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

Adamson, Brian A.; Skeen, Scott A.; Ahmed, Musahid; Hansen, Nils

doi:10.1515/zpch-2020-1638

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

Journal Article · Mon Aug 10 00:00:00 EDT 2020 · Zeitschrift fuer Physikalische Chemie

DOI:https://doi.org/10.1515/zpch-2020-1638· OSTI ID:1668356

Adamson, Brian A. ^[1]; Skeen, Scott A. ^[1]; Ahmed, Musahid ^[2]; Hansen, Nils ^[2]

Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

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.

View Accepted Manuscript (DOE)

Research Organization:: Sandia National Laboratories (SNL-CA), Livermore, CA (United States)

Sponsoring Organization:: 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)

Grant/Contract Number:: AC04-94AL85000; NA0003525

OSTI ID:: 1668356

Report Number(s):: SAND--2020-4965J; 686024

Journal Information:: Zeitschrift fuer Physikalische Chemie, Journal Name: Zeitschrift fuer Physikalische Chemie Journal Issue: 7-9 Vol. 234; ISSN 0942-9352

Publisher:: de GruyterCopyright Statement

Country of Publication:: United States

Language:: English

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

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