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Title: Nucleation of soot: experimental assessment of the role of polycyclic aromatic hydrocarbon (PAH) dimers

Abstract

The irreversible dimerization of polycyclic aromatic hydrocarbons (PAHs) – typically pyrene (C 16H 10) dimerization – is widely used in combustion chemistry models to describe the soot particle inception step. This study concerns itself with the detection and identification of dimers of flame-synthesized PAH radicals and closed-shell molecules and an experimental assessment of the role of these PAH dimers for the nucleation of soot. To this end, flame-generated species were extracted from an inverse co-flow flame of ethylene at atmospheric pressure and immediately diluted with excess nitrogen before the mixture was analyzed using flame-sampling tandem mass spectrometry with collision-induced fragmentation. Signal at m/z = 404.157 (C 32H 20) and m/z = 452.157 (C 36H 20) were detected and identified as dimers of closed-shell C 16H 10 and C 18H 10 monomers, respectively. A complex between a C 13H 9 radical and a C 24H 12 closed-shell PAH was observed at m/z = 465.164 (C 37H 21). However, a rigorous analysis of the flame-sampled mass spectra as a function of the dilution ratio, defined as the ratio of the flow rates of the diluent nitrogen to the sampled gases, indicates that the observed dimers are not flame-born, but are produced inmore » the sampling line. In agreement with theoretical considerations, this paper provides experimental evidence that pyrene dimers cannot be a key intermediate in particle inception at elevated flame temperatures.« less

Authors:
 [1];  [1];  [2];  [2]
  1. Sandia National Lab. (SNL-CA), Livermore, CA (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1668356
Report Number(s):
SAND-2020-4965J
Journal ID: ISSN 0942-9352; 686024
Grant/Contract Number:  
AC04-94AL85000; NA0003525; ACO2-05CH11231
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Zeitschrift fuer Physikalische Chemie
Additional Journal Information:
Journal Volume: 234; Journal Issue: 7-9; Journal ID: ISSN 0942-9352
Publisher:
de Gruyter
Country of Publication:
United States
Language:
English
Subject:
PAH dimerization; soot formation; tandem mass spectrometry

Citation Formats

Adamson, Brian A., Skeen, Scott A., Ahmed, Musahid, and Hansen, Nils. Nucleation of soot: experimental assessment of the role of polycyclic aromatic hydrocarbon (PAH) dimers. United States: N. p., 2020. Web. doi:10.1515/zpch-2020-1638.
Adamson, Brian A., Skeen, Scott A., Ahmed, Musahid, & Hansen, Nils. Nucleation of soot: experimental assessment of the role of polycyclic aromatic hydrocarbon (PAH) dimers. United States. doi:10.1515/zpch-2020-1638.
Adamson, Brian A., Skeen, Scott A., Ahmed, Musahid, and Hansen, Nils. Mon . "Nucleation of soot: experimental assessment of the role of polycyclic aromatic hydrocarbon (PAH) dimers". United States. doi:10.1515/zpch-2020-1638.
@article{osti_1668356,
title = {Nucleation of soot: experimental assessment of the role of polycyclic aromatic hydrocarbon (PAH) dimers},
author = {Adamson, Brian A. and Skeen, Scott A. and Ahmed, Musahid and Hansen, Nils},
abstractNote = {The irreversible dimerization of polycyclic aromatic hydrocarbons (PAHs) – typically pyrene (C16H10) dimerization – is widely used in combustion chemistry models to describe the soot particle inception step. This study concerns itself with the detection and identification of dimers of flame-synthesized PAH radicals and closed-shell molecules and an experimental assessment of the role of these PAH dimers for the nucleation of soot. To this end, flame-generated species were extracted from an inverse co-flow flame of ethylene at atmospheric pressure and immediately diluted with excess nitrogen before the mixture was analyzed using flame-sampling tandem mass spectrometry with collision-induced fragmentation. Signal at m/z = 404.157 (C32H20) and m/z = 452.157 (C36H20) were detected and identified as dimers of closed-shell C16H10 and C18H10 monomers, respectively. A complex between a C13H9 radical and a C24H12 closed-shell PAH was observed at m/z = 465.164 (C37H21). However, a rigorous analysis of the flame-sampled mass spectra as a function of the dilution ratio, defined as the ratio of the flow rates of the diluent nitrogen to the sampled gases, indicates that the observed dimers are not flame-born, but are produced in the sampling line. In agreement with theoretical considerations, this paper provides experimental evidence that pyrene dimers cannot be a key intermediate in particle inception at elevated flame temperatures.},
doi = {10.1515/zpch-2020-1638},
journal = {Zeitschrift fuer Physikalische Chemie},
issn = {0942-9352},
number = 7-9,
volume = 234,
place = {United States},
year = {2020},
month = {8}
}

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