![Orthosilicate-2D-dimensions](https://upload.wikimedia.org/wikipedia/commons/6/61/Orthosilicate-2D-dimensions.png)
In
chemistry
Chemistry is the science, scientific study of the properties and behavior of matter. It is a natural science that covers the Chemical element, elements that make up matter to the chemical compound, compounds made of atoms, molecules and ions ...
, a silicate is any member of a family of
polyatomic anion
A polyatomic ion, also known as a molecular ion, is a covalent bonded set of two or more atoms, or of a metal complex, that can be considered to behave as a single unit and that has a net charge that is not zero. The term molecule may or may not ...
s consisting of
silicon
Silicon is a chemical element with the symbol Si and atomic number 14. It is a hard, brittle crystalline solid with a blue-grey metallic luster, and is a tetravalent metalloid and semiconductor. It is a member of group 14 in the periodic tab ...
and
oxygen
Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements as wel ...
, usually with the general formula , where . The family includes
orthosilicate
In chemistry, orthosilicate is the anion , or any of its salts and esters. It is one of the silicate anions. It is occasionally called the silicon tetroxide anion or group.C. A. Kumins, and A. E. Gessler (1953), "Short-Cycle Syntheses of Ultrama ...
(),
metasilicate 320 px, Idealized structure of sodium metasilicate.
Metasilicates are silicates containing ions of empirical formula . Common stoichiometries include MSiO3 and MIISiO3. Metasilicates can be cyclic, usually the hexamer or chains .
Common comp ...
(), and
pyrosilicate
A pyrosilicate is a type of chemical compound; either an ionic compound that contains the pyrosilicate anion , or an organic compound with the hexavalent ≡-O-≡ group. The anion is also called disilicateViktor Renman (2017): "Structural and E ...
(, ). The name is also used for any
salt
Salt is a mineral composed primarily of sodium chloride (NaCl), a chemical compound belonging to the larger class of salts; salt in the form of a natural crystalline mineral is known as rock salt or halite. Salt is present in vast quantitie ...
of such anions, such as
sodium metasilicate
Sodium metasilicate is the chemical substance with formula , which is the main component of commercial sodium silicate solutions. It is an ionic compound consisting of sodium cations and the polymeric metasilicate anions €“–sub>''n''. It i ...
; or any
ester
In chemistry, an ester is a compound derived from an oxoacid (organic or inorganic) in which at least one hydroxyl group () is replaced by an alkoxy group (), as in the substitution reaction of a carboxylic acid and an alcohol. Glycerides ar ...
containing the corresponding
chemical group
In organic chemistry, a functional group is a substituent or moiety in a molecule that causes the molecule's characteristic chemical reactions. The same functional group will undergo the same or similar chemical reactions regardless of the rest ...
, such as
tetramethyl orthosilicate
Tetramethyl orthosilicate (TMOS) is the chemical compound with the formula Si(OCH3)4. This molecule consists of four methoxy groups bonded to a silicon atom. The basic properties are similar to the more popular tetraethyl orthosilicate, which is ...
.
[ The name "silicate" is sometimes extended to any anions containing silicon, even if they do not fit the general formula or contain other atoms besides oxygen; such as ]hexafluorosilicate
Hexafluorosilicic acid is an inorganic compound with the chemical formula . Aqueous solutions of hexafluorosilicic acid consist of salts of the cation and hexafluorosilicate anion. These salts and their aqueous solutions are colorless.
Hexaflu ...
.Most commonly, silicates are encountered as silicate minerals
Silicate minerals are rock-forming minerals made up of silicate groups. They are the largest and most important class of minerals and make up approximately 90 percent of Earth's crust.
In mineralogy, silica (silicon dioxide, ) is usually con ...
.
For diverse manufacturing, technological, and artistic needs, silicates are versatile materials, both natural (such as granite
Granite () is a coarse-grained (phaneritic) intrusive igneous rock composed mostly of quartz, alkali feldspar, and plagioclase. It forms from magma with a high content of silica and alkali metal oxides that slowly cools and solidifies undergro ...
, gravel
Gravel is a loose aggregation of rock fragments. Gravel occurs naturally throughout the world as a result of sedimentary and erosive geologic processes; it is also produced in large quantities commercially as crushed stone.
Gravel is classifi ...
, and garnet
Garnets () are a group of silicate minerals that have been used since the Bronze Age as gemstones and abrasives.
All species of garnets possess similar physical properties and crystal forms, but differ in chemical composition. The different s ...
) and artificial (such as Portland cement
Portland cement is the most common type of cement in general use around the world as a basic ingredient of concrete, mortar, stucco, and non-specialty grout. It was developed from other types of hydraulic lime in England in the early 19th c ...
