Zirconium(IV) iodide

Last updated
Zirconium(IV) iodide
ZrI4Troyanov.tif
Names
Other names
zirconium tetraiodide
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.034.332 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 237-780-9
PubChem CID
UNII
  • InChI=1S/4HI.Zr/h4*1H;/q;;;;+4/p-4 Yes check.svgY
    Key: XLMQAUWIRARSJG-UHFFFAOYSA-J Yes check.svgY
  • InChI=1/4HI.Zr/h4*1H;/q;;;;+4/p-4
    Key: XLMQAUWIRARSJG-XBHQNQODAZ
  • [Zr+4].[I-].[I-].[I-].[I-]
Properties
ZrI4
Molar mass 598.842 g/mol
Appearanceorange-yellow crystalline
hygroscopic
Density 4.914 g/cm3
Melting point 499 [1]  °C (930 °F; 772 K)
(triple point)
Boiling point 431 °C (808 °F; 704 K) (sublimes)
Structure
Monoclinic, mP30
P2/c, No. 13
Hazards
GHS labelling:
GHS-pictogram-acid.svg
Danger
H314
P260, P264, P280, P301+P330+P331, P303+P361+P353, P304+P340, P305+P351+P338, P310, P321, P363, P405, P501
NFPA 704 (fire diamond)
NFPA 704.svgHealth 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasFlammability 0: Will not burn. E.g. waterInstability 2: Undergoes violent chemical change at elevated temperatures and pressures, reacts violently with water, or may form explosive mixtures with water. E.g. white phosphorusSpecial hazards (white): no code
3
0
2
Related compounds
Other anions
Zirconium(IV) fluoride
Zirconium(IV) chloride
Zirconium(IV) bromide
Other cations
Titanium tetraiodide
Hafnium tetraiodide
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 ?)

Zirconium(IV) iodide is the chemical compound with the formula Zr I4. It is the most readily available iodide of zirconium. It is an orange-coloured solid that degrades in the presence of water. The compound was once prominent as an intermediate in the purification of zirconium metal.

Contents

Structure

Like most binary metal halides, zirconium(IV) iodide adopts a polymeric structure. As characterized by X-ray crystallography, the compound consists of octahedral Zr(IV) centers interconnected by four doubly bridging iodide ligands. The Zr-I distances of 2.692 (terminal) and 3.030 Å [2] [3]

Synthesis and reactions

This compound can be prepared by heating zirconium metal and an excess of iodine. [1] The solid is purified by sublimation (400 °C, 10-4 mm Hg). [4]

2 I2 + Zr → ZrI4

Pyrolysis of zirconium(IV) iodide gas by contact with a hot wire was the first industrial process for the commercial production of pure ductile metallic zirconium. This crystal bar process was developed by Anton Eduard van Arkel and Jan Hendrik de Boer in 1925. [5]

Heating the tetraiodide with zirconium metal gives zirconium triiodide: [4]

3 ZrI4 + 4 Zr → 7 ZrI3

Related Research Articles

Hafnium is a chemical element; it has symbol Hf and atomic number 72. A lustrous, silvery gray, tetravalent transition metal, hafnium chemically resembles zirconium and is found in many zirconium minerals. Its existence was predicted by Dmitri Mendeleev in 1869, though it was not identified until 1922, by Dirk Coster and George de Hevesy. Hafnium is named after Hafnia, the Latin name for Copenhagen, where it was discovered.

<span class="mw-page-title-main">Zirconium</span> Chemical element with atomic number 40 (Zr)

Zirconium is a chemical element; it has symbol Zr and atomic number 40. First identified in 1789, isolated in impure form in 1824, and manufactured at scale by 1925, pure zirconium is a lustrous transition metal with a greyish-white color that closely resembles hafnium and, to a lesser extent, titanium. It is solid at room temperature, ductile, malleable and corrosion-resistant. The name zirconium is derived from the name of the mineral zircon, the most important source of zirconium. The word is related to Persian zargun. Besides zircon, zirconium occurs in over 140 other minerals, including baddeleyite and eudialyte; most zirconium is produced as a byproduct of minerals mined for titanium and tin.

