Selenium dioxide

Last updated
Selenium dioxide
Selenium dioxide Structural Formula.svg
Selenium-dioxide-chain-3D-balls.png
Selenium dioxide sample.jpg
Names
Other names
Selenium(IV) oxide
Selenous anhydride
Identifiers
3D model (JSmol)
ChEMBL
ChemSpider
ECHA InfoCard 100.028.358 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 231-194-7
PubChem CID
RTECS number
  • VS8575000
UNII
UN number 3283
  • InChI=1S/O2Se/c1-3-2 Yes check.svgY
    Key: JPJALAQPGMAKDF-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/O2Se/c1-3-2
    Key: JPJALAQPGMAKDF-UHFFFAOYAQ
  • monomer:O=[Se]=O
  • polymer:O[Se](=O)O[Se](=O)O[Se](=O)O[Se](=O)O[Se](=O)O[Se](=O)O[Se](=O)O[Se](=O)O[Se](=O)O[Se](=O)O[Se](=O)O[Se](=O)O[Se](=O)O[Se](=O)O[Se](=O)O
Properties
SeO2
Molar mass 110.96 g/mol
AppearanceWhite crystals, turn slightly pink with trace decomposition [1]
Odor rotten radishes
Density 3.954 g/cm3, solid
Melting point 340 °C (644 °F; 613 K) (sealed tube)
Boiling point 350 °C (662 °F; 623 K) subl.
38.4 g/100 mL (20 °C)
39.5 g/100 ml (25 °C)
82.5 g/100 mL (65 °C)
Solubility soluble in benzene
Solubility in ethanol 6.7 g/100 mL (15 °C)
Solubility in acetone 4.4 g/100 mL (15 °C)
Solubility in acetic acid 1.11 g/100 mL (14 °C)
Solubility in methanol 10.16 g/100 mL (12 °C)
Vapor pressure 1.65 kPa (70 °C)
Acidity (pKa)2.62; 8.32
27.2·10−6 cm3/mol
> 1.76
Structure
see text
trigonal (Se)
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
Toxic by ingestion and inhalation [2]
GHS labelling:
GHS-pictogram-skull.svg GHS-pictogram-silhouette.svg GHS-pictogram-pollu.svg
Danger
H301, H331, H373, H410
P260, P261, P264, P270, P271, P273, P301+P310, P304+P340, P311, P314, P321, P330, P391, P403+P233, P405, P501
NFPA 704 (fire diamond)
NFPA 704.svgHealth 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasFlammability 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
3
0
0
Flash point Non-flammable
Lethal dose or concentration (LD, LC):
5890 mg/m3 (rabbit, 20 min)
6590 mg/m3 (goat, 10 min)
6590 mg/m3 (sheep, 10 min) [3]
Safety data sheet (SDS) ICSC 0946
Related compounds
Other anions
Selenium disulfide
Other cations
Sulfur dioxide
Tellurium dioxide
Related selenium oxides
Selenium trioxide
Related compounds
Selenous acid
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 ?)

Selenium dioxide is the chemical compound with the formula SeO2. This colorless solid is one of the most frequently encountered compounds of selenium. It is used in making specialized glasses as well as a reagent in organic chemistry. [4]

Contents

Properties

Solid SeO2 is a one-dimensional polymer, the chain consisting of alternating selenium and oxygen atoms. Each Se atom is pyramidal and bears a terminal oxide group. The bridging Se-O bond lengths are 179 pm and the terminal Se-O distance is 162 pm. [5] The relative stereochemistry at Se alternates along the polymer chain (syndiotactic). In the gas phase selenium dioxide is present as dimers and other oligomeric species, at higher temperatures it is monomeric. [6] The monomeric form adopts a bent structure very similar to that of sulfur dioxide with a bond length of 161 pm. [6] The dimeric form has been isolated in a low temperature argon matrix and vibrational spectra indicate that it has a centrosymmetric chair form. [5] Dissolution of SeO2 in selenium oxydichloride give the trimer [Se(O)O]3. [6] Monomeric SeO2 is a polar molecule, with the dipole moment of 2.62 D [7] pointed from the midpoint of the two oxygen atoms to the selenium atom.

