Non-stoichiometric compound
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[[Image:Defecttypes.png|thumb|350px|[[Crystallographic defects]] can cause solids to be non-stoichiometric]]'''Non-stoichiometric compounds''' are [[chemical compound]]s with an [[chemical element|elemental]] composition that cannot be represented by a ratio of well-defined [[natural number]]s, and therefore violate of the [[law of definite proportions]]. Often, they are [[solid]]s that contain [[crystallographic defect|crystallographic point defects]] that result in the excess or deficiency of an element. Since 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.<ref>J. Gopalakrishnan, Chintamani Nagesa Ramachandra Rao. ''New Directions in Solid State Chemistry''. Cambridge University Press, 1997, p. 230.</ref>
Nonstoichiometry is pervasive for [[transition metal oxides]], especially when the metal is not in its highest [[oxidation state]].<ref>{{Greenwood&Earnshaw}}. pp. 642-644</ref> For example, although [[wüstite]] ([[Iron(II) oxide|ferrous oxide]]) has an ideal ([[stoichiometric]]) formula FeO, the actual stoichiometry is closer to Fe<sub>0.95</sub>O. For each "missing" Fe<sup>2+</sup> ion, the crystal contains two Fe<sup>3+</sup> 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<sub>1-x</sub>O, where ''x'' is a small number (0.05 in the previous example) representing the deviation from the "ideal" formula.<ref>Lesley E. Smart. ''Solid State Chemistry: An Introduction'', 3rd edition. CRC Press, 2005, p. 214.</ref> Nonstoichiometry is especially important in [[solid state chemistry|solids]], which are three-dimensional polymers and which 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.
Non-stoichiometric compounds are also known as ''berthollides'' (as opposed to the stoichiometric compounds or ''daltonides''). The names come from [[Claude Louis Berthollet]] and [[John Dalton]], respectively, who in the 19th century advocated rival theories of the composition of substances. Although Dalton "won" for the most part, it was later recognized that the law of definite proportions did have important exceptions.<ref>Henry Marshall Leicester. ''The Historical Background of Chemistry''. Courier Dover Publications, 1971, p. 153.</ref>
==Examples==
===Cuprates===
Many non-stoichiometric compounds are important in [[solid state chemistry]], and have applications in [[ceramic]]s and as [[superconductor]]s. For example, [[yttrium barium copper oxide]], arguably the most notable [[high-temperature superconductor]], is a non-stoichiometric solid with a formula represented by YBa<sub>2</sub>Cu<sub>3</sub>O<sub>7−''x''</sub>. The critical temperature of the superconductor depends on the exact value of ''x''. The stoichiometric species has x = 0, but this value can be as great as 1.
===Tungsten oxides===
It is sometimes difficult to determine if a material is non-stoichiometric or if the formula is best represented by large numbers. The oxides of tungsten illustrate this situation. Starting from the idealized material tungsten trioxide, one can generate a series of related materials that are slightly deficient in oxygen. These oxygen-deficient species can be described as WO<sub>3-x</sub> but in fact they are stoichiometric species with large unit cells with the formulas W<sub>n</sub>O<sub>(3n-2)</sub> where n = 20, 24, 25, 40. Thus, the last species can be described with the stoichiometric formula W<sub>40</sub>O<sub>118</sub>, whereas the description non-stoichiometric WO<sub>2.95</sub> implies a more random distribution of oxide vacancies.<ref>Shriver, D. F.; Atkins, P. W.; Overton, T. L.; Rourke, J. P.; Weller, M. T.; Armstrong, F. A. “Inorganic Chemistry” W. H. Freeman, New York, 2006. ISBN: 0-7167-4878-9.</ref>
===Other cases===
*[[Palladium hydride]] is a nonstoichiometric material of the approximate composition PdH<sub>x</sub> (0.02 < x < 0.58). This solid conducts hydrogen by virtue of the mobility of the hydrogen atoms within the solid.
*The [[coordination polymer]] [[Prussian Blue]], nominally Fe<sub>7</sub>(CN)<sub>18</sub> is well known to form non-stoichiometrically. In fact the non-stoichiometric phases exhibit more useful properties associated with the ability of the solid to absorb [[caesium]] and [[thallium]] ions.
===Defects vs non-stoichiometry===
The cuprate superconductors highlight the concept of a "defect" structures, which is related to non-stoichiometry. YBa<sub>2</sub>Cu<sub>3</sub>O<sub>7−''x''</sub> can be viewed as a variant of the [[perovskite]] family of materials, which have idealized stoichiometry ABO<sub>3</sub>. For the cuprates, Y + Ba occupy "A sites" whereas Cu occupies the "B sites". The non-defect material would have the stoichiometry YBa<sub>2</sub>Cu<sub>3</sub>O<sub>9</sub>. Using this way of describing a structure, W<sub>40</sub>O<sub>118</sub> is said to be a defect variant of WO<sub>3</sub>.
===Oxidation catalysis===
Many useful chemicals are produced by the reactions of [[hydrocarbon]]s with [[oxygen]], a conversion that is [[catalysis|catalyzed]] by metal oxides. The process operates via the transfer of "lattice" oxygen to the hydrocarbon substrate, a step that generates temporarily a vacancy. In a subsequent step, the oxygen vacancy is replenished by the O<sub>2</sub>. Such catalysts rely on the ability of the metal oxide to form phases that are not stoichiometric. An analogous sequence of events describes other kinds of atom-transfer reactions including [[hydrogenation]] and [[hydrodesulfurization]] catalysed by solid catalysts. These considerations also highlight the fact that stoichiometry is determined by the interior of crystals: the surfaces of crystals often do not follow the stoichiometry of the bulk. The complex structures on surfaces is described by the term "surface reconstruction."
===Ion conduction===
The migration of atoms within a solid is strongly influenced by the defects associated non-stoichiometry. These defect sites provide pathways for atoms and ions to migrate through the otherwise dense ensemble of atoms that form the crystals. Oxygen sensors and solid state batteries are two applications that rely on oxide vacancies.
==See also==<!--until we can write something better than a list-->
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==References==
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[[Category:Solid-state chemistry]]
[[Category:Inorganic chemistry]]
[[ca:Berthòl·lid]]
[[es:Compuestos no estequiométricos]]
[[it:Composto non stechiometrico]]
[[ja:不定比化合物]]
[[pl:Bertolidy]]
[[uk:Бертоліди]]
[[ru:Бертоллиды]]
[[zh:非整比化合物]]