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Competitive reactions of organophosphorus radicals on coke surfaces

Saron Catak UGent, Karen Hemelsoet UGent, Laura Hermosilla UGent, Michel Waroquier UGent and Veronique Van Speybroeck UGent (2011) CHEMISTRY-A EUROPEAN JOURNAL. 17(43). p.12027-12036
abstract
The efficacy of organophosphorus radicals as anticoking agents was subjected to a computational study in which a representative set of radicals derived from industrially relevant organophosphorus additives was used to explore competitive reaction pathways on the graphene-like coke surface formed during thermal cracking. The aim was to investigate the nature of the competing reactions of different organophosphorus radicals on coke surfaces, and elucidate their mode of attack and inhibiting effect on the forming coke layer by use of contemporary computational methods. Density functional calculations on benzene and a larger polyaromatic hydrocarbon, namely, ovalene, showed that organophosphorus radicals have a high propensity to add to the periphery of the coke surface, inhibiting methyl radical induced hydrogen abstraction, which is known to be a key step in coke growth. Low addition barriers reported for a phosphatidyl radical suggest competitive aptitude against coke formation. Moreover, organophosphorus additives bearing aromatic substituents, which were shown to interact with the coke surface through dispersive π–π stacking interactions, are suggested to play a nontrivial role in hindering further stacking among coke surfaces. This may be the underlying rationale behind experimental observation of softer coke in the presence of organophosphorus radicals. The ultimate goal is to provide information that will be useful in building single-event microkinetic models. This study presents pertinent information on potential reactions that could be taken up in these models.
Please use this url to cite or link to this publication:
author
organization
year
type
journalArticle (original)
publication status
published
subject
keyword
hydrogen abstraction, density functional calculations, anticoking agents, NAPHTHA PYROLYSIS, NONCOVALENT INTERACTIONS, AB-INITIO, BENZYL DIETHYL PHOSPHITE, MOLECULAR-ORBITAL METHODS, POLYCYCLIC AROMATIC-HYDROCARBONS, PI-STACKING INTERACTIONS, DENSITY-FUNCTIONAL THEORY, radical reactions, organophosphorus radicals, THERMAL-CRACKING, THERMOCHEMICAL KINETICS
journal title
CHEMISTRY-A EUROPEAN JOURNAL
Chem.-Eur. J.
volume
17
issue
43
pages
12027 - 12036
Web of Science type
Article
Web of Science id
000297316100015
JCR category
CHEMISTRY, MULTIDISCIPLINARY
JCR impact factor
5.925 (2011)
JCR rank
18/149 (2011)
JCR quartile
1 (2011)
ISSN
0947-6539
DOI
10.1002/chem.201100712
project
HPC-UGent: the central High Performance Computing infrastructure of Ghent University
language
English
UGent publication?
yes
classification
A1
copyright statement
I have transferred the copyright for this publication to the publisher
id
1979970
handle
http://hdl.handle.net/1854/LU-1979970
date created
2012-01-06 13:54:54
date last changed
2013-09-17 10:47:36
@article{1979970,
  abstract     = {The efficacy of organophosphorus radicals as anticoking agents was subjected to a computational study in which a representative set of radicals derived from industrially relevant organophosphorus additives was used to explore competitive reaction pathways on the graphene-like coke surface formed during thermal cracking. The aim was to investigate the nature of the competing reactions of different organophosphorus radicals on coke surfaces, and elucidate their mode of attack and inhibiting effect on the forming coke layer by use of contemporary computational methods. Density functional calculations on benzene and a larger polyaromatic hydrocarbon, namely, ovalene, showed that organophosphorus radicals have a high propensity to add to the periphery of the coke surface, inhibiting methyl radical induced hydrogen abstraction, which is known to be a key step in coke growth. Low addition barriers reported for a phosphatidyl radical suggest competitive aptitude against coke formation. Moreover, organophosphorus additives bearing aromatic substituents, which were shown to interact with the coke surface through dispersive \ensuremath{\pi}--\ensuremath{\pi} stacking interactions, are suggested to play a nontrivial role in hindering further stacking among coke surfaces. This may be the underlying rationale behind experimental observation of softer coke in the presence of organophosphorus radicals. The ultimate goal is to provide information that will be useful in building single-event microkinetic models. This study presents pertinent information on potential reactions that could be taken up in these models.},
  author       = {Catak, Saron and Hemelsoet, Karen and Hermosilla, Laura and Waroquier, Michel and Van Speybroeck, Veronique},
  issn         = {0947-6539},
  journal      = {CHEMISTRY-A EUROPEAN JOURNAL},
  keyword      = {hydrogen abstraction,density functional calculations,anticoking agents,NAPHTHA PYROLYSIS,NONCOVALENT INTERACTIONS,AB-INITIO,BENZYL DIETHYL PHOSPHITE,MOLECULAR-ORBITAL METHODS,POLYCYCLIC AROMATIC-HYDROCARBONS,PI-STACKING INTERACTIONS,DENSITY-FUNCTIONAL THEORY,radical reactions,organophosphorus radicals,THERMAL-CRACKING,THERMOCHEMICAL KINETICS},
  language     = {eng},
  number       = {43},
  pages        = {12027--12036},
  title        = {Competitive reactions of organophosphorus radicals on coke surfaces},
  url          = {http://dx.doi.org/10.1002/chem.201100712},
  volume       = {17},
  year         = {2011},
}

Chicago
Catak, Saron, Karen Hemelsoet, Laura Hermosilla, Michel Waroquier, and Veronique Van Speybroeck. 2011. “Competitive Reactions of Organophosphorus Radicals on Coke Surfaces.” Chemistry-a European Journal 17 (43): 12027–12036.
APA
Catak, S., Hemelsoet, K., Hermosilla, L., Waroquier, M., & Van Speybroeck, V. (2011). Competitive reactions of organophosphorus radicals on coke surfaces. CHEMISTRY-A EUROPEAN JOURNAL, 17(43), 12027–12036.
Vancouver
1.
Catak S, Hemelsoet K, Hermosilla L, Waroquier M, Van Speybroeck V. Competitive reactions of organophosphorus radicals on coke surfaces. CHEMISTRY-A EUROPEAN JOURNAL. 2011;17(43):12027–36.
MLA
Catak, Saron, Karen Hemelsoet, Laura Hermosilla, et al. “Competitive Reactions of Organophosphorus Radicals on Coke Surfaces.” CHEMISTRY-A EUROPEAN JOURNAL 17.43 (2011): 12027–12036. Print.