✦ LIBER ✦

Kinetics and mechanism of the gas-phase thermal reaction between bis(fluoroxy) difluoromethane CF2(OF)2 and carbon monoxide

✍ Scribed by A. E. Croce; E. Castellano

Publisher: John Wiley and Sons
Year: 1982
Tongue: English
Weight: 472 KB
Volume: 14
Category: Article
ISSN: 0538-8066
DOI: 10.1002/kin.550140607

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✦ Synopsis

The kinetics of the gas-phase thermal reaction between CFz(0F)z and CO has been studied in a static system a t temperatures ranging between 110 and 140°C. The only reaction products were CFz0 and Con, giving the following stoichiometry:

The reaction is homogeneous. The rate is strictly second order in CFz(0F)z and CO, and is not affected by the total pressure or by the presence of reaction products. Oxygen promotes a sensitized oxidation of CO and inhibits the formation of CF20.

The experimental results in the absence of oxygen can be explained by a chain mechanism similar to that proposed for the reaction between FzO and CO with an overall rate constant of k = 3.63 X log exp(-20,900/RT) L/mol. s From the experimental data obtained on the oxygen-inhibited reaction, the rate constant for the primary process can be calculated:

The chain length Y = 2.5 is independent of the temperature. Taking for collision diameters

G C F ~( O F ) ~

= 6 A and uco = 3.74 A, a value (Y = 5.3 X CFz(OF)n + CO -CFz(0)OF + FCO k l = 1.45 X lo9 exp(-20,900/RT) L/mol. s for the steric factor is obtained.

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