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Title: Mechanism and kinetics of the oxidation of 1,3-butadien-1-yl (n-C4H5): a theoretical study

Journal Article · · Physical Chemistry Chemical Physics. PCCP
DOI:https://doi.org/10.1039/d1cp00567g· OSTI ID:1843944
 [1];  [2]; ORCiD logo [3]
  1. Samara National Research Univ. (Russian Federation); Russian Academy of Sciences (RAS), Samara (Russian Federation). P.N. Lebedev Physical Institute
  2. Russian Academy of Sciences (RAS), Samara (Russian Federation). P.N. Lebedev Physical Institute
  3. Samara National Research Univ. (Russian Federation); Florida International Univ. (FIU), Miami, FL (United States)
+ Show Author Affiliations

Here, ab initio CCSD(T)-F12/cc-pVTZ-f12//B3LYP/6-311G(d,p) calculations of the C4H5O2 potential energy surface have been combined with Rice–Ramsperger–Kassel–Marcus Master Equation (RRKM-ME) calculations of temperature- and pressure-dependent rate constants and product branching ratios to unravel the mechanism and kinetics of the n-C4H5 + O2 reaction. The results indicate that the reaction is fast, with the total rate constant being in the range of 3.4–5.6 × 10–11 cm3 molecule–1 s–1. The main products include 1-oxo-n-butadienyl + O and acrolein + HCO, with their cumulative yield exceeding 90% at temperatures above 1500 K. Two conformers of 1-oxo-n-butadienyl + O are formed via a simple mechanism of O2 addition to the radical site of n-C4H5 followed by the cleavage of the O–O bond proceeding via a van der Waals C4H5O∙∙∙O complex. Alternatively, the pathways leading to acrolein + HCO involve significant reorganization of the heavy-atom skeleton either via formal migration of one O atom to the opposite end of the molecule or its insertion into the C1–C2 bond. Not counting thermal stabilization of the initial peroxy adducts, which prevails at low temperatures and high pressures, all other products share a minor yield of under 5%. Rate constants for the significant reaction channels have been fitted to modified Arrhenius expressions and are proposed for kinetic modeling of the oxidation of aromatic molecules and 1,3-butadiene. As a secondary reaction, n-C4H5 + O2 can be a source for the formation of acrolein observed experimentally in oxidation of the phenyl radical at low combustion temperatures, whereas another significant (secondary) product of the C6H5 + O2 reaction, furan, could be formed through unimolecular decomposition of 1-oxo-n-butadienyl. Both the n-C4H5 + O2 reaction and unimolecular decomposition of its 1-oxo-n-butadienyl primary product are shown not to be a substantial source of ketene.

Research Organization:
Florida International Univ. (FIU), Miami, FL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Ministry of Higher Education and Science of the Russian Federation
Grant/Contract Number:
FG02-04ER15570; 14.Y26.31.0020
OSTI ID:
1843944
Alternate ID(s):
OSTI ID: 1776989
Journal Information:
Physical Chemistry Chemical Physics. PCCP, Vol. 23, Issue 15; ISSN 1463-9076
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

References (39)

Carcinogenic polycyclic aromatic hydrocarbon-DNA adducts and mechanism of action journal January 2005
Tropospheric Air Pollution: Ozone, Airborne Toxics, Polycyclic Aromatic Hydrocarbons, and Particles journal May 1997
Reaction mechanism of soot formation in flames journal February 2002
Formation and consumption of single-ring aromatic hydrocarbons and their precursors in premixed acetylene, ethylene and benzene flamesElectronic supplementary information (ESI) available: Thermodynamic and kinetic property data. See http://www.rsc.org/suppdata/cp/b1/b110089k/ journal April 2002
Thermochemistry of disputed soot formation intermediates C4H3 and C4H5 journal November 2004
The Reaction of n - and i -C 4 H 5 Radicals with Acetylene † journal May 2007
RRKM and master equation kinetic analysis of parallel addition reactions of isomeric radical intermediates in hydrocarbon flames journal August 2017
Unravelling combustion mechanisms through a quantitative understanding of elementary reactions journal January 2005
Recent contributions of flame-sampling molecular-beam mass spectrometry to a fundamental understanding of combustion chemistry journal April 2009
Studies of aromatic hydrocarbon formation mechanisms in flames: Progress towards closing the fuel gap journal January 2006
Identification and Chemistry of C 4 H 3 and C 4 H 5 Isomers in Fuel-Rich Flames journal March 2006
Reaction of the i -C 4 H 5 (CH 2 CCHCH 2 ) Radical with O 2 journal February 2011
High-Temperature Measurements and a Theoretical Study of the Reaction of OH with 1,3-Butadiene journal August 2010
Theoretical kinetics analysis for ȮH radical addition to 1,3-butadiene and application to model prediction journal November 2020
Experimental and Modeling Study of the Oxidation of 1-Butene and cis -2-Butene in a Jet-Stirred Reactor and a Combustion Vessel journal January 2015
An experimental and kinetic modeling study of three butene isomers pyrolysis at low pressure journal March 2012
Detailed mass spectrometric and modeling study of isomeric butene flames journal March 2013
Consumption and hydrocarbon growth processes in a 2-methyl-2-butene flame journal January 2017
Isomer Energy Differences for the C 4 H 3 and C 4 H 5 Isomers Using Diffusion Monte Carlo journal January 2008
Kinetic and thermodynamic issues in the formation of aromatic compounds in flames of aliphatic fuels journal October 1992
High temperature oxidation of aromatic hydrocarbons journal January 1982
Reaction mechanism, rate constants, and product yields for unimolecular and H-assisted decomposition of 2,4-cyclopentadienone and oxidation of cyclopentadienyl with atomic oxygen journal September 2017
The Reaction of Phenyl Radical with Molecular Oxygen:  A G2M Study of the Potential Energy Surface journal July 2005
Rate coefficients and product branching ratios for the oxidation of phenyl and naphthyl radicals: A theoretical RRKM-ME study journal January 2015
Toward the Oxidation of the Phenyl Radical and Prevention of PAH Formation in Combustion Systems journal November 2014
First direct kinetic measurement of i-C4H5 (CH2CHCCH2) + O2 reaction: Toward quantitative understanding of aromatic ring formation chemistry journal January 2021
Density‐functional thermochemistry. III. The role of exact exchange journal April 1993
A simple and efficient CCSD(T)-F12 approximation journal December 2007
Simplified CCSD(T)-F12 methods: Theory and benchmarks journal February 2009
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen journal January 1989
Multireference perturbation theory for large restricted and selected active space reference wave functions journal April 2000
Prediction of Reaction Barriers and Thermochemical Properties with Explicitly Correlated Coupled-Cluster Methods: A Basis Set Assessment journal August 2012
Reformulation and Solution of the Master Equation for Multiple-Well Chemical Reactions journal May 2013
Classical phase space theory for product state distributions with application to the v – j vector correlation journal October 1995
A Theoretical and Computational Analysis of the Methyl-Vinyl + O 2 Reaction and Its Effects on Propene Combustion journal November 2017
Variational transition state theory: theoretical framework and recent developments journal January 2017
Theory of thermal unimolecular reactions at low pressures. I. Solutions of the master equation journal June 1977
Pathways and Rate Coefficients for the Decomposition of Vinoxy and Acetyl Radicals journal May 2006
Temperature and Pressure-Dependent Rate Coefficients for the Reaction of Vinyl Radical with Molecular Oxygen journal February 2015

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