The solid sublimes readily. At very low concentrations the vapour has a revolting odour, resembling decayed horseradishes. At higher concentrations the vapour has an odour resembling horseradish sauce and can burn the nose and throat on inhalation. Whereas SO2 tends to be molecular and SeO2 is a one-dimensional chain, TeO2 is a cross-linked polymer. [5]

SeO2 is considered an acidic oxide: it dissolves in water to form selenous acid. [6] Often the terms selenous acid and selenium dioxide are used interchangeably. It reacts with base to form selenite salts containing the SeO2−
3
anion. For example, reaction with sodium hydroxide produces sodium selenite:

SeO2 + 2 NaOH → Na2SeO3 + H2O

Preparation

Selenium dioxide is prepared by oxidation of selenium by burning in air or by reaction with nitric acid or hydrogen peroxide, but perhaps the most convenient preparation is by the dehydration of selenous acid.

2 H2O2 + Se → SeO2 + 2 H2O
3 Se + 4 HNO3 + H2O → 3 H2SeO3 + 4 NO
H2SeO3 ⇌ SeO2 + H2O

Occurrence

The natural form of selenium dioxide, downeyite, is a very rare mineral. It is only found at a small number of burning coal banks, where it forms around vents created from escaping gasses. [8]

Uses

Organic synthesis

SeO2 is an important reagent in organic synthesis. Oxidation of paraldehyde (acetaldehyde trimer) with SeO2 gives glyoxal [9] and the oxidation of cyclohexanone gives 1,2-cyclohexanedione. [10] The selenium starting material is reduced to selenium, and precipitates as a red amorphous solid which can easily be filtered off. [10] This type of reaction is called a Riley oxidation. It is also renowned as a reagent for allylic oxidation, [11] a reaction that entails the following conversion

Allylic oxidation Seleniumdioxide oxidation.svg
Allylic oxidation

This can be described more generally as;

R2C=CR'-CHR"2 + [O] → R2C=CR'-C(OH)R"2

where R, R', R" may be alkyl or aryl substituents.

Selenium dioxide can also be used to synthesize 1,2,3-selenadiazoles from acylated hydrazone derivatives. [12]

As a colorant

Selenium dioxide imparts a red colour to glass. It is used in small quantities to counteract the colour due to iron impurities and so to create (apparently) colourless glass. In larger quantities, it gives a deep ruby red colour.

Selenium dioxide is the active ingredient in some cold-bluing solutions.

It was also used as a toner in photographic developing.

Safety

Selenium is an essential element, but ingestion of more than 5 mg/day leads to nonspecific symptoms. [13]

Related Research Articles

<span class="mw-page-title-main">Selenium</span> Chemical element, symbol Se and atomic number 34

Selenium is a chemical element; it has the symbol Se and atomic number 34. It is a nonmetal with properties that are intermediate between the elements above and below in the periodic table, sulfur and tellurium, and also has similarities to arsenic. It seldom occurs in its elemental state or as pure ore compounds in Earth's crust. Selenium was discovered in 1817 by Jöns Jacob Berzelius, who noted the similarity of the new element to the previously discovered tellurium.

<span class="mw-page-title-main">Allyl group</span> Chemical group (–CH₂–CH=CH₂)

In organic chemistry, an allyl group is a substituent with the structural formula −CH2−HC=CH2. It consists of a methylene bridge attached to a vinyl group. The name is derived from the scientific name for garlic, Allium sativum. In 1844, Theodor Wertheim isolated an allyl derivative from garlic oil and named it "Schwefelallyl". The term allyl applies to many compounds related to H2C=CH−CH2, some of which are of practical or of everyday importance, for example, allyl chloride.

<span class="mw-page-title-main">Organotin chemistry</span> Branch of organic chemistry

Organotin chemistry is the scientific study of the synthesis and properties of organotin compounds or stannanes, which are organometallic compounds containing tin–carbon bonds. The first organotin compound was diethyltin diiodide, discovered by Edward Frankland in 1849. The area grew rapidly in the 1900s, especially after the discovery of the Grignard reagents, which are useful for producing Sn–C bonds. The area remains rich with many applications in industry and continuing activity in the research laboratory.

Selenic acid is the inorganic compound with the formula H2SeO4. It is an oxoacid of selenium, and its structure is more accurately described as O2Se(OH)2. It is a colorless compound. Although it has few uses, one of its salts, sodium selenate is used in the production of glass and animal feeds.

<span class="mw-page-title-main">Selenite (ion)</span> Anion composed of selenium and oxygen

Selenite refers to the anion with the chemical formula SeO2−3. It is the oxyanion of selenium. It is the selenium analog of the sulfite ion, SO2−3. Thus selenite is pyramidal and selenium is assigned oxidation state +4. Selenite also refers to compounds that contains this ion, for example sodium selenite Na2SeO3 which is a common source of selenite. Selenite also refers to the esters of selenous acid, for example dimethyl selenite (CH3)2SeO3.

