title: Sonochemistry of acetone and acetonitrile in aqueous solutions. A spin trapping study.
abstract: The 50 kHz sonolysis of argon-saturated water-acetone and water-acetonitrile mixtures was studied by EPR and spin trapping with 3,5-dibromo-4-nitrosobenzenesulfonate over a wide range of solvent composition. For both systems a single maximum was observed for the spin adduct yield of methyl radicals and of the radicals formed by H-abstraction from acetone and acetonitrile. These results combined with previous studies of water-methanol and water-ethanol mixtures indicate that the greater the vapor pressure of the volatile organic component, the lower the concentration of organic solute at which the maximum radical yield occurs. Methyl radicals from acetone are formed by C-C bond scission in the collapsing argon bubbles. For acetonitrile, C-H bond scission at high temperature is followed by H-addition to the triple bond and the decomposition of this intermediate radical to form methyl radicals. Since Anbar has shown (Science 161, 1343, 1961) that sonoluminescence and acoustic cavitation occur during the impact of liquid water on water with linear velocities similar to those of collapsing ocean waves, the sonochemistry of nitriles is of interest to chemical evolution studies.
authors.affiliation: Radiation Oncology Branch, National Cancer Institute, National Institutes of Health, Bethesda, Maryland 20892.
authors.forename: P
authors.initials: P
authors.lastname: Riesz
authors.forename: T
authors.initials: T
authors.lastname: Kondo
authors.forename: A J
authors.initials: AJ
authors.lastname: Carmichael
mesh_terms: D000096:Acetone / Q000737:chemistry*; D000097:Acetonitriles / Q000737:chemistry*; D004578:Electron Spin Resonance Spectroscopy; D005609:Free Radicals; D012996:Solutions; D012997:Solvents / Q000737:chemistry; D013113:Spin Labels; D014465:Ultrasonics; D014867:Water
chemical_list: D000097:Acetonitriles; D005609:Free Radicals; D012996:Solutions; D012997:Solvents; D013113:Spin Labels; D014867:Water; D000096:Acetone; C032159:acetonitrile