Reaction of Methyl-d3 Radicals with Isobutane, Isobutane-2-d, and Propane

Journal Article · Mon Jan 01 04:00:00 EST 1962 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.1733349· OSTI ID:4757926

Jackson, W. M.; McNesby, J. R.; Darwent, B. deB.

The relative rates of abstraction by CDsub 3/ radicals of primary, secondary, and tertiary H atoms were measured. Using a standard rate constant for abstraction of D from acetone-d/sub 6/, the following rate constants were obtained: k(mole/sup -1/ cc sec/sup -1/); CD/sub 3/ + CD/sub 3/COCD/sub 3/ yields CD/sub 4/ + CD/sub 2/COCD/sub 3/ = 3.5 X 10/sup 10/T/sup 1/2/ exp (-11 100/RT), CD/sub 3/ + (CH/sub 3/)/sub 3/CD Y CD/sub 4/ + (CH/sub 3/)/sub 3/C =0.88 X 10/sup 10/T/sup 1/2/ exp (-11-9200/RT), CD/sub 3/ + (CH/sub 3/)/sup 3/CD yields CD/sub 3/H + CH/sub 2/ - CD(CH/sub 3/)/sub 2/ = 4.38 x 10/sup 10/Tsup 1/2/ exp ( -11 100/RT), CD/sub 3/ + (CH/sub 3/)/sub 3/CH yields CD/sub 3/H + (CH/sub 3/)/sub 3/C = 0.70 x 1 0/sub 10/T/sup 1/2/ exp (-7600/RT). Isotope effects obtained were, for secondary H and D in propane k/sub H//k/sub D/ = 1.04 exp (1400/RT), and for tertiary H and D in isobutane k/sub H//k/sub D/ = 0.80 exp (1600/RT). The isotope effects are within experimental error of that given by the general expression for the deuterium isotope effect previously proposed k/sub H//k/sub D/ = exp (1500/RT), and are in exceilent correspondence with previous theoretical treatbent.

• Research Organization: Catholic Univ. of America, Washington, D.C.
• Sponsoring Organization: USDOE
• NSA Number: NSA-17-004562
• OSTI ID: 4757926
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 8 Vol. 37; ISSN JCPSA6; ISSN 0021-9606
• Publisher: American Institute of Physics (AIP)
• Country of Publication: Country unknown/Code not available
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ACETONE
BUTANE
CHEMICAL REACTIONS
DEUTERIUM COMPOUNDS
ISOMERS
ISOTOPE EFFECTS
METHYL RADICALS
PROPANE