<span class="mw-page-title-main">Group 4 element</span> Group of chemical elements

Group 4 is the second group of transition metals in the periodic table. It contains the four elements titanium (Ti), zirconium (Zr), hafnium (Hf), and rutherfordium (Rf). The group is also called the titanium group or titanium family after its lightest member.

<span class="mw-page-title-main">Van Arkel–de Boer process</span> Process for the commercial production of pure titanium and zirconium

The van Arkel–de Boer process, also known as the iodide process or crystal-bar process, was the first industrial process for the commercial production of pure ductile titanium, zirconium and some other metals. It was developed by Anton Eduard van Arkel and Jan Hendrik de Boer in 1925 for Philips Nv. Now it is used in the production of small quantities of ultrapure titanium and zirconium. It primarily involves the formation of the metal iodides and their subsequent decomposition to yield pure metal, for example at one of the Allegheny Technologies' Albany plants.

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

Titanium tetraiodide is an inorganic compound with the formula TiI4. It is a black volatile solid, first reported by Rudolph Weber in 1863. It is an intermediate in the van Arkel–de Boer process for the purification of titanium.

Zirconium(IV) bromide is the inorganic compound with the formula ZrBr4. This colourless solid is the principal precursor to other Zr–Br compounds.

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

Zirconium(IV) fluoride describes members of a family inorganic compounds with the formula ZrF4(H2O)x. All are colorless, diamagnetic solids. Anhydrous Zirconium(IV) fluoride is a component of ZBLAN fluoride glass.

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

Zirconium(IV) sulfide is the inorganic compound with the formula ZrS2. It is a violet-brown solid. It adopts a layered structure similar to that of cadmium iodide.

<span class="mw-page-title-main">Chemical transport reaction</span> Process for purification and crystallization of non-volatile solids

In chemistry, a chemical transport reaction describes a process for purification and crystallization of non-volatile solids. The process is also responsible for certain aspects of mineral growth from the effluent of volcanoes. The technique is distinct from chemical vapor deposition, which usually entails decomposition of molecular precursors (e.g. SiH4 → Si + 2 H2) and which gives conformal coatings. The technique, which was popularized by Harald Schäfer, entails the reversible conversion of nonvolatile elements and chemical compounds into volatile derivatives. The volatile derivative migrates throughout a sealed reactor, typically a sealed and evacuated glass tube heated in a tube furnace. Because the tube is under a temperature gradient, the volatile derivative reverts to the parent solid and the transport agent is released at the end opposite to which it originated (see next section). The transport agent is thus catalytic. The technique requires that the two ends of the tube (which contains the sample to be crystallized) be maintained at different temperatures. So-called two-zone tube furnaces are employed for this purpose. The method derives from the Van Arkel de Boer process which was used for the purification of titanium and vanadium and uses iodine as the transport agent.

<span class="mw-page-title-main">Jan Hendrik de Boer</span> Dutch physicist and chemist

Jan Hendrik de Boer was a Dutch physicist and chemist.

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

Titanium ethoxide is a chemical compound with the formula Ti4(OCH2CH3)16. It is a commercially available colorless liquid that is soluble in organic solvents but hydrolyzes readily. Its structure is more complex than suggested by its empirical formula. Like other alkoxides of titanium(IV) and zirconium(IV), it finds used in organic synthesis and materials science.

<span class="mw-page-title-main">Titanium(II) iodide</span> Chemical compound

Titanium(II) iodide is the inorganic compound with the formula TiI2. It is a black micaceous solid. It adopts the cadmium iodide structure, featuring octahedral Ti(II) centers. It arises via the reaction of the elements:

The telluride iodides are chemical compounds that contain both telluride ions (Te2−) and iodide ions (I). They are in the class of mixed anion compounds or chalcogenide halides.

