Acetaldehyde autoxidation. I. Products of termination

Clinton, Nye A.; Kenley, Richard A.; Traylor, Teddy G.

doi:10.1021/ja00846a031

Cited by 41 publications

(33 citation statements)

References 8 publications

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“…and not self-reaction, since y did not depend on [PA]. This is in contrast to the results of Clinton et al, [1975] and Kenley and Traylor [1975] where it was concluded that PA self reaction was rapid, but no rates were measured. There is one study of the reactions of PA radicals with reducing agents or compounds that can be thought of as analogs for biochemical species [Schuchmann and von Sonntag, 1988].…”

Section: August 25-29 Periodmentioning

confidence: 99%

Episodic removal of NO_y species from the marine boundary layer over the North Atlantic

et al. 1996

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Measurements of ozone, carbon monoxide, NOy, NOx, HNO3, particulate NO3−, PAN, PPN, and alkyl nitrates were made at Chebogue Point, Nova Scotia, during July, August, and September 1993, and measurements of ozone, carbon monoxide, NOx and N0y were made at Sable Island, Nova Scotia, during August and September 1993 as part of the North Atlantic Regional Experiment (NARE). Periods of photochemical pollution were observed during which concentrations of the above species were elevated relative to average conditions. The best indicator of the extent of impact was found to be the sum of the C1‐C4 alkyl nitrates. The removal of PAN and PPN by fog droplets through thermal decomposition and subsequent uptake of the peroxyacetyl and peroxypropionyl radicals (PA and PP) was suggested by loss of PAN and PPN during fog. The effect of this chemistry on NOy species in the marine environment will need to be considered. The loss of inorganic nitrate (HNO3 and particulate NO3−), PAN (and to a minor extent PPN) resulted in deviation of the O3 versus NOy‐NOx correlations from that observed in eastern North America.

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Section: August 25-29 Periodmentioning

confidence: 99%

Episodic removal of NO_y species from the marine boundary layer over the North Atlantic

et al. 1996

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“…It was observed that the dissqlved oxygen molecules combined with the free radical CH,CO at a fast rate to form the free radical cH~CO;. Traylor and co-workers (18) found that several products, as well as several reaction steps, were included in the termination step involving CH?CO; free radicals.…”

Section: Discussionmentioning

confidence: 99%

Effect of interface mass transfer on the liquid-phase oxidation of acetaldehyde

Chou¹,

Lin²

1983

Can. J. Chem.

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Partial oxidation of acetaldehyde by oxygen in the liquid phase was studied in the temperature range from −10 °C to 34 °C, oxygen flow rate from 90 to 100 mL/min, concentration of acetaldehyde from 3.0 to 34.0 volume percent, and at different partial pressures of oxygen. Cobalt acetate was used as catalyst. It was found that the reaction rate was governed by two types of rate equations depending on the operating conditions as well as the loading of catalyst.In the region of higher oxygen mass transfer, the rate[Formula: see text]where K1 = 6.9 × 10−3 L mol−1 s−1 at the temperature −10 °C.In other conditions,[Formula: see text]where k2 = 5.7 × 10−4 mol L−1 atm−1 s−1, and is a pseudo rate constant which depends on the dispersion of oxygen in the reactor. The experimental results appeared to support a theoretical analysis. The key reaction steps of the reaction mechanisms were also identified.

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“…28- 30 The oxidation products of aldehydes formed from ethers 1, 3, and 7 are volatiles hardly detect able by standard analytical methods. This explains a dis advantage of the reaction products for the calculation of the material balance.…”

Section: Methodsmentioning

confidence: 99%

Oxidation of ethers with dimethyldioxirane

2005

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Oxidation of a series of tert butyl ethers Bu t OR (R = Me, Et, CH 2 CH 2 Cl, Pr i , Bu i ), diethyl ether, diisopropyl ether, 1,2 dimethoxyethane, diisobutoxymethane, 1,4 dioxane, and tetra hydrofuran with dimethyldioxirane (DMDO) was studied. The reaction kinetics obeys the second order equation w = k[DMDO] [ether]. The rate constants in a range of 5-50 °C and the activation parameters of the reaction were determined. The solvent effect on the oxidation rate was studied. The oxidation products are the corresponding alcohols and carbonyl com pounds. The competition between the nonradical (oxygen insertion) and radical mechanisms of the reaction is discussed. The reactions of the parent dioxirane and DMDO with a series of methyl ethers MeOR´ (R´ = Me, Et, CH 2 CH 2 F, Pr i ) were studied by the density functional theory (DFT). The (U)B3LYP 6 311G(d,p) method was employed to calculate the geometry and energies of the reactants and transition states. The data obtained indicate a possible increase in the probability of oxidation via the radical route and an increase in the activation barrier for the substrates containing electron withdrawing substituents.The chemistry of dioxiranes was under intense devel opment for the last two decades. 1,2 A distinctive feature of these cyclic peroxides is a combination of high reactivity and selectivity of oxidation reactions. 3 The works con cerning the oxidation of ethers with dioxiranes are few and, as rule, synthetic. For instance, the transformation of steroid ethers to the corresponding ketones was stud ied. 4 The oxidation of O isopropylidene diol derivatives to 2 hydroxyketones and the oxidation of benzyl ethers were studied, 5,6 and a nonradical nature was postulated for these reactions. The oxidation of 1,3 dihydroiso benzofuran with dimethyldioxirane (DMDO) to 2 hydr oxymethylbenzaldehyde was assumed 7 to involve radi cals; however, the total composition of the products was not reported. The study 8 of the reaction products of dialkyl ethers with dioxiranes suggested the radical nature of this reaction, which has been developed further. 9,10 The study 10 of the products and kinetics of oxidation of ethers with DMDO concluded the competition of two processes: insertion of the oxygen atom at the C-H bond of the substrate and hydrogen atom abstraction followed by fast recombination of the radical pair that formed. The effect of oxygen on the yield of the products and conversion of the substrate were demonstrated for para substituted ana logs of 1 methoxy 1 phenylethane. Analysis of the ki netic data in the framework of the Hammett equation gives ρ = -0.74±0.03 (25 °C). 10 However, the mecha nism of oxidation of different ethers was not studied sys tematically. We have previously 11,12 shown that C-H bonds of alkanes and alcohols are oxidized with DMDO via two parallel channels, nonradical and homolytic. The ratio of these processes was determined. In the present work, we studied the products and kinetics of the reac tions of DMDO with aliphatic ethers 1-12 and the influ e...

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Acetaldehyde autoxidation. I. Products of termination

Cited by 41 publications

References 8 publications

Episodic removal of NO_y species from the marine boundary layer over the North Atlantic

Episodic removal of NO_y species from the marine boundary layer over the North Atlantic

Effect of interface mass transfer on the liquid-phase oxidation of acetaldehyde

Oxidation of ethers with dimethyldioxirane

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Acetaldehyde autoxidation. I. Products of termination

Cited by 41 publications

References 8 publications

Episodic removal of NOy species from the marine boundary layer over the North Atlantic

Episodic removal of NOy species from the marine boundary layer over the North Atlantic

Effect of interface mass transfer on the liquid-phase oxidation of acetaldehyde

Oxidation of ethers with dimethyldioxirane

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Product

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About

Episodic removal of NO_y species from the marine boundary layer over the North Atlantic

Episodic removal of NO_y species from the marine boundary layer over the North Atlantic