Germanium dioxide

Last updated
Germanium dioxide
Stishovite.png
Tetragonal rutile form
GeO2powder.jpg
Names
IUPAC name
Germanium dioxide
Other names
Germanium(IV) oxide
Germania
ACC10380
G-15
Neutral germanium oxide (1:2)
Germanic oxide
Salt of germanium
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.013.801 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
RTECS number
  • LY5240000
UNII
  • InChI=1S/GeO2/c2-1-3 Yes check.svgY
    Key: YBMRDBCBODYGJE-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/GeO2/c2-1-3
    Key: YBMRDBCBODYGJE-UHFFFAOYAG
  • O=[Ge]=O
Properties
GeO2
Molar mass 104.6388 g/mol
AppearanceWhite powder or colourless crystals
Density 4.228 g/cm3
Melting point 1,115 °C (2,039 °F; 1,388 K)
4.47 g/L (25 °C)
10.7 g/L (100 °C)
Solubility Soluble in HF,
insoluble in other acid. Soluble in strong alkaline conditions.
34.3·10−6 cm3/mol
1.650
Structure
Hexagonal
Hazards
NFPA 704 (fire diamond)
NFPA 704.svgHealth 1: Exposure would cause irritation but only minor residual injury. E.g. turpentineFlammability 0: Will not burn. E.g. waterInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
1
0
0
Flash point Non-flammable
Lethal dose or concentration (LD, LC):
3700 mg/kg (rat, oral)
Related compounds
Other anions
Germanium disulfide
Germanium diselenide
Other cations
Carbon dioxide
Silicon dioxide
Tin dioxide
Lead dioxide
Related compounds
Germanium monoxide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Yes check.svgY  verify  (what is  Yes check.svgYX mark.svgN ?)

Germanium dioxide, also called germanium(IV) oxide, germania, and salt of germanium, [1] is an inorganic compound with the chemical formula Ge O 2. It is the main commercial source of germanium. It also forms as a passivation layer on pure germanium in contact with atmospheric oxygen.

Contents

Structure

The two predominant polymorphs of GeO2 are hexagonal and tetragonal. Hexagonal GeO2 has the same structure as β-quartz, with germanium having coordination number 4. Tetragonal GeO2 (the mineral argutite) has the rutile-like structure seen in stishovite. In this motif, germanium has the coordination number 6. An amorphous (glassy) form of GeO2 is similar to fused silica. [2]

Germanium dioxide can be prepared in both crystalline and amorphous forms. At ambient pressure the amorphous structure is formed by a network of GeO4 tetrahedra. At elevated pressure up to approximately 9  GPa the germanium average coordination number steadily increases from 4 to around 5 with a corresponding increase in the Ge–O bond distance. [3] At higher pressures, up to approximately 15  GPa, the germanium coordination number increases to 6, and the dense network structure is composed of GeO6 octahedra. [4] When the pressure is subsequently reduced, the structure reverts to the tetrahedral form. [3] [4] At high pressure, the rutile form converts to an orthorhombic CaCl2 form. [5]

Reactions

Heating germanium dioxide with powdered germanium at 1000 °C forms germanium monoxide (GeO). [2]

The hexagonal (d = 4.29 g/cm3) form of germanium dioxide is more soluble than the rutile (d = 6.27 g/cm3) form and dissolves to form germanic acid, H4GeO4, or Ge(OH)4. [6] GeO2 is only slightly soluble in acid but dissolves more readily in alkali to give germanates. [6] The germanic acid forms stable complexes with di- and polyfunctional carboxylic acids, poly-alcohols, and o-diphenols. [7]

In contact with hydrochloric acid, it releases the volatile and corrosive germanium tetrachloride.

Uses

The refractive index (1.7) and optical dispersion properties of germanium dioxide make it useful as an optical material for wide-angle lenses, in optical microscope objective lenses, and for the core of fiber-optic lines. See Optical fiber for specifics on the manufacturing process. Both germanium and its glass oxide, GeO2, are transparent to the infrared (IR) spectrum. The glass can be manufactured into IR windows and lenses, used for night-vision technology in the military, luxury vehicles, [8] and thermographic cameras. GeO2 is preferred over other IR transparent glasses because it is mechanically strong and therefore preferred for rugged military usage. [9]

A mixture of silicon dioxide and germanium dioxide ("silica-germania") is used as an optical material for optical fibers and optical waveguides. [10] Controlling the ratio of the elements allows precise control of refractive index. Silica-germania glasses have lower viscosity and higher refractive index than pure silica. Germania replaced titania as the silica dopant for silica fiber, eliminating the need for subsequent heat treatment, which made the fibers brittle. [11]

Germanium dioxide is also used as a catalyst in production of polyethylene terephthalate resin, [12] and for production of other germanium compounds. It is used as a feedstock for production of some phosphors and semiconductor materials.

