Nonstoichiometric compound

Non-stoichiometric compounds are chemical compounds, almost always solid inorganic compounds, having elemental composition whose proportions cannot be represented by integers; most often, in such materials, some small percentage of atoms are missing or too many atoms are packed into an otherwise perfect lattice work.

Contrary to earlier definitions, modern understanding of non-stoichiometric compounds view them as homogenous, and not mixtures of stoichiometric chemical compounds. Since the solids are overall electrically neutral, the defect is compensated by a change in the charge of other atoms in the solid, either by changing their oxidation state, or by replacing them with atoms of different elements with a different charge. Many metal oxides and sulfides have non-stoichiometry examples; for example, stoichiometric iron(II) oxide, which is rare, has the formula FeO, whereas the more common material is nonstoichiometric, with the formula Fe_0.95O. Non-stoichiometric compounds exhibit special electrical or chemical properties because of the defects; for example, when atoms are missing, the other atoms can move through the solid more rapidly. Non-stoichiometric compounds have applications in ceramic and superconductive material and in electrochemical (i.e., battery) system designs.

Nonstoichiometry is pervasive for metal oxides, especially when the metal is not in its highest oxidation state. For example, although wüstite (ferrous oxide) has an ideal (stoichiometric) formula FeO, the actual stoichiometry is closer to Fe_0.95O. The non-stoichiometry reflect the ease of oxidation of Fe²⁺ to Fe³⁺ effectively replacing a small portion of Fe²⁺ with two thirds their number of Fe³⁺. Thus for every three "missing" Fe²⁺ ions, the crystal contains two Fe³⁺ ions to balance the charge. The composition of a non-stoichiometric compound usually varies in a continuous manner over a narrow range. Thus, the formula for wüstite is written as Fe_1−xO, where x is a small number (0.05 in the previous example) representing the deviation from the "ideal" formula. Nonstoichiometry is especially important in solid, three-dimensional polymers that can tolerate mistakes. To some extent, entropy drives all solids to be non-stoichiometric. But for practical purposes, the term describes materials where the non-stoichiometry is measurable, usually at least 1% of the ideal composition.

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