Allotropy

Allotropy or allotropism (from Greek, Modern ἄλλος (allos), meaning 'other', and
τρόπος (tropos), meaning 'manner, form') is the property of some chemical elements to
exist in two or more different forms, in the same physical state, known as allotropes of
these elements. Allotropes are different structural modifications of an element;[1] the
atoms of the element are bonded together in a different manner. For example, the
allotropes of carbon include diamond (the carbon atoms are bonded together in a
tetrahedral lattice arrangement), graphite (the carbon atoms are bonded together in sheets
of a hexagonal lattice), graphene (single sheets of graphite), and fullerenes (the carbon
atoms are bonded together in spherical, tubular, or ellipsoidal formations). The term
allotropy is used for elements only, not for compounds. The more general term, used for
Diamond and graphite are two
any crystalline material, is polymorphism. Allotropy refers only to different forms of an
allotropes of carbon: pure forms
element within the same phase (i.e., different solid, liquid or gas forms); these different of the same element that differ
states are not, themselves, considered to be examples of allotropy
. in crystalline structure.

For some elements, allotropes have different molecular formulae which can persist in
different phases; for example, two allotropes of oxygen (dioxygen, O2, and ozone, O3) can both exist in the solid, liquid and gaseous
states. Conversely, some elements do not maintain distinct allotropes in dif
ferent phases; for example,phosphorus has numerous solid
allotropes, which all revert to the same P4 form when melted to the liquid state.

Contents
History
Differences in properties of an element's allotropes
List of allotropes
Non-metals
Metalloids
Metals
Lanthanides and actinides

Nanoallotropes
See also
Notes
References
External links

History
The concept of allotropy was originally proposed in 1841 by the Swedish scientist Baron Jöns Jakob Berzelius (1779–1848).[2] The
term is derived from Greek, Modern άλλοτροπἱα (allotropia), meaning 'variability, changeableness'.[3] After the acceptance of
Avogadro's hypothesis in 1860, it was understood that elements could exist as polyatomic molecules, and two allotropes of oxygen
were recognized as O2 and O3.[2] In the early 20th century, it was recognized that other cases such as carbon were due to differences
in crystal structure.
By 1912, Ostwald noted that the allotropy of elements is just a special case of the phenomenon of polymorphism known for
compounds, and proposed that the terms allotrope and allotropy be abandoned and replaced by polymorph and polymorphism.[2]
Although many other chemists have repeated this advice, IUPAC and most chemistry texts still favour the usage of allotrope and
allotropy for elements only.[4]

Differences in properties of an element's allotropes

Allotropes are different structural forms of the same element and can exhibit quite different physical properties and chemical
behaviours. The change between allotropic forms is triggered by the same forces that affect other structures, i.e., pressure, light, and
temperature. Therefore, the stability of the particular allotropes depends on particular conditions. For instance, iron changes from a
body-centered cubic structure (ferrite) to a face-centered cubic structure (austenite) above 906 °C, and tin undergoes a modification
known as tin pest from a metallic form to a semiconductor form below 13.2 °C (55.8 °F). As an example of allotropes having
different chemical behaviour, ozone (O3) is a much stronger oxidizing agent than dioxygen (O
2).

List of allotropes
Typically, elements capable of variable coordination number and/or oxidation states tend to exhibit greater numbers of allotropic
forms. Another contributing factor is the ability of an element tocatenate.

Examples of allotropes include:

Non-metals
 Element Allotropes

Diamond – an extremely hard, transparent crystal, with the carbon atoms arranged in a tetrahedral
lattice. A poor electrical conductor. An excellent thermal conductor.
Lonsdaleite – also called hexagonal diamond.
Graphene - is the basic structural element of other allotropes, nanotubes, charcoal, and fullerenes.
Q-carbon – a ferromagnetic, tough, and brilliant crystal structure that is harder and brighter than
diamonds.
Carbon
Graphite – a soft, black, flaky solid, a moderate electrical conductor. The C atoms are bonded in
flat hexagonal lattices (graphene), which are then layered in sheets.
Linear acetylenic carbon(Carbyne)
Amorphous carbon
Fullerenes, including Buckminsterfullerene, a.k.a. "buckyballs", such as C60.
Carbon nanotubes – allotropes of carbon with a cylindrical nanostructure.

