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| Verifiedfields = changed
|  verifiedrevid = 476995335
|  PIN = Silicon monoxide
| Section1 = {{Chembox Identifiers
|  InChI = 1/OSi/c1-2
| InChIKey = LIVNPJMFVYWSIS-UHFFFAOYAO
| InChI1 = 1S/OSi/c1-2
| InChIKey1 = LIVNPJMFVYWSIS-UHFFFAOYSA-N
| CASNo = 10097-28-6
|  CASNo_Ref = {{cascite|correct|CAS}}
|  PubChem = 66241
|  PubChem_Ref = {{Pubchemcite | correct | PubChem}}
|  ChemSpiderID = 59626
|  ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
| EINECS = 233-232-8
|  MeSHName = Silicon+monoxide
|  ChEBI_Ref = {{ebicite|correct|EBI}}
| ChEBI = 30588
|  SMILES = [O+]#[Si-]
|  StdInChI_Ref = {{stdinchicite|changed|chemspider}}
| StdInChI = 1S/H3OSi/c1-2/h2H3
|  StdInChIKey_Ref = {{stdinchicite|changed|chemspider}}
| StdInChIKey = UXMAWJKSGBRJKV-UHFFFAOYSA-N
|  Gmelin = 382}}
| Section2 = {{Chembox Properties
|  Formula = SiO
|  MolarMass = 44.08 g/mol
|  Appearance = brown-black glassy solid
|  Density = 2.13 g/cm<sup>3</sup>
|  MeltingPtC = 1702
|  BoilingPtC = 1880
|  Solubility = insoluble
  }}
| Section7 = {{Chembox Hazards
|  ExternalMSDS =
|  EUIndex = Not listed
|  EUClass =
|  RPhrases =
|  SPhrases =
|  MainHazards =
|  NFPA-H = 1
|  NFPA-F = 0
|  NFPA-R = 0
|  NFPA-O =
|  FlashPt = Non-flammable
  }}
| Section8 = {{Chembox Related
|  OtherAnions = [[Silicon sulfide]]<br />[[Silicon selenide]]<br />[[Silicon telluride]]
|  OtherCations = [[Carbon monoxide]]<br />[[Germanium(II) oxide]]<br />[[Tin(II) oxide]]<br />[[Lead(II) oxide]]
|  OtherFunctn = [[Silicon dioxide]]
|    Function = [[silicon]] [[oxide]]s
|  OtherCpds =
  }}
}}
'''Silicon monoxide''' is the chemical compound with the formula SiO where silicon is present in the oxidation state +II. In the vapour phase it is a diatomic molecule.<ref name="Wiberg&Holleman">{{Holleman&Wiberg}}</ref> It has been detected in stellar objects<ref>Gibb, A.G.; Davis, C.J.; Moore, T.J.T., A survey of SiO 5 → 4 emission towards outflows from massive young stellar objects. Monthly Notices of the Royal Astronomical Society, 382, 3, 1213-1224. {{doi|10.1111/j.1365-2966.2007.12455.x}}, {{arXiv|0709.3088v1}}.</ref> and it has been described as the most common oxide of silicon in the universe.<ref name="Jutzi">Peter Jutzi and Ulrich Schubert (2003) ''Silicon chemistry: from the atom to extended systems''. Wiley-VCH ISBN 3-527-30647-1.</ref><br />
When SiO gas is cooled rapidly, it condenses to form a brown/black polymeric [[glass]]y material, (SiO)<sub>''n''</sub>, which is available commercially and used to deposit films of SiO. Glassy (SiO)<sub>''n''</sub> is air- and moisture-sensitive. Its surface readily oxidizes in air at room temperature, giving an SiO<sub>2</sub> surface layer that [[passivation (chemistry)|protects the material from further oxidation]]. However, (SiO)<sub>''n''</sub> irreversibly [[Disproportionation|disproportionates]] into SiO<sub>2</sub> and Si in a few hours between 400 and 800°C, and very rapidly between 1,000 and 1,440°C, although the reaction does not go to completion.<ref>W. Hertl and W. W. Pultz, ''J. Am. Ceramic Soc''. Vol. 50, Issue 7, (1967) pp. 378-381.</ref>
 
