title: Polycyclic aromatic hydrocarbon reaction rates with peroxy-acid treatment: prediction of reactivity using local ionization potential.
abstract: Property-Encoded Surface Translator (PEST) descriptors were found to be correlated with the degradation rates of polycyclic aromatic hydrocarbons (PAHs) by the peroxy-acid process. Reaction rate constants (k) in hr(-1) for nine PAHs (acenaphthene, anthracene, benzo[a]pyrene, benzo[k]fluoranthene, fluoranthene, fluorene, naphthalene, phenanthrene, and pyrene) were determined by a peroxy-acid treatment method that utilized acetic acid, hydrogen peroxide, and a sulphuric acid catalyst to degrade the polyaromatic structures. Molecular properties of the selected nine PAHs were derived from structures optimized at B3LYP/6-31G(d) and HF/6-31G(d) levels of theory. Properties of adiabatic and vertical ionization potential (IP), highest occupied molecular orbitals (HOMO), HOMO/lowest unoccupied molecular orbital (LUMO) gap energies and HOMO/singly occupied molecular orbital (SOMO) gap energies were not correlated with rates of peroxy-acid reaction. PEST descriptors were calculated from B3LYP/6-31G(d) optimized structures and found to have significant levels of correlation with k. PIP Min described the minimum local IP on the surface of the molecule and was found to be related to k. PEST technology appears to be an accurate method in predicting reactivity and could prove to be a valuable asset in building treatment models and in remediation design for PAHs and other organic contaminants in the environment.
authors.affiliation: Department of Chemistry and Chemical Biology, Rensselaer Polytechnic Institute, Troy, USA.
authors.forename: J M
authors.initials: JM
authors.lastname: Shoulder
authors.forename: N S
authors.initials: NS
authors.lastname: Alderman
authors.forename: C M
authors.initials: CM
authors.lastname: Breneman
authors.forename: M C
authors.initials: MC
authors.lastname: Nyman
mesh_terms: D004785:Environmental Pollutants / Q000737:chemistry / Q000378:metabolism*; D006861:Hydrogen Peroxide / Q000378:metabolism; D007700:Kinetics; D010463:Peracetic Acid / Q000378:metabolism*; D011084:Polycyclic Aromatic Hydrocarbons / Q000737:chemistry / Q000378:metabolism*; D013464:Sulfuric Acids / Q000378:metabolism
chemical_list: D004785:Environmental Pollutants; D011084:Polycyclic Aromatic Hydrocarbons; D013464:Sulfuric Acids; D006861:Hydrogen Peroxide; D010463:Peracetic Acid; C033158:sulfuric acid