Hypofluorous acid

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Hypofluorous acid
Hypofluorous-acid-2D-dimensions.png
Gas-phase structure
Hypofluorous-acid-3D-vdW.png
   Hydrogen, H
   Oxygen, O
   Fluorine, F
Names
IUPAC name
Hypofluorous acid
Other names
  • Fluoranol
  • Fluoric(-I) acid
  • Hydrogen hypofluorite
  • Hydrogen fluorate(-I)
  • Hydrogen monofluoroxygenate(0)
  • Hydroxyl fluoride
Identifiers
3D model (JSmol)
ChemSpider
PubChem CID
  • InChI=1S/FHO/c1-2/h2H X mark.svgN
    Key: AQYSYJUIMQTRMV-UHFFFAOYSA-N X mark.svgN
  • InChI=1/FHO/c1-2/h2H
    Key: AQYSYJUIMQTRMV-UHFFFAOYAN
  • OF
Properties
HOF
Molar mass 36.0057 g/mol
Appearancepale yellow liquid above −117 °C
white solid below −117 °C
Melting point −117 °C (−179 °F; 156 K)
Boiling point decomposes at 0 °C (32 °F; 273 K)[ citation needed ]
Structure
Cs
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
Explosive, strong oxidizer, corrosive
NFPA 704 (fire diamond)
NFPA 704.svgHealth 4: Very short exposure could cause death or major residual injury. E.g. VX gasFlammability 0: Will not burn. E.g. waterInstability 4: Readily capable of detonation or explosive decomposition at normal temperatures and pressures. E.g. nitroglycerinSpecial hazard OX: Oxidizer. E.g. potassium perchlorate
4
0
4
OX
Related compounds
Other cations
Lithium hypofluorite
Related compounds
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Hypofluorous acid, chemical formula H O F , is the only known oxyacid of fluorine and the only known oxoacid in which the main atom gains electrons from oxygen to create a negative oxidation state. The oxidation state of the oxygen in this acid (and in the hypofluorite ion OF and in its salts called hypofluorites) is 0, while its valence is 2. It is also the only hypohalous acid that can be isolated as a solid. HOF is an intermediate in the oxidation of water by fluorine, which produces hydrogen fluoride, oxygen difluoride, hydrogen peroxide, ozone and oxygen. HOF is explosive at room temperature, forming HF and O2: [1]

Contents

2 HOF → 2 HF + O2

This reaction is catalyzed by water. [2]

It was isolated in the pure form by passing F2 gas over ice at −40 °C, rapidly collecting the HOF gas away from the ice, and condensing it: [2]

F2 + H2O → HOF + HF

The compound has been characterized in the solid phase by X-ray crystallography [1] as a bent molecule with an angle of 101°. The O–F and O–H bond lengths are 144.2 and 96.4 picometres, respectively. The solid framework consists of chains with O–H···O linkages. The structure has also been analyzed in the gas phase, a state in which the H–O–F bond angle is slightly narrower (97.2°).

Thiophene chemists commonly call a solution of hypofluorous acid in acetonitrile (generated in situ by passing gaseous fluorine through water in acetonitrile) Rozen's reagent. [3]

Difference from other hypohalous acids

The formal oxidation state of oxygen in hypofluorous acid and hypofluorite is 0; the same oxidation state found in molecular oxygen. In most oxygen compounds, including the other hypohalous acids, oxygen takes on a state of -2. The oxygen (0) atom is the root of hypofluorous acid's strength as an oxidizer, in contrast to the halogen (+1) atom in other hypohalic acids.

This alters the acid's chemistry. Where reduction of a general hypohalous acid reduces the halogen atom and yields the corresponding elemental halogen gas,

2 HOX + 2 H+ + 2 e → 2 H2O + X2

reduction of hypofluorous acid instead reduces the oxygen atom and yields fluoride directly.

HOF + H+ + 2 e → H2O + F

Unlike other hypohalous acids, HOF is a weaker oxidant than elemental fluorine.