<span class="mw-page-title-main">Selenous acid</span> Chemical compound

Selenous acid is the chemical compound with the formula H2SeO3. Structurally, it is more accurately described by O=Se(OH)2. It is the principal oxoacid of selenium; the other being selenic acid.

Organoselenium chemistry is the science exploring the properties and reactivity of organoselenium compounds, chemical compounds containing carbon-to-selenium chemical bonds. Selenium belongs with oxygen and sulfur to the group 16 elements or chalcogens, and similarities in chemistry are to be expected. Organoselenium compounds are found at trace levels in ambient waters, soils and sediments.

<span class="mw-page-title-main">Hydroperoxide</span> Class of chemical compounds

Hydroperoxides or peroxols are compounds of the form ROOH, where R stands for any group, typically organic, which contain the hydroperoxy functional group. Hydroperoxide also refers to the hydroperoxide anion and its salts, and the neutral hydroperoxyl radical (•OOH) consist of an unbond hydroperoxy group. When R is organic, the compounds are called organic hydroperoxides. Such compounds are a subset of organic peroxides, which have the formula ROOR. Organic hydroperoxides can either intentionally or unintentionally initiate explosive polymerisation in materials with unsaturated chemical bonds.

Selenium oxydichloride is the inorganic compound with the formula SeOCl2. It is a colorless liquid. With a high dielectric constant (55) and high specific conductance, it is an attractive solvent. Structurally, it is a close chemical relative of thionyl chloride SOCl2, being a pyramidal molecule.

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

Selenium tetrafluoride (SeF4) is an inorganic compound. It is a colourless liquid that reacts readily with water. It can be used as a fluorinating reagent in organic syntheses (fluorination of alcohols, carboxylic acids or carbonyl compounds) and has advantages over sulfur tetrafluoride in that milder conditions can be employed and it is a liquid rather than a gas.

Selenium trioxide is the inorganic compound with the formula SeO3. It is white, hygroscopic solid. It is also an oxidizing agent and a Lewis acid. It is of academic interest as a precursor to Se(VI) compounds.

<span class="mw-page-title-main">Selenium compounds</span> Chemical compounds containing selenium

Selenium compounds are compounds containing the element selenium (Se). Among these compounds, selenium has various oxidation states, the most common ones being −2, +4, and +6. Selenium compounds exist in nature in the form of various minerals, such as clausthalite, guanajuatite, tiemannite, crookesite etc., and can also coexist with sulfide minerals such as pyrite and chalcopyrite. For many mammals, selenium compounds are essential. For example, selenomethionine and selenocysteine are selenium-containing amino acids present in the human body. Selenomethionine participates in the synthesis of selenoproteins. The reduction potential and pKa (5.47) of selenocysteine are lower than those of cysteine, making some proteins have antioxidant activity. Selenium compounds have important applications in semiconductors, glass and ceramic industries, medicine, metallurgy and other fields.

<span class="mw-page-title-main">Sodium selenate</span> Chemical compound

Sodium selenate is the inorganic compound with the formula Na
2
SeO
4
, not to be confused with sodium selenite. It exists as the anhydrous salt, the heptahydrate, and the decahydrate. These are white, water-soluble solids. The decahydrate is a common ingredient in multivitamins and livestock feed as a source of selenium. The anhydrous salt is used in the production of some glass. Although the selenates are much more toxic, many physical properties of sodium selenate and sodium sulfate are similar.

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

Selenium tetrachloride is the inorganic compound composed with the formula SeCl4. This compound exists as yellow to white volatile solid. It is one of two commonly available selenium chlorides, the other example being selenium monochloride, Se2Cl2. SeCl4 is used in the synthesis of other selenium compounds.

Oxophilicity is the tendency of certain chemical compounds to form oxides by hydrolysis or abstraction of an oxygen atom from another molecule, often from organic compounds. The term is often used to describe metal centers, commonly the early transition metals such as titanium, niobium, and tungsten. Oxophilicity is often stated to be related to the hardness of the element, within the HSAB theory, but it has been shown that oxophilicity depends more on the electronegativity and effective nuclear charge of the element than on its hardness. This explains why the early transition metals, whose electronegativities and effective nuclear charges are low, are very oxophilic. Many main group compounds are also oxophilic, such as derivatives of aluminium, silicon, and phosphorus(III). The handling of oxophilic compounds often requires air-free techniques.

