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Title: A combined photoionization time-of-flight mass spectrometry and laser absorption spectrometry flash photolysis apparatus for simultaneous determination of reaction rates and product branching

Abstract

In recent years, predictions of product branching for reactions of consequence to both combustion and atmospheric chemistry have outpaced validating experiments. An apparatus is described that aims to fill this void by combining several well-known experimental techniques into one: flash photolysis for radical generation, multiple-pass laser absorption spectrometry (LAS) for overall kinetics measurements, and time-resolved photoionization time-of-flight mass spectrometry (PI TOF-MS) for product branching quantification. The sensitivity of both the LAS and PI TOF-MS detection techniques is shown to be suitable for experiments with initial photolytically generated radical concentrations of ~1 × 10 12 molecules cm -3. As it is fast (μs time resolution) and non-intrusive, LAS is preferred for accurate kinetics (time-dependence) measurements. By contrast, PI TOF-MS is preferred for product quantification because it provides a near-complete picture of the reactor composition in a single mass spectrum. The value of simultaneous LAS and PI TOF-MS detection is demonstrated for the chemically interesting phenyl radical + propene system.

Authors:
ORCiD logo [1]; ORCiD logo [1];  [2]; ORCiD logo [1];  [1];  [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Chemical Engineering
  2. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Chemical Engineering; ENSTA ParisTech, Palaiseau (France). Dept. of Chemical Engineering
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Combustion Energy Frontier Research Center (CEFRC); Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1526021
Alternate Identifier(s):
OSTI ID: 1461246
Grant/Contract Number:  
SC0001198; SC0014901
Resource Type:
Accepted Manuscript
Journal Name:
Review of Scientific Instruments
Additional Journal Information:
Journal Volume: 89; Journal Issue: 7; Journal ID: ISSN 0034-6748
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
47 OTHER INSTRUMENTATION

Citation Formats

Middaugh, Joshua E., Buras, Zachary J., Matrat, Mickael, Chu, Te-Chun, Kim, Young-Seok, Alecu, Ionut M., Vasiliou, AnGayle K., Goldsmith, C. Franklin, and Green, William H. A combined photoionization time-of-flight mass spectrometry and laser absorption spectrometry flash photolysis apparatus for simultaneous determination of reaction rates and product branching. United States: N. p., 2018. Web. doi:10.1063/1.5024399.
Middaugh, Joshua E., Buras, Zachary J., Matrat, Mickael, Chu, Te-Chun, Kim, Young-Seok, Alecu, Ionut M., Vasiliou, AnGayle K., Goldsmith, C. Franklin, & Green, William H. A combined photoionization time-of-flight mass spectrometry and laser absorption spectrometry flash photolysis apparatus for simultaneous determination of reaction rates and product branching. United States. doi:10.1063/1.5024399.
Middaugh, Joshua E., Buras, Zachary J., Matrat, Mickael, Chu, Te-Chun, Kim, Young-Seok, Alecu, Ionut M., Vasiliou, AnGayle K., Goldsmith, C. Franklin, and Green, William H. Mon . "A combined photoionization time-of-flight mass spectrometry and laser absorption spectrometry flash photolysis apparatus for simultaneous determination of reaction rates and product branching". United States. doi:10.1063/1.5024399. https://www.osti.gov/servlets/purl/1526021.
@article{osti_1526021,
title = {A combined photoionization time-of-flight mass spectrometry and laser absorption spectrometry flash photolysis apparatus for simultaneous determination of reaction rates and product branching},
author = {Middaugh, Joshua E. and Buras, Zachary J. and Matrat, Mickael and Chu, Te-Chun and Kim, Young-Seok and Alecu, Ionut M. and Vasiliou, AnGayle K. and Goldsmith, C. Franklin and Green, William H.},
abstractNote = {In recent years, predictions of product branching for reactions of consequence to both combustion and atmospheric chemistry have outpaced validating experiments. An apparatus is described that aims to fill this void by combining several well-known experimental techniques into one: flash photolysis for radical generation, multiple-pass laser absorption spectrometry (LAS) for overall kinetics measurements, and time-resolved photoionization time-of-flight mass spectrometry (PI TOF-MS) for product branching quantification. The sensitivity of both the LAS and PI TOF-MS detection techniques is shown to be suitable for experiments with initial photolytically generated radical concentrations of ~1 × 1012 molecules cm-3. As it is fast (μs time resolution) and non-intrusive, LAS is preferred for accurate kinetics (time-dependence) measurements. By contrast, PI TOF-MS is preferred for product quantification because it provides a near-complete picture of the reactor composition in a single mass spectrum. The value of simultaneous LAS and PI TOF-MS detection is demonstrated for the chemically interesting phenyl radical + propene system.},
doi = {10.1063/1.5024399},
journal = {Review of Scientific Instruments},
number = 7,
volume = 89,
place = {United States},
year = {2018},
month = {7}
}

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