Arrhenius parameters for the reactions of O(³P) atoms with several aldehydes and the trend in aldehydic C—H bond dissociation energies

Abstract

, 55,3321 (1977). The phase-shift technique has been used to determine the temperature dependence of the reaction of ground state oxygen atoms with several aldehydes. Oxygen atoms were generated by modulated photosensitized decomposition of nitrous oxide and were monitored by the chemiluminescence from their reaction with nitric oxide. The Arrhenius expressions determined over the temperature interval 298-472 K are: k,(acetaldehyde) = (7.21 k 1.49) x lo9 exp (-1960 + 153/RT); kl(propionaldehyde) = (7.78 _+ 0.75) x lo9 exp (-1727 k 66/RT); k,(butyraldehyde) = (9.99 f 0.56) x lo9 exp (-1702 + 40/RT); k,(isobutyraldehyde) = (7.92 + 1.02)

Chemical kinetic data needs for modeling the lower troposphere

“…The most extensive data are those obtained by Singleton et al (1977) for four aldehydes-acetalde hyde, propionaldehyde, n-and iso-butyraldehyde. These workers used a phase shift technique and covered a temperature range of 298-472 K. They re4 ported that at the high end of their temperature range, abstraction of the alky!…”

Role of conformational structures and torsional anharmonicity in controlling chemical reaction rates and relative yields: butanal + HO2reactions

“…In combustion engines, aldehydes are produced as primary pollutants formed by partial oxidation of hydrocarbon fuels. [1][2][3][4][5][6][7] They are also produced by the photo oxidation of hydrocarbons in the tropospheric zone of the earth's atmosphere. Acting as a precursor for free radicals, aldehydes react with OH radicals, which is one of the main initiating steps towards their atmospheric degradation.…”

Environmental effects of large igneous province magmatism: a Siberian perspective

“…O + CH 3 CHO. The recommended k(298 K) is the average of three measurements by Cadle and Powers [215], Mack and Thrush [855], and Singleton et al [1200], which are in good agreement. Cadle and Powers and Singleton et al studied this reaction as a function of temperature between 298 and 475 K and obtained very similar Arrhenius parameters.…”

“…The recommended E/R value was obtained by considering both sets of data. This reaction is known to proceed via H-atom abstraction (Mack and Thrush [855], Avery and Cvetanovic [56], and Singleton et al [1200]). (Table 87 [39], which is the lowest value obtained and therefore perhaps the most accurate.…”