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Kinetic Studies on the Gas-Phase Decomposition Of KINETIC STUDIES ON THE GAS-PHASE DECOMPOSITION OF TRIMETHYLBORANE DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University , By JOSEPH ARLAN LOVINGER, B.S. The Ohio State University 1959 Approved by Adviser Department of Chemistry ACKNOWLEDGMENT The author wishes to acknowledge the guidance and suggestions of Professor Frank Verhoek during the course of this study. The author gratefully acknowledges the financial assistance afforded hy the University Grants-in-Aid, the DuPont Research Grants-in-Aid, and the General Electric Company for the General Electric Fellowship. CONTENTS Page Part I. THE "TOLUENE CARRIER" TECHNIQUE I. INTRODUCTION ......................................... 2 II. APPARATUS AND TECHNIQUES............................. 1+ The Furnace....................................... U The Reaction System ............................... 7 Chemicals .’ ....................... 9 Procedure......................................... II Analysis of Methane and H y d r o g e n .................. 13 Low Temperature B a t h s ............................. lU III. RESULTS.............................................. 15 Preliminary Experiments ........................... 15 The Effect of Pre-pyrolysis on the Decomposition of Toluene ..... ......................... 17 Reaction of Trimethylhorane and Toluene ............ 23 Effect of the Wall on the Pyrolysis of Toluene . 23 IV. DISCUSSION.......................................... 27 Part II. STATIC PYROLYSIS OF TRIMETHYLBORANE V. INTRODUCTION......................................... 30 VI. APPARATUS AND TECHNIQUES............................. 31 The Furnace....................................... 31 The Reaction S y s t e m ........................... 32 Chemicals......................................... 35 Gas Chromatography............................... 36 Procedure......................................... 37 Analysis of Products ............................. ^2 E r r o r s ........................................... ^ VII. R E S U L T S ............................................ ^7 iii iv CONTENTS (contd.) Page Trimethylborane................................... kj Trimethylborane and Propylene ...................... 7^ Trimethylborane and E t h y l e n e ...................... 79 Trimethylborane and Azomethane .................... 82 Trimethylborane and Nitric Oxide .................. 8j VIII. DISCUSSION.......................................... 91 O r d e r ............................................. 91 Activation En e r g y..................... 93 Stoichiometry....................... 95 Mechanism......................................... 101 IX. S U M M A R Y ............................................. 120 X. SUGGESTIONS FOR FUTURE WO R K .......................... 122 Appendix A ................................................. 125 Appendix B ................................................. 131 Appendix C ..................................... 138 Bibliography ............................................... 1^5 Autobiography ............................................... 1^7 LIST OF TABLES Table Page 1. Low Temperature B a t h s ................................ ].L 2. Data for Preliminary Experiments for the Reaction of Trimethylborane and Toluene .......... 16 3. Analysis of Condensable Material from Experiment 15 . l8 Conditions for the Pre-pyrolysis of Toluene.......... 20 5. Data for the Pyrolysis of Toluene.................... 21 6 . Data for the Pyrolysis of Trimethylborane and Toluene . 2k 7. Effect of the Wall Coating on the Pyrolysis of Toluene. 25 8. Pyrolysis of 2L-2.6 Micromoles of Trimethylborane at L68° C ......................................... 5^ 9. Pyrolysis of 97-3 Micromoles of Trimethylborane at L88° C ......................................... 55 10. Pyrolysis of 175*1 Micromoles of Trimethylborane at L8 8 ° C ......................................... 56 11. Pyrolysis of 2^3.^ Micromoles of Trimethylborane at k 8 Q ° C ........... 57 12. Pyrolysis of 2kk.7 Micromoles of Trimethylborane at lf-98°C................... 58 13. Pyrolysis of 95.6 Micromoles of Trimethylborane at 5 0 8 ° C ......................................... 59 v Vi LIST OF TABLES (contd.) Table Page ]A. Pyrolysis of 239-9 Micromoles of Trimethylborane at 508°C . ........ -....................... 60 1 5 . Pyrolysis of Trimethylborane in the 229-5 cc Packed Quartz Flask at U8 8°C 70 1 6 . Pyrolysis of Trimethylborane in the 229-5 cc Packed Quartz Flask at 50 8 ° C .......................... 71 17. The Effect of a Fresh Wall Coating on the Pyrolysis of Trimethylborane at W 3 8 ° C ................... 73 18. Experiment 21-11. Pyrolysis of Propylene at ^88°C . 