Selenium trioxide

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Selenium trioxide[1]
Structural formula of the monomer as found in the gas phase
Space-filling model of the monomer as found in the gas phase
Identifiers
13768-86-0 N
ChemSpider 103019 YesY
Jmol 3D model Interactive image
PubChem 115128
Properties
SeO3
Molar mass 126.96 g/mol
Appearance white hygroscopic crystals
Density 3.44 g/cm3
Melting point 118.35 °C (245.03 °F; 391.50 K)
Boiling point sublimes
very soluble
Structure
tetragonal
Vapor pressure {{{value}}}
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
N verify (what is YesYN ?)
Infobox references

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.[2]

Preparation

Selenium trioxide is difficult to prepare because it is unstable with respect to the dioxide:

2 SeO3 → 2 SeO2 + O2

It has been generated in a number of ways despite the fact that the dioxide does not combust under normal conditions.[2] One method entails dehydration of anhydrous selenic acid with phosphorus pentoxide at 150-160 °C. The reaction of liquid sulfur trioxide with potassium selenate

SO3 + K2SeO4 → K2SO4 + SeO3

Reactions

In its chemistry SeO3 generally resembles sulfur trioxide, SO3, rather than tellurium trioxide, TeO3.[2]

At 120 °C SeO3 reacts with selenium dioxide to form the Se(VI)-Se(IV) compound diselenium pentoxide:[3]

SeO3 + SeO2 → Se2O5

It reacts with selenium tetrafluoride to form selenoyl fluoride, the selenium analogue of sulfuryl fluoride

SeO3 + SeF4 → SeO2F2

As with SO3 adducts are formed with Lewis bases such as pyridine, dioxane and ether.[2]

With lithium oxide and sodium oxide it reacts to form salts of SeVIO54− and SeVIO66−:[4] With Li2O, it gives Li4SeO5, containing the trigonal pyramidal anion SeVIO54− with equatorial bonds, 170.6-171.9 pm; and longer axial Se-O bonds of 179.5 pm. With Na2O it gives Na4SeO5, containing the square pyramidal SeVIO54−, with Se-O bond lengths ranging from range 1.729 → 1.815 pm, and Na12(SeO4)3(SeO6), containing octahedral SeVIO66−. SeVIO66− is the conjugate base of the unknown orthoselenic acid (Se(OH)6).

Structure

In the solid phase SeO3 consists of cyclic tetramers, with an 8 membered (Se-O)4 ring. Selenium atoms are 4-coordinate, bond lengths being Se-O bridging are 175 pm and 181pm, non-bridging 156 and 154 pm.[4]

SeO3 in the gas phase consists of tetramers and monomeric SeO3 which is trigonal planar with an Se-O bond length of 168.78 pm.[5]

References

  1. Lide, David R. (1998). Handbook of Chemistry and Physics (87 ed.). Boca Raton, FL: CRC Press. pp. 4–81. ISBN 0-8493-0594-2. 
  2. 2.0 2.1 2.2 2.3 Egon Wiberg, Arnold Frederick Holleman (2001) Inorganic Chemistry, Elsevier ISBN 0123526515
  3. Z. Žák "Crystal structure of diselenium pentoxide Se2O5" Zeitschrift für anorganische und allgemeine Chemie 1980, volume 460, pp. 81–85. doi:10.1002/zaac.19804600108
  4. 4.0 4.1 Handbook of Chalcogen Chemistry: New Perspectives in Sulfur, Selenium and Tellurium, Franceso A. Devillanova, Royal Society of Chemistry, 2007, ISBN 9780854043668
  5. Brassington, N. J.; Edwards, H. G. M.; Long, D. A.; Skinner, M. (1978). "The pure rotational Raman spectrum of SeO3". Journal of Raman Spectroscopy. 7 (3): 158–160. ISSN 0377-0486. doi:10.1002/jrs.1250070310. 

Further reading