White phosphorus – crystalline solid of tetraphosphorus (P4) molecules

Red phosphorus – amorphous polymeric solid
Scarlet phosphorus
Phosphorus
Violet phosphorus with monoclinic crystalline structure
Black phosphorus – semiconductor, analogous to graphite
Diphosphorus - gaseous form composed of P2 molecules, stable between 1200 °C and 2000 °C;
created e.g. by dissociation of P4 molecules of white phosphorus at around 827°C

Dioxygen, O2 – colorless (faint blue)

Oxygen Ozone, O3 – blue
Tetraoxygen, O4 – metastable
Octaoxygen, O8 – red

Sulfur Sulfur has a large number of allotropes, second only to carbon

"Red selenium," cyclo-Se8

Selenium Gray selenium, polymeric Se
Black selenium, irregular polymeric rings up to 1000 atoms long
Monoclinic selenium, dark red transparent crystals

Metalloids
 Element Allotropes

Amorphous boron – brown powder – B12 regular icosahedra

α-rhombohedral boron
β-rhombohedral boron
Boron γ-orthorhombic boron
α-tetragonal boron
β-tetragonal boron
High-pressure superconducting phase

Amorphous silicon
Silicon crystalline silicon, Diamond cubic structure
Silicene, buckled planar single layer Silicon, similar to graphene

Yellow arsenic – molecular non-metallic As4, with the same structure as white phopshorus
Arsenic Gray arsenic, polymeric As (metalloid)
Black arsenic – molecular and non-metallic, with the same structure as red phosphorus

α-germanium – semimetallic, with the same structure as diamond

Germanium β-germanium – metallic, with the same structure as beta-tin
Germanene - Buckled planar Germanium, similar to graphene

blue-white antimony – stable form (metalloid), with the same structure as gray arsenic
Antimony yellow antimony (non-metallic)
black antimony (non-metallic)
explosive antimony

amorphous tellurium - gray-black or brown powder [5]

Tellurium
crystalline tellurium - hexagonal crystalline structure (metalloid)

Metals
Among the metallic elements that occur in nature in significant quantities (56 up to U, without Tc and Pm), almost half (27) are
allotropic at ambient pressure: Li, Be, Na, Ca, Ti, Mn, Fe, Co, Sr, Y, Zr, Sn, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Yb, Hf, Tl, Th, Pa and
U. Some phase transitions between allotropic forms of technologically relevant metals are those of Ti at 882 °C, Fe at 912 °C and
1394 °C, Co at 422 °C, Zr at 863 °C, Sn at 13 °C and U at 668 °C and 776 °C.
 Element Allotropes

grey tin (alpha tin, Tin pest)

white tin (beta tin)
Tin rhombic tin (gamma tin)
stanene
sigma tin (forms at very high pressure)[6]

ferrite (α-iron): the ferromagnetic form at T < 770 °C (theCurie point, TC); BCC crystal structure
β-iron: T = 770 – 912 °C; theparamagnetic form of α-iron; same structure as α
Iron austenite (γ-iron): 912 – 1,394 °C;FCC crystal structure
δ-iron: 1,394 – 1,538 °C; forms from cooling down molten iron; same structure as α
ε-iron (also called hexaferrum): forms at high pressures;HCP crystal structure

Cobalt α-cobalt – forms above 417 °Csimple cubic (metallic)

β-cobalt – forms below 417 °Chexagonal close packed (hcp)(metallic)

Polonium α-polonium – simple cubic (metallic)

β-polonium – rhombohedral (metallic)

Lanthanides and actinides

Cerium, samarium, dysprosium and ytterbium have three

allotropes.
Praseodymium, neodymium, gadolinium and terbium have two
allotropes.
Plutonium has six distinct solid allotropes under "normal"
pressures. Their densities vary within a ratio of some 4:3, which
vastly complicates all kinds of work with the metal (particularly
casting, machining, and storage). A seventh plutonium allotrope
exists at very high pressures. The transuranium metals Np, Am,
and Cm are also allotropic.
Promethium, americium, berkelium and californium have three
allotropes each.[7] Phase diagram of the actinide elements.

