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Title: Theoretical Kinetics Analysis for $$\dot{H}$$ Atom Addition to 1,3-Butadiene and Related Reactions on the $$\dot{C}$$ 4H 7 Potential Energy Surface

Abstract

The oxidation chemistry of the simplest conjugated hydrocarbon, 1,3-butadiene, can provide a first step in understanding the role of poly-unsaturated hydrocarbons in combustion and, in particular, an understanding of their contribution towards soot formation. Based on our previous work on propene and the butene isomers (1-, 2- and isobutene), it was found that the reaction kinetics of H-atom addition to the C=C double bond plays a significant role in fuel consumption kinetics and influences the predictions of high-temperature ignition delay times, product species concentrations and flame speed measurements. In this study, the rate constants and thermodynamic properties for $$\dot{H}$$-atom addition to 1,3-butadiene and related reactions on the $$\dot{C}$$ 4H 7 potential energy surface have been calculated using two different series of quantum chemical methods and two different kinetic codes. Excellent agreement is obtained between the two different kinetics codes. The calculated results including zero point energies, single point energies, rate constants, barrier heights and thermochemistry are systematically compared among the two quantum chemical methods. 1-methylallyl ($$\dot{C}$$ 4H 71-3) and 3-buten-1- yl ($$\dot{C}$$ 4H 71-4) radicals and C 2H 4 + $$\dot{C}$$2H3 are found to be the most important channels and reactivity promoting products, respectively. We calculated that terminal addition is dominant (> 80%) compared to internal $$\dot{H}$$-atom addition at all temperatures in the range 298 – 2000 K. However, this dominance decreases with increasing temperature. The calculated rate constants for the bimolecular reaction C 4H 6 + $$\dot{H}$$ → products and C 2H 4 + $$\dot{C}$$ 2H 3 → products are in excellent agreement with both experimental and theoretical results from the literature. For selected C 4 species the calculated thermochemical values are also in good agreement with literature data. In addition, the rate constants for H-atom abstraction by $$\dot{H}$$ atoms have also been calculated, and it is found that abstraction from the central carbon atoms is the dominant channel (> 70%) at temperatures in the range 298 – 2000 K. Lastly, by incorporating our calculated rate constants for both H-atom addition and abstraction into our recently developed 1,3-butadiene model, we show that laminar flame speed predictions are significantly improved, emphasizing the value of this study.

Authors:
 [1];  [2];  [3];  [1]
  1. National Univ. of Ireland, Galway (Ireland). Combustion Chemistry Centre
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
  3. Beihang Univ., Beihang (China). School of Energy and Power Engineering
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1416976
DOE Contract Number:
AC02-06CH11357
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory; Journal Volume: 121; Journal Issue: 40
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Li, Yang, Klippenstein, Stephen J., Zhou, Chong-Wen, and Curran, Henry J. Theoretical Kinetics Analysis for $\dot{H}$ Atom Addition to 1,3-Butadiene and Related Reactions on the $\dot{C}$4H7 Potential Energy Surface. United States: N. p., 2017. Web. doi:10.1021/acs.jpca.7b05996.
Li, Yang, Klippenstein, Stephen J., Zhou, Chong-Wen, & Curran, Henry J. Theoretical Kinetics Analysis for $\dot{H}$ Atom Addition to 1,3-Butadiene and Related Reactions on the $\dot{C}$4H7 Potential Energy Surface. United States. doi:10.1021/acs.jpca.7b05996.
Li, Yang, Klippenstein, Stephen J., Zhou, Chong-Wen, and Curran, Henry J. Fri . "Theoretical Kinetics Analysis for $\dot{H}$ Atom Addition to 1,3-Butadiene and Related Reactions on the $\dot{C}$4H7 Potential Energy Surface". United States. doi:10.1021/acs.jpca.7b05996.
@article{osti_1416976,
title = {Theoretical Kinetics Analysis for $\dot{H}$ Atom Addition to 1,3-Butadiene and Related Reactions on the $\dot{C}$4H7 Potential Energy Surface},
author = {Li, Yang and Klippenstein, Stephen J. and Zhou, Chong-Wen and Curran, Henry J.},
abstractNote = {The oxidation chemistry of the simplest conjugated hydrocarbon, 1,3-butadiene, can provide a first step in understanding the role of poly-unsaturated hydrocarbons in combustion and, in particular, an understanding of their contribution towards soot formation. Based on our previous work on propene and the butene isomers (1-, 2- and isobutene), it was found that the reaction kinetics of H-atom addition to the C=C double bond plays a significant role in fuel consumption kinetics and influences the predictions of high-temperature ignition delay times, product species concentrations and flame speed measurements. In this study, the rate constants and thermodynamic properties for $\dot{H}$-atom addition to 1,3-butadiene and related reactions on the $\dot{C}$4H7 potential energy surface have been calculated using two different series of quantum chemical methods and two different kinetic codes. Excellent agreement is obtained between the two different kinetics codes. The calculated results including zero point energies, single point energies, rate constants, barrier heights and thermochemistry are systematically compared among the two quantum chemical methods. 1-methylallyl ($\dot{C}$4H71-3) and 3-buten-1- yl ($\dot{C}$4H71-4) radicals and C2H4 + $\dot{C}$2H3 are found to be the most important channels and reactivity promoting products, respectively. We calculated that terminal addition is dominant (> 80%) compared to internal $\dot{H}$-atom addition at all temperatures in the range 298 – 2000 K. However, this dominance decreases with increasing temperature. The calculated rate constants for the bimolecular reaction C4H6 + $\dot{H}$ → products and C2H4 + $\dot{C}$2H3 → products are in excellent agreement with both experimental and theoretical results from the literature. For selected C4 species the calculated thermochemical values are also in good agreement with literature data. In addition, the rate constants for H-atom abstraction by $\dot{H}$ atoms have also been calculated, and it is found that abstraction from the central carbon atoms is the dominant channel (> 70%) at temperatures in the range 298 – 2000 K. Lastly, by incorporating our calculated rate constants for both H-atom addition and abstraction into our recently developed 1,3-butadiene model, we show that laminar flame speed predictions are significantly improved, emphasizing the value of this study.},
doi = {10.1021/acs.jpca.7b05996},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 40,
volume = 121,
place = {United States},
year = {Fri Sep 29 00:00:00 EDT 2017},
month = {Fri Sep 29 00:00:00 EDT 2017}
}