Reactions of O(3P) with secondary C-H bonds of saturated hydrocarbons in nonequilibrium plasmas

Patiño, Pedro; Hernández, Florencio E.; Rondon, Sonia

doi:10.1007/bf01459694

Cited by 24 publications

(19 citation statements)

References 16 publications

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“…The vapor pressure (vp) for each of them at the particular working temperature is given. In agreement with previous works, ,− the ratio p (O 2 )/vp is higher than 20. This guarantees that the amount of hydrocarbon molecules in the gas phase is low enough to preclude homogeneous gas-phase reactions to take place.…”

Section: Resultssupporting

confidence: 93%

“…Under certain conditions, electrical discharges through molecular oxygen produce predominantly O( 3 P) atoms. These species in turn react with liquid organic compounds. − At short to moderate times alkenes produce epoxides and carbonyl compounds. Monoalkyl benzenes produce phenols, in the order ortho > para > meta .…”

Section: Introductionmentioning

confidence: 99%

“…To understand the role of this fraction of the mixture in the reactions that take place in such treatment and those of two more fuels to be presented in this paper, the objective of this investigation is to fully analyze the reactions of eight model cycloalkanes with the same plasmas. Despite results for the reactions of O( 3 P) with aromatic compounds, olefins and noncyclic alkanes have been reported, − no study had been published on the oxidation of naphthenic compounds.…”

Section: Introductionmentioning

confidence: 99%

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Oxidation of Cycloalkanes and Diesel Fuels by Means of Oxygen Low Pressure Plasmas

et al. 2002

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Oxidation of eight liquid cycloalkanes and two diesel fuels has been studied by using a low pressure high voltage oxygen plasma. Naphthenes were individually oxidized to alcohols and ketones, O( 3 P) being the active species in the plasma. Tertiary C-H bonds were the most reactive. At long treatment times the main products suffered successive oxidation to produce two oxygenated groups in the same molecule. cis-Decaline was four times more reactive than transdecaline. For this two isomers and bicyclohexyl the conversions were the lowest, the yield of the tertiary carbon being between 40 and 80% of the total. Methyl-, ethyl-, and n-propylcyclohexane gave similar results. The reactivity of the two tertiary carbons of iso-propylcyclohexane amounted to c.a. 80%. This compound was the most reactive. Due to steric effects of the alkyl group, tertbutylcyclohexane showed low reactivity. Addition of 4.7-7.0 wt % of oxygen to the diesel fuels has been achieved in one-step process with the plasma.

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Section: Resultssupporting

confidence: 93%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Oxidation of Cycloalkanes and Diesel Fuels by Means of Oxygen Low Pressure Plasmas

et al. 2002

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“…A final point of discussion involves the possible role of intersystem crossing from O( 3 P) to O( 1 D) in the C−C bond-breaking channel. Triplet−singlet intersystem crossing has been reported in studies of O( 3 P) reactions with CH 3 I, cyclohexane clusters, organized organic thin films, and liquid saturated hydrocarbons . The importance of intersystem crossing varies with reactants and with collision energy, increasing with the longer residence times that reactants spend in the crossing region and decreasing with higher collision energies.…”

Section: Discussionmentioning

confidence: 96%

Hyperthermal Reactions of O and O₂ with a Hydrocarbon Surface: Direct C−C Bond Breakage by O and H-Atom Abstraction by O₂

et al. 2006

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A C-C bond-breaking reaction has been observed when a beam containing hyperthermal oxygen was directed at a continuously refreshed saturated hydrocarbon liquid (squalane) surface. The dynamics of this C-C bond-breaking reaction have been investigated by monitoring time-of-flight and angular distributions of the volatile product, OCH3 or H2CO. The primary product is believed to be the methoxy radical, OCH3, but if this radical is highly internally excited, then it may undergo secondary dissociation to form formaldehyde, H2CO. Either the primary or the secondary product may scatter directly into the gas phase before thermal equilibrium with the surface is reached, or they may become trapped on the surface and desorb in thermal equilibrium with the surface. Direct, single-collision scattering events that produce a C-C bond-breaking product are described with a kinematic picture that allows the determination of the effective surface mass encountered by an incident O atom, the atom-surface collision energy in the center-of-mass frame, and the fraction of the center-of-mass collision energy that goes into translation of the scattered gaseous product and the recoiling surface fragment. The dynamical behavior of the C-C bond-breaking reaction is compared with that of the H-atom abstraction reaction, which was the subject of an earlier study. Another reaction, H-atom abstraction by O2 (which is present in the hyperthermal beam), has also been observed, and the dynamics of this reaction are compared with the inelastic scattering dynamics of O2 and the dynamics of H-atom abstraction by O. The dynamics involving direct inelastic and reactive scattering of O2 are also described in terms of a kinematic picture where the incident O2 molecule is viewed as interacting with a local region of the surface.

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“…Intersystem crossing between singlet and triplet surfaces may lead to apparent abstraction reactions for O(1D) and insertion reactions for O(3P). Naaman and coworkers have proposed a singlet-to-triplet crossing mechanism to explain the observation of some of the OH products in reactions of O(1D) with small clusters of and Likewise, a tripletÈsinglet crossing mechanism can explain CH 4 product detected in a crossed-beams study of the reaction of O(3P) with cyclohexane clusters.20 Further evidence for tripletÈsinglet crossing to form an insertion product comes from Patin8 o et al, who reported that reactions of liquid saturated hydrocarbons with O(3P) in an oxygen plasma yield secondary alcohols and ketones 21.…”

mentioning

confidence: 96%

Reactive scattering of ground-state and electronically excited oxygen atoms on a liquid hydrocarbon surface

Garton¹,

Minton²,

Alagia³

et al. 1997

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108

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Reactions of O(3P) with secondary C-H bonds of saturated hydrocarbons in nonequilibrium plasmas

Cited by 24 publications

References 16 publications

Oxidation of Cycloalkanes and Diesel Fuels by Means of Oxygen Low Pressure Plasmas

Oxidation of Cycloalkanes and Diesel Fuels by Means of Oxygen Low Pressure Plasmas

Hyperthermal Reactions of O and O₂ with a Hydrocarbon Surface: Direct C−C Bond Breakage by O and H-Atom Abstraction by O₂

Reactive scattering of ground-state and electronically excited oxygen atoms on a liquid hydrocarbon surface

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Reactions of O(3P) with secondary C-H bonds of saturated hydrocarbons in nonequilibrium plasmas

Cited by 24 publications

References 16 publications

Oxidation of Cycloalkanes and Diesel Fuels by Means of Oxygen Low Pressure Plasmas

Oxidation of Cycloalkanes and Diesel Fuels by Means of Oxygen Low Pressure Plasmas

Hyperthermal Reactions of O and O2 with a Hydrocarbon Surface: Direct C−C Bond Breakage by O and H-Atom Abstraction by O2

Reactive scattering of ground-state and electronically excited oxygen atoms on a liquid hydrocarbon surface

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Hyperthermal Reactions of O and O₂ with a Hydrocarbon Surface: Direct C−C Bond Breakage by O and H-Atom Abstraction by O₂