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Electrochemical Oxidation of N-Nitrosodimethylamine with Boron-doped Diamond Film Electrodes

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journal contribution
posted on 01.11.2009, 00:00 by Brian P. Chaplin, Glenn Schrader, James Farrell
This research investigated NDMA oxidation by boron-doped diamond (BDD) film electrodes. Oxidation rates were measured as a function of electrode potential, current density, and temperature using rotating disk and flow-through reactors. Final NDMA reaction products were carbon dioxide, ammonium, and nitrate, with dimethylamine and methylamine as intermediate products. Reaction rates were first-order with respect to NDMA concentration and surface area normalized oxidation rates as high as 850 ± 50 L/m2-hr were observed at a current density of 10 mA/cm2. The flow-through reactor yielded mass transfer limited reaction rates that were first-order in NDMA concentration, with a half-life of 2.1 ± 0.1 min. Experimental evidence indicates that NDMA oxidation proceeds via a direct electron transfer at potentials >1.8 V/SHE with a measured apparent activation energy of 3.1 ± 0.5 kJ/mol at a potential of 2.5 V/SHE. Density functional theory calculations indicate that a direct two-electron transfer can produce a stable NDMA(+2) species that is stabilized by forming an adduct with water. The transfer of two electrons from NDMA to the electrode allows an activation-less attack of hydroxyl radicals on the NDMA(+2) water adduct. At higher overpotentials the oxidation of NDMA occurs by a combination of direct electron transfer and hydroxyl radicals produced via water electrolysis.