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- Title
Methylphosphonic Acid Oxidation Kinetics in Supercritical Water.
- Authors
Sullivan, Patricia A.; Tester, Jefferson W.
- Abstract
Oxidation and hydrolysis rates of the model organo-phosphorus compound, methylphosphonic acid (MPA), were measured in supercritical water. The effects of MPA concentration (0.5 to 1.0 mM), oxygen concentration (1.0 to 3.8 mM), temperature (478 to 572°C) and pressure (138 to 277 bar) on oxidation rates were determined for residence times ranging from 3.0 to 9.5 s. The MPA oxidation rate was dependent on both oxygen concentration and pressure (or water density), but was relatively independent of initial MPA concentration. The only phosphorus-containing product was phosphoric acid, while the primary carbon-containing products included carbon monoxide, methane, and carbon dioxide. Data were regressed to an empirical global rate law with a pre- exponential factor of 1014.0±1.6 (s-1 M-1.47), an activation energy of 228±22 kJ/mol, a first-order MPA dependence, an oxygen order of 0.30±0.18, and a water order of 1.17±0.30 (all parameters to 95% confidence). A macroscopic model was also developed to estimate reaction rate constants and oxygen dependences of the major identified reaction pathways.
- Subjects
HYDROLYSIS; ORGANOPHOSPHORUS compounds; PHOSPHONIC acids; OXYGEN; OXIDATION; PHOSPHORIC acid; CARBON; CARBON monoxide; CARBON dioxide
- Publication
AIChE Journal, 2004, Vol 50, Issue 3, p673
- ISSN
0001-1541
- Publication type
Article
- DOI
10.1002/aic.10061