Abstract
The thermal decomposition of
trifluoroacetaldehyde has been studied at temperatures between 471� and 519�,
and at pressures up to 180 mm. The main products of reaction are
trifluoromethane and carbon monoxide in equal amounts; small amounts of hexafluoroethane
and hydrogen are also formed. The experimental rate equation governing the
observed kinetics is of the form Rate = k?[CF3CHO]3/2,
where
k?
= 1012.2exp(-49000/RT) l.� mole-1 sec-1
A small surface effect is
apparent, an increase in surface area causing an increase in rate.
Inert gases, namely carbon monoxide and
dioxide, increase the rate of decomposition, the experimental rate equation
assuming the form
Rate = (k'[CF3CHO]3 + k"[CF3CHO]2.2[M])�
A mechanism is proposed which predict,^ the experimental form of the rate
equation and involves initiation through a second-order energy transfer process
followed by a radical chain mechanism, the length of which is 1200 with P(CF3CHO) = 200 mm.
Termination is considered to be through the third-order recombination of
trifluoromethyl radicals.
Cited by
8 articles.
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