Cited by 46Lignin and Wood ChemistryThermochemical Biomass Conversion ProcessesAdvanced Combustion Engine Technologies

Molecular Products and Fundamentally Based Reaction Pathways in the Gas-Phase Pyrolysis of the Lignin Model Compound p-Coumaryl Alcohol

Open access
Asatryan, Rubik, Bennadji, Hayat, Bozzelli, Joseph W., Ruckenstein, Eli, Khachatryan, Lavrent·2017·The Journal of Physical Chemistry A

Abstract

The fractional pyrolysis of lignin model compound para-coumaryl alcohol (p-CMA) containing a propanoid side chain and a phenolic OH group was studied using the System for Thermal Diagnostic Studies at temperatures from 200 to 900 °C, in order to gain mechanistic insight into the role of large substituents in high-lignin feedstocks pyrolysis. Phenol and its simple derivatives p-cresol, ethyl-, propenyl-, and propyl-phenols were found to be the major products predominantly formed at low pyrolysis temperatures (<500 °C). A cryogenic trapping technique was employed combined with EPR spectroscopy to identify the open-shell intermediates registered at pyrolysis temperatures above 500 °C. These were characterized as radical mixtures primarily consisting of oxygen-linked conjugated radicals. A comprehensive potential energy surface analysis of p-CMA and p-CMA + H atom systems was performed using various DFT protocols to examine the possible role of concerted molecular eliminations and free-radical mechanisms in the formation of major products. Other significant unimolecular concerted reactions along with formation and decomposition of primary radicals are also described and evaluated. The calculations suggest that a set of the chemically activated secondary radical channels is relevant to the low temperature product formation under fractional pyrolysis conditions.

The claims and statistics of this paper haven’t been checked yet.

Run the check — free, no account needed. It reads the open-access text and checks the sources it cites.

A few free checks a day · papers already verified open instantly · results are public

Integrity signals

Registry

Crossref · 10.1021/acs.jpca.7b01656

Cites

84 of 84 references verified0 citation errors · 0 not checkable

Statistics

Claims the paper makes

The claims and statistics of this paper haven’t been checked yet.

Run the check — free, no account needed. It reads the open-access text and checks the sources it cites.

A few free checks a day · papers already verified open instantly · results are public

Claims other papers make about this one

Each is checked against this paper’s own text: does it say what the citing paper says it does?

  • Cresol-type compounds can also be generated from p-hydroxyphenyl units via depolymerization (P3 and P4).

    “In addition, cresol-type compounds can also be generated from p-hydroxyphenyl units via depolymerization (P3 and P4) [167].”

    From A review on lignin pyrolysis: pyrolytic behavior, mechanism, and relevant upgrading for improving process efficiency (2022) · cites this paper as [167]

    The Introduction identifies p-coumaryl alcohol as a lignin model, and the Summary of Mechanisms Relevant to the Major Product Formation reports p-cresol formation during its pyrolysis. The paper studies decomposition of the model compound, not depolymerization of p-hydroxyphenyl units within lignin; it does not establish the specified P3 and P4 routes. Page numbers are unavailable in our copy. (LLM, conf=0.88)

    Experimental — accuracy not yet measured

Self-check

Percentages, sums and reported differences re-computed from the paper’s own numbers.

The self-check needs the paper’s full text.

Cites

Flagged first, then by citations

1 of the 85 references couldn’t be matched to a known paper.

