Trioxidane (systematically named dihydrogen trioxide,[2][3]), also called hydrogen trioxide[4][5] or is an inorganic compound with the chemical formulaH[O] 3H (can be written as [H(μ-O 3)H] or [H 2O 3]). It is one of the unstable hydrogen polyoxides.[4] In aqueous solutions, trioxidane decomposes to form water and singlet oxygen:
Reaction of trioxidane (blue) with water (red) results in decomposition to oxygen and an additional water molecule.
The reverse reaction, the addition of singlet oxygen to water, typically does not occur in part due to the scarcity of singlet oxygen. In biological systems, however, ozone is known to be generated from singlet oxygen, and the presumed mechanism is an antibody-catalyzed production of trioxidane from singlet oxygen.[2]
Trioxidane can be obtained in small, but detectable, amounts in reactions of ozone and hydrogen peroxide, or by the electrolysis of water. Larger quantities have been prepared by the reaction of ozone with organic reducing agents at low temperatures in a variety of organic solvents, such as the anthraquinone process. It is also formed during the decomposition of organic hydrotrioxides (ROOOH).[3] Alternatively, trioxidane can be prepared by reduction of ozone with 1,2-diphenylhydrazine at low temperature. Using a resin-bound version of the latter, relatively pure trioxidane can be isolated as a solution in organic solvent. Preparation of high purity solutions is possible using the methyltrioxorhenium(VII) catalyst.[5] In acetone-d6 at −20 °C, the characteristic 1H NMR signal of trioxidane could be observed at a chemical shift of 13.1 ppm.[3] Solutions of hydrogen trioxide in diethyl ether can be safely stored at −20 °C for as long as a week.[5]
The reaction of ozone with hydrogen peroxide is known as the "peroxone process". This mixture has been used for some time for treating groundwater contaminated with organic compounds. The reaction produces H2O3 and H2O5.[6]
Structure
In 1970-75, Giguère et al. observed infrared and Raman spectra of dilute aqueous solutions of trioxidane.[4] In 2005, trioxidane was observed experimentally by microwave spectroscopy in a supersonic jet. The molecule exists in a skewed structure, with an oxygen–oxygen–oxygen–hydrogen dihedral angle of 81.8°. The oxygen–oxygen bond lengths of 142.8 picometer are slightly shorter than the 146.4 pm oxygen–oxygen bonds in hydrogen peroxide.[7] Various dimeric and trimeric forms also seem to exist.
There is a trend of increasing gas-phase acidity and corresponding pKa as the number of oxygen atoms in the chain increases in HOnH structures (n=1,2,3).[8]
Reactions
Trioxidane readily decomposes into water and singlet oxygen, with a half-life of about 16 minutes in organic solvents at room temperature, but only milliseconds in water. It reacts with organic sulfides to form sulfoxides, but little else is known of its reactivity.
Recent research found that trioxidane is the active ingredient responsible for the antimicrobial properties of the well known ozone/hydrogen peroxide mix. Because these two compounds are present in biological systems as well it is argued that an antibody in the human body can generate trioxidane as a powerful oxidant against invading bacteria.[2][9] The source of the compound in biological systems is the reaction between singlet oxygen and water (which proceeds in either direction, of course, according to concentrations), with the singlet oxygen being produced by immune cells.[3][10]
Computational chemistry predicts that more oxygen chain molecules or hydrogen polyoxides exist and that even indefinitely long oxygen chains can exist in a low-temperature gas. With this spectroscopic evidence a search for these type of molecules can start in interstellar space.[7] A 2022 publication suggested the possibility of the presence of detectable concentrations of polyoxides in the atmosphere.[11]
^Nomenclature of Organic Chemistry : IUPAC Recommendations and Preferred Names 2013 (Blue Book). Cambridge: Royal Society of Chemistry. 2014. p. 1024. doi:10.1039/9781849733069-FP001. ISBN978-0-85404-182-4.
^ abcNyffeler, P.T.; Boyle, N.A.; Eltepu, L.; Wong, C.-H.; Eschenmoser, A.; Lerner, R.A.; Wentworth Jr., P. (2004). "Dihydrogen Trioxide (HOOOH) Is Generated during the Thermal Reaction between Hydrogen Peroxide and Ozone". Angew. Chem. Int. Ed.43 (35): 4656–4659. doi:10.1002/anie.200460457. PMID 15317003.
^ abcdPlesničar, B. (2005). "Progress in the Chemistry of Dihydrogen Trioxide (HOOOH)" (PDF). Acta Chim. Slov.52: 1–12.
^ abcCerkovnik, J.; Plesničar, B. (2013). "Recent Advances in the Chemistry of Hydrogen Trioxide (HOOOH)". Chem. Rev.113 (10): 7930–7951. doi:10.1021/cr300512s. PMID 23808683.
