Global Kinetics of 2-Chlorophenol Disappearance with NaOH in Supercritical Water.

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Global power-law rate expressions were determined for the decomposition of 2-chlorophenol (2CP) when NaOH was added to supercritical water (SCW). The experiments were conducted in a plug-flow reactor at temperatures between 673 K and 733 K and pressures from 20 to 30 MPa. Reactor residence time ranged from 0.05 to 0.42 s. The initial 2CP concentrations were between 1.95 × 10–3 and 1.56 × 10–2 mol/L and the initial NaOH concentrations ranged from 1.56 × 10–2 to 7.78 × 10–2 mol/L. The global kinetics for 2CP decomposition was described by a rate law which was obtained by nonlinear regression analysis. The global power-law rate expression is rate = 109.7±1.1exp(–15600 ± 3000/RT)[2CP]1.41±0.12[NaOH]0.30±0.07[H2O]–2.71±0.21, where the activation energy is in calories per mole and all concentrations are in moles per liter. This global kinetics is very fast when it is compared to that of 2CP oxidation in SCW.

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