Research works printed but not linked: 9

  1. [4]Lignin and Lignans: Advances in Chemistry; Heitner C, Dimmel D, Schmidt J, Eds.; CRC Press: New York, 2010; pp 1– 10.
  2. [29]Beste A; Buchanan AC III. Challenges in the Computation of Rate Constants for Lignin Model Compounds In Rate Constant Calculation for Thermal Reactions: Methods and Applications; DaCosta H, Fan M, Eds.; John Wiley & Sons, Inc.: Hoboken, NJ, 2012; pp 191– 238.
  3. [34]Hosoya T; Kawamoto H; Saka S Role of Methoxyl Group in Char Formation. J. Anal. Appl. Pyrolysis 2009, 84, 79– 83.
  4. [47]Akazawa M; Kojima Y; Kato Y Pyrolysate Formation from Four Different Phenyl Propanols and Classification of the Initial Reaction Pathways. Int. J. Renewable Energy Technol 2015, 4, 1– 14.
  5. [50]Koirala Y; Villano SM; Dean AM; Carstensen H-H; Reyniers MF; Marin GB Development of an Improved Kinetic Mechanism for the Pyrolysis of Anisole in H2 Environment, Int. Congress On Energy (Ice 2014) - Topical Conf. 2014 AIChE Annual Meeting, Atlanta, Georgia, November, 2014, 2, 1255– 1257.
  6. [69]Cramer CJ Essentials of Computational Chemistry: Theories and Methods; Wiley: New York, 2002.
  7. [85]Asatryan R; Raman S; Bielenberg PA; Peterson B; Bozzelli JW; Weissman W Fundamentally Based Mechanism for Oxidation of Iso-Octane. Proceedings, 7th US National Combustion Meeting, Atlanta, GA, USA 2011, Vol. 1, 382– 395.
  8. [91]Mach K; Mills GP; Raynor JB Low Pressure Pyrolysis of Hexamethyldisilane: ESR Identification of Radical Intermediates. J. Organomet. Chem 1997, 532, 229– 233.
  9. [93]Asatryan R; Davtyan AH; Khachatryan L; Dellinger B Theoretical Study of Open-Shell ipso-Addition and bis-keto Dimer Interconversion Reactions Related to Gas-Phase Formation of PCDD/Fs from Chlorinated Phenols. Organohalogen Compd. 2002, 56, 277– 280.

Cited by

Sorted by citations

Authors
Asatryan, R., Bennadji, H., Bozzelli, J. W., Ruckenstein, E., & Khachatryan, L.
Affiliations
  • University at Buffalo, State University of New York (US)
  • Louisiana State University (US)
  • New Jersey Institute of Technology (US)
Corresponding author
Asatryan, Rubik
Venue
The Journal of Physical Chemistry A
Published
2017-04-26
Volume
121
Issue
18
Pages
3352-3371
ISSN
  • 1089-5639 (ISSN-L)
  • 1520-5215
OpenAlex
W2606203583
Cited by
46
References
85
Citations by year
2026: 2 · 2025: 5 · 2024: 4 · 2023: 5 · 2022: 3 · 2021: 6 · 2020: 9 · 2019: 6 · 2018: 4 · 2017: 2
FWCI
2.59
Type
journal article
Language
en
Open access
Locations
  • The Journal of Physical Chemistry A (publishedVersion)
  • PubMed (publishedVersion)
  • PubMed Central (acceptedVersion)
  • Civil War Book Review (submittedVersion)
Funders
National Science Foundation (CBET 1330311)
Topics
  • Physical Sciences › Engineering › Biomedical Engineering › Lignin and Wood Chemistry
  • Physical Sciences › Engineering › Biomedical Engineering › Thermochemical Biomass Conversion Processes
  • Physical Sciences › Chemical Engineering › Fluid Flow and Transfer Processes › Advanced Combustion Engine Technologies
Keywords
p-coumaryl alcohol, lignin model compounds, gas-phase pyrolysis, reaction mechanism, phenol formation, p-cresol, phenyl radical, potential energy surface, concerted elimination, radical mechanism, unimolecular reactions, substituent effects

About these checks

Registry, retraction, Cites and statistics results are computed, not judged, with one exception: a printed reference that no index lists is read once by a model before it counts as a citation error. Claims are extracted by a model and kept only when their quote appears verbatim in the text; each cited source is then checked, with a model’s help, for whether it says what the claim relies on. Those verdicts can be wrong — read the claim’s quote and the cited source before relying on one.

Statistics and arithmetic are recomputed, not judged.

Confidence bands are shown only for fields calibrated on our annotated test set. None is calibrated yet, so no band is shown.

What counts as a claim ›How we measure confidence ›How we check this ›

Are you an author, or do you see a problem with this page? Request a review