, ceramic
A ceramic is any of the various hard, brittle, heat-resistant and corrosion-resistant materials made by shaping and then firing an inorganic, nonmetallic material, such as clay, at a high temperature. Common examples are earthenware, porcelain ...
s, glass
Glass is a non-crystalline, often transparent, amorphous solid that has widespread practical, technological, and decorative use in, for example, window panes, tableware, and optics. Glass is most often formed by rapid cooling (quenching) of ...
, and waterglass).
Structural principles
In all silicates, silicon atom occupies the center of an idealized tetrahedron
In geometry, a tetrahedron (plural: tetrahedra or tetrahedrons), also known as a triangular pyramid, is a polyhedron composed of four triangular faces, six straight edges, and four vertex corners. The tetrahedron is the simplest of all the o ...
whose corners are four oxygen atoms, connected to it by single covalent bond
A covalent bond is a chemical bond that involves the sharing of electrons to form electron pairs between atoms. These electron pairs are known as shared pairs or bonding pairs. The stable balance of attractive and repulsive forces between atoms ...
s according to the octet rule
The octet rule is a chemical rule of thumb that reflects the theory that main-group elements tend to bond in such a way that each atom has eight electrons in its valence shell, giving it the same electronic configuration as a noble gas. The rule i ...
. The oxygen atoms, which bears some negative charge, link to other cations (Mn+). This Si-O-M-O-Si linkage is strong and rigid, which properties are manifested in the rock-like silicates. The silicates can be classified according to the length and crosslinking of the silicate anions.
Isolated silicates
Isolated orthosilicate
In chemistry, orthosilicate is the anion , or any of its salts and esters. It is one of the silicate anions. It is occasionally called the silicon tetroxide anion or group.C. A. Kumins, and A. E. Gessler (1953), "Short-Cycle Syntheses of Ultrama ...
anions have the formula . A common mineral in this group is olivine
The mineral olivine () is a magnesium iron silicate with the chemical formula . It is a type of nesosilicate or orthosilicate. The primary component of the Earth's upper mantle, it is a common mineral in Earth's subsurface, but weathers quickl ...
().
Ttwo or more silicon atoms can share oxygen atoms in various ways, to form more complex anions, such as pyrosilicate
A pyrosilicate is a type of chemical compound; either an ionic compound that contains the pyrosilicate anion , or an organic compound with the hexavalent ≡-O-≡ group. The anion is also called disilicateViktor Renman (2017): "Structural and E ...
.
Chains
With two shared oxides bound to each silicon, cyclic or polymeric structures can result. The cyclic metasilicate 320 px, Idealized structure of sodium metasilicate.
Metasilicates are silicates containing ions of empirical formula . Common stoichiometries include MSiO3 and MIISiO3. Metasilicates can be cyclic, usually the hexamer or chains .
Common comp ...
ring is a hexamer
In chemistry and biochemistry, an oligomer () is a molecule that consists of a few repeating units which could be derived, actually or conceptually, from smaller molecules, monomers.Quote: ''Oligomer molecule: A molecule of intermediate relative ...
of SiO32-. Polymer
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic a ...
ic silicate anions of can exist also as long chains.
In single-chain silicates, which are a type of inosilicate
Silicate minerals are rock-forming minerals made up of silicate groups. They are the largest and most important class of minerals and make up approximately 90 percent of Earth's crust.
In mineralogy, silica (silicon dioxide, ) is usually consid ...
, tetrahedra link to form a chain by sharing two oxygen atoms each. A common mineral in this group is pyroxene
The pyroxenes (commonly abbreviated to ''Px'') are a group of important rock-forming inosilicate minerals found in many igneous and metamorphic rocks. Pyroxenes have the general formula , where X represents calcium (Ca), sodium (Na), iron (Fe II) ...
.
Double-chain silicates, the other category of inosilicates, occur when tetrahedra form a double chain (not always but mostly) by sharing two or three oxygen atoms each. Common minerals for this group are amphiboles
Amphibole () is a group of inosilicate minerals, forming prism or needlelike crystals, composed of double chain tetrahedra, linked at the vertices and generally containing ions of iron and/or magnesium in their structures. Its IMA symbol is A ...
.
Sheets
In this group, known as phyllosilicates
Silicate minerals are rock-forming minerals made up of silicate groups. They are the largest and most important class of minerals and make up approximately 90 percent of Earth's crust.
In mineralogy, silica (silicon dioxide, ) is usually consid ...
, tetrahedra all share three oxygen atoms each and in turn link to form two-dimensional sheets. This structure does lead to minerals in this group having one strong cleavage plane. Micas
Micas ( ) are a group of silicate minerals whose outstanding physical characteristic is that individual mica crystals can easily be split into extremely thin elastic plates. This characteristic is described as perfect basal cleavage. Mica is ...
fall into this group. Both muscovite
Muscovite (also known as common mica, isinglass, or potash mica) is a hydrated phyllosilicate mineral of aluminium and potassium with formula K Al2(Al Si3 O10)( F,O H)2, or ( KF)2( Al2O3)3( SiO2)6( H2O). It has a highly perfect basal cleavage ...
and biotite
Biotite is a common group of phyllosilicate minerals within the mica group, with the approximate chemical formula . It is primarily a solid-solution series between the iron-endmember annite, and the magnesium-endmember phlogopite; more alumino ...
have very weak layers that can be peeled off in sheets.
