Thallium(I) iodide

Last updated
Thallium(I) iodide
TlI structure.png
Names
Other names
Thallium monoiodide
Thallous iodide
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.029.272 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 232-199-7
PubChem CID
UNII
  • InChI=1S/HI.Tl/h1H;/q;+1/p-1 Yes check.svgY
    Key: CMJCEVKJYRZMIA-UHFFFAOYSA-M Yes check.svgY
  • InChI=1/HI.Tl/h1H;/q;+1/p-1
    Key: CMJCEVKJYRZMIA-REWHXWOFAG
  • I[Tl]
Properties
TlI
Molar mass 331.287 g/mol [1]
Appearanceyellow crystals [1]
Density 7.1 g/cm3 [1]
Melting point 441.7 °C (827.1 °F; 714.8 K) [1]
Boiling point 824 °C (1,515 °F; 1,097 K) [1]
0.085 g/L (25 °C) [1]
Solubility insoluble in alcohol [1]
−82.2·10−6 cm3/mol [2]
Hazards
GHS labelling:
GHS-pictogram-skull.svg GHS-pictogram-silhouette.svg GHS-pictogram-pollu.svg
Danger
H300, H330, H373, H411
P260, P264, P270, P271, P273, P284, P301+P310, P304+P340, P310, P314, P320, P321, P330, P391, P403+P233, P405, P501
Flash point Non-flammable
Related compounds
Other anions
Thallium(I) fluoride
Thallium(I) chloride
Thallium(I) bromide
Other cations
Gallium(I) iodide
Indium(I) iodide
Related compounds
Mercury(II) iodide
Lead(II) iodide
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 ?)

Thallium(I) iodide is a chemical compound with the formula . It is unusual in being one of the few water-insoluble metal iodides, along with , , , , and .

Contents

Chemistry

TlI can be formed in aqueous solution by metathesis of any soluble thallium salt with iodide ion. It is also formed as a by-product in thallium-promoted iodination of phenols with thallium(I) acetate.

Attempts to oxidise TlI to thallium(III) iodide fail, since oxidation produces thallium(I) triiodide, Tl+I3.

Physical properties

The room temperature form of TlI is yellow and has an orthorhombic structure [3] which can be considered to be a distorted NaCl structure. The distorted structure is believed to be caused by favourable thallium-thallium interactions, the closest Tl-Tl distance is 383 pm. [4] At 175 °C the yellow form transforms to a red CsCl form. This phase transition is accompanied by about two orders of magnitude jump in electrical conductivity. The CsI structure can be stabilized down to room temperature by doping TlI with other halides such as RbI, CsI, KI, AgI, TlBr and TlCl. [5] Thus, presence of impurities might be responsible for coexistence of the cubic and orthorhombic TlI phases at ambient conditions. [3] Under high pressure, 160 kbar, TlI becomes a metallic conductor. Nanometer-thin TlI films grown on LiF, NaCl or KBr substrates exhibit the cubic rocksalt structure. [6]

Applications

Thallium(I) iodide was initially added to mercury arc lamps to improve their performance [7] The light produced was mainly in the blue green part of the visible light spectrum least absorbed by water, so these have been used for underwater lighting. [8] In modern times, it is added to quartz and ceramic metal halide lamps that uses rare-earth halides like dysprosium, to increase their efficiency and to get the light color more close to the blackbody locus. Thallium iodide alone can be used to produces green colored metal halide lamps. Thallium(I) iodide is also used in trace amounts with NaI or CsI to produce scintillators used in radiation detectors.

Natural occurrence

Natural thallium(I) iodide was first discovered in a naturally occurring setting in 2017 as a orthorhombic polymorph called nataliyamalikite. Small grains were found embedded in mascagnite sourced from fumaroles at Avachinsky, a volcano in Russia's Kamchatka Peninsula that can reach temperatures of 640 °C (1,184 °F). The geologists that discovered it speculate that further research into this mineral is likely to add to the understanding of the geochemical evolution of the planet [9] [10]

Safety

Like all thallium compounds, thallium(I) iodide is highly toxic.

Related Research Articles

<span class="mw-page-title-main">Thallium</span> Chemical element, symbol Tl and atomic number 81

Thallium is a chemical element; it has symbol Tl and atomic number 81. It is a gray post-transition metal that is not found free in nature. When isolated, thallium resembles tin, but discolors when exposed to air. Chemists William Crookes and Claude-Auguste Lamy discovered thallium independently in 1861, in residues of sulfuric acid production. Both used the newly developed method of flame spectroscopy, in which thallium produces a notable green spectral line. Thallium, from Greek θαλλός, thallós, meaning "green shoot" or "twig", was named by Crookes. It was isolated by both Lamy and Crookes in 1862; Lamy by electrolysis, and Crookes by precipitation and melting of the resultant powder. Crookes exhibited it as a powder precipitated by zinc at the international exhibition, which opened on 1 May that year.