Hypofluorites

Hypofluorites are formally derivatives of OF, which is the conjugate base of hypofluorous acid. One example is trifluoromethyl hypofluorite (CF3OF), which is a trifluoromethyl ester of hypofluorous acid. The conjugate base is known in salts such as lithium hypofluorite.

See also

Related Research Articles

<span class="mw-page-title-main">Redox</span> Chemical reaction in which oxidation states of atoms are changed

Redox is a type of chemical reaction in which the oxidation states of the reactants change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is the gain of electrons or a decrease in the oxidation state. The oxidation and reduction processes occur simultaneously in the chemical reaction.

<span class="mw-page-title-main">Haloalkane</span> Group of chemical compounds derived from alkanes containing one or more halogens

The haloalkanes are alkanes containing one or more halogen substituents. They are a subset of the general class of halocarbons, although the distinction is not often made. Haloalkanes are widely used commercially. They are used as flame retardants, fire extinguishants, refrigerants, propellants, solvents, and pharmaceuticals. Subsequent to the widespread use in commerce, many halocarbons have also been shown to be serious pollutants and toxins. For example, the chlorofluorocarbons have been shown to lead to ozone depletion. Methyl bromide is a controversial fumigant. Only haloalkanes that contain chlorine, bromine, and iodine are a threat to the ozone layer, but fluorinated volatile haloalkanes in theory may have activity as greenhouse gases. Methyl iodide, a naturally occurring substance, however, does not have ozone-depleting properties and the United States Environmental Protection Agency has designated the compound a non-ozone layer depleter. For more information, see Halomethane. Haloalkane or alkyl halides are the compounds which have the general formula "RX" where R is an alkyl or substituted alkyl group and X is a halogen.

<span class="mw-page-title-main">Oxidizing agent</span> Chemical compound used to oxidize another substance in a chemical reaction

An oxidizing agent is a substance in a redox chemical reaction that gains or "accepts"/"receives" an electron from a reducing agent. In other words, an oxidizer is any substance that oxidizes another substance. The oxidation state, which describes the degree of loss of electrons, of the oxidizer decreases while that of the reductant increases; this is expressed by saying that oxidizers "undergo reduction" and "are reduced" while reducers "undergo oxidation" and "are oxidized". Common oxidizing agents are oxygen, hydrogen peroxide, and the halogens.

In chemistry, halogenation is a chemical reaction which introduces one or more halogens into a chemical compound. Halide-containing compounds are pervasive, making this type of transformation important, e.g. in the production of polymers, drugs. This kind of conversion is in fact so common that a comprehensive overview is challenging. This article mainly deals with halogenation using elemental halogens. Halides are also commonly introduced using salts of the halides and halogen acids. Many specialized reagents exist for and introducing halogens into diverse substrates, e.g. thionyl chloride.

<span class="mw-page-title-main">Oxygen fluoride</span> Any binary compound of oxygen and fluorine

Oxygen fluorides are compounds of elements oxygen and fluorine with the general formula OnF2, where n = 1 to 6. Many different oxygen fluorides are known:

<span class="mw-page-title-main">Potassium fluoride</span> Ionic compound (KF)

Potassium fluoride is the chemical compound with the formula KF. After hydrogen fluoride, KF is the primary source of the fluoride ion for applications in manufacturing and in chemistry. It is an alkali halide salt and occurs naturally as the rare mineral carobbiite. Solutions of KF will etch glass due to the formation of soluble fluorosilicates, although HF is more effective.

<span class="mw-page-title-main">Cobalt(III) fluoride</span> Chemical compound

Cobalt(III) fluoride is the inorganic compound with the formula CoF3. Hydrates are also known. The anhydrous compound is a hygroscopic brown solid. It is used to synthesize organofluorine compounds.

<span class="mw-page-title-main">Xenon difluoride</span> Chemical compound

Xenon difluoride is a powerful fluorinating agent with the chemical formula XeF
2
, and one of the most stable xenon compounds. Like most covalent inorganic fluorides it is moisture-sensitive. It decomposes on contact with water vapor, but is otherwise stable in storage. Xenon difluoride is a dense, colourless crystalline solid.

