Chlorine pentafluoride

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Chlorine pentafluoride
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Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.033.734 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
RTECS number
  • FO2975000
UNII
  • InChI=1S/ClF5/c2-1(3,4,5)6 X mark.svgN
    Key: KNSWNNXPAWSACI-UHFFFAOYSA-N X mark.svgN
  • FCl(F)(F)(F)F
Properties
ClF5
Molar mass 130.445 g mol−1
Appearancecolorless gas
Density 4.5 kg/m3 (g/L)
Melting point −103 °C (−153 °F; 170 K)
Boiling point −13.1 °C (8.4 °F; 260.0 K)
Hydrolyzes
Structure
Square pyramidal
Thermochemistry
Std molar
entropy
(S298)
310.73 J K−1 mol−1
−238.49 kJ mol−1
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Chlorine pentafluoride is an interhalogen compound with formula ClF5. This colourless gas is a strong oxidant that was once a candidate oxidizer for rockets. The molecule adopts a square pyramidal structure with C4v symmetry, [1] as confirmed by its high-resolution 19F NMR spectrum. [2] It was first synthesized in 1963. [3]

Contents

Preparation

Some of the earliest research on the preparation was classified. [4] [5] It was first prepared by fluorination of chlorine trifluoride at high temperatures and high pressures: [4]

ClF3 + F2 → ClF5
ClF + 2F2 → ClF5
Cl2 + 5F2 → 2ClF5
CsClF4 + F2 → CsF + ClF5

NiF2 catalyzes this reaction. [6]

Certain metal fluorides, MClF4 (i.e. KClF4, RbClF4, CsClF4), react with F2 to produce ClF5 and the corresponding alkali metal fluoride. [5]

Reactions

In a highly exothermic reaction, ClF5 reacts with water to produce chloryl fluoride and hydrogen fluoride: [7]

ClF
5
+ 2 H
2
O
ClO
2
F
+ 4 HF

It is also a strong fluorinating agent. At room temperature it reacts readily with all elements (including otherwise "inert" elements like platinum and gold) except noble gases, nitrogen, oxygen and fluorine. [2]

Uses

Rocket propellant

Chlorine pentafluoride was once considered for use as an oxidizer for rockets. As a propellant, it has a higher maximum specific impulse than ClF3, but with the same difficulties in handling. [4] Due to the hazardous nature of chlorine pentafluoride, it has yet to be used in a large scale rocket propulsion system.

See also

Related Research Articles

In chemistry, halogenation is a chemical reaction that entails the introduction of one or more halogens into a 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 (F2, Cl2, Br2, I2). 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.

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.

Chlorine trifluoride is an interhalogen compound with the formula ClF3. This colorless, poisonous, corrosive, and extremely reactive gas condenses to a pale-greenish yellow liquid, the form in which it is most often sold. The compound is primarily of interest in plasmaless cleaning and etching operations in the semiconductor industry, in nuclear reactor fuel processing, historically as a component in rocket fuels, and various other industrial operations owing to its corrosive nature.

Phosphorus trifluoride (formula PF3), is a colorless and odorless gas. It is highly toxic and reacts slowly with water. Its main use is as a ligand in metal complexes. As a ligand, it parallels carbon monoxide in metal carbonyls, and indeed its toxicity is due to its binding with the iron in blood hemoglobin in a similar way to carbon monoxide.

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

Bromine trifluoride is an interhalogen compound with the formula BrF3. At room temperature, it is a straw-coloured liquid with a pungent odor which decomposes violently on contact with water and organic compounds. It is a powerful fluorinating agent and an ionizing inorganic solvent. It is used to produce uranium hexafluoride (UF6) in the processing and reprocessing of nuclear fuel.

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

Bromine pentafluoride, BrF5, is an interhalogen compound and a fluoride of bromine. It is a strong fluorinating agent.

Iodine pentafluoride is an interhalogen compound with chemical formula IF5. It is one of the fluorides of iodine. It is a colorless liquid, although impure samples appear yellow. It is used as a fluorination reagent and even a solvent in specialized syntheses.

