ISSN:
0001-1541
Keywords:
Chemistry
;
Chemical Engineering
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
,
Process Engineering, Biotechnology, Nutrition Technology
Notes:
This work determines the rate constant of hydrogen peroxide decomposition in supercritical water. Experiments were conducted at pressures ranging from 5.0 to 34.0 MPa and for temperatures up to 450°C. The rate of the homogeneous decomposition reaction is distinguished from the rate of the catalytic decomposition on the reactor surface by conducting experiments at different surface-to-volume ratios. The rate constant of H2O2 decomposition follows the expression k(s-1) = 1013.4 ± 1.2 exp[(- 180 ± 16 kJ/mol)/RT], providing a higher value than that derived from RRKM calculations. Comparison between experiments at supercritical conditions (P = 24.5 and 34.0 MPa) and experiments in high-pressure steam (P = 5.0 and 10.0 MPa) show that the efficiency of the catalytic surface reactions decreases significantly under supercritical conditions. The rate constant just mentioned was incorporated into a methanol oxidation model and the new prediction is compared with the experimental data of Rice et al. (1996), showing a distinct improvement compared to the original prediction.
Additional Material:
8 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/aic.690430919
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