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Perchloryl fluoride is a reactive gas with the chemical formula ClO
3
F
. It has a characteristic sweet odor that resembles gasoline and kerosene. It is toxic and is a powerful oxidizing and fluorinating agent. It is the acid fluoride of perchloric acid.

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The Fleming–Tamao oxidation, or Tamao–Kumada–Fleming oxidation, converts a carbon–silicon bond to a carbon–oxygen bond with a peroxy acid or hydrogen peroxide. Fleming–Tamao oxidation refers to two slightly different conditions developed concurrently in the early 1980s by the Kohei Tamao and Ian Fleming research groups.

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<span class="mw-page-title-main">Trifluoromethyl hypofluorite</span> Chemical compound

Trifluoromethyl hypofluorite is an organofluorine compound with the chemical formula CF3OF. It exists as a colorless gas at room temperature and is highly toxic. It is a rare example of a hypofluorite. It can be seen as a similar chemical compound to methanol where every hydrogen atom is replaced by a fluorine atom. It is a trifluoromethyl ester of hypofluorous acid. It is prepared by the reaction of fluorine gas with carbon monoxide:

Fluorine forms a great variety of chemical compounds, within which it always adopts an oxidation state of −1. With other atoms, fluorine forms either polar covalent bonds or ionic bonds. Most frequently, covalent bonds involving fluorine atoms are single bonds, although at least two examples of a higher order bond exist. Fluoride may act as a bridging ligand between two metals in some complex molecules. Molecules containing fluorine may also exhibit hydrogen bonding. Fluorine's chemistry includes inorganic compounds formed with hydrogen, metals, nonmetals, and even noble gases; as well as a diverse set of organic compounds. For many elements the highest known oxidation state can be achieved in a fluoride. For some elements this is achieved exclusively in a fluoride, for others exclusively in an oxide; and for still others the highest oxidation states of oxides and fluorides are always equal.

A hypohalous acid is an oxyacid consisting of a hydroxyl group single-bonded to any halogen. Examples include hypofluorous acid, hypochlorous acid, hypobromous acid, and hypoiodous acid. The conjugate base is a hypohalite. They can be formed by reacting the corresponding diatomic halogen molecule with water in the reaction:

<span class="mw-page-title-main">Peroxymonophosphoric acid</span> Oxyacid of phosphorus

Peroxymonophosphoric acid is an oxyacid of phosphorus. It is a colorless viscous oil. Its salts are called peroxymonophosphates. Another peroxyphosphoric acid is peroxydiphosphoric acid, H4P2O8.

<span class="mw-page-title-main">Protactinium(V) fluoride</span> Chemical compound

Protactinium(V) fluoride is a fluoride of protactinium with the chemical formula PaF5.

Lithium hypofluorite is an inorganic compound with the chemical formula of LiOF. It is a compound of lithium, fluorine, and oxygen. This is a lithium salt of hypofluorous acid, and contains lithium cations Li+ and hypofluorite anions OF.

References

  1. 1 2 W. Poll; G. Pawelke; D. Mootz; E. H. Appelman (1988). "The Crystal Structure of Hypofluorous Acid : Chain Formation by O-H ··· O Hydrogen Bonds". Angew. Chem. Int. Ed. Engl. 27 (3): 392–3. doi:10.1002/anie.198803921.
  2. 1 2 Appelman, Evan H. (1973-04-01). "Nonexistent compounds. Two case histories". Accounts of Chemical Research. 6 (4): 113–117. doi:10.1021/ar50064a001. ISSN   0001-4842.
  3. For Rozen's original popularizations, see: For subsequent use, see, e.g.
    • Singh, Raman; Kaur, Rajneesh; Gupta, Tarang; Kulbir, Kulbir; Singh, Kuldeep (2019). "Applications of Rozen's Reagent in Oxygen-Transfer and C-H Activation Reactions". Synthesis. 51 (2): 371–383. doi:10.1055/s-0037-1609638. S2CID   104572566.
    • Dell, Emma J.; Campos, Luis M. (2012). "The preparation of thiophene-S,S-dioxides and their role in organic electronics". J. Mater. Chem. 22 (26): 12945–12952. doi:10.1039/C2JM31220D.