Atmospheric chemistry of 4:2 fluorotelomer acrylate [C4F9CH2CH2OC(O)CH=CH2]: kinetics, mechanisms, and products of chlorine-atom- and OH-radical-initiated oxidation

J Phys Chem A. 2009 Apr 2;113(13):3155-61. doi: 10.1021/jp810358k.

Abstract

Relative rate techniques were used to measure the rate constants k[Cl + C(4)F(9)CH(2)CH(2)OC(O)CH=CH(2)] = (2.21 +/- 0.16) x 10(-10) and k[OH + C(4)F(9)CH(2)CH(2)OC(O)CH=CH(2)] = (1.13 +/- 0.12) x 10(-11) cm(3) molecule(-1) s(-1) in 700 Torr of N(2) or air diluent at 296 K. The atmospheric lifetime of C(4)F(9)CH(2)CH(2)OC(O)CHCH(2) (4:2 FTAc) is determined by its reaction with OH radicals and is approximately 1 day. The chlorine-atom-initiated oxidation of 4:2 FTAc in 700 Torr of air at 296 K gives C(4)F(9)CH(2)C(O)H in molar yields of 18% and 10% in the absence and presence of NO, respectively. The OH-radical-initiated oxidation of 4:2 FTAc in 700 Torr of air in the presence of NO gives HCHO in a molar yield of (102 +/- 7)%, with C(4)F(9)CH(2)CH(2)OC(O)C(O)H (4:2 fluorotelomer glyoxylate) as the expected coproduct. The atmospheric fate of the 4:2 fluorotelomer glyoxylate will be photolysis and reaction with OH radicals, which will lead to the formation of C(4)F(9)CH(2)C(O)H and ultimately perfluorinated carboxylic acids. The atmospheric oxidation of fluorotelomer acrylates is a potential source of perfluorinated carboxylic acids in remote locations.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Acrylates / chemistry*
  • Chlorine / chemistry*
  • Fluorocarbon Polymers
  • Hydrocarbons, Fluorinated / chemistry*
  • Hydroxyl Radical / chemistry*
  • Kinetics
  • Molecular Structure
  • Nitric Oxide / chemistry
  • Oxidation-Reduction
  • Spectroscopy, Fourier Transform Infrared

Substances

  • Acrylates
  • Fluorocarbon Polymers
  • Hydrocarbons, Fluorinated
  • fluorotelomer acrylate polymers
  • Nitric Oxide
  • Hydroxyl Radical
  • Chlorine