Nonequilibrium Chemical Reactivity of Polycrystalline Iron Foils

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Abstract
It is shown that continuous oxide films form on iron specimens in contaminated hydrogen atmospheres in which the metal is the thermodynamically favored phase; the explanation being that (1) oxygen in the gas does not come to equilibrium with the hydrogen but reacts with the iron, (2) the high activation energy of nucleation prevents reduction at the oxide-gas interface, and (3) hydrogen cannot diffuse through the continuous oxide film to the oxide-metal interface. The nonequilibrium nature of the oxidation is demonstrated by the finding that simultaneously with the formation of the continuous oxide films, bulk iron oxides on iron specimens become reduced. Also, reduction of the continuous oxide films proceeds readily when iron nuclei are formed by the addition of small quantities of iron carbonyl to the hydrogen stream.

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