title: Reaction of hydroxyl radical with aromatic hydrocarbons in nonaqueous solutions: A laser flash photolysis study in acetonitrile.
abstract: Laser flash photolysis (LFP) of acetonitrile solutions of N-hydroxypyridin-2-thione in the presence of trans-stilbene generates a transient absorbance at 392 nm, attributed to the addition of hydroxyl radical to stilbene. The observed transient absorbance was used in competitive LFP experiments to determine relative rates of reaction for hydroxyl radical with a range of aromatic hydrocarbons in acetonitrile. Structure-reactivity relationships for the reaction of hydroxyl radical with arenes are derived. With these aromatic hydrocarbons, we observe a good correlation between the rates of hydroxyl-radical reaction and the ionization potential of the arene. Kinetic isotope effects are consistent with hydroxyl-radical addition being the dominant reaction pathway with the arene.
authors.affiliation: Department of Chemistry, The Ohio State University, 100 West 18th Avenue, Columbus, Ohio 43210, USA. jspoole@bsu.edu
authors.forename: James S
authors.initials: JS
authors.lastname: Poole
authors.forename: Xiaofeng
authors.initials: X
authors.lastname: Shi
authors.forename: Christopher M
authors.initials: CM
authors.lastname: Hadad
authors.forename: Matthew S
authors.initials: MS
authors.lastname: Platz
mesh_terms: D000097:Acetonitriles; D006841:Hydrocarbons, Aromatic / Q000737:chemistry*; D017665:Hydroxyl Radical / Q000737:chemistry*; D010782:Photolysis; D012996:Solutions; D013329:Structure-Activity Relationship
chemical_list: D000097:Acetonitriles; D006841:Hydrocarbons, Aromatic; D012996:Solutions; D017665:Hydroxyl Radical; C032159:acetonitrile