In chemistry, a halide is a binary chemical compound, of which one part is a halogen atom and the other part is an element or radical that is less electronegative than the halogen, to make a fluoride, chloride, bromide, iodide, astatide, or theoretically tennesside compound. The alkali metals combine directly with halogens under appropriate conditions forming halides of the general formula, MX. Many salts are halides; the hal- syllable in halide and halite reflects this correlation. All Group 1 metals form halides that are white solids at room temperature.

<span class="mw-page-title-main">Scintillator</span> Material which glows when excited by ionizing radiation

A scintillator is a material that exhibits scintillation, the property of luminescence, when excited by ionizing radiation. Luminescent materials, when struck by an incoming particle, absorb its energy and scintillate. Sometimes, the excited state is metastable, so the relaxation back down from the excited state to lower states is delayed. The process then corresponds to one of two phenomena: delayed fluorescence or phosphorescence. The correspondence depends on the type of transition and hence the wavelength of the emitted optical photon.

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

Lead(II) iodide is a chemical compound with the formula PbI
2
. At room temperature, it is a bright yellow odorless crystalline solid, that becomes orange and red when heated. It was formerly called plumbous iodide.

<span class="mw-page-title-main">Silver chloride</span> Chemical compound with the formula AgCl

Silver chloride is an inorganic chemical compound with the chemical formula AgCl. This white crystalline solid is well known for its low solubility in water and its sensitivity to light. Upon illumination or heating, silver chloride converts to silver, which is signaled by grey to black or purplish coloration in some samples. AgCl occurs naturally as the mineral chlorargyrite.

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

Caesium iodide or cesium iodide is the ionic compound of caesium and iodine. It is often used as the input phosphor of an X-ray image intensifier tube found in fluoroscopy equipment. Caesium iodide photocathodes are highly efficient at extreme ultraviolet wavelengths.

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

Caesium chloride or cesium chloride is the inorganic compound with the formula CsCl. This colorless salt is an important source of caesium ions in a variety of niche applications. Its crystal structure forms a major structural type where each caesium ion is coordinated by 8 chloride ions. Caesium chloride dissolves in water. CsCl changes to NaCl structure on heating. Caesium chloride occurs naturally as impurities in carnallite, sylvite and kainite. Less than 20 tonnes of CsCl is produced annually worldwide, mostly from a caesium-bearing mineral pollucite.

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

Sodium iodide (chemical formula NaI) is an ionic compound formed from the chemical reaction of sodium metal and iodine. Under standard conditions, it is a white, water-soluble solid comprising a 1:1 mix of sodium cations (Na+) and iodide anions (I) in a crystal lattice. It is used mainly as a nutritional supplement and in organic chemistry. It is produced industrially as the salt formed when acidic iodides react with sodium hydroxide. It is a chaotropic salt.

<span class="mw-page-title-main">Iodic acid</span> Chemical compound (HIO3)

Iodic acid is a white water-soluble solid with the chemical formula HIO3. Its robustness contrasts with the instability of chloric acid and bromic acid. Iodic acid features iodine in the oxidation state +5 and is one of the most stable oxo-acids of the halogens. When heated, samples dehydrate to give iodine pentoxide. On further heating, the iodine pentoxide further decomposes, giving a mix of iodine, oxygen and lower oxides of iodine.

<span class="mw-page-title-main">Thallium(I) bromide</span> Chemical compound

Thallium(I) bromide is a chemical compound of thallium and bromine with a chemical formula TlBr. This salt is used in room-temperature detectors of X-rays, gamma-rays and blue light, as well as in near-infrared optics.

<span class="mw-page-title-main">Thallium(I) chloride</span> Chemical compound

Thallium(I) chloride, also known as thallous chloride, is a chemical compound with the formula TlCl. This colourless salt is an intermediate in the isolation of thallium from its ores. Typically, an acidic solution of thallium(I) sulfate is treated with hydrochloric acid to precipitate insoluble thallium(I) chloride. This solid crystallizes in the caesium chloride motif.

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

Tin selenide, also known as stannous selenide, is an inorganic compound with the formula SnSe. Tin(II) selenide is a typical layered metal chalcogenide as it includes a group 16 anion (Se2−) and an electropositive element (Sn2+), and is arranged in a layered structure. Tin(II) selenide is a narrow band-gap (IV-VI) semiconductor structurally analogous to black phosphorus. It has received considerable interest for applications including low-cost photovoltaics, and memory-switching devices.

