Papers - A Study of the Homogeneity Limits of Wustite (FeO) by X-ray Methods (With Discussion)

In a recent article,1 the authors reported the results of an X-ray investigation on the range of solid solutions that occurs in the iron-oxygen system in the vicinity of the compound FeO, which frequently is called "wüstite." The object of that investigation was primarily to study the unusual type of solid solution phenomena involved in this range. Briefly summarized the results were: 1. The NaCl type of lattice found by earlier workers was confirmed. 2. The lattice dimensions decrease rapidly with decrease in iron content. 3. No alloy that was a homogeneous single phase was ever found at compositions beyond 76.80 per cent Fe, while the theoretical iron content of FeO is 77.73 per cent Fe. 4. Measurements of the densities and lattice constants led to the conclusion that the form of substitution was complex, an FeO group being replaced by oxygen. Such a substitution, of course, is equivalent to removing an iron atom (or ion). The ideal unit cell of FeO can be considered as containing four groups of FeO and, thus, when this type of substitution takes place, there remain in the unit cell three FeO groups and an oxygen, or a total of seven atoms with a gross formula of Fe3O4 instead of the original Fe4O4. 5. This was the only interpretation that would fit the experimental results and at the same time be consistent with (a) the previously determined fact that the FeO lattice is ionic (i, e., consists of Fe++ and O? ions) and (b) the chemical fact that as the oxygen content of the substance increases, ferrous iron becomes oxidized to ferric iron. The experimental results of this investigation are included in Fig. 1. The purpose of the present investigation was to determine the limits of this homogeneity range by means of the X-ray structure analysis. This method has been applied frequently to the study of solid solutions by Westgren and his coworkers as well as by other investigators. The principle is simple: if the change in lattice constant with composition is