Germanium dioxide is used in algaculture as an inhibitor of unwanted diatom growth in algal cultures, since contamination with the comparatively fast-growing diatoms often inhibits the growth of or outcompetes the original algae strains. GeO2 is readily taken up by diatoms and leads to silicon being substituted by germanium in biochemical processes within the diatoms, causing a significant reduction of the diatoms' growth rate or even their complete elimination, with little effect on non-diatom algal species. For this application, the concentration of germanium dioxide typically used in the culture medium is between 1 and 10 mg/L, depending on the stage of the contamination and the species. [13]

Toxicity and medical

Germanium dioxide has low toxicity, but it is nephrotoxic in higher doses.[ citation needed ]

Germanium dioxide is used as a germanium supplement in some questionable dietary supplements and "miracle cures". [14] High doses of these resulted in several cases of germanium poisonings.

Related Research Articles

<span class="mw-page-title-main">Germanium</span> Chemical element, symbol Ge and atomic number 32

Germanium is a chemical element; it has symbol Ge and atomic number 32. It is lustrous, hard-brittle, grayish-white and similar in appearance to silicon. It is a metalloid in the carbon group that is chemically similar to its group neighbors silicon and tin. Like silicon, germanium naturally reacts and forms complexes with oxygen in nature.

<span class="mw-page-title-main">Silicon</span> Chemical element, symbol Si and atomic number 14

Silicon is a chemical element; it has 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 table: carbon is above it; and germanium, tin, lead, and flerovium are below it. It is relatively unreactive.

<span class="mw-page-title-main">Rutile</span> Oxide mineral composed of titanium dioxide

Rutile is an oxide mineral composed of titanium dioxide (TiO2), the most common natural form of TiO2. Rarer polymorphs of TiO2 are known, including anatase, akaogiite, and brookite.

<span class="mw-page-title-main">Silicon dioxide</span> Oxide of silicon

Silicon dioxide, also known as silica, is an oxide of silicon with the chemical formula SiO2, commonly found in nature as quartz. In many parts of the world, silica is the major constituent of sand. Silica is abundant as it comprises several minerals and as a synthetic products. All forms are white or colorless, although impure samples can be colored.

<span class="mw-page-title-main">Carbon group</span> Periodic table group

The carbon group is a periodic table group consisting of carbon (C), silicon (Si), germanium (Ge), tin (Sn), lead (Pb), and flerovium (Fl). It lies within the p-block.

<span class="mw-page-title-main">Titanium dioxide</span> Chemical compound often used as a white pigment, Including in food and paints.

Titanium dioxide, also known as titanium(IV) oxide or titania, is the inorganic compound with the chemical formula TiO
2
. When used as a pigment, it is called titanium white, Pigment White 6 (PW6), or CI 77891. It is a white solid that is insoluble in water, although mineral forms can appear black. As a pigment, it has a wide range of applications, including paint, sunscreen, and food coloring. When used as a food coloring, it has E number E171. World production in 2014 exceeded 9 million tonnes. It has been estimated that titanium dioxide is used in two-thirds of all pigments, and pigments based on the oxide have been valued at a price of $13.2 billion.

<span class="mw-page-title-main">Fused quartz</span> Glass consisting of pure silica

Fused quartz,fused silica or quartz glass is a glass consisting of almost pure silica (silicon dioxide, SiO2) in amorphous (non-crystalline) form. This differs from all other commercial glasses in which other ingredients are added which change the glasses' optical and physical properties, such as lowering the melt temperature. Fused quartz, therefore, has high working and melting temperatures, making it less desirable for most common applications.

<span class="mw-page-title-main">Stishovite</span> Tetragonal form of silicon dioxide

Stishovite is an extremely hard, dense tetragonal form (polymorph) of silicon dioxide. It is very rare on the Earth's surface; however, it may be a predominant form of silicon dioxide in the Earth, especially in the lower mantle.

<span class="mw-page-title-main">Tellurium dioxide</span> Chemical compound

Tellurium dioxide (TeO2) is a solid oxide of tellurium. It is encountered in two different forms, the yellow orthorhombic mineral tellurite, β-TeO2, and the synthetic, colourless tetragonal (paratellurite), α-TeO2. Most of the information regarding reaction chemistry has been obtained in studies involving paratellurite, α-TeO2.

<span class="mw-page-title-main">Germanium tetrachloride</span> Chemical compound

Germanium tetrachloride is a colourless, fuming liquid with a peculiar, acidic odour. It is used as an intermediate in the production of purified germanium metal. In recent years, GeCl4 usage has increased substantially due to its use as a reagent for fiber optic production.

