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 ]

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]

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:

FClO4 can also react with tetrafluoroethylene: [6]

It may be a radical addition reaction. [7]

Related Research Articles

<span class="mw-page-title-main">Chlorine</span> Chemical element, symbol Cl and atomic number 17

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. 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.

<span class="mw-page-title-main">Potassium chlorate</span> Chemical compound

Potassium chlorate is a compound containing potassium, chlorine and oxygen, with the molecular formula KClO3. In its pure form, it is a white crystalline substance. After sodium chlorate, it is the second most common chlorate in industrial use. It is a strong oxidizing agent and its most important application is in safety matches. In other applications it is mostly obsolete and has been replaced by safer alternatives in recent decades. It has been used

An oxyanion, or oxoanion, is an ion with the generic formula A
x
Oz
y
. Oxyanions are formed by a large majority of the chemical elements. The formulae of simple oxyanions are determined by the octet rule. The corresponding oxyacid of an oxyanion is the compound H
z
A
x
O
y
. The structures of condensed oxyanions can be rationalized in terms of AOn polyhedral units with sharing of corners or edges between polyhedra. The oxyanions adenosine monophosphate (AMP), adenosine diphosphate (ADP) and adenosine triphosphate (ATP) are important in biology.

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">Chlorine oxide</span> Index of chemical compounds with the same name

Chlorine and oxygen can bond in many ways:

<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.

An oxyacid, oxoacid, or ternary acid is an acid that contains oxygen. Specifically, it is a compound that contains hydrogen, oxygen, and at least one other element, with at least one hydrogen atom bonded to oxygen that can dissociate to produce the H+ cation and the anion of the acid.

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.

<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">Tetrafluoroammonium</span> Chemical compound

The tetrafluoroammonium cation is a positively charged polyatomic ion with chemical formula NF+
4
. It is equivalent to the ammonium ion where the hydrogen atoms surrounding the central nitrogen atom have been replaced by fluorine. Tetrafluoroammonium ion is isoelectronic with tetrafluoromethane CF
4
, trifluoramine oxide ONF
3
and the tetrafluoroborate BF
4
anion.

<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.

Nitrogen pentafluoride (NF5) is a theoretical compound of nitrogen and fluorine that is hypothesized to exist based on the existence of the pentafluorides of the atoms below nitrogen in the periodic table, such as phosphorus pentafluoride. Theoretical models of the nitrogen pentafluoride molecule are either a trigonal bipyramidal covalently bound molecule with symmetry group D3h, or NF+
4
F, which would be an ionic solid.

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.

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.

Zirconium perchlorate is a molecular substance containing zirconium and perchlorate groups with formula Zr(ClO4)4. Zr(ClO4)4 is a volatile crystalline product. It can be formed by reacting zirconium tetrachloride with dry perchloric acid at liquid nitrogen temperatures. Zr(ClO4)4 sublimes slowly in a vacuum at 70°C showing that the molecule is covalently bound rather than being ionic. The reaction also forms some zirconyl perchlorate (or zirconium oxyperchlorate) ZrO(ClO4)2 as even apparently pure perchloric acid is in equilibrium with dichlorine heptoxide, hydronium ions and perchlorate ions. This side product can be minimised by adding more dichlorine heptoxide or doing the reaction as cold as possible.

<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.

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.