Fluorine perchlorate

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Fluorine perchlorate
Fluorine-perchlorate-2D.png
Fluorine perchlorate molecule ball.png
Names
IUPAC name
Perchloryl hypofluorite
Other names
Fluorine perchlorate
Identifiers
3D model (JSmol)
ChemSpider
PubChem CID
UNII
  • InChI=1S/ClFO4/c2-6-1(3,4)5 X mark.svgN
    Key: DRFVFUCINMEBEQ-UHFFFAOYSA-N X mark.svgN
  • InChI=1/ClFO4/c2-6-1(3,4)5
    Key: DRFVFUCINMEBEQ-UHFFFAOYAO
  • FOCl(O)(O)O
Properties
FClO
4
Melting point −167.3 °C (−269.1 °F; 105.8 K)
Boiling point −16 °C (3 °F; 257 K)
Thermochemistry
9 kcal/mol [1]
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
Highly explosive gas
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Fluorine perchlorate, also called perchloryl hypofluorite is the rarely encountered chemical compound of fluorine, chlorine, and oxygen with the chemical formula ClO
4
F
or FOClO
3
. It is an extremely unstable gas that explodes spontaneously [2] and has a penetrating odor. [3]

Contents

Synthesis

One synthesis uses fluorine and perchloric acid, [4] though the action of ClF5 on water is another method.[ citation needed ]

F2 + HClO4 → FClO4 + HF

Another method of synthesis involves the thermal decomposition of tetrafluoroammonium perchlorate, NF
4
ClO
4
, which yields very pure FClO
4
that may be manipulated and frozen without explosions. [5]

NF4ClO4 → NF3 + FClO4

Structure

Fluorine perchlorate is not analogous to perchloric acid because the fluorine atom is more electronegative than oxygen. It contains an oxygen atom in a rare oxidation state of 0 due to the electronegativity of oxygen, which is higher than that of chlorine but lower than that of fluorine.

Safety

FClO4 has a very dangerous and unpredictable series of reactions associated with it, as a covalent perchlorate (chlorine in the +7 oxidation state) and a compound featuring a very sensitive O-F single bond. Small amounts of reducing agents, such as organic compounds, can trigger explosive detonation. Products of these decomposition reactions could include oxygen halides, interhalogen compounds, and other hazardous substances.

Accidental synthesis is possible if precursors are carelessly mixed. Like similar covalent fluorides and perchlorates, it needs to be handled with extreme caution.

Reaction

FClO4 is a strong oxidant and it reacts with the iodide ion:

FOClO3 + 2 I → ClO4 + F + I2

FClO4 can also react with tetrafluoroethylene: [6]

CF2=CF2 + FOClO3 → CF3CF2OClO3

It may be a radical addition reaction. [7]

Related Research Articles

<span class="mw-page-title-main">Chlorine</span> Chemical element with atomic number 17 (Cl)

Chlorine is a chemical element; it has symbol Cl and atomic number 17. The second-lightest of the halogens, it appears between fluorine and bromine in the periodic table and its properties are mostly intermediate between them. Chlorine is a yellow-green gas at room temperature. It is an extremely reactive element and a strong oxidising agent: among the elements, it has the highest electron affinity and the third-highest electronegativity on the revised Pauling scale, behind only oxygen and fluorine.

<span class="mw-page-title-main">Perchloric acid</span> Chemical compound

Perchloric acid is a mineral acid with the formula HClO4. It is an oxoacid of chlorine. Usually found as an aqueous solution, this colorless compound is a stronger acid than sulfuric acid, nitric acid and hydrochloric acid. It is a powerful oxidizer when hot, but aqueous solutions up to approximately 70% by weight at room temperature are generally safe, only showing strong acid features and no oxidizing properties. Perchloric acid is useful for preparing perchlorate salts, especially ammonium perchlorate, an important rocket fuel component. Perchloric acid is dangerously corrosive and readily forms potentially explosive mixtures.

<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, an interhalogen compound is a molecule which contains two or more different halogen atoms and no atoms of elements from any other group.

<span class="mw-page-title-main">Dichlorine heptoxide</span> Chemical compound

Dichlorine heptoxide is the chemical compound with the formula Cl2O7. This chlorine oxide is the anhydride of perchloric acid. It is produced by the careful distillation of perchloric acid in the presence of the dehydrating agent phosphorus pentoxide:

<span class="mw-page-title-main">Sodium perchlorate</span> Chemical compound

Sodium perchlorate is an inorganic compound with the chemical formula NaClO4. It consists of sodium cations Na+ and perchlorate anions ClO−4. It is a white crystalline, hygroscopic solid that is highly soluble in water and ethanol. It is usually encountered as sodium perchlorate monohydrate NaClO4·H2O. The compound is noteworthy as the most water-soluble of the common perchlorate salts.

<span class="mw-page-title-main">Lithium perchlorate</span> Chemical compound

Lithium perchlorate is the inorganic compound with the formula LiClO4. This white or colourless crystalline salt is noteworthy for its high solubility in many solvents. It exists both in anhydrous form and as a trihydrate.

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.

Organofluorine chemistry describes the chemistry of organofluorine compounds, organic compounds that contain a carbon–fluorine bond. Organofluorine compounds find diverse applications ranging from oil and water repellents to pharmaceuticals, refrigerants, and reagents in catalysis. In addition to these applications, some organofluorine compounds are pollutants because of their contributions to ozone depletion, global warming, bioaccumulation, and toxicity. The area of organofluorine chemistry often requires special techniques associated with the handling of fluorinating agents.

