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Group additive modeling of substituent effects in monocyclic aromatic hydrocarbon radicals
Author(s) -
Ince Alper,
Carstensen HansHeinrich,
Sabbe Maarten,
Reyniers MarieFrançoise,
Marin Guy B.
Publication year - 2017
Publication title -
aiche journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.958
H-Index - 167
eISSN - 1547-5905
pISSN - 0001-1541
DOI - 10.1002/aic.15588
Subject(s) - substituent , chemistry , radical , standard enthalpy of formation , additive function , bond dissociation energy , computational chemistry , dissociation (chemistry) , hydrocarbon , aromatic hydrocarbon , aromaticity , medicinal chemistry , organic chemistry , molecule , mathematical analysis , mathematics
The thermodynamic properties of the unsubstituted and substituted phenyl, phenoxy, anisyl, benzoyl, styryl and benzyl radicals with six substituents (hydroxy, methoxy, formyl, vinyl, methyl, and ethyl) are calculated with the bond additivity corrected (BAC) post‐Hartree‐Fock G4 method. Bond dissociation energies of monocyclic aromatic hydrocarbons are calculated and used to identify substituent interactions in these radicals. Benson's Group Additivity (GA) scheme is extended to aromatic radicals by defining 6 GAV and 29 NNI parameters through least squares regression to a database of thermodynamic properties of 369 radicals. Comparison between G4/BAC and GA calculated thermodynamic values shows that the standard enthalpies of formation generally agree within 4 kJ mol −1 , whereas the entropies and the heat capacities deviate less than 4 J mol −1 K −1 . © 2016 American Institute of Chemical Engineers AIChE J , 63: 2089–2106, 2017