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Thermochemical properties from ab initio calculations: π‐ and σ‐Free radicals of importance in soot formation: • C 3 H 3 (propargyl), • C 4 H 3 , • C 13 H 9 (phenalenyl), • C 6 H 5 (phenyl), • C 10 H 7 (naphthyl), • C 14 H 9 (anthryl), • C 14 H 9 (phenanthryl), • C 16 H 9 (pyrenyl), • C 12 H 7 (acenaphthyl), and • C 12 H 9 (biphenylyl)
Author(s) -
Rossi Michel J.
Publication year - 2008
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.20326
Subject(s) - radical , chemistry , standard enthalpy of formation , bond dissociation energy , propargyl , benzene , soot , hydrocarbon , ab initio , ab initio quantum chemistry methods , thermochemistry , dissociation (chemistry) , combustion , computational chemistry , analytical chemistry (journal) , organic chemistry , molecule , catalysis
The calculated difference in the standard heat of formation Δ Δ f H°(298.15) of n ‐ and i ‐C 4 H 3 • free radicals is 37.9 kJ mol −1 for G3MP2B3 and 45.0 kJ mol −1 for CCSD(T)‐CBS (W1U) calculations, which seems to preclude the direct even‐carbon radical pathway to benzene and higher PAH (polycyclic aromatic hydrocarbon) formation including soot in a hydrocarbon flame. For the phenyl‐type σ‐radicals listed in the title, absolute values of Δ f H°(298.15) have been calculated using G3MP2B3‐computed values of bond dissociation energies D°(298.15) and combined with experimental values of Δ f H° (298.15) for the parent hydrocarbon because of a slight systematic overprediction of the thermodynamic stability of large PAHs by the applied computational G3MP2B3 method. Standard enthalpies of formation Δ f H°(298.15) as well as absolute entropies S° and heat capacities C° p are given for a series of π‐ and σ‐free radicals important to combustion as a function of temperature. A spread of roughly 40 kJ mol −1 in the average CH bond strength of PAH leading to σ‐radicals has been calculated, the lowest leading to 4‐phenanthryl (463.6 kJ mol −1 ), the highest leading to 2‐biphenylyl radical (502.5 kJ mol −1 ). © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 395–415, 2008