An oxide // is a chemical compound that contains at least one oxygen atom and one other element in its chemical formula. "Oxide" itself is the dianion of oxygen, an O2– atom. Metal oxides thus typically contain an anion of oxygen in the oxidation state of −2. Most of the Earth's crust consists of solid oxides, the result of elements being oxidized by the oxygen in air or in water. Hydrocarbon combustion affords the two principal carbon oxides: carbon monoxide and carbon dioxide. Even materials considered pure elements often develop an oxide coating. For example, aluminium foil develops a thin skin of Al2O3 (called a passivation layer) that protects the foil from further corrosion. Individual elements can often form multiple oxides, each containing different amounts of the element and oxygen. In some cases these are distinguished by specifying the number of atoms as in carbon monoxide and carbon dioxide, and in other cases by specifying the element's oxidation number, as in iron(II) oxide and iron(III) oxide. Certain elements can form many different oxides, such as those of nitrogen.
Due to its electronegativity, oxygen forms stable chemical bonds with almost all elements to give the corresponding oxides. Noble metals (such as gold or platinum) are prized because they resist direct chemical combination with oxygen, and substances like gold(III) oxide must be generated by indirect routes.
Two independent pathways for corrosion of elements are hydrolysis and oxidation by oxygen. The combination of water and oxygen is even more corrosive. Virtually all elements burn in an atmosphere of oxygen, or an oxygen rich environment. In the presence of water and oxygen (or simply air), some elements— sodium—react rapidly, even dangerously, to give the hydroxides. In part for this reason, alkali and alkaline earth metals are not found in nature in their metallic, i.e., native, form. Caesium is so reactive with oxygen that it is used as a getter in vacuum tubes, and solutions of potassium and sodium, so-called NaK are used to deoxygenate and dehydrate some organic solvents. The surface of most metals consists of oxides and hydroxides in the presence of air. A well-known example is aluminium foil, which is coated with a thin film of aluminium oxide that passivates the metal, slowing further corrosion. The aluminium oxide layer can be built to greater thickness by the process of electrolytic anodising. Though solid magnesium and aluminium react slowly with oxygen at STP—they, like most metals, burn in air, generating very high temperatures. Finely grained powders of most metals can be dangerously explosive in air. Consequently, they are often used in solid-fuel rockets.
In dry oxygen, iron readily forms iron(II) oxide, but the formation of the hydrated ferric oxides, Fe2O3−x(OH)2x, that mainly comprise rust, typically requires oxygen and water. Free oxygen production by photosynthetic bacteria some 3.5 billion years ago precipitated iron out of solution in the oceans as Fe2O3 in the economically important iron ore hematite.
Oxides have a range of different structures, from individual molecules to polymeric and crystalline structures. At standard conditions, oxides may range from solids to gases.
Oxides of metalsEdit
Oxides of most metals adopt polymeric structures. The oxide typically links three metal atoms (e.g., rutile structure) or six metal atoms (carborundum or rock salt structures). Because the M-O bonds are typically strong and these compounds are crosslinked polymers, the solids tend to be insoluble in solvents, though they are attacked by acids and bases. The formulas are often deceptively simple. Many are nonstoichiometric compounds.
Carbon dioxide is the main product of fossil fuel combustion.
Carbon monoxide is the product of the incomplete combustion of carbon-based fuels and precursor to many useful chemicals.
Sulfur dioxide, the principal oxide of sulfur, is emitted from volcanoes.
Nitrous oxide ("laughing gas") is a potent greenhouse gas produced by soil bacteria.
Although most metal oxides are polymeric, some oxides are molecules. Examples of molecular oxides are carbon dioxide and carbon monoxide. All simple oxides of nitrogen are molecular, e.g., NO, N2O, NO2 and N2O4. Phosphorus pentoxide is a more complex molecular oxide with a deceptive name, the real formula being P4O10. Some polymeric oxides depolymerize when heated to give molecules, examples being selenium dioxide and sulfur trioxide. Tetroxides are rare. The more common examples: ruthenium tetroxide, osmium tetroxide, and xenon tetroxide.
Many oxyanions are known, such as polyphosphates and polyoxometalates. Oxycations are rarer, some examples being nitrosonium (NO+), vanadyl (VO2+), and uranyl (UO2+
2). Of course many compounds are known with both oxides and other groups. In organic chemistry, these include ketones and many related carbonyl compounds. For the transition metals, many oxo complexes are known as well as oxyhalides.