==Formation of SiO==
The first precise report on the formation of SiO was in 1887<ref name="Vol VI 1947 p. 235">J. W. Mellor "A Comprehensive Treatise on Inorganic and Theoretical Chemistry" Vol VI, Longmans, Green and Co. (1947) p. 235.</ref> by the chemist [http://ech.cwru.edu/ech-cgi/article.pl?id=MCF Charles F. Maybery] (1850–1927) at the [http://www.case.edu/its/archives/downtown/case.htm Case School of Applied Science] in Cleveland.  Maybery claimed that SiO formed as an amorphous greenish-yellow substance with a vitreous luster when silica was reduced with charcoal in the absence of metals in an electric furnace.<ref>C. F. Maybery ''Amer. Chem. Journ.'' 9, 11, (1887).</ref>  The substance was always found at the interface between the charcoal and silica particles. By investigating some of the chemical properties of the substance, its specific gravity, and a combustion analysis, Maybery deduced that the substance must be SiO. The equation representing the partial chemical reduction of SiO<sub>2</sub> with C can be represented as:
 
:<math>SiO_{2} + C  \rightleftharpoons SiO + CO</math>
 
Complete reduction of SiO<sub>2</sub> with twice the amount of carbon yields elemental silicon and twice the amount of carbon monoxide.  In 1890, the German chemist [[Clemens Winkler]] (the discoverer of germanium) was the first to attempt to synthesize SiO by heating silicon dioxide with silicon in a combustion furnace.<ref>C. Winkler ''Ber''. 23, (1890) p. 2652.</ref>  
 
:<math>SiO_{2} + Si  \rightleftharpoons 2 SiO</math>
 
However, Winkler was not able to produce the monoxide since the temperature of the mixture was only around 1000°C. The experiment was repeated in 1905 by [http://books.google.com/books?id=MJPmAAAAMAAJ&pg=PA284&dq=henry+noel+potter+westinghouse&hl=en&ei=BgNhTp_bL4jRiAKd5-2zDg&sa=X&oi=book_result&ct=result&resnum=1&sqi=2&ved=0CC4Q6AEwAA#v=onepage&q=henry%20noel%20potter%20&f=false Henry Noel Potter] (1869–1942), a [[Westinghouse Electric (1886)|Westinghouse]] engineer. Using an electric furnace, Potter was able to attain a temperature of 1700°C and observe the generation of SiO.<ref name="Vol VI 1947 p. 235"/> [http://books.google.com/books?id=ivssAAAAYAAJ&pg=PA1406&dq=henry+noel+potter&hl=en&ei=swFhTpSmCOLjiALYkqnTDg&sa=X&oi=book_result&ct=result&resnum=4&ved=0CDcQ6AEwAzgK#v=onepage&q=henry%20noel%20potter&f=false Potter] also investigated the properties and applications of the solid form of SiO.<ref>U.S. Patent 182,082, July 26, 1905.</ref><ref>E. F. Roeber H. C. Parmelee (Eds.) [http://books.google.com/books?id=4pPmAAAAMAAJ&pg=PA443&lpg=PA443&dq=silicon+monoxide+dissociates+in+molten+silicon&source=bl&ots=pCjdTkrZUW&sig=2nhu_KDjGEnDRQ9b2UlLWzcryjM&hl=en&ei=DedgTv-xGZHViALOmunHDg&sa=X&oi=book_result&ct=result&resnum=3&sqi=2&ved=0CCsQ6AEwAg#v=onepage&q&f=false Electrochemical and Metallurgical Industry, Vol. 5] (1907) p. 442.</ref>
 
Because of the volatility of SiO, silica  can be removed from ores or minerals by heating them with silicon to produce gaseous SiO in this manner.<ref name="Wiberg&Holleman" />  However, due to the difficulties associated with accurately measuring its vapor pressure, and because of the dependency on the specifics of the experimental design, various values have been reported in the literature for the vapor pressure of SiO (g). For the p<sub>SiO</sub> above molten silicon in a quartz (SiO<sub>2</sub>) crucible at the melting point of silicon, one study yielded a value of 0.002 atm.<ref>"Handbook of Semiconductor Silicon Technology," W. C. O'Mara, R. B. Herring, L. P. Hunt, Noyes Publications (1990), p. 148</ref>  For the direct vaporization of pure, amorphous SiO solid, 0.001 atm has been reported.<ref>J. A. Nuth III, F. T. Ferguson, The Astrophysical Journal, 649, 1178-1183 (2006)</ref> For a coating system, at the phase boundary between SiO<sub>2</sub> and a silicide, 0.01 atm was reported.<ref>"High-Temperature Oxidation-Resistant Coatings ," National Academy of Sciences/National Academy of Engineering (1970), p. 40</ref>
 
Silica itself, or refractories containing SiO<sub>2</sub>, can be reduced with H<sub>2</sub> or CO at high temperatures, e.g.:<ref>Charles A. (2004) Schacht Refractories handbook. CRC Press, ISBN 0-8247-5654-1.</ref>
 
