Dioxidanylium

Protonated molecular oxygen or just protonated oxygen is an ion with formula HO2+. It is formed when hydrogen containing substances combust, and exists in the ionosphere, and in plasmas that contain oxygen and hydrogen.[3] Oxidation by O2 in superacids could be by way of the production of protonated molecular oxygen.

Dioxidanylium
Names
IUPAC name
oxooxidanium
Other names
Hydroperoxy cation; Hydridodioxygen(1+); Dioxidenium; dioxidanylium
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
508
Properties
HO2+1
Molar mass 33.005 g·mol−1
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

It is the conjugate acid of dioxygen. The proton affinity of dioxygen (O2) is 4.4 eV.[4]

Significance

Protonated molecular oxygen is of interest in trying to detect dioxygen in space. Because Earth's atmosphere is full of O2, its spectrum from a space object is impossible to observe from the ground. However HO2+ should be much more detectable.[5]

Formation

Reaction of O2+ with hydrogen: O2+ + H2 → HO2+ + H·.[6]

The reaction of the trihydrogen cation with dioxygen is approximately thermoneutral: O2 + H3+ → HO2+ + H2[4]

When atomic hydrogen, created in an electric discharge is rapidly cooled with oxygen and condensed in solid neon, several reactive ions and molecules are produced. These include HO2 (hydroperoxyl), HOHOH−, H2O(HO), HOHO− as well as HO2+.[7] This reaction also forms hydrogen peroxide (H2O2) and hydrogen tetroxide (H2O4).[8]

Properties

In the infrared spectrum HO2+ the v1 band due to vibrating O-H has a band head at 3016.73 cm−1.[9]

Reactions

A helium complex (He-O2H+) also is known.[9]

O2H+ appears to react rapidly with hydrogen O2H+ + H2 → O2 + H3+.[10] O2H+ also reacts with dinitrogen and water. O2H+ + H2 O → O2 + H3O+.[10]

The protonated molecular oxygen dimer, O4H+ has a lower energy than that of protonated molecular oxygen.[4]

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References
  1. "HO2+". webbook.nist.gov.
  2. "HO2+". webbook.nist.gov.
  3. Robbe, J.M.; Monnerville, M.; Chambaud, G.; Rosmus, P.; Knowles, P.J. (January 2000). "Theoretical spectroscopic data of the HO2+ ion". Chemical Physics. 252 (1–2): 9–16. doi:10.1016/S0301-0104(99)00350-X.
  4. Xavier, George D.; Bernal-Uruchurtu, Margarita I.; Hernández-Lamoneda, Ramón (28 August 2014). "Communication: study of O4H+ : A tracer molecule in the interstellar medium?". The Journal of Chemical Physics. 141 (8): 081101. doi:10.1063/1.4894068.
  5. Widicus Weaver, Susanna L.; Woon, David E.; Ruscic, Branko; McCall, Benjamin J. (20 May 2009). "IS HO2+ A DETECTABLE INTERSTELLAR MOLECULE?". The Astrophysical Journal. 697 (1): 601–609. doi:10.1088/0004-637X/697/1/601.
  6. Ajello, J. M. (1974). "Formation of HO2+ by reaction of metastable O2+ ions with H2". The Journal of Chemical Physics. 60 (4): 1211. doi:10.1063/1.1681184.
  7. Jacox, Marilyn E.; Thompson, Warren E. (24 December 2012). "Infrared Spectra of Products of the Reaction of H Atoms with O2 Trapped in Solid Neon: HO2, HO2+ , HOHOH− , and H2O(HO)". The Journal of Physical Chemistry A. 117 (39): 9380–9390. doi:10.1021/jp310849s.
  8. Levanov, A. V.; Isaikina, O. Ya.; Antipenko, E. E.; Lunin, V. V. (5 August 2014). "Mechanism of the formation of hydrogen tetroxide and peroxide via low-temperature interaction between hydrogen atoms and molecular oxygen". Russian Journal of Physical Chemistry A. 88 (9): 1488–1492. doi:10.1134/S0036024414090222.
  9. Kohguchi, Hiroshi; Jusko, Pavol; Yamada, Koichi M. T.; Schlemmer, Stephan; Asvany, Oskar (14 April 2018). "High-resolution infrared spectroscopy of O2H+ in a cryogenic ion trap". The Journal of Chemical Physics. 148 (14): 144303. doi:10.1063/1.5023633.
  10. Kluge, Lars; Gärtner, Sabrina; Brünken, Sandra; Asvany, Oskar; Gerlich, Dieter; Schlemmer, Stephan (13 November 2012). "Transfer of a proton between H2 and O2". Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences. 370 (1978): 5041–5054. doi:10.1098/rsta.2012.0170.
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