^ abcStrle, G.; Cerkovnik, J. (2015), "A Simple and Efficient Preparation of High‐Purity Hydrogen Trioxide (HOOOH)", Angew. Chem. Int. Ed., 54 (34): 9917–9920, doi:10.1002/anie.201504084, PMID 26234421
^Xu, X.; Goddard, W.A. (2002). "Nonlinear partial differential equations and applications: Peroxone chemistry: Formation of H2O3 and ring-(HO2)(HO3) from O3/H2O2". PNAS. 99 (24): 15308–15312. doi:10.1073/pnas.202596799. PMC137712. PMID 12438699.
^ abSuma, K.; Sumiyoshi, Y.; Endo, Y. (2005). "The Rotational Spectrum and Structure of HOOOH". J. Am. Chem. Soc.127 (43): 14998–14999. doi:10.1021/ja0556530. PMID 16248618.
^Plesničar, Božo (2005). "Progress in the Chemistry of Dihydrogen Trioxide (HOOOH)" (PDF). Acta Chim. Slov. 52: 1–12.
^A Time-Honored Chemical Reaction Generates an Unexpected Product, News & Views, September 13, 2004
^Hoffmann, R. (2004). "The Story of O" (PDF). Am. Sci.92: 23. doi:10.1511/2004.1.23.
^Berndt, Torsten; Chen, Jing; Kjærgaard, Eva R.; Møller, Kristian H.; Tilgner, Andreas; Hoffmann, Erik H.; Herrmann, Hartmut; Crounse, John D.; Wennberg, Paul O. (2022-05-27). "Hydrotrioxide (ROOOH) formation in the atmosphere". Science. Vol. 376, no. 6596. pp. 979–982. doi:10.1126/science.abn6012. ISSN 0036-8075. Retrieved 2022-05-27.
March 03, 2023
trioxidane, hydrogen, trioxide, redirects, here, hydrogen, ozonide, confused, with, trioxane, systematically, named, dihydrogen, trioxide, also, called, hydrogen, trioxide, inorganic, compound, with, chemical, formula, written, unstable, hydrogen, polyoxides, . Hydrogen trioxide redirects here For HO3 see hydrogen ozonide Not to be confused with Trioxane Trioxidane systematically named dihydrogen trioxide 2 3 also called hydrogen trioxide 4 5 or is an inorganic compound with the chemical formula H O 3 H can be written as H m O3 H or H2 O3 It is one of the unstable hydrogen polyoxides 4 In aqueous solutions trioxidane decomposes to form water and singlet oxygen Trioxidane NamesPreferred IUPAC name Trioxidane only preselected name 1 Systematic IUPAC name Dihydrogen trioxideOther names Hydrogen trioxideDihydroxy etherIdentifiersCAS Number 14699 99 1 Y3D model JSmol Interactive imageChEBI CHEBI 46736 YChemSpider 145859 YGmelin Reference 200290PubChem CID 166717CompTox Dashboard EPA DTXSID60932994InChI InChI 1S H2O3 c1 3 2 h1 2H YKey JSPLKZUTYZBBKA UHFFFAOYSA N YInChI 1 H2O3 c1 3 2 h1 2HKey JSPLKZUTYZBBKA UHFFFAOYAVSMILES OOOPropertiesChemical formula H 2O 3Molar mass 50 013 g mol 1Related compoundsRelated compounds Hydrogen peroxide Hydrogen ozonide HydroperoxylExcept where otherwise noted data are given for materials in their standard state at 25 C 77 F 100 kPa N verify what is Y N Infobox references Reaction of trioxidane blue with water red results in decomposition to oxygen and an additional water molecule The reverse reaction the addition of singlet oxygen to water typically does not occur in part due to the scarcity of singlet oxygen In biological systems however ozone is known to be generated from singlet oxygen and the presumed mechanism is an antibody catalyzed production of trioxidane from singlet oxygen 2 Contents 1 Preparation 2 Structure 3 Reactions 4 See also 5 ReferencesPreparation EditTrioxidane can be obtained in small but detectable amounts in reactions of ozone and hydrogen peroxide or by the electrolysis of water Larger quantities have been prepared by the reaction of ozone with organic reducing agents at low temperatures in a variety of organic solvents such as the anthraquinone process It is also formed during the decomposition of organic hydrotrioxides ROOOH 3 Alternatively trioxidane can be prepared by reduction of ozone with 1 2 diphenylhydrazine at low temperature Using a resin bound version of the latter relatively pure trioxidane can be isolated as a solution in organic solvent Preparation of high purity solutions is possible using the methyltrioxorhenium VII catalyst 5 In acetone d6 at 20 C the characteristic 1H NMR signal of trioxidane could be observed at a chemical shift of 13 1 ppm 3 Solutions of hydrogen trioxide in diethyl ether can be safely stored at 20 C for as long as a week 5 The