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DFT Analyses of Reaction Pathways and Temperature Effects on various Guaiacol Conversion Reactions in Gas Phase Environment
Author(s) -
Verma Anand Mohan,
Kishore Nanda
Publication year - 2016
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.201601139
Subject(s) - guaiacol , thermochemistry , chemistry , atmospheric temperature range , exothermic reaction , thermodynamics , cyclohexanone , density functional theory , transition state , cyclopentanone , computational chemistry , organic chemistry , catalysis , physics
Guaiacol component represents the phenolic fraction of bio‐oil. In this numerical study, six reaction pathways originating from guaiacol and yielding anisole, phenol, cyclopentanone and cyclohexanone as the major end products with various intermediates, are carried out. The transition state optimizations, normal mode vibrational frequencies, and intrinsic reaction coordinate calculations are performed under the density functional theory (DFT) framework at B3LYP/6‐311+g(d,p) level of theory. The thermochemistry calculations are carried out at 1 atm pressure and at a wide range of temperature between 298–898 K with an interval temperature of 100 K. Results indicate that all six reactions are both exothermic and spontaneous at each temperature point, however, pathways 1, 2, and 3 show increase in exothermicity and spontaneity with increase in temperature but pathways 4, 5, and 6 show the increase in exothermicity only with increase in temperature while decrement in reaction free energies with increasing temperature.