Framework
In a framework silicate, known as a tectosilicate
Silicate minerals are rock-forming minerals made up of silicate groups. They are the largest and most important class of minerals and make up approximately 90 percent of Earth's crust.
In mineralogy, silica (silicon dioxide, ) is usually consid ...
, each tetrahedron shares all 4 oxygen atoms with its neighbours, forming a 3D structure. Quartz
Quartz is a hard, crystalline mineral composed of silica (silicon dioxide). The atoms are linked in a continuous framework of SiO4 silicon-oxygen tetrahedra, with each oxygen being shared between two tetrahedra, giving an overall chemical form ...
and feldspars
Feldspars are a group of rock-forming aluminium tectosilicate minerals, also containing other cations such as sodium, calcium, potassium, or barium. The most common members of the feldspar group are the ''plagioclase'' (sodium-calcium) feldsp ...
are in this group.
Silicates with non-tetrahedral silicon
Although the tetrahedron is a common coordination geometry for silicon(IV) compounds, silicon may also occur with higher coordination numbers. For example, in the anion hexafluorosilicate
Hexafluorosilicic acid is an inorganic compound with the chemical formula . Aqueous solutions of hexafluorosilicic acid consist of salts of the cation and hexafluorosilicate anion. These salts and their aqueous solutions are colorless.
Hexaflu ...
, the silicon atom is surrounded by six fluorine
Fluorine is a chemical element with the symbol F and atomic number 9. It is the lightest halogen and exists at standard conditions as a highly toxic, pale yellow diatomic gas. As the most electronegative reactive element, it is extremely reacti ...
atoms in an octahedral
In geometry, an octahedron (plural: octahedra, octahedrons) is a polyhedron with eight faces. The term is most commonly used to refer to the regular octahedron, a Platonic solid composed of eight equilateral triangles, four of which meet at ea ...
arrangement. This structure is also seen in the hexahydroxysilicate anion that occurs in thaumasite
Thaumasite is a calcium silicate mineral, containing Si atoms in unusual octahedron, octahedral configuration, with chemical formula calcium, Ca3silicon, Si(Ohydrogen, H)6(carbon, Coxygen, O3)(sulfur, SO4)·12water, H2O, also sometimes more simply ...
, a mineral found rarely in nature but sometimes observed among other calcium silicate hydrate
Calcium silicate hydrate (or C-S-H) is the main product of the hydration of Portland cement and is primarily responsible for the strength in cement based materials (e.g. concrete).
Preparation
When water is added to cement, each of the compounds u ...
s artificially formed in cement
A cement is a binder, a chemical substance used for construction that sets, hardens, and adheres to other materials to bind them together. Cement is seldom used on its own, but rather to bind sand and gravel ( aggregate) together. Cement mix ...
and concrete
Concrete is a composite material composed of fine and coarse aggregate bonded together with a fluid cement (cement paste) that hardens (cures) over time. Concrete is the second-most-used substance in the world after water, and is the most wi ...
submitted to a severe sulfate attack.
At very high pressure, such as exists in the majority of the earth's crust, even SiO2 adopts the six-coordinated octahedral geometry in the mineral stishovite, a dense polymorph of silica
Silicon dioxide, also known as silica, is an oxide of silicon with the chemical formula , most commonly found in nature as quartz and in various living organisms. In many parts of the world, silica is the major constituent of sand. Silica is one ...
found in the lower mantle
The lower mantle, historically also known as the mesosphere, represents approximately 56% of Earth's total volume, and is the region from 660 to 2900 km below Earth's surface; between the transition zone and the outer core. The preliminar ...
of the Earth and also formed by shock during meteorite
A meteorite is a solid piece of debris from an object, such as a comet, asteroid, or meteoroid, that originates in outer space and survives its passage through the atmosphere to reach the surface of a planet or Natural satellite, moon. When the ...
impacts.
Chemical properties
Silicates with alkali
In chemistry, an alkali (; from ar, القلوي, al-qaly, lit=ashes of the saltwort) is a basic, ionic salt of an alkali metal or an alkaline earth metal. An alkali can also be defined as a base that dissolves in water. A solution of a ...
cations and small or chain-like anions, such as sodium ortho- and metasilicate 320 px, Idealized structure of sodium metasilicate.
Metasilicates are silicates containing ions of empirical formula . Common stoichiometries include MSiO3 and MIISiO3. Metasilicates can be cyclic, usually the hexamer or chains .
