen was Converted to Hydrogen Deuteride .... ............................................................... 80 26. The Effect of Temperature and the Mole Fraction of CO on G(C02), G(D2), G(T), and the Separation Factor .... 82 27. Mass Spectrum of the Samples Collected at -78°C ..................... 84 28. Values o f G(D)/G(HD) and iA h2 Taken from the Data of Baxendale and G ilbert.......................... 135 29. Comparison of the G Values for the Chain Mechanism at 278°C for the D2 0tH2 and the H20:D2 S y s t e m s.................... 142 v i ILLUSTRATIONS Figure Page 1. Sample Preparation Vacuum System................................................ 13 2. Collection Vacuum System . ............................................................... 14 3 . Io n iza tio n Chamber .................................................................................. 16 4 . Mass Spectrometer I n le t S y s t e m............................................ 18 5. Calibration of the Metering Tube . ........................................ 23 6 . Samplers . ................................................................................................... 27 7. Determination of V totalA cal ............................................................... 34 8 . Determination of VtotalAcal " ^unk.................................................. ^ 9. Chromatograph Calibration . ............................ ...............................42 10. Effect of Time on the Ratio Rhd,H2 * ......................................... ^ 11. Temperature Dependence of G(HD), Vapor D ensity of the Chain Region is 0.595 mg/ml .................................... 94 12. Temperature Dependence of (G(HD)-G(HD)0 ) at Vapor D e n sitie s of 0.319 mg/ml and 0.595 mg/ml ................................ 13. Temperature Dependence of (G(T)-G(T)0) at Vapor D e n sitie s o f 0.319 mg/ml and 0.595 m g / m l.................................. H ° 14. Temperature Dependence of G(D2) and G(C02) in the D2 0 sC0 S y s te m................................................................................................ ^ 2 15. Temperature Dependence of (G(D2 ) - G(D2 )g ) a t a Vapor Density of 0.319 m g/m............................................................. l *2 2 16. Variation of (G(HD) - G(HD)0) with Vapor Density at 319°C . ............................................................................................12 2 17. Yield of HD in the D2OSH2 System. Taken from Baxendale and Gilbert, Disc. Faraday Soc., 36, 295 (1963) .............................................................................................. 1 3 4 v i i ILLUSTRATIONS (con td .) Figure Page 18. Kinetic Analysis of the Data of Baxendale and Gilbert . 134 19. Comparison of G(HD) for the Radiolysis of the D2 0 :H2 and H2 0 :D2 S y ste m s..................................................... 138 20. The Separation Factor at Several Temperatures ........................ 138 v i i i CHAPTER I INTRODUCTION The object of this research was an examination of the chemical reactions induced by ionizing radiation in mixtures of heavy water (D2 O) and hydrogen or carbon monoxide. It has been observed
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