Potassium superoxide explained

Potassium superoxide is an inorganic compound with the formula .[1] It is a yellow paramagnetic solid that decomposes in moist air. It is a rare example of a stable salt of the superoxide anion. It is used as a scrubber, dehumidifier, and generator in rebreathers, spacecraft, submarines, and spacesuits.

Production and reactions

Potassium superoxide is produced by burning molten potassium in an atmosphere of excess oxygen.[2]

The salt consists of and ions, linked by ionic bonding. The O–O distance is 1.28 Å.[3]

Reactivity

Potassium superoxide is a source of superoxide, which is an oxidant and a nucleophile, depending on its reaction partner.[4]

Upon contact with water, it undergoes disproportionation to potassium hydroxide, oxygen, and hydrogen peroxide:

[5]

It reacts with carbon dioxide, releasing oxygen:

Potassium superoxide finds only niche uses as a laboratory reagent. Because it reacts with water, is often studied in organic solvents. Since the salt is poorly soluble in nonpolar solvents, crown ethers are typically used. The tetraethylammonium salt is also known. Representative reactions of these salts involve using superoxide as a nucleophile, e.g., in converting alkyl bromides to alcohols and acyl chlorides to diacyl peroxides.[6]

Ion exchange with tetramethylammonium hydroxide gives tetramethylammonium superoxide, a yellow solid.[7]

Applications

The Russian Space Agency has had success using potassium superoxide in chemical oxygen generators for its spacesuits and Soyuz spacecraft. has also been used in canisters for rebreathers for fire fighting and mine rescue work, but had limited use in scuba rebreathers because of its highly exothermic reaction with water. Potassium superoxide was used in a rudimentary life support system for five mice as part of the Biological Cosmic Ray Experiment on Apollo 17.[8]

Theoretically, 1 kg of absorbs 0.310 kg of while releasing 0.338 kg of . One mole of absorbs 0.5 moles of and releases 0.75 moles of oxygen.

References

  1. Hayyan M. . Hashim M. A. . AlNashef I. M. . Superoxide Ion: Generation and Chemical Implications. Chem. Rev.. 2016. 116. 5. 3029–3085. 10.1021/acs.chemrev.5b00407. 26875845. free.
  2. Book: Harald . Jakob . Stefan . Leininger . Thomas . Lehmann . Sylvia . Jacobi . Sven . Gutewort . Peroxo Compounds, Inorganic . Ullmann's Encyclopedia of Industrial Chemistry . Wiley-VCH . 2007 . 978-3527306732. 10.1002/14356007.a19_177.pub2.
  3. Abrahams . S. C. . Kalnajs . J. . 1955 . The Crystal Structure of α-Potassium Superoxide . Acta Crystallographica . 8 . 8 . 503–6 . 10.1107/S0365110X55001540 . free.
  4. Book: 10.1002/047084289X.rp250.pub2 . Potassium Superoxide . Encyclopedia of Reagents for Organic Synthesis . 2007 . Johnson . Roy A. . Adrio . Javier . Ribagorda . María . 978-0471936237.
  5. Book: Kumar De, Anil. A Text Book of Inorganic Chemistry. New Age International. 2007. 978-8122413847. 247.
  6. Book: Roy A. . Johnson . Javier . Adrio . María . Ribagorda . Potassium Superoxide . e-EROS Encyclopedia of Reagents for Organic Synthesis . Wiley . 2001 . 0471936235. 10.1002/047084289X.rp250.pub2.
  7. Book: 10.1002/0471653683.ch1. Tetramethylammonium Salts of Superoxide and Peroxynitrite . Inorganic Syntheses . 2004 . Bohle . D. Scott . Sagan . Elisabeth S.. 36.
  8. Haymaker . Webb . Look . Bonne C. . Benton . Eugene V. . Richard C. Simmonds . 1975-01-01 . The Apollo 17 pocket mouse experiment (Biocore) . Biomedical Results of Apollo . en . NASA-SP-368.