Rates of OH radical reactions. XII. The reactions of OH with cC3H6, cC5H10, and cC7H14. Correlation of hydroxyl rate constants with bond dissociation energies

✍ Scribed by Gurvinder S. Jolly; George Paraskevopoulos; Donald L. Singleton

• Publisher: John Wiley and Sons
• Year: 1985
• Tongue: English
• Weight: 537 KB
• Volume: 17
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.550170102

✦ Synopsis

Absolute rate constants for H-atom abstraction by OH radicals from cyclopropane, cyclopentane, and cycloheptane have been determined in the gas phase a t 298 K. Hydroxyl radicals were generated by flash photolysis of H,O vapor in the vacuum UV, and monitored by time-resolved resonance absorption a t 308.2 nm [OH(AL87+X'nl. The rate constants in units of cm3 mol-' s a t the 955% confidence limits were as follows: k(c-C3H,) = (3.74 -+ 0.83) x lo'', k(c-C5Hlo) = (3.12 5 0.23) x lo", k(c-C,H,,) = (7.88 5 1.38) x 10". A linear correlation was found to exist between the logarithm of the rate constant per C-H bond and the corresponding bond dissociation energy for several classes of organic compounds with equivalent C-H bonds. The correlation favors a value of D(c-C3H, -H) = (101 -+ 2) kcal mol-'.