Common comp ...
, are fairly soluble in water. They form several solid hydrate
In chemistry, a hydrate is a substance that contains water or its constituent elements. The chemical state of the water varies widely between different classes of hydrates, some of which were so labeled before their chemical structure was understo ...
s when crystallized from solution. Soluble sodium silicate
Sodium silicate is a generic name for chemical compounds with the formula or ·, such as sodium metasilicate , sodium orthosilicate , and sodium pyrosilicate . The anions are often polymeric. These compounds are generally colorless transparent ...
s and mixtures thereof, known as waterglass are in fact important industrial and household chemicals. Silicates of non-alkali cations, or with sheet and tridimensional polymeric anions, generally have negligible solubility in water at normal conditions.
Reactions
Silicates are generally inert chemically. Hence they are common minerals. Their resiliency also recommends their use as building materials.
When treated with calcium oxides and water, silicate minerals form Portland cement
Portland cement is the most common type of cement in general use around the world as a basic ingredient of concrete, mortar, stucco, and non-specialty grout. It was developed from other types of hydraulic lime in England in the early 19th c ...
.
Equilibria involving hydrolysis of silicate minerals are difficult to study. The chief challenge is the very low solubility of SiO44- and its various protonated forms. Such equilibria are relevant to the processes occurring on geological time scales.[G. B. Alexander (1953): "The Reaction of Low Molecular Weight Silicic Acids with Molybdic Acid". ''Journal of the American Chemical Society, volume 75, issue 22, pages 5655–5657. ] Some plants excrete ligands that dissolve silicates, a step in biomineralization
Biomineralization, also written biomineralisation, is the process by which living organisms produce minerals, often to harden or stiffen existing tissues. Such tissues are called mineralized tissues. It is an extremely widespread phenomenon; ...
.
Detection
Silicate anions in solution react with molybdate
In chemistry a molybdate is a compound containing an oxoanion with molybdenum in its highest oxidation state of 6. Molybdenum can form a very large range of such oxoanions which can be discrete structures or polymeric extended structures, althou ...
anions yielding yellow silicomolybdate complexes. In a typical preparation, monomer
In chemistry, a monomer ( ; ''mono-'', "one" + '' -mer'', "part") is a molecule that can react together with other monomer molecules to form a larger polymer chain or three-dimensional network in a process called polymerization.
Classification
Mo ...
ic orthosilicate was found to react completely in 75 seconds; dimer
Dimer may refer to:
* Dimer (chemistry), a chemical structure formed from two similar sub-units
** Protein dimer, a protein quaternary structure
** d-dimer
* Dimer model, an item in statistical mechanics, based on ''domino tiling''
* Julius Dimer ...
ic pyrosilicate in 10 minutes; and higher oligomer
In chemistry and biochemistry, an oligomer () is a molecule that consists of a few repeating units which could be derived, actually or conceptually, from smaller molecules, monomers.Quote: ''Oligomer molecule: A molecule of intermediate relativ ...
s in considerably longer time. In particular, the reaction is not observed with suspensions of colloidal silica {{Unreferenced, date=November 2021Colloidal silicas are suspensions of fine amorphous, nonporous, and typically spherical silica particles in a liquid phase. It may be produced by Stöber process from Tetraethyl orthosilicate (TEOS).
Properties
U ...
.[
]
Zeolite formation
The nature of soluble silicates is relevant to understanding biomineralization
Biomineralization, also written biomineralisation, is the process by which living organisms produce minerals, often to harden or stiffen existing tissues. Such tissues are called mineralized tissues. It is an extremely widespread phenomenon; ...
and the synthesis of aluminosilicates, such as the industrially important catalyst
Catalysis () is the process of increasing the rate of a chemical reaction by adding a substance known as a catalyst (). Catalysts are not consumed in the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recyc ...
s called zeolite
Zeolites are microporous, crystalline aluminosilicate materials commonly used as commercial adsorbents and catalysts. They mainly consist of silicon, aluminium, oxygen, and have the general formula ï½¥y where is either a metal ion or H+. These pos ...
s.
See also
*
* Alkali-silica reaction
* Carbon cycle
The carbon cycle is the biogeochemical cycle by which carbon is exchanged among the biosphere, pedosphere, geosphere, hydrosphere, and Earth's atmosphere, atmosphere of the Earth. Carbon is the main component of biological compounds as well as ...
* Carbonate-silicate cycle
* Ocean acidification
Ocean acidification is the reduction in the pH value of the Earth’s ocean. Between 1751 and 2021, the average pH value of the ocean surface has decreased from approximately 8.25 to 8.14. The root cause of ocean acidification is carbon dioxid ...
References
{{DEFAULTSORT:Silicon-oxygen tetrahedron
Silicates