Liquid-phase autoxidation of organic compounds at elevated temperatures. 2. Kinetics and mechanisms of the formation of cleavage products in n-hexadecane autoxidation

Jensen, R. K.; Korček, Š.; Mahoney, L. R.; Zinbo, M.

doi:10.1021/ja00397a026

Cited by 106 publications

(84 citation statements)

References 2 publications

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“…The reaction techniques, analytical procedures, and materials used to prepare and analyze samples of oxidized hexadecane were described previously [3,4]. The batch reactor design and procedure used in inhibition studies were also previously described [6].…”

Section: Methodsmentioning

confidence: 99%

Initiation in hydrocarbon autoxidation at elevated temperatures

Jensen

Korček

Zinbo

et al. 1990

Int J of Chemical Kinetics

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Kinetic and mechanistic investigations of liquid phase autcxidation of hexadecane at 120 to 190°C have shown that, in the early stages of oxidation, the initiation process involves homolytic decomposition of hydroperoxides. The values of a composite first order rate constant for this decomposition, k l , have been determined in stirred flow reactor experiments from the rate of formation of termination products and in batch reactor studies using inhibitor methods.Arrhenius parameters derived from these studies (log (A/s-') = 8.5 and E, = 26 kcal mol-') allow calculation of k l as a function of temperature. This permits determination of the rate of initiation as a function of hydroperoxide concentration and facilitates determination of absolute rate constants for other oxidation reactions occurring in this system.

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Section: Methodsmentioning

confidence: 99%

Initiation in hydrocarbon autoxidation at elevated temperatures

Jensen

Korček

Zinbo

et al. 1990

Int J of Chemical Kinetics

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“…The appearance of carbonic acid might be explained by a decomposition mechanism which was postulated by Korcek and coworkers. [89][90][91][92][93] This mechanism involves the decomposition of the keto-hydroperoxide via a cyclic intermediate forming an acid and another carbonyl species. 94 In the case of DME two decomposition pathways are conceivable (depicted in Fig.…”

Section: Detection Of Performic Acid [Hc(o)ooh] and Carbonic Acid [Homentioning

confidence: 99%

Detection and Identification of the Keto-Hydroperoxide (HOOCH₂OCHO) and Other Intermediates during Low-Temperature Oxidation of Dimethyl Ether

et al. 2015

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In this paper we report the detection and identification of the keto-hydroperoxide (hydroperoxymethyl formate, HPMF, HOOCH 2 OCHO) and other partially oxidized intermediate species arising from the low-temperature (540 K) oxidation of dimethyl ether (DME). These observations were made possible by coupling a jet-stirred reactor with molecular-beam sampling capabilities, operated near atmospheric pressure, to a reflectron time-of-flight mass spectrometer that employs single-photon ionization via tunable synchrotron-generated vacuum-ultraviolet radiation. Based on experimentally observed ionization thresholds and fragmentation appearance energies, interpreted with the aid of ab initio calculations, we have identified HPMF and its

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“…oxygen consumption, to a point where it is difficult to maintain molecular oxygen saturation in the liquid. 176 If this occurs, the reaction rate becomes controlled by the rate of oxygen mass transfer rather than the catalytic oxidation process itself. If a metal is also present, this may render kinetic interpretations of the results of such experiments meaningless.…”

Section: Characterization Of the Reaction Products In Autoxidation Prmentioning

confidence: 99%

Catalytic oxygen activation versus autoxidation for industrial applications: a physicochemical approach

Liu

Ryabenkova

Conte

2015

Phys. Chem. Chem. Phys.

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The activation and use of oxygen for the oxidation and functionalization of organic substrates is among the most important reactions in a chemist's toolbox. Nevertheless, despite the vast literature on catalytic oxidation, the phenomenon of autoxidation, an ever-present background reaction that occurs in virtually every oxidation process, is often neglected. In contrast, autoxidation can affect the selectivity to a desired product, to those dictated by pure freeradical chain pathways, thus affecting the activity of any catalyst used to carry out a reaction.This critical review compares catalytic oxidation routes by transition metals versus autoxidation, particularly focusing on the industrial context, where highly selective and "green" processes are needed. Furthermore, the application of useful tests to discriminate between different oxygen activation routes, especially in the area of hydrocarbon oxidation, with the aim of an enhanced catalyst design, is described and discussed. In fact, one of the major targets of selective oxidation is the use of molecular oxygen as ultimate oxidant, combined with the development of catalysts capable to perform the catalytic cycle in a real energy and cost effective manner on a large scale. To achieve this goal, insights from metallo-proteins that could find application in some areas of industrial catalysis are presented, as well as considering the physicochemical principles that are at the fundament of oxidation and autoxidation processes.3

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Liquid-phase autoxidation of organic compounds at elevated temperatures. 2. Kinetics and mechanisms of the formation of cleavage products in n-hexadecane autoxidation

Cited by 106 publications

References 2 publications

Initiation in hydrocarbon autoxidation at elevated temperatures

Initiation in hydrocarbon autoxidation at elevated temperatures

Detection and Identification of the Keto-Hydroperoxide (HOOCH₂OCHO) and Other Intermediates during Low-Temperature Oxidation of Dimethyl Ether

Catalytic oxygen activation versus autoxidation for industrial applications: a physicochemical approach

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Liquid-phase autoxidation of organic compounds at elevated temperatures. 2. Kinetics and mechanisms of the formation of cleavage products in n-hexadecane autoxidation

Cited by 106 publications

References 2 publications

Initiation in hydrocarbon autoxidation at elevated temperatures

Initiation in hydrocarbon autoxidation at elevated temperatures

Detection and Identification of the Keto-Hydroperoxide (HOOCH2OCHO) and Other Intermediates during Low-Temperature Oxidation of Dimethyl Ether

Catalytic oxygen activation versus autoxidation for industrial applications: a physicochemical approach

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Product

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About

Detection and Identification of the Keto-Hydroperoxide (HOOCH₂OCHO) and Other Intermediates during Low-Temperature Oxidation of Dimethyl Ether