7h 1 9. Pyrolysis of a 1:1 Trimethylborane-Propylene Mixture at kQQ°C . ..................................... 77 20. Pyrolysis of Trimethylborane and Ethylene at U88°C . 79 21. Pyrolysis of Trimethylborane and Azomethane in a 110 cc Quartz F l a s k ................................... 83 22. Pyrolysis of Trimethylborane in the Presence of Nitric Oxide at 1+88°C................................. 88 2 3 . Data for the Order Dependence of Trimethylborane . 92 2k. Pyrolysis of Trimethylborane at if37°C by Goubeau and E p p l e .............. .......................... 101 25. Mass Spectra........................................ 135 LIST OF FIGURES Figure Page 1. High Temperature Core Furnace for the Flow System . 5 2. Temperature Distribution of the Core F u r n a c e ........ 6 3. Vacuum System - "Toluene Carrier" Experiments ........ 8 1+. Automatic Toepler Pump and Controls................. 10 5 . Arrhenius Plot for the Pyrolysis of Toluene.......... 22 6. Reaction System for the Static P y r o l y s i s ............ 33 7 . Pressure-Time Curves for Some Preliminary Experiments . L8 8. Pressure-Time Curves Showing the Effect of Adding Air to the Reactor Between Experiments.......... 50 9 . Pressure-Time Curves Showing Apparent Irreproducxbility at 1j8 8 ° C ....................................... 51 10. Relationship Between the Observed Pressure Increase and the Moles of Trimethylborane Reacted........ 53 11. Change in Composition for the Pyrolysis of 2^2.6 Micromoles (97*1 mm-) of Trimethylborane at L-68°C. 63 12. Change in Composition for the Pyrolysis of 97-3 Micromoles (^0.7 mm.) of Trimethylborane at L88°C. 6h 1 3 . Change in Composition for the Pyrolysis of 175*1 Micromoles (72.6 mm.) of Trimethylborane at L8S8°C. 65 lL. Change in Composition for the Pyrolysis of 2L3 A Micromoles (101.7 mm.) of Trimethylborane at L88°C 66 15. Change in Composition for the Pyrolysis of 2kb.J Micromoles (102.2 mm.) of Trimethylborane at L98°C 67 16. Change in Composition for the Pyrolysis of 95.6 Micromoles (lj-0.6 mm.) of Trimethylborane at 508°C. 68 vii LIST OF FIGURES (contd.) Figure Page 17. Change in Composition for the Pyrolysis of 239-9 Micromoles (102.7 mm.) of Trimethylborane at 508°C 69 18. Comparison of the Decomposition of Trimethylborane Alone and in a 1:1 Mixture with Propylene at L88°C . ..................................... 76 19. The Effect of Added Substances on the Pyrolysis of Trimethylborane............................... 80 20. Falling-Off of the Rate Constant for Azomethane Ramsperger (20) - . 85 21. Activation Energy for the Pyrolysis of Trimethylborane. 9k 22. Stoichiometry Curves for Hydrogen Formation.......... 97 23. Stoichiometry Curves for Methane F o r m a t i o n .......... 98 2k. Tetra-B-methylcyclo-l,3>5>7 boroctane ................ 99 PART I TEE "TOLUENE CARRIER" TECHNIQUE 1 I. INTRODUCTION This portion of the work is concerned with attempts to determine the kinetic bond energy of the boron-carbon bond in tri­ methylborane by use of the "toluene carrier" technique developed by Szwarc (l) . In this method the compound under study is mixed with a large excess of toluene and the mixed gases passed through a reactor in a flow system. At the high temperatures at which this method is used, the toluene acts as an excellent radical trap. Thus if a methyl radical is formed it reacts with toluene to give methane and the benzyl radical which is a stable radical at high temperatures and will not undergo any radical reactions except recombination after leaving the reactor. Therefore there can be no radical chain reactions occurring. The activation energy of the reaction is equated to the kinetic bond energy of the first bond broken. The "toluene carrier" technique has been applied to the study of the decomposition of dimethylmercury (2 ,3) and dimethyl- cadmium (3). The mechanisms for these decompositions are similar; that for dimethylmercury (2) is as follows: Hg(CH3) 2 - HgCH3 ♦ CH3 (1) HgCH3 - Hg + CH3 (2) CH3 + CgH5CE3 s 0% ♦ CgH5CH2 (3) 3 CH3 ♦ CH3 = CgHg (h) C6 H5 CH2 + C6 H5CH2 = (c6 h5 ch2) 2 (5) There have been many estimates of the average bond energy of the boron-carbon bond in trimethylborane, mostly from thermodynamic data. These include 8 9.0, 70, 80 and 59 Kcal/mole (^,5,6,7)* It should be noted that these are the average bond energies for the breaking of all three bonds, i.e., for the reaction i B'CE3>3 ■ 3 E + aH3- As is true for other compounds of this type the kinetic bond energy for the reaction b(ch3) 3 = b(ch3) 2 + ch3 will be larger than the average bond energy. This value has been estimated as 107 Kcal/mole (6 ). II. APPARATUS AND TECHNIQUES The Furnace The furnace is shown in Figure 1. It consists of a 30" long Alundum Electric Furnace Core, manufactured by the Norton Company, Worcester, Mass., with
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