Formation of small aromatic molecules in a sooting ethylene flame

Harris, Stephen J.; Weiner, Anita M.; Blint, Richard J.

doi:10.1016/0010-2180(88)90099-5

Cited by 139 publications

(54 citation statements)

References 13 publications

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“…If we were to extend the first two steps in the reaction sequence as shown above to the oxidation of activated 2-fused aromatic rings and higher then the overall reaction step, C2n+4Hn+4+02~C2n+3Hn+4+CO+O (n=l,3,5 ...), indicates fused-rings containing a shared C5 side structure can readily react with cyclopentadienyl radicals by the same mechanism as cyclopentadienyl self-combination 1261 and form larger PAHs. However, self-combination of fused-rings containing a shared C5 side structure to form larger PAHs is not likely to occur because aromaticity in either fused-ring structure would have to be destroyed, which would require overcoming a high energy barrier.…”

Section: C@5ch3+h++cand6+ch3 and C @~C H~+ H O~h C~h~c H O + O H Then Cmentioning

confidence: 99%

Experimental and modeling investigation of aromatic and polycyclic aromatic hydrocarbon formation in a premixed ethylene flame

Castaldi

Marinov

Melius

et al. 1996

Symposium (International) on Combustion

172

119

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Section: C@5ch3+h++cand6+ch3 and C @~C H~+ H O~h C~h~c H O + O H Then Cmentioning

confidence: 99%

Experimental and modeling investigation of aromatic and polycyclic aromatic hydrocarbon formation in a premixed ethylene flame

Castaldi

Marinov

Melius

et al. 1996

Symposium (International) on Combustion

172

119

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“…Herein BDEs of various aryl radicals formed from 13 PAHs, that is, benzene, naphthalene, anthracene, tetracene, phenanthrene, benzo [c] Figure 1) are studied, to determine the influence of the local polyaromatic environment on the CÀH bond strength. In view of further applications, it would be desirable to classify all possible aryl radicals of PAHs into a limited set of groups, each characterized by a given reactivity.…”

Section: Introductionmentioning

confidence: 99%

“…[11][12][13][14][15][16] They can arise from incomplete combustion of organic matter and as side-products in thermal cracking units used in the petroleum industry for the production of light olefines such as ethylene and propylene. For each of these processes the homolytic bond dissociation of the organic structures of coal into smaller molecules is an important reaction step and an understanding of the thermochemistry and reactivity of specific bonds may lead to advances in coal processing.…”

Section: Introductionmentioning

confidence: 99%

Hydrocarbon Bond Dissociation Enthalpies: From Substituted Aromatics to Large Polyaromatics

2006

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Hydrocarbon-bond dissociation enthalpies (BDE) at 298 K are calculated for a set of hydrocarbons. An efficient method for calculating the BDE values is derived on the basis of a comparative study with experimental data. The methods considered are based on density functional theory (DFT) including the B3LYP, MPW1PW91, B3P86, B3PW91, MPW1P86, KMLYP, MPW1K and BMK functionals. The commonly known sequence for radical stability is quantified on the basis of BDE values. The recommended procedure is extrapolated to substituted aromatics and large polyaromatic hydrocarbons (PAHs) to obtain insight into the factors that govern the stability of the radicals. Furthermore it is shown that BDEs are also good reactivity descriptors for subsequent additions involving the formed radicals. Linear correlations, similar to classical Evans-Polanyi-Semenov plots, between the BDE and the reaction barriers for addition reactions with ethene, ethyne, propene, propyne and butadiene are found, as the exothermicity is primarily determined by the stability of the originating reactant radical.

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“…Among the proposed reactions, recombination of propargyl radicals is believed to be an important step that leads (22) to cyclic products such as benzene and C 6 H 5 (23,24). Other important radical reactions include reactions of C 4 H 3 and C 4 H 5 with acetylene (25)(26)(27). In cooler…”

mentioning

confidence: 99%

Ab initio dynamics and photoionization mass spectrometry reveal ion–molecule pathways from ionized acetylene clusters to benzene cation

Stein

Bandyopadhyay

Troy

et al. 2017

Proc. Natl. Acad. Sci. U.S.A.

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The growth mechanism of hydrocarbons in ionizing environments, such as the interstellar medium (ISM), and some combustion conditions remains incompletely understood. Ab initio molecular dynamics (AIMD) simulations and molecular beam vacuum-UV (VUV) photoionization mass spectrometry experiments were performed to understand the ion-molecule growth mechanism of small acetylene clusters (up to hexamers). A dramatic dependence of product distribution on the ionization conditions is demonstrated experimentally and understood from simulations. The products change from reactive fragmentation products in a higher temperature, higher density gas regime toward a very cold collision-free cluster regime that is dominated by products whose empirical formula is (C 2 H 2 ) n + , just like ionized acetylene clusters. The fragmentation products result from reactive ionmolecule collisions in a comparatively higher pressure and temperature regime followed by unimolecular decomposition. The isolated ionized clusters display rich dynamics that contain bonded C 4 H 4 + and C 6 H 6 + structures solvated with one or more neutral acetylene molecules. Such species contain large amounts (>2 eV) of excess internal energy. The role of the solvent acetylene molecules is to affect the barrier crossing dynamics in the potential energy surface (PES) between (C 2 H 2 ) n + isomers and provide evaporative cooling to dissipate the excess internal energy and stabilize products including the aromatic ring of the benzene cation. Formation of the benzene cation is demonstrated in AIMD simulations of acetylene clusters with n > 3, as well as other metastable C 6 H 6 + isomers. These results suggest a path for aromatic ring formation in cold acetylene-rich environments such as parts of the ISM.ion-molecule reactions | polycyclic aromatic hydrocarbons | molecular dynamics | quantum chemistry | photoionization mass spectrometry

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Formation of small aromatic molecules in a sooting ethylene flame

Cited by 139 publications

References 13 publications

Experimental and modeling investigation of aromatic and polycyclic aromatic hydrocarbon formation in a premixed ethylene flame

Experimental and modeling investigation of aromatic and polycyclic aromatic hydrocarbon formation in a premixed ethylene flame

Hydrocarbon Bond Dissociation Enthalpies: From Substituted Aromatics to Large Polyaromatics

Ab initio dynamics and photoionization mass spectrometry reveal ion–molecule pathways from ionized acetylene clusters to benzene cation

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