Kinetics of the HCCO + NO<sub>2</sub> Reaction

Meyer, Justin P.; Hershberger, John F.

doi:10.1021/jp0580423

Cited by 21 publications

(14 citation statements)

References 46 publications

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“…This radical may be a key intermediate in the combustion of sulfur-containing fuels and may play an important role in the RAPRENO x (rapid reduction of nitrogen oxides) process. , There have been numerous reports on theoretical and experimental approaches to eliminate NO, − many of which contain cyanogen species as an effective reagent to remove NO. Our purpose of this study is to find the possible reactants which may react with NO to form the stable product such as N 2 , which is not harmful to our environment and possibly with lower energy barriers.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Study on Reaction Mechanisms and Kinetics of Cyanomidyl Radical with NO

et al. 2010

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The mechanisms and kinetics of the reaction of the cyanomidyl radical (HNCN) with the NO have been investigated by the high-level ab initio molecular orbital method in conjunction with VTST and RRKM theory. The species involved have been optimized at the B3LYP/6-311++G(3df,2p) level and their single-point energies are refined by the CCSD(T)/aug-cc-PVQZ//B3LYP/6-311++G(3df,2p) method. Our calculated results indicate that the favorable pathways for the formation of several isomers of an HNCN-NO complex. Formations of HNC + N(2)O (P1) and HNCO + N(2) (P2) are also possible, although these two pathways involve little activation energy. Employing the Fukui functions and HSAB theory, we are able to rationalize the scenario of the calculated outcome. The predicted total rate constants, k(total), at a 760 Torr Ar pressure can be represented by the equations k(total) = 4.39 x 10(8) T(-7.30) exp(-1.76 kcal mol(-1)/RT) at T = 298-1000 K and 1.01 x 10(-32) T(5.32) exp(11.27 kcal mol(-1)/RT) at T = 1050-3000 K, respectively, in units of cm(3) molecule(-1) s(-1). In addition, the rate constants for key individual product channels are provided in a table for different temperature and pressure conditions. These results are recommended for combustion modeling applications.

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Section: Introductionmentioning

confidence: 99%

Theoretical Study on Reaction Mechanisms and Kinetics of Cyanomidyl Radical with NO

et al. 2010

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“…An even cleaner, and perhaps more promising HCCO source than ketene is the photo-dissociation at 193 nm of ethyl ethynyl ether, [33][34][35] as recently employed by Meyer and Hershberger in their study of the HCCO + NO 2 reaction, in which HCCO was monitored by transient infrared absorption. 36…”

Section: Mass Spectrometric and Infrared Detection Methodsmentioning

confidence: 99%

Kinetic parameters for gas-phase reactions: Experimental and theoretical challenges

Carl

Vereecken

Peeters

2007

Phys. Chem. Chem. Phys.

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This article aims to illustrate the added value provided to experimental kinetics investigations by complementary theoretical kinetics studies, using as examples (i) reactions of two major hydrocarbon flame radicals, HCCO and C(2)H, and (ii) reactions of several oxygenated organic compounds with hydroxyl radicals of interest to atmospheric chemistry. The first part, on HCCO and C(2)H kinetics, does not attempt to give an extensive literature review, but rather addresses some major experimental techniques, mainly specific ones, that have allowed a great part of the available reactivity databases on these two species to be established. For several key reactions, it is shown how potential energy surfaces and statistical rate predictions based thereon have provided insight into the molecular mechanisms and have allowed estimates of product distributions as well as reliable extrapolations of experimental rate coefficients and branching ratios to higher temperatures. The second part addresses current issues in atmospheric chemistry relating mainly to hydroxyl radical reactions with oxygenated organics, and focuses on the experimental characterization of the often unusual temperature dependence of their rate coefficients and on the theoretical rationalization thereof, through the formation of hydrogen-bonded pre-reactive complexes and resulting tunnelling-enhanced H-abstraction. Finally, the development of general structure-activity relationships for OH reactions with organics, H-abstractions as well as OH-additions for unsaturated compounds, is briefly discussed.

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“…However, subsequent studies reported that the HCCO + H formation process 3a is a minor product channel (<20%) of reaction 3. − The main product channel (>60%) is CH 2 ( 3 B 1 and 1 A 1 ) + CO, processes 3b and 3c. Subsequently, the photodissociation of ethyl ethynyl ether (EEE, C 2 H 5 OCCH) at 193 nm has been employed , as an even cleaner HCCO source than ketene. …”

Section: Introductionmentioning

confidence: 99%

“…20−22 The main product channel (>60%) is CH 2 ( 3 B 1 and 1 A 1 ) + CO, processes 3b and 3c. Subsequently, the photodissociation of ethyl ethynyl ether (EEE, C 2 H 5 OC CH) at 193 nm has been employed 10,23 as an even cleaner HCCO source than ketene.…”

Section: Introductionmentioning

confidence: 99%

Rate Constants for Reactions of HCCO and HCCCO Radicals with O₂ over the Temperature Range 243–423 K

et al. 2020

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A pulsed laser photolysis–photoionization mass spectrometer system has been employed to measure the rate constants of HCCO + O2 and HCCCO + O2 over the temperature range 243–423 K in 1.2–8.4 Torr of He or N2. Radicals of HCCO and HCCCO were produced by 193 nm ArF laser photolysis of ethyl ethynyl ether and methyl propiolate, respectively. HCCO was photoionized by a Kr resonance lamp with a CaF2 window (10.03 eV), and HCCCO was ionized by a Xe lamp with a sapphire window (8.44 eV). Both ions were detected as parent ions in a quadrupole mass spectrometer. From analysis of the time profiles of the ion signals for various O2 concentrations, the overall rate constants at 298 K are represented by the values k 2 = (6.3 ± 1.0) × 10–13 for HCCO + O2 and k 5 = (5.7 ± 0.6) × 10–12 for HCCCO + O2 in the units cm3 molecule–1 s–1. The rate coefficients for the two reactions can be described by k 2(T) = (1.5–0.7 +1.5) × 10–12 exp[−(225 ± 220)/T] and k 5(T) = (1.8–0.9 +1.9) × 10–12 exp[(343 ± 228)/T] in the units cm3 molecule–1 s–1 over the temperature range 243–423 K.

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Kinetics of the HCCO + NO₂ Reaction

Cited by 21 publications

References 46 publications

Theoretical Study on Reaction Mechanisms and Kinetics of Cyanomidyl Radical with NO

Theoretical Study on Reaction Mechanisms and Kinetics of Cyanomidyl Radical with NO

Kinetic parameters for gas-phase reactions: Experimental and theoretical challenges

Rate Constants for Reactions of HCCO and HCCCO Radicals with O₂ over the Temperature Range 243–423 K

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Kinetics of the HCCO + NO2 Reaction

Cited by 21 publications

References 46 publications

Theoretical Study on Reaction Mechanisms and Kinetics of Cyanomidyl Radical with NO

Theoretical Study on Reaction Mechanisms and Kinetics of Cyanomidyl Radical with NO

Kinetic parameters for gas-phase reactions: Experimental and theoretical challenges

Rate Constants for Reactions of HCCO and HCCCO Radicals with O2 over the Temperature Range 243–423 K

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Product

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Kinetics of the HCCO + NO₂ Reaction

Rate Constants for Reactions of HCCO and HCCCO Radicals with O₂ over the Temperature Range 243–423 K