:Coupled substitution
{{short description|Geological process by which two elements simultaneously substitute into a crystal}}
File:Feldspar series.jpg Al Si3O8) changes to anorthite (Ca Al2Si2O8), {{chem|link=Aluminium|Al|3+}} replaces {{chem|link=Silicon|Si|4+}} and {{chem|link=Calcium|Ca|2+}} for {{chem|link=Sodium|Na|+}}]]
Coupled substitution is the geological process by which two elements simultaneous substitute into a crystal in order to maintain overall electrical neutrality and keep the charge constant. In forming a solid solution series, ionic size is more important than ionic charge, as this can be compensated for elsewhere in the structure.
Ionic size
To make a geometrically stable structure in a mineral, atoms must fit together in terms of both their size and charge. The atoms have to fit together so that their electron shells can interact with one another and they also have to produce a neutral molecule. For these reasons the sizes and electron shell structure of atoms determine what element combinations are possible and the geometrical form that various minerals take. Because electrons are donated and received, it is the ionic radius of the element that controls the size and determines how atoms fit together in minerals.{{cite book |isbn=9780691140063|title=How to Build a Habitable Planet: The Story of Earth from the Big Bang to Humankind|last1=Langmuir|first1=Charles Herbert|last2=Broecker|first2=Wallace S.|year=2012|publisher=Princeton University Press }}
Examples
- Coupled substitutions are common in the silicate minerals where {{chem|link=Aluminium|Al|3+}} substitutes for {{chem|link=Silicon|Si|4+}} in tetrahedral sites.{{cite web|url=https://www.tulane.edu/~sanelson/eens211/mineral_chemistry.htm|title=Tulane course|access-date=2019-03-26|archive-url=https://web.archive.org/web/20170709184311/http://www.tulane.edu/~sanelson/eens211/mineral_chemistry.htm|archive-date=2017-07-09|url-status=live}}
For example, when a plagioclase feldspar solid solution series forms, albite (Na Al Si3O8) can change to anorthite (Ca Al2Si2O8) by having {{chem|link=Aluminium|Al|3+}} replace {{chem|link=Silicon|Si|4+}}. However, this leaves a negative charge that has to be balanced by the (coupled) substitution of {{chem|link=Calcium|Ca|2+}} for {{chem|link=Sodium|Na|+}}.{{cite book |isbn=9780199653065|title=A Dictionary of Geology and Earth Sciences|last1=Allaby|first1=Michael|date=2013-07-04|publisher=OUP Oxford }}
- {{Main|Pyrite}} Despite being nicknamed fool's gold, pyrite is sometimes found in association with small quantities of gold. Gold and arsenic occur as a coupled substitution in the pyrite structure. In the Carlin–type gold deposits, arsenian pyrite contains up to 0.37% gold by weight.{{cite journal |author1=Fleet, M. E. |author2=Mumin, A. Hamid |url=http://www.minsocam.org/msa/AmMin/toc/Articles_Free/1997/Fleet_p182-193_97.pdf |title=Gold-bearing arsenian pyrite and marcasite and arsenopyrite from Carlin Trend gold deposits and laboratory synthesis |journal=American Mineralogist |volume=82 |issue=1–2 |year=1997 |pages=182–193 |bibcode=1997AmMin..82..182F |doi=10.2138/am-1997-1-220 |s2cid=55899431 |access-date=2019-03-27 |archive-url=https://web.archive.org/web/20170810053609/http://www.minsocam.org/msa/ammin/toc/Articles_Free/1997/Fleet_p182-193_97.pdf |archive-date=2017-08-10 |url-status=live }}
- The possible replacement of {{chem2|(Al(3+))2|link=aluminium}} by {{chem2|Fe(2+)Ti(4+)|auto=1}} in Corundum.{{cite web|url=http://scienceworld.wolfram.com/chemistry/CoupledSubstitution.html|title=Coupled Substitution -- from Eric Weisstein's World of Chemistry|access-date=2019-03-26|archive-url=https://web.archive.org/web/20190325065705/http://scienceworld.wolfram.com/chemistry/CoupledSubstitution.html|archive-date=2019-03-25|url-status=live}}
- {{chem|link=Nickel(II) oxide|Ni|O}} and {{chem|link=Titanium dioxide|Ti|O|2}} in Haematite{{cite journal |doi=10.1007/BF00349032|title=Coupled substitution of NiO and TiO2 in haematite|journal=Journal of Materials Science|volume=28|issue=1|pages=52–56|year=1993|last1=Park|first1=B. -H.|last2=Suito|first2=H.|bibcode=1993JMatS..28...52P|s2cid=97048742}}
- {{chem|Ca|2+|Mg|2+}} → {{chem|Na|1+|Al|3+}} Diopside (MgCaSi2O6) → Jadeite: (NaAlSi2O6 or {{chem|Na|(Al|,Fe|3+|)|Si|2|O|6|)}} File:Diopside Aoste.jpg File:Jadeite Sodium aluminum silicate Burma 3025.jpg
- {{chem|Mg|2+}} 2{{chem|Al|3+}} → 2{{chem|Fe|2+}} {{chem|Ti|4+}} As in the Spinel groups
- The site being filled to maintain charge does not have to be a substitution. It can also involve filling a site that is normally vacant in order to achieve charge balance. For example, in the amphibole mineral Tremolite - (Ca2(Mg5.0-4.5Fe2+0.0-0.5)Si8O22(OH)2), {{chem|link=Aluminium|Al|3+}} replaces {{chem|link=Silicon|Si|4+}} then {{chem|link=Sodium|Na|1+}} can go into a site that is normally vacant to maintain charge balance. This new mineral would then be edenite {{chem|(Na|Ca|2|Mg|5|(Si|7|Al|)O|22|(O|H)|2}} a variety of hornblende.
- {{Main|Bityite}} Bityite’s structure consists of a coupled substitution it exhibits between the sheets of polyhedra; the coupled substitution of beryllium for aluminium within the tetrahedral sites allows a single lithium substitution for a vacancy without any additional octahedral substitutions.Lin, J-C. and Guggenheim, S. (1983). "The crystal structure of a Li,Be-rich brittle mica: a dioctaheral-trioctahedral intermediate". American Mineralogist, 68, 130-142. The transfer is completed by creating a tetrahedral sheet composition of Si2BeAl. The coupled substitution of lithium for vacancy and the beryllium for the tetrahedral aluminium maintains all the charges balanced; thereby, resulting in the trioctahedral end member for the margarite sub-group of the phyllosilicate group.Guggenheim, S. (1984). "The brittle micas". Reviews in Mineralogy, 13, 61-104.
- {{Main|Ferrogedrite}} Ferrogedrite is related to anthophyllite amphibole and gedrite through coupled substitution of (Al, Fe3+) for (Mg, Fe2+, Mn) and Al for Si.Deer, William Alexander, Robert Andrew Howie, and Jack Zussman (1997). Rock-forming minerals. 2B. Double-chain silicates, Vol. 2. Geological Society.{{rp|12–78}}
