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