Chlorine tetroxide

Last updated
Chlorine tetroxide
Names
IUPAC name
Tetraoxidochlorine
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
239881
PubChem CID
  • InChI=1S/ClO4/c2-1(3,4)5
    Key: UXZQWBXGIHHEHG-UHFFFAOYSA-N
  • O=Cl(=O)(=O)[O]
Properties
ClO4
Molar mass 99.45 g mol−1
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Chlorine tetroxide is an unstable chlorine oxide with the chemical formula ClO4.

Contents

History

Gomberg's mistaken 1923 production

In 1923, chemist Moses Gomberg proposed a production method of chlorine tetroxide. He claimed that treating iodine and silver perchlorate in anhydrous diethyl ether produced it. [1]

I2 + 2 AgClO4 → 2 AgI + (ClO4)2

However, later researchers claimed that the product was iodine perchlorate. [2] So far, however, there is no certain evidence for the existence of iodine perchlorate either.

Eachus' 1968 production

In 1968, Eachus synthesized it by exposing potassium chlorate to gamma rays at 77 K. It is a reaction intermediate of the decomposition of dichlorine heptoxide.[ citation needed ]

Properties

The electron affinity energy of chlorine tetroxide can be figured out using the Born–Haber cycle and the lattice energy data of perchlorates. It is about 561 kJ/mol. [3]

The structure of chlorine tetroxide is uncertain; the molecular point group may be Cs, C2v, or Td. [4]

In a solid oxygen matrix ClO4 reacts to form ClO6Cl, which has three double bonded oxygen atoms, and a chain of three oxygen atoms -O-O-O attached to the chlorine. [4]

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">Osmium tetroxide</span> Chemical compound

Osmium tetroxide (also osmium(VIII) oxide) is the chemical compound with the formula OsO4. The compound is noteworthy for its many uses, despite its toxicity and the rarity of osmium. It also has a number of unusual properties, one being that the solid is volatile. The compound is colourless, but most samples appear yellow. This is most likely due to the presence of the impurity OsO2, which is yellow-brown in colour. In biology, its property of binding to lipids has made it a widely-used stain in electron microscopy.

<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.

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.

Xenon tetroxide is a chemical compound of xenon and oxygen with molecular formula XeO4, remarkable for being a relatively stable compound of a noble gas. It is a yellow crystalline solid that is stable below −35.9 °C; above that temperature it is very prone to exploding and decomposing into elemental xenon and oxygen (O2).

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

A permanganate is a chemical compound with the manganate(VII) ion, MnO
4
, the conjugate base of permanganic acid. Because the manganese atom has a +7 oxidation state, the permanganate(VII) ion is a strong oxidising agent. The ion is a transition metal ion with a tetrahedral structure. Permanganate solutions are purple in colour and are stable in neutral or slightly alkaline media. The exact chemical reaction depends on the carbon-containing reactants present and the oxidant used. For example, trichloroethane (C2H3Cl3) is oxidised by permanganate ions to form carbon dioxide (CO2), manganese dioxide (MnO2), hydrogen ions (H+), and chloride ions (Cl).

<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.

<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.

<span class="mw-page-title-main">Moses Gomberg</span> American chemist (1866–1947)

Moses Gomberg was a chemistry professor at the University of Michigan. He was elected to the National Academy of Sciences and the American Philosophical Society, and served as president of the American Chemical Society.

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

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 and has a penetrating odor.

<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.

<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:

In chemistry, 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, where X is a halogen. Known oxohalides have fluorine (F), chlorine (Cl), bromine (Br), and/or iodine (I) in their molecules. The element A may be a main group element, a transition element, a rare earth 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.

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">Titanium perchlorate</span> Chemical compound

Titanium perchlorate is a molecular compound of titanium and perchlorate groups with formula Ti(ClO4)4. Anhydrous titanium perchlorate decomposes explosively at 130 °C and melts at 85 °C with a slight decomposition. It can sublime in a vacuum as low as 70 °C, and can form vapour at up to 120°. Titanium perchlorate is quite volatile. It has density 2.35. It decomposes to TiO2, ClO2 and dioxygen O2 Also TiO(ClO4)2 is formed during decomposition.

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">Astatine compounds</span>

Astatine compounds are compounds that contain the element astatine (At). As this element is very radioactive, few compounds have been studied. Less reactive than iodine, astatine is the least reactive of the halogens. Its compounds have been synthesized in nano-scale amounts and studied as intensively as possible before their radioactive disintegration. The reactions involved have been typically tested with dilute solutions of astatine mixed with larger amounts of iodine. Acting as a carrier, the iodine ensures there is sufficient material for laboratory techniques to work. Like iodine, astatine has been shown to adopt odd-numbered oxidation states ranging from −1 to +7.

References

  1. Gomberg, M. (1 February 1923). "The Reaction Between Silver Perchlorate and Iodine. Chlorine Tetra-Oxide". Journal of the American Chemical Society. 45 (2): 398–421. doi:10.1021/ja01655a017.
  2. Alcock, N. W.; Waddington, T. C. (1 January 1962). "478. The reaction between iodine and silver perchlorate". Journal of the Chemical Society (Resumed): 2510. doi:10.1039/JR9620002510.
  3. (in Chinese)张青莲. 《无机化学丛书》第六卷:卤素、铜分族、锌分族. 北京: 科学出版社. p. 272. ISBN   7-03-002238-6.
  4. 1 2 Kopitzky, Rodion; Grothe, Hinrich; Willner, Helge (16 December 2002). "Chlorine Oxide Radicals ClOx (x=1–4) Studied by Matrix Isolation Spectroscopy". Chemistry: A European Journal. 8 (24): 5601–5621. doi:10.1002/1521-3765(20021216)8:24<5601::AID-CHEM5601>3.0.CO;2-Z.