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Title: Reactions of OH with Butene Isomers. Measurements of the Overall Rates and a Theoretical Study

Abstract

Reactions of hydroxyl (OH) radicals with 1-butene (k 1), trans-2-butene (k 2), and cis-2-butene (k 3) were studied behind reflected shock waves over the temperature range 880-1341 K and at pressures near 2.2 atm. OH radicals were produced by shock-heating tert-butyl hydroperoxide, (CH 3) 3-CO-OH, and monitored by narrow-line width ring dye laser absorption of the well-characterized R 1(5) line of the OH A-X (0, 0) band near 306.7 nm. OH time histories were modeled using a comprehensive C 5 oxidation mechanism, and rate constants for the reaction of OH with butene isomers were extracted by matching modeled and measured OH concentration time histories. We present the first high-temperature measurement of OH + cis-2-butene and extend the temperature range of the only previous high-temperature study for both 1-butene and trans-2-butene. With the potential energy surface calculated using CCSD(T)/6-311++G(d,p)//QCISD/6-31G(d), the rate constants and branching fractions for the H-abstraction channels of the reaction of OH with 1-butene were calculated in the temperature range 300-1500 K. Corrections for variational and tunneling effects as well as hindered-rotation treatments were included. The calculations are in good agreement with current and previous experimental data and with a recent theoretical study.

Authors:
 [1];  [2];  [3];  [3];  [3]
  1. Stanford Univ., CA (United States); Sandia National Lab., Livermore, CA (United States)
  2. International Univ. VNUHCM (Vietnam); Inst. for Computational Science and Technology, Ho Chi Minh City (Vietnam); Colorado School of Mines, Golden, CO (United States)
  3. Stanford Univ., CA (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC); Combustion Energy Frontier Research Center (CEFRC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1065199
DOE Contract Number:  
SC0001198
Resource Type:
Journal Article
Resource Relation:
Journal Name: J. Phys. Chem. A; Journal Volume: 115; Journal Issue: 12; Related Information: CEFRC partners with Princeton University (lead); Argonne National Laboratory; University of Connecticut; Cornell University; Massachusetts Institute of Technology; University of Minnesota; Sandia National Laboratories; University of Southern California; Stanford University; University of Wisconsin, Madison
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; biofuels (including algae and biomass); hydrogen and fuel cells; combustion; carbon capture

Citation Formats

Vasu, Subith, Huynh, Lam, Davidson, David F., Hanson, Ronald K., and Golden, David. Reactions of OH with Butene Isomers. Measurements of the Overall Rates and a Theoretical Study. United States: N. p., 2011. Web. doi:10.1021/jp112294h.
Vasu, Subith, Huynh, Lam, Davidson, David F., Hanson, Ronald K., & Golden, David. Reactions of OH with Butene Isomers. Measurements of the Overall Rates and a Theoretical Study. United States. doi:10.1021/jp112294h.
Vasu, Subith, Huynh, Lam, Davidson, David F., Hanson, Ronald K., and Golden, David. Wed . "Reactions of OH with Butene Isomers. Measurements of the Overall Rates and a Theoretical Study". United States. doi:10.1021/jp112294h.
@article{osti_1065199,
title = {Reactions of OH with Butene Isomers. Measurements of the Overall Rates and a Theoretical Study},
author = {Vasu, Subith and Huynh, Lam and Davidson, David F. and Hanson, Ronald K. and Golden, David},
abstractNote = {Reactions of hydroxyl (OH) radicals with 1-butene (k1), trans-2-butene (k2), and cis-2-butene (k3) were studied behind reflected shock waves over the temperature range 880-1341 K and at pressures near 2.2 atm. OH radicals were produced by shock-heating tert-butyl hydroperoxide, (CH3)3-CO-OH, and monitored by narrow-line width ring dye laser absorption of the well-characterized R1(5) line of the OH A-X (0, 0) band near 306.7 nm. OH time histories were modeled using a comprehensive C5 oxidation mechanism, and rate constants for the reaction of OH with butene isomers were extracted by matching modeled and measured OH concentration time histories. We present the first high-temperature measurement of OH + cis-2-butene and extend the temperature range of the only previous high-temperature study for both 1-butene and trans-2-butene. With the potential energy surface calculated using CCSD(T)/6-311++G(d,p)//QCISD/6-31G(d), the rate constants and branching fractions for the H-abstraction channels of the reaction of OH with 1-butene were calculated in the temperature range 300-1500 K. Corrections for variational and tunneling effects as well as hindered-rotation treatments were included. The calculations are in good agreement with current and previous experimental data and with a recent theoretical study.},
doi = {10.1021/jp112294h},
journal = {J. Phys. Chem. A},
number = 12,
volume = 115,
place = {United States},
year = {Wed Mar 09 00:00:00 EST 2011},
month = {Wed Mar 09 00:00:00 EST 2011}
}