<span class="mw-page-title-main">Chloryl fluoride</span> Chemical compound

Chloryl fluoride is the chemical compound with the formula ClO2F. It is commonly encountered as side-product in reactions of chlorine fluorides with oxygen sources. It is the acyl fluoride of chloric acid.

<span class="mw-page-title-main">Hypofluorous acid</span> Chemical compound

Hypofluorous acid, chemical formula HOF, 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 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:

<span class="mw-page-title-main">Carbon–fluorine bond</span> Covalent bond between carbon and fluorine atoms

The carbon–fluorine bond is a polar covalent bond between carbon and fluorine that is a component of all organofluorine compounds. It is one of the strongest single bonds in chemistry, and relatively short, due to its partial ionic character. The bond also strengthens and shortens as more fluorines are added to the same carbon on a chemical compound. As such, fluoroalkanes like tetrafluoromethane are some of the most unreactive organic compounds.

<span class="mw-page-title-main">Dichlorine hexoxide</span> Chemical compound

Dichlorine hexoxide is the chemical compound with the molecular formula Cl
2
O
6
, which is correct for its gaseous state. However, in liquid or solid form, this chlorine oxide ionizes into the dark red ionic compound chloryl perchlorate [ClO
2
]+
[ClO
4
]
, which may be thought of as the mixed anhydride of chloric and perchloric acids. This compound is a notable perchlorating agent.

<span class="mw-page-title-main">Chlorine perchlorate</span> Chemical compound

Chlorine perchlorate is a chemical compound with the formula Cl2O4. This chlorine oxide is an asymmetric oxide, with one chlorine atom in +1 oxidation state and the other +7, with proper formula ClOClO3. It is produced by the photodimerization of chlorine dioxide (ClO2) at room temperature by 436 nm ultraviolet light:

<span class="mw-page-title-main">Chloryl</span> Ion

In chemistry, chloryl refers to a triatomic cation with chemical formula ClO+
2
. This species has the same general structure as chlorite (ClO
2
) but it is electronically different, with chlorine having a +5 oxidation state (rather than the +3 of chlorite). This makes it a rare example of a positively charged oxychloride. Chloryl compounds, such as FClO
2
and [ClO2][RuF6], are all highly reactive and react violently with water and most organic compounds.

Perchloratoborate is an anion of the form [B(ClO4)4]. It can form partly stable solid salts with heavy alkali metals. They are more stable than nitratoborate salts. K[B(ClO4)4] decomposes at 35 °C, Rb[B(ClO4)4] is stable to 50 °C, and Cs[B(ClO4)4] can exist up to 80 °C.

<span class="mw-page-title-main">Vanadyl perchlorate</span> Chemical compound

Vanadyl perchlorate or vanadyl triperchlorate is a golden yellow coloured liquid or crystalline compound of vanadium, oxygen and perchlorate group. The substance consists of molecules covalently bound and is quite volatile; it ignites organic solvents on contact and explodes at temperatures above 80 °C.

<span class="mw-page-title-main">Zirconium perchlorate</span> Chemical compound

Zirconium perchlorate is an inorganic compound with the formula Zr(ClO4)4. It is a hygroscopic colorless solid that sublimes in a vacuum at 70 °C. These properties show that the compound is covalently bonded molecule, rather than a salt. It is an example of a transition metal perchlorate complex.

<span class="mw-page-title-main">Chlorine trifluoride oxide</span> Chemical compound

Chlorine oxide trifluoride or chlorine trifluoride oxide is a corrosive liquid molecular compound with formula ClOF3. It was developed secretly as a rocket fuel oxidiser.

<span class="mw-page-title-main">Bromine perchlorate</span> Chemical compound

Bromine perchlorate is an inorganic chemical compound with the formula BrOClO3. It is a shock and light-sensitive red liquid which decomposes above -20 °C.

References

  1. Breazeale, J. D.; MacLaren, R. O.. Thermochemistry of oxygen-fluorine bonding, United Technology Center, Sunnyvale, CA, 1963. Accession Number: AD0402889. Retrieved online from on 2009-05-21.
  2. Pradyot Patnaik. A comprehensive guide to the hazardous properties of chemical substances, 3rd ed., Wiley-Interscience, 2007. ISBN   0-471-71458-5
  3. Robert Alan Lewis. Lewis' dictionary of toxicology, CRC Press, 1998, p. 508. ISBN   1-56670-223-2
  4. Rohrback, G. H.; Cady, G. H. (1947). "The Preparation of Fluorine Perchlorate from Fluorine and Perchloric Acid". Journal of the American Chemical Society. 69 (3): 677–678. doi:10.1021/ja01195a063.
  5. Schack, C. J.; Christe, K. O. (1979). "Reactions of fluorine perchlorate with fluorocarbons and the polarity of the oxygen-fluorine bond in covalent hypofluorites". Inorganic Chemistry. 18 (9): 2619–2620. doi:10.1021/ic50199a056.
  6. Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN   978-0-08-037941-8.
  7. Schack, Carl J.; Christe, Karl O. (1979). "Reactions of fluorine perchlorate with fluorocarbons and the polarity of the oxygen-fluorine bond in covalent hypofluorites". Inorganic Chemistry. 18 (9): 2619. doi:10.1021/ic50199a056.