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Title: Critical Assessment of Photoionization Efficiency Measurements for Characterization of Soot-Precursor Species

Abstract

We present a critical evaluation of photoionization efficiency (PIE) measurements coupled with aerosol mass spectrometry for the identification of condensed soot-precursor species extracted from a premixed atmospheric-pressure ethylene/oxygen/nitrogen flame. Definitive identification of isomers by any means is complicated by the large number of potential isomers at masses likely to comprise particles at flame temperatures. This problem is compounded using PIE measurements by the similarity in ionization energies and PIE-curve shapes among many of these isomers. Nevertheless, PIE analysis can provide important chemical information. For example, our PIE curves show that neither pyrene nor fluoranthene alone can describe the signal from C16H10isomers and that coronene alone cannot describe the PIE signal from C24H12species. A linear combination of the reference PIE curves for pyrene and fluoranthene yields good agreement with flame-PIE curves measured at 202 u, which is consistent with pyrene and fluoranthene being the two major C16H10isomers in the flame samples, but does not provide definite proof. The suggested ratio between fluoranthene and pyrene depends on the sampling conditions. We calculated the values of the adiabatic-ionization energy (AIE) of 24 C16H10isomers. Despite the small number of isomers considered, the calculations show that the differences in AIEs between several of the isomersmore » can be smaller than the average thermal energy at room temperature. The calculations also show that PIE analysis can sometimes be used to separate hydrocarbon species into those that contain mainly aromatic rings and those that contain significant aliphatic content for species sizes investigated in this study. Our calculations suggest an inverse relationship between AIE and the number of aromatic rings. We have demonstrated that further characterization of precursors can be facilitated by measurements that test species volatility. (Graph Presented).« less

Authors:
ORCiD logo [1]; ORCiD logo [1];  [2];  [1];  [1];  [3];  [3]; ORCiD logo [2];  [1]
  1. Sandia National Lab. (SNL-CA), Livermore, CA (United States)
  2. Univ. of Michigan, Ann Arbor, MI (United States)
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-CA), Livermore, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1365807
Alternate Identifier(s):
OSTI ID: 1456974
Report Number(s):
SAND-2017-5882J
Journal ID: ISSN 1089-5639; 653852
Grant/Contract Number:  
AC04-94AL85000; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 121; Journal Issue: 23; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Johansson, K. Olof, Z?dor, Judit, Elvati, Paolo, Campbell, Matthew F., Schrader, Paul E., Richards-Henderson, Nicole K., Wilson, Kevin R., Violi, Angela, and Michelsen, Hope A. Critical Assessment of Photoionization Efficiency Measurements for Characterization of Soot-Precursor Species. United States: N. p., 2017. Web. https://doi.org/10.1021/acs.jpca.7b02992.
Johansson, K. Olof, Z?dor, Judit, Elvati, Paolo, Campbell, Matthew F., Schrader, Paul E., Richards-Henderson, Nicole K., Wilson, Kevin R., Violi, Angela, & Michelsen, Hope A. Critical Assessment of Photoionization Efficiency Measurements for Characterization of Soot-Precursor Species. United States. https://doi.org/10.1021/acs.jpca.7b02992
Johansson, K. Olof, Z?dor, Judit, Elvati, Paolo, Campbell, Matthew F., Schrader, Paul E., Richards-Henderson, Nicole K., Wilson, Kevin R., Violi, Angela, and Michelsen, Hope A. Thu . "Critical Assessment of Photoionization Efficiency Measurements for Characterization of Soot-Precursor Species". United States. https://doi.org/10.1021/acs.jpca.7b02992. https://www.osti.gov/servlets/purl/1365807.
@article{osti_1365807,
title = {Critical Assessment of Photoionization Efficiency Measurements for Characterization of Soot-Precursor Species},
author = {Johansson, K. Olof and Z?dor, Judit and Elvati, Paolo and Campbell, Matthew F. and Schrader, Paul E. and Richards-Henderson, Nicole K. and Wilson, Kevin R. and Violi, Angela and Michelsen, Hope A.},
abstractNote = {We present a critical evaluation of photoionization efficiency (PIE) measurements coupled with aerosol mass spectrometry for the identification of condensed soot-precursor species extracted from a premixed atmospheric-pressure ethylene/oxygen/nitrogen flame. Definitive identification of isomers by any means is complicated by the large number of potential isomers at masses likely to comprise particles at flame temperatures. This problem is compounded using PIE measurements by the similarity in ionization energies and PIE-curve shapes among many of these isomers. Nevertheless, PIE analysis can provide important chemical information. For example, our PIE curves show that neither pyrene nor fluoranthene alone can describe the signal from C16H10isomers and that coronene alone cannot describe the PIE signal from C24H12species. A linear combination of the reference PIE curves for pyrene and fluoranthene yields good agreement with flame-PIE curves measured at 202 u, which is consistent with pyrene and fluoranthene being the two major C16H10isomers in the flame samples, but does not provide definite proof. The suggested ratio between fluoranthene and pyrene depends on the sampling conditions. We calculated the values of the adiabatic-ionization energy (AIE) of 24 C16H10isomers. Despite the small number of isomers considered, the calculations show that the differences in AIEs between several of the isomers can be smaller than the average thermal energy at room temperature. The calculations also show that PIE analysis can sometimes be used to separate hydrocarbon species into those that contain mainly aromatic rings and those that contain significant aliphatic content for species sizes investigated in this study. Our calculations suggest an inverse relationship between AIE and the number of aromatic rings. We have demonstrated that further characterization of precursors can be facilitated by measurements that test species volatility. (Graph Presented).},
doi = {10.1021/acs.jpca.7b02992},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 23,
volume = 121,
place = {United States},
year = {2017},
month = {5}
}