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

Caesium bromide or cesium bromide is an ionic compound of caesium and bromine with the chemical formula CsBr. It is a white or transparent solid with melting point at 636 °C that readily dissolves in water. Its bulk crystals have the cubic CsCl structure, but the structure changes to the rocksalt type in nanometer-thin film grown on mica, LiF, KBr or NaCl substrates.

The thallium halides include monohalides, where thallium has oxidation state +1, trihalides in which thallium generally has oxidation state +3, and some intermediate halides containing thallium with mixed +1 and +3 oxidation states. These salts find use in specialized optical settings, such as focusing elements in research spectrophotometers. Compared to the more common zinc selenide-based optics, materials such as thallium bromoiodide enable transmission at longer wavelengths. In the infrared, this allows for measurements as low as 350 cm−1 (28 μm), whereas zinc selenide is opaque by 21.5 μm, and ZnSe optics are generally only usable to 650 cm−1 (15 μm).

There are three sets of Indium halides, the trihalides, the monohalides, and several intermediate halides. In the monohalides the oxidation state of indium is +1 and their proper names are indium(I) fluoride, indium(I) chloride, indium(I) bromide and indium(I) iodide.

Rubidium silver iodide is a ternary inorganic compound with the formula RbAg4I5. Its conductivity involves the movement of silver ions within the crystal lattice. It was discovered while searching for chemicals which had the ionic conductivity properties of alpha-phase silver iodide at temperatures below 146 °C for AgI.

<span class="mw-page-title-main">Methylammonium lead halide</span>

Methylammonium lead halides (MALHs) are solid compounds with perovskite structure and a chemical formula of [CH3NH3]+Pb2+(X)3, where X = Cl, Br or I. They have potential applications in solar cells, lasers, light-emitting diodes, photodetectors, radiation detectors, scintillator, magneto-optical data storage and hydrogen production.

Nickel is one of the metals that can form Tutton's salts. The singly charged ion can be any of the full range of potassium, rubidium, cesium, ammonium (), or thallium. As a mineral the ammonium nickel salt, (NH4)2Ni(SO4)2 · 6 H2O, can be called nickelboussingaultite. With sodium, the double sulfate is nickelblödite Na2Ni(SO4)2 · 4 H2O from the blödite family. Nickel can be substituted by other divalent metals of similar sized to make mixtures that crystallise in the same form.

Indium(I) chloride is the chemical compound with the formula InCl. Indium monochloride occurs as a yellow cubic form below 120 °C and above this temperature as a red orthorhombic form. InCl is one of three known indium chlorides.

References

  1. 1 2 3 4 5 6 7 Haynes, p. 4.94
  2. Haynes, p. 4.136
  3. 1 2 Lowndes, R. P.; Perry, C. H. (1973). "Molecular structure and anharmonicity in thallium iodide". The Journal of Chemical Physics. 58 (1): 271–278. Bibcode:1973JChPh..58..271L. doi:10.1063/1.1678917.
  4. Mudring, Anja-Verena (2007). "Thallium Halides – New Aspects of the Stereochemical Activity of Electron Lone Pairs of Heavier Main-Group Elements". European Journal of Inorganic Chemistry . 2007 (6): 882–890. doi:10.1002/ejic.200600975.
  5. Sultana, Saima; Rafiuddin (2009). "Electrical conductivity in TlI–TiO2 composite solid electrolyte". Physica B: Condensed Matter. 404 (1): 36–40. Bibcode:2009PhyB..404...36S. doi:10.1016/j.physb.2008.10.002.
  6. Schulz, L. G. (1951). "Polymorphism of cesium and thallium halides". Acta Crystallographica. 4 (6): 487–489. Bibcode:1951AcCry...4..487S. doi:10.1107/S0365110X51001641.
  7. Reiling, Gilbert H. (1964). "Characteristics of Mercury Vapor–Metallic Iodide Arc Lamps". Journal of the Optical Society of America. 54 (4): 532. Bibcode:1964JOSA...54..532R. doi:10.1364/JOSA.54.000532.
  8. Underwater Journal and information bulletin, IPC Science and Technology Press, (1973), p 245
  9. "Nataliyamalikite: Mineral information, data and localities". www.mindat.org.
  10. Anderson, Natali (July 6, 2017). "New Mineral Discovered: Nataliyamalikite". Sci News. Retrieved March 16, 2022.

Cited sources