Abstract
By use of reaction vessels with specially treated surfaces the homogeneous decomposition of formic acid has been studied kinetically in the range 436 to 532°C. Neither of the two simultaneous reactions (
a
) HCOOH = CO
2
+ H
2
, (
b
) HCOOH = CO + H
2
O, is retarded by the usual inhibitors of chain processes. Each appears to be molecular. Reaction (
a
) is of the first order in the range 3 to 650 mm, the first-order rate constant being given by
k
CO
2
= 10
4⋅8
exp (–30600/
RT
)s
-1
. It is suggested tentatively that the abnormal kinetic parameters might be explained by regarding the reaction as a decarboxylation of (H
+
) (HCOO¯) ion pairs present in minute concentration. Reaction (
b
) shows a pressure dependence most simply explained by a superposition of a predominant second-order component with a small first-order component. The most satisfactory interpretation of the second-order reaction is that it represents the unimolecular decomposition of dimer molecules, known to be present in formic-acid vapour. On this basis the rate constant is given by
k
CO
dimer
= 10
13⋅58
exp (–42600/
RT
)s
-1
, the kinetic parameters thus being in the normal range. The various alternative interpretations are discussed.
Cited by
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