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Works referenced in this record:

Simultaneously Mitigating Near-Term Climate Change and Improving Human Health and Food Security
journal, January 2012


Atmospheric brown clouds: Impacts on South Asian climate and hydrological cycle
journal, March 2005

  • Ramanathan, V.; Chung, C.; Kim, D.
  • Proceedings of the National Academy of Sciences, Vol. 102, Issue 15
  • DOI: 10.1073/pnas.0500656102

Climate Effects of Black Carbon Aerosols in China and India
journal, September 2002


Aerosols, Climate, and the Hydrological Cycle
journal, December 2001


Bounding the role of black carbon in the climate system: A scientific assessment: BLACK CARBON IN THE CLIMATE SYSTEM
journal, June 2013

  • Bond, T. C.; Doherty, S. J.; Fahey, D. W.
  • Journal of Geophysical Research: Atmospheres, Vol. 118, Issue 11
  • DOI: 10.1002/jgrd.50171

Formation of polycyclic aromatic hydrocarbons and their growth to soot—a review of chemical reaction pathways
journal, August 2000


Formation of nascent soot and other condensed-phase materials in flames
journal, January 2011


Combustion-formed nanoparticles
journal, January 2009


Probing soot formation, chemical and physical evolution, and oxidation: A review of in situ diagnostic techniques and needs
journal, January 2017


Enols Are Common Intermediates in Hydrocarbon Oxidation
journal, June 2005


Photoionization mass spectrometer for studies of flame chemistry with a synchrotron light source
journal, September 2005

  • Cool, Terrill A.; McIlroy, Andrew; Qi, Fei
  • Review of Scientific Instruments, Vol. 76, Issue 9
  • DOI: 10.1063/1.2010307

Recent contributions of flame-sampling molecular-beam mass spectrometry to a fundamental understanding of combustion chemistry
journal, April 2009

  • Hansen, Nils; Cool, Terrill A.; Westmoreland, Phillip R.
  • Progress in Energy and Combustion Science, Vol. 35, Issue 2
  • DOI: 10.1016/j.pecs.2008.10.001

Recent Applications of Synchrotron VUV Photoionization Mass Spectrometry: Insight into Combustion Chemistry
journal, January 2010

  • Li, Yuyang; Qi, Fei
  • Accounts of Chemical Research, Vol. 43, Issue 1
  • DOI: 10.1021/ar900130b

Identification and Chemistry of C 4 H 3 and C 4 H 5 Isomers in Fuel-Rich Flames
journal, March 2006

  • Hansen, Nils; Klippenstein, Stephen J.; Taatjes, Craig A.
  • The Journal of Physical Chemistry A, Vol. 110, Issue 10
  • DOI: 10.1021/jp056769l

Advances and challenges in laminar flame experiments and implications for combustion chemistry
journal, August 2014


Formation of Oxygenated and Hydrocarbon Intermediates in Premixed Combustion of 2-Methylfuran
journal, January 2015

  • Moshammer, Kai; Lucassen, Arnas; Togbé, Casimir
  • Zeitschrift für Physikalische Chemie, Vol. 229, Issue 4
  • DOI: 10.1515/zpch-2014-0606

The link between the ionization potential and heat of formation for organic homologous compounds
journal, January 2007

  • Cao, Chenzhong
  • Journal of Physical Organic Chemistry, Vol. 20, Issue 9
  • DOI: 10.1002/poc.1198