<span class="mw-page-title-main">Germanium telluride</span> Chemical compound

Germanium telluride (GeTe) is a chemical compound of germanium and tellurium and is a component of chalcogenide glasses. It shows semimetallic conduction and ferroelectric behaviour.

<span class="mw-page-title-main">Ruthenium(IV) oxide</span> Chemical compound

Ruthenium(IV) oxide is the inorganic compound with the formula RuO2. This black solid is the most common oxide of ruthenium. It is widely used as an electrocatalyst for producing chlorine, chlorine oxides, and O2. Like many dioxides, RuO2 adopts the rutile structure.

Amorphous carbonia, also called a-carbonia or a-CO2, is an exotic amorphous solid form of carbon dioxide that is analogous to amorphous silica glass. It was first made in the laboratory in 2006 by subjecting dry ice to high pressures (40-48 gigapascal, or 400,000 to 480,000 atmospheres), in a diamond anvil cell. Amorphous carbonia is not stable at ordinary pressures—it quickly reverts to normal CO2.

<span class="mw-page-title-main">Silicon monoxide</span> Chemical compound

Silicon monoxide is the chemical compound with the formula SiO where silicon is present in the oxidation state +2. In the vapour phase, it is a diatomic molecule. It has been detected in stellar objects and has been described as the most common oxide of silicon in the universe.

<span class="mw-page-title-main">Niobium dioxide</span> Chemical compound

Niobium dioxide, is the chemical compound with the formula NbO2. It is a bluish-black non-stoichiometric solid with a composition range of NbO1.94-NbO2.09. It can be prepared by reducing Nb2O5 with H2 at 800–1350 °C. An alternative method is reaction of Nb2O5 with Nb powder at 1100 °C.

<span class="mw-page-title-main">Germanium tetrafluoride</span> Chemical compound

Germanium tetrafluoride (GeF4) is a chemical compound of germanium and fluorine. It is a colorless gas.

Silicon carbonate is a crystalline substance formed under pressure from silica and carbon dioxide. The formula of the substance is SiCO4. To produce it silicalite is compressed with carbon dioxide at a pressure of 18 Gpa and a temperature around 740 K (467 °C; 872 °F). The silicon carbonate made this way has carbonate linked to silicon by way of oxygen in unidentate, bidentate, or bridged positions. However a stable crystal structure is not formed in these conditions. The phase produced is amorphous, but it has carbon in three-fold coordination, and silicon in six-fold coordination. When decompressed, not all carbon is released as carbon dioxide. If this really exists, the substance should be dynamically stable when reduced to atmospheric pressure.

Germanium compounds are chemical compounds formed by the element germanium (Ge). Germanium is insoluble in dilute acids and alkalis but dissolves slowly in hot concentrated sulfuric and nitric acids and reacts violently with molten alkalis to produce germanates ([GeO
3
]2−
). Germanium occurs mostly in the oxidation state +4 although many +2 compounds are known. Other oxidation states are rare: +3 is found in compounds such as Ge2Cl6, and +3 and +1 are found on the surface of oxides, or negative oxidation states in germanides, such as −4 in Mg
2
Ge
. Germanium cluster anions (Zintl ions) such as Ge42−, Ge94−, Ge92−, [(Ge9)2]6− have been prepared by the extraction from alloys containing alkali metals and germanium in liquid ammonia in the presence of ethylenediamine or a cryptand. The oxidation states of the element in these ions are not integers—similar to the ozonides O3.

References

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  4. 1 2 M. Guthrie; C. A. Tulk; C. J. Benmore; J. Xu; J. L. Yarger; D. D. Klug; J. S. Tse; H.-k. Mao; R. J. Hemley (2004). "Formation and Structure of a Dense Octahedral Glass". Physical Review Letters. 93 (11): 115502. Bibcode:2004PhRvL..93k5502G. doi:10.1103/PhysRevLett.93.115502. PMID   15447351.
  5. Structural evolution of rutile-type and CaCl2-type germanium dioxide at high pressure, J. Haines, J. M. Léger, C. Chateau, A. S. Pereira, Physics and Chemistry of Minerals, 27, 8 ,(2000), 575–582, doi : 10.1007/s002690000092.
  6. 1 2 Egon Wiberg, Arnold Frederick Holleman, (2001) Inorganic Chemistry, Elsevier ISBN   0-12-352651-5.
  7. Patel, Madhav; Karamalidis, Athanasios K. (2021-05-21). "Germanium: A review of its US demand, uses, resources, chemistry, and separation technologies". Separation and Purification Technology. 275: 118981. doi: 10.1016/j.seppur.2021.118981 . ISSN   1383-5866.
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  13. Robert Arthur Andersen (2005). Algal culturing techniques. Elsevier Academic Press. ISBN   9780120884261.
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