Kinetic Studies on the Reactions of Hydroxyl Radicals with Cyclic Ethers and Aliphatic Diethers

Moriarty, Jennie; Sidebottom, Howard; Wenger, John C.; Mellouki, Abdelwahid; Bras, G. Le

doi:10.1021/jp061536v

Cited by 9 publications

(13 citation statements)

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“…In the case of the highly reactive hydroxyl radical, this distinction is blurred, and the cyclic and acyclic ethers have comparable reactivities. 57,58 For diethyl ether, abstraction of a secondary H atom leads to the formation of 1-ethoxyethanol, C 2 H 5 OCH(OH)CH 3 , and O 2 ( 1 Δ g ). The former was probably observed during a study of the atmospheric oxidation of diethyl ether initiated by chlorine atom, but the author could not be certain.…”

Section: ■ Resultsmentioning

confidence: 99%

“…Their rates of reactions with hydroxyl radical, for example, have been extensively studied. 7 We are concerned here with their reactivity toward ozone O 3 (X 1 A 1 ), and although ozone is present in the troposphere, the highest concentrations are to be found in heavily polluted urban areas where solvent spills might reasonably be expected to occur.…”

Section: ■ Introductionmentioning

confidence: 99%

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H-Atom Abstraction Reactions by Ground-State Ozone from Saturated Oxygenates

Würmel

Simmie

2017

J. Phys. Chem. A

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Theoretical insights into H-abstraction by ozone from saturated species have been virtually nonexistent, in sharp contrast to the situation for reactions with unsaturated species. Our computed rate constants for reactions with tetrahydrofuran and its methyl derivatives, obtained at various levels of theory, show that abstraction occurs primarily at the carbons situated beside the heterocyclic oxygen, with least likely reaction from the methyl groups. All of the methods tested are in broad relative agreement with this conclusion and with recent experiments although they do differ widely in terms of their absolute values. Abstraction leads variously to the formation of hydrotrioxides, ROOOH, or more directly to R-OH + O(Δ). To understand some of the observed behaviors, dimethyl and diethyl acyclic ethers, methyl and ethyl hydroperoxides, and the alcohols methanol and ethanol were also included in this study. For the simplest system, CHOH + O → HC═O + HO, an all-electron scalar relativistic CCSD(T)/CBS approach yields a barrier height that differs by >5 kJ mol when an additional multireference treatment up to CCSDT(Q) is considered.

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Section: ■ Resultsmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

H-Atom Abstraction Reactions by Ground-State Ozone from Saturated Oxygenates

Würmel

Simmie

2017

J. Phys. Chem. A

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“…The chemical oxygen demand (COD), biochemical oxygen demand (BOD), total nitrogen and total phosphorus concentrations were 528 mg/L, 127 mg/L, 25 mgN/L and 1.7 mgP/L, respectively. We added 1,4-dioxane as a ·OH probe, because it shows high reactivity with ·OH (Moriarty et al, 2003) and low reactivity with ozone (Hoigné and Bader, 1983). The pH of the wastewater was adjusted by the addition of adequate portions of 1 M sulfuric acid or 1 M sodium hydroxide.…”

Section: Introductionmentioning

confidence: 99%

Catalytic Effect of Several Iron Species on Ozonation

Kishimoto

Ueno

2012

J. of Wat. ^|^ Envir. Tech.

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“…As is shown in Figure 3, the formation of carbon monoxide derives from two additions with oxygen, it is why it is so significantly favored in lean mixtures. The rapid atmospheric degradation (Moriarty et al, 2003) of heavy low-temperature oxidation species could lead to the formation of toxic oxygenated products, such aldehydes. The reduced formation of these heavy species under lean conditions is a good point to promote the developments of cleaner advanced internal combustion engine strategies based on the use of low fuel/air ratio (Dec, 2009).…”

Section: Influence Of the Equivalence Ratio On Reactivity And Productmentioning

confidence: 99%

Comparison study of the gas-phase oxidation of alkylbenzenes and alkylcyclohexanes

Herbinet

Husson

Gall

et al. 2015

Chemical Engineering Science

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International audienceThe goal of this paper is to present new experimental results obtained during the study of the gas phase oxidation of ethyl-benzene, n-hexyl-benzene, ethyl-cyclohexane and n-butyl-cyclohexane which belongs to two molecule families present in diesel fuels: alkylbenzenes and alkylcyclohexanes. Experiments were carried out in a jet-stirred reactor over the temperature range 550–1100 K. The new results have been compared with existing literature data obtained for alkylbenzenes and alkylcyclohexanes with alkyl chains of different size to highlight the influence of the chain size on the reactivity. The comparison showed that both alkylcyclohexanes exhibit reactivity at both low-and high-temperatures such as cyclohexane and that the reactivity was similar whatever the size of the alkyl chain. For the three compared alkylbenzenes, important differences were observed in the reactivity at low-temperature: ethylbenzene started to react only above 750 K, while other compounds reacted from 550 K. The comparison also showed that alkylbenzenes were less reactive than their alkylcyclohexane homologs and that the production of aromatic compounds known to promote soot formation was also significantly larger for alkylbenzenes. This paper also presents the effect of the equivalence ratio and pressure on the reaction kinetics. In a general manner, a decrease of the fuel/air ratio significantly increased the reactivity and the carbon monoxide selectivity below 800 K, but decreased the selectivity of heavy oxygenated products, the atmospheric degradation of which can be a source of toxic oxygenated products. This decrease had a more limited effect on the reactivity at higher temperatures but disfavored the production of unburned species (oxygenated species like acetaldehyde and unsaturated hydrocarbons which are known to be soot precursors). A pressure increase from 1 to 10 bar enhanced the reactivity of all these hydrocarbons over the full studied temperature range, with a start of the reaction at lower temperatures. A larger production of toxic oxygenated products was observed with increasing pressures, while low pressures promoted the formation of soot precursors. Alkylbenzene results were generally well reproduced by simulations using literature models

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Kinetic Studies on the Reactions of Hydroxyl Radicals with Cyclic Ethers and Aliphatic Diethers

Cited by 9 publications

References 2 publications

H-Atom Abstraction Reactions by Ground-State Ozone from Saturated Oxygenates

H-Atom Abstraction Reactions by Ground-State Ozone from Saturated Oxygenates

Catalytic Effect of Several Iron Species on Ozonation

Comparison study of the gas-phase oxidation of alkylbenzenes and alkylcyclohexanes

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