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- W2024232105 abstract "The pyrolyosis of CF 3 OOCF 3 (BTMP) was studied in the gas phase from 5 to 100 Torr BTMP pressure and between 197 and 244 °C in a clean nickel reactor by the static method. CF 3 O radicals, due to the initial split[Formula: see text] were scavenged by SO 3 F radicals produced in situ by the thermal decomposition of their dimer S 2 O 6 F 2 . Under these conditions, CF 3 OOSO 2 F is the only product of BTMP pyrolysis, as shown by gas chromatographic analysis. Thus the BTMP pyrolysis becomes fully inhibited and the rate of accumulation of CF 3 OOSO 2 F is a measure of k 1 . The rate constant k 1 turns out to be pressure-insensitive under the experimental conditions, from which it is inferred that k 1 is actually k 1∞ , the limiting high-pressure unimolecular rate constant for reaction 1. Its temperature dependence yields the result[Formula: see text]This result is compared with other values of the O—O bond dissociation energy in BTMP. The experimental expression for k 1 ∞ is used to construct the pressure falloff of k 1 following the procedure of Forst. The calculation confirms that falloff begins only below 10 Torr." @default.
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- W2024232105 date "1975-05-15" @default.
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- W2024232105 title "Kinetics of the Fully Inhibited Thermal Decomposition of Bistrifluoromethyl Peroxide, CF<sub>3</sub>OOCF<sub>3</sub>" @default.
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- W2024232105 doi "https://doi.org/10.1139/v75-199" @default.
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