Nonstoichiometric compounds

Article By:

Sienko, Michell J. Formerly, Department of Chemistry, Cornell University, Ithaca, New York.

Last reviewed:January 2020

DOI:https://doi.org/10.1036/1097-8542.456100

Chemical compounds in which the relative number of atoms is not expressible as the ratio of small whole numbers, hence compounds for which the subscripts in the chemical formula are not rational (for example, Cu_1.987S). Sometimes they are called berthollide compounds to distinguish them from daltonides, in which the ratio of atoms is generally simple. Nonstoichiometry is a property of the solid state and arises because a fraction of the atoms of a given kind may be (1) missing from the regular structure (for example, Fe_1−δO), (2) present in excess over the requirements of the structure (for example, Zn_1+δO), or (3) substituted by atoms of another kind (for example, Bi₂Te_3±δ). The resulting materials are generally of variable composition, intensely colored, metallic or semiconducting, and different in chemical reactivity from the parent stoichiometric compounds from which they are derived. Nonstoichiometry is best known in the binary compounds of the transition elements, particularly the hydrides, oxides, chalcogenides, pnictides, carbides, and borides. It is also well represented in the so-called insertion or intercalation compounds, in which a metallic element or neutral molecule has been inserted in a stoichiometric host. Nonstoichiometric compounds are important in some solid-state devices (such as rectifiers, thermoelectric generators, and photodetectors) and are probably formed as chemical intermediates in many reactions involving solids (for example, heterogeneous catalysis and metal corrosion).

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