RESUMEN
The gliding electric discharge (or "glidarc") technique is a new advanced oxidation process used for the degradation of organic solutes or spent solvents. Discharges in humid air at atmospheric pressure produce active species (i.e., .OH and .NO) that are able to oxidize organic target up to carbon oxides and water. Aqueous solutions of triethylphosphate (TEP), a warfare agent simulant, are exposed to a glidarc in humid air to evaluate the solute stability under the impinging flux of active species. TEP was degraded and the overall zero order kinetic rate (k(0)=3.4 x 10(-4)mol h(-1)) was compared with that of previously considered tributylphosphate. The total degradation of TEP is monitored by the formation of H(3)PO(4) as the ultimate oxidation product of phosphorus by total organic carbon measurements. Extra investigation was performed on dimethylmethylphosphonate to examine the potential influence of the molecule symmetry on the degradation rate.
Asunto(s)
Sustancias para la Guerra Química/química , Oxígeno/química , Fósforo/química , Eliminación de Residuos/métodos , Solventes/química , Carbono/química , Técnicas de Química Analítica/métodos , Radical Hidroxilo , Cinética , Modelos Químicos , Organofosfatos/química , Organofosfonatos/química , Fosfitos/química , Ácidos Fosfóricos/química , Presión , TemperaturaRESUMEN
The gliding arc in humid air is a relevant source of free radicals and strongly oxidising species such as HO* (shown by emission spectroscopy), which are able to degrade organic wastes. This feature was used in a new process for mineralising spent tributylphosphate (TBP) which is an important waste from nuclear industry. The degradation kinetics is examined by monitoring the conversion of TBP into phosphoric acid in a batch reactor. The kinetics exhibits three steps and especially an overall zero-order linear step with a rate of 10 mmol h(-1) at the beginning of the treatment. This zero-order step agrees with a surface oxidation process. After a 13.7h treatment, about 45% of the TBP is converted into inorganic phosphorus compounds, with phosphoric acid as the major product (63% of inorganic phosphorus compounds), and at least 19.5% is not degraded. Dibutylphosphoric acid (HDBP) was identified as the main by-product by a nuclear magnetic resonance technique, infrared spectroscopy and gas chromatography.