<span class="mw-page-title-main">Sulfur tetrafluoride</span> Chemical compound

Sulfur tetrafluoride is the chemical compound with the formula SF4. It is a colorless corrosive gas that releases dangerous HF upon exposure to water or moisture. Despite these unwelcome characteristics, this compound is a useful reagent for the preparation of organofluorine compounds, some of which are important in the pharmaceutical and specialty chemical industries.

Bromine compounds are compounds containing the element bromine (Br). These compounds usually form the -1, +1, +3 and +5 oxidation states. Bromine is intermediate in reactivity between chlorine and iodine, and is one of the most reactive elements. Bond energies to bromine tend to be lower than those to chlorine but higher than those to iodine, and bromine is a weaker oxidising agent than chlorine but a stronger one than iodine. This can be seen from the standard electrode potentials of the X2/X couples (F, +2.866 V; Cl, +1.395 V; Br, +1.087 V; I, +0.615 V; At, approximately +0.3 V). Bromination often leads to higher oxidation states than iodination but lower or equal oxidation states to chlorination. Bromine tends to react with compounds including M–M, M–H, or M–C bonds to form M–Br bonds.

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.

Antimony trifluoride is the inorganic compound with the formula SbF3. Sometimes called Swarts' reagent, is one of two principal fluorides of antimony, the other being SbF5. It appears as a white solid. As well as some industrial applications, it is used as a reagent in inorganic and organofluorine chemistry.

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

Gold(V) fluoride is the inorganic compound with the formula Au2F10. This fluoride compound features gold in its highest known oxidation state. This red solid dissolves in hydrogen fluoride but these solutions decompose, liberating fluorine.

<span class="mw-page-title-main">Phosphorus pentafluoride</span> Chemical compound

Phosphorus pentafluoride, PF5, is a phosphorus halide. It is a colourless, toxic gas that fumes in air.

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

Gold(III) fluoride, AuF3, is an orange solid that sublimes at 300 °C. It is a powerful fluorinating agent. It is very sensitive to moisture, yielding gold(III) hydroxide and hydrofluoric acid.

Arsenic trifluoride is a chemical compound of arsenic and fluorine with the chemical formula AsF3. It is a colorless liquid which reacts readily with water.

Arsenic pentafluoride is a chemical compound of arsenic and fluorine. It is a toxic, colorless gas. The oxidation state of arsenic is +5.

<span class="mw-page-title-main">Vanadium pentafluoride</span> Chemical compound

Vanadium(V) fluoride is the inorganic compound with the chemical formula VF5. It is a colorless volatile liquid. It is a highly reactive compound, as indicated by its ability to fluorinate organic substances.

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.

<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.

Rhodium(IV) fluoride is a chemical compound of rhodium and fluorine. It is formed when rhodium(III) bromide reacts with bromine trifluoride. Iridium(IV) fluoride, palladium(IV) fluoride and platinum(IV) fluoride have the same crystal structure.

References

  1. Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. p. 833. ISBN   978-0-08-037941-8.
  2. 1 2 Pilipovich, D.; Maya, W.; Lawton, E.A.; Bauer, H.F.; Sheehan, D. F.; Ogimachi, N. N.; Wilson, R. D.; Gunderloy, F. C.; Bedwell, V. E. (1967). "Chlorine pentafluoride. Preparation and Properties". Inorganic Chemistry . 6 (10): 1918. doi:10.1021/ic50056a036.
  3. Smith D. F. (1963). "Chlorine Pentafluoride". Science . 141 (3585): 1039–1040. doi:10.1126/science.141.3585.1039. PMID   17739492.
  4. 1 2 3 Clark, John D. (1972). Ignition! An Informal History of Liquid Rocket Propellants (PDF). Rutgers University Press. pp. 87–88. ISBN   0-8135-0725-1.
  5. 1 2 Smith D. F. (1963). "Chlorine Pentafluoride". Science . 141 (3585): 1039–1040. Bibcode:1963Sci...141.1039S. doi:10.1126/science.141.3585.1039. PMID   17739492. S2CID   39767609.
  6. Šmalc A, Žemva B, Slivnik J, Lutar K (1981). "On the Synthesis of Chlorine Pentafluoride". Journal of Fluorine Chemistry. 17 (4): 381–383. doi:10.1016/S0022-1139(00)81783-2.
  7. Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. p. 834. ISBN   978-0-08-037941-8.