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Kinetics and mechanism of hydrogen–oxygen difluoride reaction in magnesium

✍ Scribed by Thomas J. Houser

Publisher
John Wiley and Sons
Year
1978
Tongue
English
Weight
424 KB
Volume
10
Category
Article
ISSN
0538-8066

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✦ Synopsis

The kinetics of the Hz-OFz reaction was studied in the temperature range of 16O0-31O"C a t 1 atm total pressure in a magnesium stirred-flow reactor. initial concentration ranges were '/s-'/z mol-% OFz, 3/16-5 mol-% Hz, and ' /4-5.0 mol.% 0 2 ; helium was used as the diluent. When the reactants were in a mole ratio of 3/2 (H,/OFz), the rate of disappearance of HZ was 1.5 times that of OFz, consistent with the previously reported stoichiometry. The rate of disappearance of OF2 was strongly influenced by OF2 concentration, weakly influenced by Hz concentration, and inhibited by the oxygen formed in the reaction. An increase in the surface area did not produce a significant change in the rate of reaction. These concentration dependencies led to a proposed ten-step mechanism from which was derived the following rate equation:

where ko is a complex combination of elementary rate constants and a and 0 are elementary rate constants. An Arrhenius treatment of ko gave k o = 108.41+0.24 exp (-17,300 f 500/RT)(l./m0l)"~/sec These experimental Arrhenius parameters are lower than those predicted from reported and estimated elementary rate constants. The possibility of heterogeneous contributions is discussed.

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