A chloride nitride is a mixed anion compound containing both chloride (Cl) and nitride ions (N3−). Another name is metallochloronitrides. They are a subclass of halide nitrides or pnictide halides.

<span class="mw-page-title-main">Neodymium(II) iodide</span> Chemical compound

Neodymium(II) iodide or neodymium diiodide is an inorganic salt of iodine and neodymium the formula NdI2. Neodymium uses the +2 oxidation state in the compound.

Arsenide iodides or iodide arsenides are compounds containing anions composed of iodide (I) and arsenide (As3−). They can be considered as mixed anion compounds. They are in the category of pnictidehalides. Related compounds include the arsenide chlorides, arsenide bromides, phosphide iodides, and antimonide iodides.

An iodide nitride is a mixed anion compound containing both iodide (I) and nitride ions (N3−). Another name is metalloiodonitrides. They are a subclass of halide nitrides or pnictide halides. Some different kinds include ionic alkali or alkaline earth salts, small clusters where metal atoms surround a nitrogen atom, layered group 4 element 2-dimensional structures, and transition metal nitrido complexes counter-balanced with iodide ions. There is also a family with rare earth elements and nitrogen and sulfur in a cluster.

Carbide chlorides are mixed anion compounds containing chloride anions and anions consisting entirely of carbon. In these compounds there is no bond between chlorine and carbon. But there is a bond between a metal and carbon. Many of these compounds are cluster compounds, in which metal atoms encase a carbon core, with chlorine atoms surrounding the cluster. The chlorine may be shared between clusters to form polymers or layers. Most carbide chloride compounds contain rare earth elements. Some are known from group 4 elements. The hexatungsten carbon cluster can be oxidised and reduced, and so have different numbers of chlorine atoms included.

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

Zirconium(III) iodide is an inorganic compound with the formula ZrI3.

Hafnium compounds are compounds containing the element hafnium (Hf). Due to the lanthanide contraction, the ionic radius of hafnium(IV) (0.78 ångström) is almost the same as that of zirconium(IV) (0.79 angstroms). Consequently, compounds of hafnium(IV) and zirconium(IV) have very similar chemical and physical properties. Hafnium and zirconium tend to occur together in nature and the similarity of their ionic radii makes their chemical separation rather difficult. Hafnium tends to form inorganic compounds in the oxidation state of +4. Halogens react with it to form hafnium tetrahalides. At higher temperatures, hafnium reacts with oxygen, nitrogen, carbon, boron, sulfur, and silicon. Some compounds of hafnium in lower oxidation states are known.

References

  1. 1 2 Eberly, K. C. (1963). "Zirconium(IV) Iodide". Inorganic Syntheses. Vol. 7. pp. 52–54. doi:10.1002/9780470132388.ch13. ISBN   978-0-470-13238-8..
  2. Krebs, B.; Henkel, G.; Dartmann, M. (1979). "Kristallstruktur von Zirkoniumtetrajodid ZrI4: ein neuer AB4-Strukturtyp". Acta Crystallogr. B35 (2): 274-278. doi:10.1107/S0567740879003344.
  3. Troyanov, S. I. (1986). "Crystal Structure of γ-ZrI4". Kristallografiya. 31: 446-449.
  4. 1 2 Guthrie, Dennis H.; Corbett, John D. (1981). "Synthesis and Structure of an Infinite-Chain Form of ZrI2 (α)". Journal of Solid State Chemistry. 37 (2): 256–263. doi:10.1016/0022-4596(81)90092-X.
  5. van Arkel, A. E.; de Boer, J. H. (1925). "Darstellung von reinem Titanium-, Zirkonium-, Hafnium- und Thoriummetall". Zeitschrift für anorganische und allgemeine Chemie (in German). 148 (1): 345–350. doi:10.1002/zaac.19251480133.