Selenium monochloride or diselenium dichloride is an inorganic compound with the formula Se2Cl2. Although a common name for the compound is selenium monochloride, reflecting its empirical formula, IUPAC does not recommend that name, instead preferring the more descriptive diselenium dichloride.

<span class="mw-page-title-main">Sodium bismuthate</span> Chemical compound

Sodium bismuthate is an inorganic compound, and a strong oxidiser with chemical formula NaBiO3. It is somewhat hygroscopic, but not soluble in cold water, which can be convenient since the reagent can be easily removed after the reaction. It is one of the few water insoluble sodium salts. Commercial samples may be a mixture of bismuth(V) oxide, sodium carbonate and sodium peroxide.

<span class="mw-page-title-main">Potassium selenate</span> Chemical compound

Potassium selenate, K
2
SeO
4
, is an odorless, white solid that forms as the potassium salt of selenic acid.

The Riley oxidation is a selenium dioxide-mediated oxidation of methylene groups adjacent to carbonyls. It was first reported by Riley and co-workers in 1932. In the decade that ensued, selenium-mediated oxidation rapidly expanded in use, and in 1939, Guillemonat and co-workers disclosed the selenium dioxide-mediated oxidation of olefins at the allylic position. Today, selenium-dioxide-mediated oxidation of methylene groups to alpha ketones and at the allylic position of olefins is known as the Riley Oxidation.

A selenate selenite is a chemical compound or salt that contains selenite and selenate anions (SeO32- and SeO42-). These are mixed anion compounds. Some have third anions.

References

  1. "Safety data sheet: Selenium dioxide" (PDF). integrachem.com. 27 March 2015. Retrieved 2022-12-02.
  2. "Selenium dioxide safety and hazards". pubchem.ncbi.nlm.nih.gov. Retrieved 2022-12-02.
  3. "Selenium compounds (as Se)". Immediately Dangerous to Life or Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).
  4. Hoekstra, William J.; Fairlamb, Ian J. S.; Giroux, Simon; Chen, Yuzhong (2017). "Selenium(IV) Oxide". Encyclopedia of Reagents for Organic Synthesis. pp. 1–12. doi:10.1002/047084289X.rs008.pub3. ISBN   978-0-470-84289-8.
  5. 1 2 3 Handbook of Chalcogen Chemistry: New Perspectives in Sulfur, Selenium and Tellurium, Franceso A. Devillanova, Royal Society of Chemistry, 2007, ISBN   9780854043668
  6. 1 2 3 4 Holleman, Arnold Frederik; Wiberg, Egon (2001), Wiberg, Nils (ed.), Inorganic Chemistry, translated by Eagleson, Mary; Brewer, William, San Diego/Berlin: Academic Press/De Gruyter, ISBN   0-12-352651-5
  7. Takeo, Harutoshi; Hirota, Eizi; Morino, Yonezo (1972). "Third-order potential constants and dipole moment of SeO2 by microwave spectroscopy". Journal of Molecular Spectroscopy. 41 (2): 420–422. Bibcode:1972JMoSp..41..420T. doi:10.1016/0022-2852(72)90216-0. ISSN   0022-2852.
  8. Finkelman, Robert B.; Mrose, Mary E. (1977). "Downeyite, the first verified natural occurrence of SeO2" (PDF). American Mineralogist . 62: 316–320.
  9. Ronzio, A. R.; Waugh, T. D. (1955). "Glyoxal Bisulfite". Organic Syntheses .{{cite journal}}: CS1 maint: multiple names: authors list (link); Collective Volume, vol. 3, p. 438
  10. 1 2 Hach, C. C. Banks, C. V.; Diehl, H. (1963). "1,2-Cyclohexanedione Dioxime". Organic Syntheses .{{cite journal}}: CS1 maint: multiple names: authors list (link); Collective Volume, vol. 4, p. 229
  11. Coxon, J. M.; Dansted, E.; Hartshorn, M. P. (1977). "Allylic Oxidation with Hydrogen Peroxide–Selenium Dioxide: trans-Pinocarveol". Organic Syntheses . 56: 25. doi:10.15227/orgsyn.056.0025.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  12. Lalezari, Iraj; Shafiee, Abbas; Yalpani, Mohamed (1969). "A novel synthesis of selenium heterocycles: substituted 1,2,3-selenadiazoles". Tetrahedron Letters. 10 (58): 5105–5106. doi:10.1016/S0040-4039(01)88895-X.
  13. Bernd E. Langner "Selenium and Selenium Compounds" in Ullmann's Encyclopedia of Industrial Chemistry, 2005, Wiley-VCH, Weinheim. doi : 10.1002/14356007.a23_525