The gas-phase chemistry of butanal, propanal, and acetaldehyde has been investigated using electron bombardment matrix isolation techniques. Each aldehyde was diluted in excess argon gas and subjected to electron bombardment with 300eV electrons. The products of subsequent reaction processes were matrix isolated and analyzed by FTIR absorption spectroscopy. Ionized butanal produced a variety of decomposition products including propane, propene, propyne, ethene, ethyne, CCCO, ketene, formaldehyde, CO, CH2=CHCH2•, CH2CHO•, HCO• and methane. Products resulting from ionized propanal included the ethyl radical, ethane, ethene, ethyne, CO, CH2CHO•, HCO• and methane. In both cases the products are believed to be formed from C—C cleavages of the parent ion followed by hydrogen atom scavenging and/or hydrogen atom abstraction from proximally located species. Dehydrogenation products of propane and ethane are proposed to result from product secondary ionization, a process dependent on high electron currents. Surprisingly, in the case of butanal, the McLafferty Rearrangement, a dominant process in electron ionization mass spectrometry, was not observed to occur.
Electron bombardment of acetaldehyde:Ar mixtures produced many decomposition products including methane, CO, HCO•, CH3CO•, CH2CHO•, CH3• and ketene. The isomerization product, vinyl alcohol, was also observed. As way of investigating the mechanisms of the above products, experiments were performed in which the acetaldehyde:Ar mole ratio was varied. Variations in the acetaldehyde:Ar mole ratio produced dramatic variations in the products formed, demonstrating a transition from unimolecular chemistry at low acetaldehyde mole ratios, to processes consistent with bimolecular processes at intermediate mole ratios. Variations in the total flow rate of gas resulted in nonsystematic changes in product yields but provided further evidence for unimolecular methane formation via the elimination of neutral CO. Finally, an investigation into the mechanism of vinyl alcohol using the acetaldehyde isotopomer, CD3CHO, in conjunction with computational methods provided further evidence that enol formation occurs as a result of a direct 1,3-H-transfer and not consecutive 1,2-H-transfers. / Thesis (Master, Chemistry) -- Queen's University, 2009-06-26 10:51:32.331
| Identifer | oai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:OKQ.1974/1974 |
| Date | 29 June 2009 |
| Creators | WHITE, MATTHEW |
| Contributors | Queen's University (Kingston, Ont.). Theses (Queen's University (Kingston, Ont.)) |
| Source Sets | Library and Archives Canada ETDs Repository / Centre d'archives des thèses électroniques de Bibliothèque et Archives Canada |
| Language | English, English |
| Detected Language | English |
| Type | Thesis |
| Format | 1917813 bytes, application/pdf |
| Rights | This publication is made available by the authority of the copyright owner solely for the purpose of private study and research and may not be copied or reproduced except as permitted by the copyright laws without written authority from the copyright owner. |
| Relation | Canadian theses |
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