The Kinetics of the reactions involving alkyl and silyl hydrides were studied by the flash photolysis / resonance fluorescence technique. The reactions of alkyl radicals (R = C₂H₅, i-C₃H₇, t-C₄H₉) with HBr have been studied at room temperature and the rate constants obtained (units are in cm³ s^-1 ) are: k₃.₃ = (7.01 ± 0.15) x 10^-12, k₃.₂ = (1.25 ± 0.06) x 10^-11, k₃.₁ = (2.67 ± 0.13) x 10^-11 These results, combined with previously determined reverse rate constants and other kinetic information, yield bond dissociation enthalpies (units in kJ mol^-1) at 298 K : primary C-H in C₂H₅-H (423.6 ± 2), secondary C-H in i-C₃H₇-H (409.9 ± 2), tertiary C-H in t-C₄H₉-H (405.1 ± 2). These rate constants and bond energies are in good agreement with previous results.
| Identifer | oai:union.ndltd.org:unt.edu/info:ark/67531/metadc277864 |
| Date | 08 1900 |
| Creators | Yuan, Jessie (Jessie Win-Jae) |
| Contributors | Marshall, Paul, 1960-, Schwartz, Martin, Acree, William E. (William Eugene), Melton, Lynn A., Richmond, Michael G. |
| Publisher | University of North Texas |
| Source Sets | University of North Texas |
| Language | English |
| Detected Language | English |
| Type | Thesis or Dissertation |
| Format | ix, 125 leaves : ill., Text |
| Rights | Public, Copyright, Copyright is held by the author, unless otherwise noted. All rights reserved., Yuan, Jessie (Jessie Win-Jae) |
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