Conversion of a metal oxide to the metal is called reduction. Reduction can be induced with many reagents. Many metal oxides convert to metals simply by heating.
Reduction by carbonEdit
Metals are "won" from their oxides by chemical reduction, i.e. by the addition of a chemical reagent. A common and cheap reducing agent is carbon in the form of coke. The most prominent example is that of iron ore smelting. Many reactions are involved, but the simplified equation is usually shown as:
- 2 Fe2O3 + 3 C → 4 Fe + 3 CO2
Metal oxides can be reduced by organic compounds. This redox process is the basis for many important transformations in chemistry, such as the detoxification of drugs by the P450 enzymes and the production of ethylene oxide, which is converted to antifreeze. In such systems the metal centre transfers an oxide ligand to the organic compound followed by regeneration of the metal oxide, often by oxygen in air.
Reduction by heatingEdit
- 2 Ag2O → 4 Ag + O2
Reduction by displacementEdit
- Zn + CuO → ZnO + Cu
Reduction by hydrogenEdit
Apart from metals, hydrogen can also displace metal oxides to form hydrogen oxide, also known as water:
- H2 + CuO → Cu + H2O
Reduction by electrolysisEdit
Since metals that are reactive form oxides that are stable, some metal oxides must be electrolyzed to be reduced. This includes sodium oxide, potassium oxide, calcium oxide, magnesium oxide, and aluminium oxide. The oxides must be molten before immersing graphite electrodes in them:
- 2Al2O3 → 4Al + 3O2
Hydrolysis and dissolutionEdit
Oxides typically react with acids or bases, sometimes both. Those reacting only with acids are labeled basic oxides. Those reacting only by bases are called "acidic oxides". Oxides that react with both are amphoteric. Metals tend to form basic oxides, non-metals tend to form acidic oxides, and amphoteric oxides are formed by elements near the boundary between metals and non-metals (metalloids). This reactivity is the basis of many practical processes, such as the extraction of some metals from their ores in the process called hydrometallurgy.
Oxides of more electropositive elements tend to be basic. They are called basic anhydrides. Exposed to water, they may form basic hydroxides. For example, sodium oxide is basic—when hydrated, it forms sodium hydroxide. Oxides of more electronegative elements tend to be acidic. They are called "acid anhydrides"; adding water, they form oxoacids. For example, dichlorine heptoxide is an acid anhydride; perchloric acid is its fully hydrated form. Some oxides can act as both acid and base. They are amphoteric. An example is aluminium oxide. Some oxides do not show behavior as either acid or base.
The oxide ion has the formula O2−. It is the conjugate acid of the hydroxide ion, OH−, and is encountered in ionic solids such as calcium oxide. O2− is unstable in aqueous solution − its affinity for H+ is so great (pKb ~ −38) that it abstracts a proton from a solvent H2O molecule:
- O2− + H2O → 2 OH−
The equilibrium constant of aforesaid reactions is pKeq ~ −22
In the 18th century, oxides were named calxes or calces after the calcination process used to produce oxides. Calx was later replaced by oxyd.
The reductive dissolution of a transition metal oxide occurs when dissolution is coupled to a redox event. For example, ferric oxides dissolve in the presence of reductants, which can include organic compounds. or bacteria Reductive dissolution is integral to geochemical phenomena such as the iron cycle.
Reductive dissolution does not necessarily occur at the site where the reductant adsorbs. Instead, the added electron travel through the particle, causing reductive dissolution elsewhere on the particle.
Nomenclature and formulasEdit
Sometimes, metal-oxygen ratios are used to name oxides. Thus, NbO would be called niobium monoxide and TiO2 is titanium dioxide. This naming follows the Greek numerical prefixes. In the older literature and continuing in industry, oxides are named by adding the suffix -a to the element's name. Hence alumina, magnesia and chromia, are, respectively, Al2O3, MgO and Cr2O3.
The chemical formulas of the oxides of the chemical elements in their highest oxidation state are predictable and are derived from the number of valence electrons for that element. Even the chemical formula of O4, tetraoxygen, is predictable as a group 16 element. One exception is copper, for which the highest oxidation state oxide is copper(II) oxide and not copper(I) oxide. Another exception is fluoride, which does not exist as one might expect—as F2O7—but as OF2.
Examples of oxidesEdit
The following table gives examples of commonly encountered oxides. Only a few representatives are given, as the number of polyatomic ions encountered in practice is very large.
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