Addition of methyl radicals to carbon monoxide: Chemically and thermally activated decomposition of acetyl radicals

✍ Scribed by K. W. Watkins; William W. Word

• Publisher: John Wiley and Sons
• Year: 1974
• Tongue: English
• Weight: 761 KB
• Volume: 6
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.550060608

✦ Synopsis

Abstract

Chemically activated acetyl radicals, with an excitation energy of 78 kJ/mole, were formed by the addition of methyl radicals to carbon monoxide. At 273·K the pressure required to stabilize one half of the excited radicals was 500 torr. From measurements of the acetyl radical yield at pressures in the range of 700–2100 torr, and at temperatures in the range of 260–413 K, extrapolations to infinite pressure yielded kinetic parameters for the addition of methyl radicals to carbon monoxide, and for the thermal decomposition of acetyl radicals. The rate constants were found to be log k[cm^3^ / (mole·s)] = 11.2–25(kJ/mole/2.3) RT, and log k(s^−1^) = 13.5−72 (kJ/mole)/2.3__RT__, respectively. Estimated thermochemical properties of the acetyl radical are ΔH~f~º = −17 kJ/mole and __S__º = 262 J/K°mole.