Thermal Decomposition of Ethylene Oxide:  Potential Energy Surface, Master Equation Analysis, and Detailed Kinetic Modeling

Joshi, Ameya; You, Xiaoqing; Barckholtz, Timothy A.; Wang, Shuangfeng

doi:10.1021/jp0516442

Cited by 41 publications

(53 citation statements)

References 58 publications

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“…It is usually not permitted to replace the equal sign in the stoichiometric equation by an arrow when entering the field of chemical kinetics [11]. This reaction has been investigated experimentally to determine the Arrhenius parameters of a first order kinetics (see [31,32] and refs. therein) where the rate of reaction depends only linearly on the amount concentration of oxirane, as indicated in eq.…”

Section: (2)]: M(x) = M(x)/n(x) and M(y) = M(y)/n(y)mentioning

confidence: 99%

A critical review of the proposed definitions of fundamental chemical quantities and their impact on chemical communities (IUPAC Technical Report)

Marquardt

Meija

Mester

et al. 2017

Pure and Applied Chemistry

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Abstract:In the proposed new SI, the kilogram will be redefined in terms of the Planck constant and the mole will be redefined in terms of the Avogadro constant. These redefinitions will have some consequences for measurements in chemistry. The goal of the Mole Project (IUPAC Project Number 2013-048-1-100) was to compile published work related to the definition of the quantity 'amount of substance', its unit the 'mole', and the consequence of these definitions on the unit of the quantity mass, the kilogram. The published work has been reviewed critically with the aim of assembling all possible aspects in order to enable IUPAC to judge the adequateness of the existing definitions or new proposals. Compilation and critical review relies on the broadest spectrum of interested IUPAC members.

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Section: (2)]: M(x) = M(x)/n(x) and M(y) = M(y)/n(y)mentioning

confidence: 99%

A critical review of the proposed definitions of fundamental chemical quantities and their impact on chemical communities (IUPAC Technical Report)

Marquardt

Meija

Mester

et al. 2017

Pure and Applied Chemistry

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“…A subset for oxyrane (c-C 2 H 4 O) and the oxyranyl radical (c-C 2 H 3 O) were drawn from literature [31,35].…”

Section: Detailed Kinetic Modelmentioning

confidence: 99%

Experimental and kinetic modeling study of C2H4 oxidation at high pressure

López

Rasmussen

Alzueta

et al. 2009

Proceedings of the Combustion Institute

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A detailed chemical kinetic model for oxidation of C 2 H 4 in the intermediate temperature range and high pressure has been developed and validated experimentally. New ab initio calculations and RRKM analysis of the important C 2 H 3 + O 2 reaction was was used to obtain rate coefficients over a wide range of conditions (0.003-100 bar, 200-3000 K). The results indicate that at 60 bar vinyl peroxide, rather than CH 2 O and HCO, is the dominant product.The experiments, involving C 2 H 4 /O 2 mixtures diluted in N 2 , were carried out in a high pressure flow reactor at 600-900 K and 60 bar, varying the reaction stoichiometry from very lean to fuel-rich conditions. Model predictions are generally satisfactory. The governing reaction mechanisms are outlined based on calculations with the kinetic model. Under the investigated conditions the oxidation pathways for C 2 H 4 are more complex than those prevailing at higher temperatures and lower pressures. The major differences are the importance of the hydroxyethyl (CH 2 CH 2 OH) and 2-hydroperoxyethyl 1 (CH 2 CH 2 OOH) radicals, formed from addition of OH and HO 2 to C 2 H 4 , and vinyl peroxide, formed from C 2 H 3 + O 2 . Hydroxyethyl is oxidized through the peroxide HOCH 2 CH 2 OO (lean conditions) or through ethenol (low O 2 concentration), while 2-hydroperoxyethyl is converted through oxirane. [2][3][4][5][6][7], shock tubes [8][9][10][11][12] and premixed laminar flames [13][14][15][16][17], covering a wide range of stoichiometries and temperatures. Most of the reported work, however, have been carried out at near atmospheric pressure. A few results are available from flow reactor studies at 5-10 bar [6], but despite their relevance for the chemistry in engines, gas turbines, and gas-to-liquid processes, data at high pressures are limited.The objective of the present study is to obtain experimental results for the oxidation of C 2 H 4 at high pressure (60 bar) as functions of temperature (600-900 K) and stoichiometry (lean to fuel-rich) and analyze them in terms of a detailed chemical kinetic model. The oxidation pathways for C 2 H 4 under these conditions are different from those prevailing at higher temperatures and lower pressures and the results of the current work help to extend the validation range for chemical kinetic modeling of C 2 H 4 oxidation. This paper is part of a series investigating the high-pressure, medium temperature oxidation of simple fuels: previously work has been reported for CO/H 2 , CH 4 , and CH 4 /C 2 H 6 mixtures [18,19]. The present kinetic model draws on this work, as well as recent results in tropospheric chemistry. Furthermore, the important reaction of C 2 H 3 with O 2 was characterized from ab initio calculations over a wide range of pressure and temperature. 3 ExperimentalThe experimental setup is a laboratory-scale high pressure laminar flow reactor designed to approximate plug-flow. The setup is described in detail elsewhere [18] and only a brief description is provided here. The system enables well-defined investigations of...