A VUV Photoionization Study of the Formation of the Indene Molecule and Its Isomers
journal, June 2011

  • Zhang, Fangtong; Kaiser, Ralf I.; Kislov, Vadim V.
  • The Journal of Physical Chemistry Letters, Vol. 2, Issue 14
  • DOI: 10.1021/jz200715u

Unexpected Chemistry from the Reaction of Naphthyl and Acetylene at Combustion-Like Temperatures
journal, March 2015

  • Parker, Dorian S. N.; Kaiser, Ralf. I.; Bandyopadhyay, Biswajit
  • Angewandte Chemie, Vol. 127, Issue 18
  • DOI: 10.1002/ange.201411987

High-temperature stabilities of hydrocarbons
journal, August 1985

  • Stein, Stephen E.; Fahr, A.
  • The Journal of Physical Chemistry, Vol. 89, Issue 17
  • DOI: 10.1021/j100263a027

Reaction mechanism of soot formation in flames
journal, February 2002

  • Frenklach, Michael
  • Physical Chemistry Chemical Physics, Vol. 4, Issue 11
  • DOI: 10.1039/b110045a

Nucleation of soot: Molecular dynamics simulations of pyrene dimerization
journal, January 2002


Intermolecular Potential Calculations for Polynuclear Aromatic Hydrocarbon Clusters
journal, July 2008

  • Herdman, Jennifer D.; Miller, J. Houston
  • The Journal of Physical Chemistry A, Vol. 112, Issue 28
  • DOI: 10.1021/jp800483h

Thermodynamics of poly-aromatic hydrocarbon clustering and the effects of substituted aliphatic chains
journal, January 2013


Exploring the Role of PAHs in the Formation of Soot: Pyrene Dimerization
journal, September 2010

  • Sabbah, Hassan; Biennier, Ludovic; Klippenstein, Stephen J.
  • The Journal of Physical Chemistry Letters, Vol. 1, Issue 19
  • DOI: 10.1021/jz101033t

The evolution of soot precursor particles in a diffusion flame
journal, November 1998


Near-threshold photoionization mass spectra of combustion-generated high-molecular-weight soot precursors
journal, April 2013


Soot precursor formation and limitations of the stabilomer grid
journal, January 2015

  • Johansson, K. O.; Lai, J. Y. W.; Skeen, S. A.
  • Proceedings of the Combustion Institute, Vol. 35, Issue 2
  • DOI: 10.1016/j.proci.2014.05.033

Radical–radical reactions, pyrene nucleation, and incipient soot formation in combustion
journal, January 2017

  • Johansson, K. Olof; Dillstrom, Tyler; Elvati, Paolo
  • Proceedings of the Combustion Institute, Vol. 36, Issue 1
  • DOI: 10.1016/j.proci.2016.07.130

An examination of soot composition in premixed hydrocarbon flames via laser ablation particle mass spectrometry
journal, October 2009


Chemical species associated with the early stage of soot growth in a laminar premixed ethylene–oxygen–argon flame
journal, September 2005


Molecular species adsorbed on soot particles issued from low sooting methane and acetylene laminar flames: A laser-based experiment
journal, January 2007


Hydrocarbon Nanoparticles Formed in Flames and Diesel Engines
journal, April 2007


The existence of young soot in the exhaust of inverse diffusion flames
journal, January 2002

  • Blevins, Linda G.; Fletcher, Robert A.; Benner, Bruce A.
  • Proceedings of the Combustion Institute, Vol. 29, Issue 2
  • DOI: 10.1016/S1540-7489(02)80283-8

Polycyclic Aromatic Hydrocarbons Identified in Soot Extracts from Domestic Coal-Burning Stoves of Henan Province, China
journal, May 2001

  • Wornat, Mary J.; Ledesma, Elmer B.; Sandrowitz, Alyssa K.
  • Environmental Science & Technology, Vol. 35, Issue 10
  • DOI: 10.1021/es001664b

Photoionization Efficiencies of Five Polycyclic Aromatic Hydrocarbons
journal, June 2017

  • Johansson, K. Olof; Campbell, Matthew F.; Elvati, Paolo
  • The Journal of Physical Chemistry A, Vol. 121, Issue 23
  • DOI: 10.1021/acs.jpca.7b02991

Single- and double-ionization potentials of polycyclic aromatic hydrocarbons and fullerenes by photon and electron impact
journal, November 1994

  • Tobita, S.; Leach, S.; Jochims, H. W.
  • Canadian Journal of Physics, Vol. 72, Issue 11-12
  • DOI: 10.1139/p94-138

Radial-profile and divergence measurements of combustion-generated soot focused by an aerodynamic-lens system
journal, April 2013


