Fluorine perchlorate

Last updated
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).
X mark.svgN  verify  (what is  Yes check.svgYX mark.svgN ?)

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 does not exist as a positive ion. 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 agent, 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 iodide ion:

FClO4 can also react with tetrafluoroethylene: [6]

It may be a radical addition reaction. [7]

Related Research Articles

Chlorine Chemical element, symbol Cl and atomic number 17

Chlorine is a chemical element with the 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. On several scales other than the revised Pauling scale, nitrogen's electronegativity is also listed as greater than chlorine's, such as on the Allen, Allred-Rochow, Martynov-Batsanov, Mulliken-Jaffe, Nagle, and Noorizadeh-Shakerzadeh electronegativity scales.

Perchloric acid 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.

Fluorocarbon Class of chemical compounds

Fluorocarbons, sometimes referred to as perfluorocarbons or PFCs, are organofluorine compounds with the formula CxFy, i.e., they contain only carbon and fluorine. The terminology is not strictly followed and many fluorine-containing organic compounds are called fluorocarbons. Compounds with the prefix perfluoro- are hydrocarbons, including those with heteroatoms, wherein all C-H bonds have been replaced by C-F bonds. Fluorocarbons includes perfluoroalkanes, fluoroalkenes, fluoroalkynes, and perfluoroaromatic compounds. Fluorocarbons and their derivatives are used as fluoropolymers, refrigerants, solvents, and anesthetics.

Sodium hypochlorite Chemical compound

Sodium hypochlorite is a chemical compound with the formula NaOCl or NaClO, comprising a sodium cation and a hypochlorite anion. It may also be viewed as the sodium salt of hypochlorous acid. The anhydrous compound is unstable and may decompose explosively. It can be crystallized as a pentahydrate NaOCl·5H
2
O
, a pale greenish-yellow solid which is not explosive and is stable if kept refrigerated.

Potassium chlorate 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

Hypochlorite Ion

In chemistry, hypochlorite is an anion with the chemical formula ClO. It combines with a number of cations to form hypochlorite salts. Common examples include sodium hypochlorite and calcium hypochlorite. The Cl-O distance in ClO is 1.69 Å.

Chlorine oxide Index of chemical compounds with the same name

Chlorine and oxygen can bond in many ways:

Dichlorine heptoxide 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:

Selenium tetrafluoride Chemical compound

Selenium tetrafluoride (SeF4) is an inorganic compound. It is a colourless liquid that reacts readily with water. It can be used as a fluorinating reagent in organic syntheses (fluorination of alcohols, carboxylic acids or carbonyl compounds) and has advantages over sulfur tetrafluoride in that milder conditions can be employed and it is a liquid rather than a gas.

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 the organofluorines, organic compounds that contain the 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.

Chloryl fluoride 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.

Dichlorine hexoxide 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.

Chlorine perchlorate 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:

Chloryl 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.

Molecular oxohalides (oxyhalides) are a group of chemical compounds in which both oxygen and halogen atoms are attached to another chemical element A in a single molecule. They have the general formula AOmXn, X = F, Cl, Br, I. The element A may be a main group element, a transition element or an actinide. The term oxohalide, or oxyhalide, may also refer to minerals and other crystalline substances with the same overall chemical formula, but having an ionic structure.

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.

Vanadyl perchlorate 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.

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.

Chlorine trifluoride oxide 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.