Journal
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
Volume 60, Issue 25, Pages 9080-9087Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.iecr.1c01504
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- Australian Research Council
- Ventia Pty Ltd.
- SUEZ Ventia Joint Venture
- Australian Government
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The kinetics of pyrolysis of PFOS in inert bath gases were studied in two flow reactors made of alpha-alumina and stainless steel, showing that PFOS decomposes by first eliminating HF to form an unstable sultone, followed by rapid liberation of SO2 and formation of perfluorooctanoyl fluoride. The rate constant for the formation of HF and SO2 was found to be k(1) = (1.3 +/- 0.5) x 10(14) exp(-253 +/- 5 kJ/mol/RT) s(-1) in the stainless steel reactor.
Kinetics of pyrolysis of the pollutant perfluorooctane-sulfonic acid (PFOS) in inert bath gases have been studied in two flow reactors constructed of alpha-alumina and of stainless steel (SS) at temperatures between 400 and 615 degrees C. Results from the SS reactor give support to previous and our own quantum chemical calculations based on smaller perfluorinated sulfonates, according to which initiation of decomposition of PFOS first takes place by elimination of HF to form an unstable alpha-sultone with a rate constant, k(1). The sultone then rapidly liberates SO2 and forms perfluorooctanoyl fluoride with a rate constant, k(2) with k(2) >> k(1) such that the overall rate constant k' approximate to k(1). Products observed from both reactors in the above temperature range comprised HF, SO2, and perfluorooctanoyl fluoride. The value of the rate constant for the formation of HF and SO2 measured in the SS reactor was found to be k(1) = (1.3 +/- 0.5) x 10(14) exp(-253 +/- 5 kJ/mol/RT) s(-1).
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