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Title: Direct measurements of channel specific rate constants in OH + C 3H 8 illuminates prompt dissociations of propyl radicals

Abstract

OH + molecules are an important class of reactions in combustion and atmospheric chemistry. Consequently, numerous studies have measured rate constants for these processes over an extended temperature range. A large majority of these experimental studies have utilized the decay of [OH] profiles (monitored either by absorption or laser-induced fluorescence) to obtain total rate constants. However, there are limited direct measurements of channel specific rate constants in this important class of reactions, particularly at combustion relevant temperatures. In the present experiments, we have directly measured site-specific rate constants for abstraction of the secondary C–H bond in OH + C 3H 8 at high temperatures. Atomic resonance absorption spectrometry (ARAS) was used to monitor the formation of H-atoms from shock-heated mixtures of tert-butylhydroperoxide and C 3H 8 at high temperatures. Simulations for the experimental H-atom profiles are sensitive only to abstraction of the secondary C–H bond leading to unambiguous measurements of the rate constants for this reaction. Over the T-range, 921 K < T < 1146 K, rate constants from the present experiments for OH + C 3H 8 →H 2O + i-C 3H 7 can be represented by the Arrhenius expression, k = (3.935 ± 1.387) × 10-11 exp(-1681 ±more » 362 K/T )cm 3 molecule -1s -1 Simulations of the lower temperature data (T < 1000 K) indicate that the H-atom profiles are also influenced to a minor extent by the thermal dissociation of iso-propyl, i-C 3H 7 →H + C 3H 6, at short time-scales.« less

Authors:
; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science - Office of Basic Energy Sciences - Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1491102
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Conference
Resource Relation:
Conference: 37th International Symposium on Combustion, Dublin, IE, 07/29/18 - 08/03/18
Country of Publication:
United States
Language:
English
Subject:
Shock Tube, H-ARAS, Prompt Dissociation, Bimolecular Reaction, Alkyl Radicals

Citation Formats

Sivaramakrishnan, Raghu, Goldsmith, C. Franklin, Peukert, Sebastian, and Michael, Joe V. Direct measurements of channel specific rate constants in OH + C3H8 illuminates prompt dissociations of propyl radicals. United States: N. p., 2018. Web. doi:10.1016/j.proci.2018.05.130.
Sivaramakrishnan, Raghu, Goldsmith, C. Franklin, Peukert, Sebastian, & Michael, Joe V. Direct measurements of channel specific rate constants in OH + C3H8 illuminates prompt dissociations of propyl radicals. United States. doi:10.1016/j.proci.2018.05.130.
Sivaramakrishnan, Raghu, Goldsmith, C. Franklin, Peukert, Sebastian, and Michael, Joe V. Mon . "Direct measurements of channel specific rate constants in OH + C3H8 illuminates prompt dissociations of propyl radicals". United States. doi:10.1016/j.proci.2018.05.130. https://www.osti.gov/servlets/purl/1491102.
@article{osti_1491102,
title = {Direct measurements of channel specific rate constants in OH + C3H8 illuminates prompt dissociations of propyl radicals},
author = {Sivaramakrishnan, Raghu and Goldsmith, C. Franklin and Peukert, Sebastian and Michael, Joe V.},
abstractNote = {OH + molecules are an important class of reactions in combustion and atmospheric chemistry. Consequently, numerous studies have measured rate constants for these processes over an extended temperature range. A large majority of these experimental studies have utilized the decay of [OH] profiles (monitored either by absorption or laser-induced fluorescence) to obtain total rate constants. However, there are limited direct measurements of channel specific rate constants in this important class of reactions, particularly at combustion relevant temperatures. In the present experiments, we have directly measured site-specific rate constants for abstraction of the secondary C–H bond in OH + C3H8 at high temperatures. Atomic resonance absorption spectrometry (ARAS) was used to monitor the formation of H-atoms from shock-heated mixtures of tert-butylhydroperoxide and C3H8 at high temperatures. Simulations for the experimental H-atom profiles are sensitive only to abstraction of the secondary C–H bond leading to unambiguous measurements of the rate constants for this reaction. Over the T-range, 921 K < T < 1146 K, rate constants from the present experiments for OH + C3H8 →H2O + i-C3H7 can be represented by the Arrhenius expression, k = (3.935 ± 1.387) × 10-11 exp(-1681 ± 362 K/T )cm3 molecule-1s-1 Simulations of the lower temperature data (T < 1000 K) indicate that the H-atom profiles are also influenced to a minor extent by the thermal dissociation of iso-propyl, i-C3H7 →H + C3H6, at short time-scales.},
doi = {10.1016/j.proci.2018.05.130},
journal = {},
number = ,
volume = ,
place = {United States},
year = {2018},
month = {1}
}

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