:<math>SiO_{2}(s) + H_{2}(g) \rightleftharpoons SiO (g) + H_{2}O (g)</math>
 
As the SiO product volatilizes off (is removed), the equilibrium shifts to the right, resulting in the continued consumption of SiO<sub>2</sub>.  Based on the dependence of the rate of silica weight loss on the gas flow rate normal to the interface, the rate of this reduction appears to be controlled by convective diffusion or mass transfer from the reacting surface.<ref>G. Han; H. Y. Sohn J. Am. Ceram. Soc. 88 [4] 882-888 (2005)</ref><ref>R. A. Gardner J. Solid State Chem. 9, 336-344 (1974)</ref>
 
==Gaseous (molecular) SiO==
Silicon monoxide molecules have been trapped in an argon matrix cooled by helium. The SiO bond length determined from SiO molecules isolated in argon is between 148.9 pm<ref name="Jutzi" /> and 151 pm.<ref name="Inorganic Chemistry 2001 p. 858">Inorganic Chemistry, Holleman-Wiberg, Academci Press (2001) p. 858.</ref> This bond length is similar to the Si=O double bonds (''r''<sub>SiO</sub> = 148 pm) in matrix isolated linear, molecular, SiO<sub>2</sub> (O=S=O), indicative of the absence of a triple bond as in [[carbon monoxide|CO]].<ref name="Jutzi" />  However, the SiO triple bond has a calculated bond length of 150 pm and a bond energy of 794 kJ/mol, which are also very close to those reported for SiO.<ref name="Inorganic Chemistry 2001 p. 858"/>  The SiO double bond structure is, notably, an exception to Lewis' [[octet rule]] for molecules composed of the light main group elements, whereas the SiO triple bond satisfies this rule. That anomaly not withstanding, the observation that monomeric SiO is short-lived and that (SiO)<sub>n</sub> [[oligomer]]s with n = 2,3,4,5 are known, all having closed ring structures in which the silicon atoms are connected through bridging oxygen atoms (i.e. each oxygen atom is singly bonded to two silicon atoms; no Si-Si bonds), suggests the Si=O double bond structure, with a hypovalent silicon atom, is likely for the monomer.<ref name="Jutzi" />
 
SiO condensed with [[fluorine|F<sub>2</sub>]], [[chlorine|Cl<sub>2</sub>]] or COS, followed by irradiation with light, the planar molecules OSiF<sub>2</sub>,(Si-O 148 pm); OSiCl<sub>2</sub>, (Si-O 149 pm) and linear OSiS (Si-O 149 pm, Si-S 190 pm) are produced.<ref name="Jutzi" />
 
SiO condensed with oxygen atoms generated by microwave discharge produces molecular SiO<sub>2</sub> which has a linear structure.<br />
When metal atoms are co-deposited (i.e.: Na, Al, Pd, Ag, Au)  triatomic molecules are produced with linear, (AlSiO and PdSiO), non-linear (AgSiO and AuSiO), and ring (NaSiO) structures.<ref name="Jutzi" />
 
==Solid (polymeric) SiO==
Potter reported SiO solid as yellowish-brown in color and as being an electrical and thermal insulator.  The solid burns in oxygen and decomposes water with the liberation of hydrogen. It dissolves in warm alkali hydroxides and in hydrofluoric acid.  Although Potter reported the heat of combustion of SiO to be 200 to 800 calories higher than that of an equilibrium mixture of Si and SiO<sub>2</sub> (which could, arguably, be used as evidence that SiO is a unique chemical compound),<ref>J. W. Mellor "A Comprehensive Treatise on Inorganic and Theoretical Chemistry" Vol VI, Longmans, Green and Co. (1947) p. 234.</ref> recent microscopy and spectroscopy studies suggest that amorphous solid SiO is best considered as an inhomogeneous mixture of amorphous [[silicon dioxide|SiO<sub>2</sub>]] and amorphous [[silicon|Si]] with some chemical bonding at the interface of the Si and  SiO<sub>2</sub> phases.<ref>Friede B., Jansen M. (1996) Some comments on so-called silicon monoxide. Journal of Non-Crystalline Solids, 204, 2, 202-203. {{doi|10.1016/S0022-3093(96)00555-8}}.</ref><ref>Schulmeister K. and Mader W. (2003) TEM investigation on the structure of amorphous silicon monoxide. Journal of Non-Crystalline Solids, 320, 1-3, 143-150. {{doi|10.1016/S0022-3093(03)00029-2}}.</ref>
 
==References==
{{reflist}}
 
[[Category:Oxides]]
[[Category:Inorganic silicon compounds]]

Latest revision as of 21:58, 16 August 2014

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