reaction of ozone with hydrogen peroxide is known as the peroxone process This mixture has been used for some time for treating groundwater contaminated with organic compounds The reaction produces H2O3 and H2O5 6 Structure EditIn 1970 75 Giguere et al observed infrared and Raman spectra of dilute aqueous solutions of trioxidane 4 In 2005 trioxidane was observed experimentally by microwave spectroscopy in a supersonic jet The molecule exists in a skewed structure with an oxygen oxygen oxygen hydrogen dihedral angle of 81 8 The oxygen oxygen bond lengths of 142 8 picometer are slightly shorter than the 146 4 pm oxygen oxygen bonds in hydrogen peroxide 7 Various dimeric and trimeric forms also seem to exist There is a trend of increasing gas phase acidity and corresponding pKa as the number of oxygen atoms in the chain increases in HOnH structures n 1 2 3 8 Reactions EditTrioxidane readily decomposes into water and singlet oxygen with a half life of about 16 minutes in organic solvents at room temperature but only milliseconds in water It reacts with organic sulfides to form sulfoxides but little else is known of its reactivity Recent research found that trioxidane is the active ingredient responsible for the antimicrobial properties of the well known ozone hydrogen peroxide mix Because these two compounds are present in biological systems as well it is argued that an antibody in the human body can generate trioxidane as a powerful oxidant against invading bacteria 2 9 The source of the compound in biological systems is the reaction between singlet oxygen and water which proceeds in either direction of course according to concentrations with the singlet oxygen being produced by immune cells 3 10 Computational chemistry predicts that more oxygen chain molecules or hydrogen polyoxides exist and that even indefinitely long oxygen chains can exist in a low temperature gas With this spectroscopic evidence a search for these type of molecules can start in interstellar space 7 A 2022 publication suggested the possibility of the presence of detectable concentrations of polyoxides in the atmosphere 11 See also EditMolozonideReferences Edit Nomenclature of Organic Chemistry IUPAC Recommendations and Preferred Names 2013 Blue Book Cambridge Royal Society of Chemistry 2014 p 1024 doi 10 1039 9781849733069 FP001 ISBN 978 0 85404 182 4 a b c Nyffeler P T Boyle N A Eltepu L Wong C H Eschenmoser A Lerner R A Wentworth Jr P 2004 Dihydrogen Trioxide HOOOH Is Generated during the Thermal Reaction between Hydrogen Peroxide and Ozone Angew Chem Int Ed 43 35 4656 4659 doi 10 1002 anie 200460457 PMID 15317003 a b c d Plesnicar B 2005 Progress in the Chemistry of Dihydrogen Trioxide HOOOH PDF Acta Chim Slov 52 1 12 a b c Cerkovnik J Plesnicar B 2013 Recent Advances in the Chemistry of Hydrogen Trioxide HOOOH Chem Rev 113 10 7930 7951 doi 10 1021 cr300512s PMID 23808683 a b c Strle G Cerkovnik J 2015 A Simple and Efficient Preparation of High Purity Hydrogen Trioxide HOOOH Angew Chem Int Ed 54 34 9917 9920 doi 10 1002 anie 201504084 PMID 26234421 Xu X Goddard W A 2002 Nonlinear partial differential equations and applications Peroxone chemistry Formation of H2O3 and ring HO2 HO3 from O3 H2O2 PNAS 99 24 15308 15312 doi 10 1073 pnas 202596799 PMC 137712 PMID 12438699 a b Suma K Sumiyoshi Y Endo Y 2005 The Rotational Spectrum and Structure of HOOOH J Am Chem Soc 127 43 14998 14999 doi 10 1021 ja0556530 PMID 16248618 Plesnicar Bozo 2005 Progress in the Chemistry of Dihydrogen Trioxide HOOOH PDF Acta Chim Slov 52 1 12 A Time Honored Chemical Reaction Generates an Unexpected Product News amp Views September 13 2004 Hoffmann R 2004 The Story of O PDF Am Sci 92 23 doi 10 1511 2004 1 23 Berndt Torsten Chen Jing Kjaergaard Eva R Moller Kristian H Tilgner Andreas Hoffmann Erik H Herrmann Hartmut Crounse John D Wennberg Paul O 2022 05 27 Hydrotrioxide ROOOH formation in the atmosphere Science Vol 376 no 6596 pp 979 982 doi 10 1126 science abn6012 ISSN 0036 8075 Retrieved 2022 05 27 Retrieved from https en wikipedia org w index php title Trioxidane amp oldid 1131913884, wikipedia, wiki, book, books, library,