Numerical Characterization of Particle Beam Collimation: Part II Integrated Aerodynamic-Lens–Nozzle System
journal, June 2004

  • Zhang, Xuefeng; Smith, Kenneth A.; Worsnop, Douglas R.
  • Aerosol Science and Technology, Vol. 38, Issue 6
  • DOI: 10.1080/02786820490479833

Transmission Efficiency of an Aerodynamic Focusing Lens System: Comparison of Model Calculations and Laboratory Measurements for the Aerodyne Aerosol Mass Spectrometer
journal, July 2007

  • Liu, Peter S. K.; Deng, Rensheng; Smith, Kenneth A.
  • Aerosol Science and Technology, Vol. 41, Issue 8
  • DOI: 10.1080/02786820701422278

Formation and emission of large furans and oxygenated hydrocarbons from flames
journal, July 2016

  • Johansson, K. Olof; Dillstrom, Tyler; Monti, Matteo
  • Proceedings of the National Academy of Sciences, Vol. 113, Issue 30
  • DOI: 10.1073/pnas.1604772113

Direct Coherent Raman Temperature Imaging and Wideband Chemical Detection in a Hydrocarbon Flat Flame
journal, February 2015


An improved low-flow thermodenuder
journal, November 2007


Synchrotron photoionization measurements of combustion intermediates: Photoionization efficiency and identification of C3H2 isomers
journal, January 2005

  • TaatjesJILA visiting fellow, Septem, Craig A.; Klippenstein, Stephen J.; Hansen, Nils
  • Physical Chemistry Chemical Physics, Vol. 7, Issue 5
  • DOI: 10.1039/b417160h

Computer Generation of Molecular Structures by the SMOG Program
journal, January 1996

  • Molchanova, M. S.; Shcherbukhin, V. V.; Zefirov, N. S.
  • Journal of Chemical Information and Computer Sciences, Vol. 36, Issue 4
  • DOI: 10.1021/ci950393z

A highly efficient growth mechanism of polycyclic aromatic hydrocarbons
journal, January 2010

  • Shukla, Bikau; Koshi, Mitsuo
  • Physical Chemistry Chemical Physics, Vol. 12, Issue 10
  • DOI: 10.1039/b919644g

Comparative study on the growth mechanisms of PAHs
journal, February 2011


Two-laser photoionization supersonic jet mass spectrometry of aromatic molecules
journal, January 1988

  • Hager, James W.; Wallace, Stephen C.
  • Analytical Chemistry, Vol. 60, Issue 1
  • DOI: 10.1021/ac00152a003

Time-Dependent Mass Spectra and Breakdown Graphs. 19. Fluoranthene
journal, July 1995

  • Ling, Yun; Lifshitz, Chava
  • The Journal of Physical Chemistry, Vol. 99, Issue 28
  • DOI: 10.1021/j100028a006

Photoelektronenspektren von Phenylethinen, I. Phenylethin - Mustersonde für Substituenteneffekte
journal, October 1981

  • Elbel, Susanne; Lienert, Klaus; Krebs, Adolf
  • Liebigs Annalen der Chemie, Vol. 1981, Issue 10
  • DOI: 10.1002/jlac.198119811007

Rapid quantitative prediction of ionization energies and electron affinities of polycyclic aromatic hydrocarbons
journal, February 2007


Formation Mechanism of Polycyclic Aromatic Hydrocarbons beyond the Second Aromatic Ring
journal, May 2013

  • Kislov, V. V.; Sadovnikov, A. I.; Mebel, A. M.
  • The Journal of Physical Chemistry A, Vol. 117, Issue 23
  • DOI: 10.1021/jp402481y

A detailed kinetic modeling study of aromatics formation in laminar premixed acetylene and ethylene flames
journal, July 1997


    Works referencing / citing this record:

    Influences of the molecular fuel structure on combustion reactions towards soot precursors in selected alkane and alkene flames
    journal, January 2018

    • Ruwe, Lena; Moshammer, Kai; Hansen, Nils
    • Physical Chemistry Chemical Physics, Vol. 20, Issue 16
    • DOI: 10.1039/c7cp07743b

    An experimental study of indene pyrolysis with synchrotron vacuum ultraviolet photoionization mass spectrometry
    journal, January 2019

    • Jin, Hanfeng; Yang, Jiuzhong; Xing, Lili
    • Physical Chemistry Chemical Physics, Vol. 21, Issue 10
    • DOI: 10.1039/c8cp07285j

    Resonance-stabilized hydrocarbon-radical chain reactions may explain soot inception and growth
    journal, September 2018