Nanoallotropes
In 2017, the concept of nanoallotropy was proposed by Prof. Rafal Klajn of the Organic Chemistry Department of the Weizmann
Institute of Science.[8] Nanoallotropes, or allotropes of nanomaterials, are nanoporous materials that have the same chemical
composition (e.g., Au), but differ in their architecture at the nanoscale (that is, on a scale 10 to 100 times the dimensions of individual
atoms).[9] Such nanoallotropes may help create ultra-small electronic devices and find other industrial applications.[9] The different
nanoscale architectures translate into different properties, as was demonstrated for surface-enhanced Raman scattering performed on
several different nanoallotropes of gold.[8] A two-step method for generating nanoallotropes was also created.
[9]

See also
Isomer
Polymorphism (materials science)
Superdense carbon allotropes

Notes
 1. IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online corrected version: (2006–)
"Allotrope (http://goldbook.iupac.org/A00243.html)".
2. Jensen, W. B. (2006), "The Origin of the Term Allotrope", J. Chem. Educ., 83 (6): 838–39,
Bibcode:2006JChEd..83..838J (http://adsabs.harvard.edu/abs/2006JChEd..83..838J) , doi:10.1021/ed083p838 (http
s://doi.org/10.1021%2Fed083p838).
3. "allotropy", A New English Dictionary on Historical Principles
, 1, Oxford University Press, 1888, p. 238.
4. Jensen 2006, citing Addison, W. E. The Allotropy of the Elements (Elsevier 1964) that many have repeated this
advice.
5. Raj, G. Advanced Inorganic Chemistry Vol-1 (https://books.google.co.uk/books?id=0uwDT
rxyaB8C&pg=PA1327).
Krishna Prakashan. p. 1327.ISBN 9788187224037. Retrieved January 6, 2017.
6. Molodets, A. M.; Nabatov, S. S. (2000). "Thermodynamic Potentials, Diagram of State, and Phase rTansitions of Tin
on Shock Compression".High Temperature. 38 (5): 715–721. doi:10.1007/BF02755923 (https://doi.org/10.1007%2F
BF02755923).
7. http://www.iop.org/EJ/article/0305-4608/15/2/002/jfv15i2pL29.pdf?request-id=AFlRqDDL3BGhbarg2wi7Kg
8. Udayabhaskararao, Thumu; Altantzis, Thomas; Houben, Lothar; Coronado-Puchau, Marc; Langer , Judith; Popovitz-
Biro, Ronit; Liz-Marzán, Luis M.; Vuković, Lela; Král, Petr (2017-10-27)."Tunable porous nanoallotropes prepared by
post-assembly etching of binary nanoparticle superlattices"(http://science.sciencemag.org/content/358/6362/514) .
Science. 358 (6362): 514–518. Bibcode:2017Sci...358..514U (http://adsabs.harvard.edu/abs/2017Sci...358..514U) .
doi:10.1126/science.aan6046(https://doi.org/10.1126%2Fscience.aan6046) . ISSN 0036-8075 (https://www.worldcat.
org/issn/0036-8075). PMID 29074773 (https://www.ncbi.nlm.nih.gov/pubmed/29074773).
9. "Materials That Don't Exist in Nature Might Lead to New Fabricationechniques"
T (http://israelbds.org/materials-that-d
ont-exist-in-nature-might-lead-to-new-fabrication-techniques/)
. israelbds.org. Retrieved 2017-12-08.

References
Chisholm, Hugh, ed. (1911). "Allotropy". Encyclopædia Britannica(11th ed.). Cambridge University Press.

External links
"Untitled". web.archive.org. Archived from the original on January 31, 2008
. Retrieved January 6, 2017.
Allotropes – Chemistry Encyclopedia

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