Selenium trioxide explained

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.[1]

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.[1] One method entails dehydration of anhydrous selenic acid with phosphorus pentoxide at 150–160 °C. Another method is 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. The substance reacts explosively with oxidizable organic compounds.

At 120 °C SeO3 reacts with selenium dioxide to form the Se(VI)-Se(IV) compound diselenium pentaoxide:[2]

SeO3 + SeO2 → Se2O5

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

2SeO3 + SeF4 → 2SeO2F2 + SeO2

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

With lithium oxide and sodium oxide it reacts to form salts of SeVIO54− and SeVIO66−:[3] 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 172.9 → 181.5 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 181 pm, non-bridging 156 and 154 pm.[3]

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.[4]

Further reading

Notes and References

  1. Egon Wiberg, Arnold Frederick Holleman (2001) Inorganic Chemistry, Elsevier
  2. Z. Žák "Crystal structure of diselenium pentoxide Se2O5" Zeitschrift für anorganische und allgemeine Chemie 1980, volume 460, pp. 81–85.
  3. Handbook of Chalcogen Chemistry: New Perspectives in Sulfur, Selenium and Tellurium, Francesco A. Devillanova, Royal Society of Chemistry, 2007,
  4. Brassington. N. J.. Edwards. H. G. M.. Long. D. A.. Skinner. M.. The pure rotational Raman spectrum of SeO3. Journal of Raman Spectroscopy. 7. 3. 1978. 158–160. 0377-0486. 10.1002/jrs.1250070310. 1978JRSp....7..158B.