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“…This work was followed by the calculations of Nguyen et al [6] considered above and those of Hu et al [12], who studied the reaction in substantial detail at different levels of theory on both the triplet and singlet PESs. In addition, Joshi et al [13] studied oxirane decomposition with B3LYP/6-311? ?G(d, p) optimized geometries and G3B3/6-311?…”

Section: Introductionmentioning

confidence: 99%

O + C2H4 potential energy surface: excited states and biradicals at the multireference level

West

Lynch²,

Sellner

et al. 2012

Theor Chem Acc

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The focus of this study is to understand the multiconfigurational nature of the biradical species involved in the early reaction paths of the oxygen plus ethylene PES. In previous work (J Phys Chem A 113, 12663, 2009), the lowest-lying O( 3 P) ? C 2 H 4 PES was extensively explored at the MCSCF, MRMP2, and MR-AQCC levels of theory. In the current work, ground and excited, triplet-and singlet-state reaction paths for the initial addition of oxygen to ethylene were found at the MCSCF and MRMP2 levels along with five singlet pathways near the Á CH 2 CH 2 O Á biradical at the MCSCF, MRMP2, and CR-CC(2,3) levels. One of these five paths can lead to the CH 2 CO ? H 2 products from CH 3 CHO rather than from the Á CH 2 CH 2 O Á biradical, and this pathway was investigated with a variety of CAS sizes. To provide further comparison between the MRMP2 and CR-CC(2,3) levels, MR-AQCC single-point energies and optimizations were performed for select geometries. After the initial exploration of this region of the surface, the lowest singlettriplet surface crossings were explicitly determined at the MCSCF level. Additional MRMP2 calculations were performed to demonstrate the limitations of single-state perturbation theory in this biradical region of the PES, and SO-MCQDPT2 single-point energies using SA MCSCF were calculated on a grid of geometries around the primary surface crossing. In particular, these calculations were examined to determine a proper active space and a physically reasonable number of electronic states. The results of this examination show that at least four states must be considered to represent this very complex region of the PES.

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Thermal Decomposition of Ethylene Oxide: Potential Energy Surface, Master Equation Analysis, and Detailed Kinetic Modeling

Cited by 41 publications

References 58 publications

A critical review of the proposed definitions of fundamental chemical quantities and their impact on chemical communities (IUPAC Technical Report)

A critical review of the proposed definitions of fundamental chemical quantities and their impact on chemical communities (IUPAC Technical Report)

Experimental and kinetic modeling study of C2H4 oxidation at high pressure

O + C2H4 potential energy surface: excited states and biradicals at the multireference level

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