Post-transition metal
Thallium is a chemical element; it has symbol Tl and atomic number 81. It is a silvery-white 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.
Thallium tends to form the +3 and +1 oxidation states. The +3 state resembles that of the other elements in group 13 (boron, aluminium, gallium, indium). However, the +1 state, which is far more prominent in thallium than the elements above it in the periodic table, recalls the chemistry of alkali metals. Thallium(I) ions are found geologically mostly in potassium-based ores and (when ingested) are handled in many ways like potassium ions (K+) by ion pumps in living cells.
Commercially, thallium is produced not from potassium ores, but as a byproduct from refining of heavy-metal sulfide ores. …
Thallium (Greek θαλλός, thallos, meaning "a green shoot or twig") was discovered by William Crookes and Claude Auguste Lamy, working independently, both using flame spectroscopy (Crookes was first to publish his findings, on March 30, 1861). The name comes from thallium's bright green spectral emission lines.
After the publication of the improved method of flame spectroscopy by Robert Bunsen and Gustav Kirchhoff and the discovery of caesium and rubidium in the years 1859 to 1860, flame spectroscopy became an approved method to determine the composition of minerals and chemical products. Crookes and Lamy both started to use the new method. Crookes used it to make spectroscopic determinations for tellurium on selenium compounds deposited in the lead chamber of a sulfuric acid production plant near Tilkerode in the Harz mountains. He had obtained the samples for his research on selenium cyanide from August Hofmann years earlier. By 1862, Crookes was able to isolate small quantities of the new element and determine the properties of a few compounds. Claude-Auguste Lamy used a spectrometer that was similar to Crookes' to determine the composition of a selenium-containing substance which was deposited during the production of sulfuric acid from pyrite. He also noticed the new green line in the spectra and concluded that a new element was present. …
A thallium atom has 81 electrons, arranged in the electron configuration [Xe]4f145d106s26p1; of these, the three outermost electrons in the sixth shell are valence electrons. Due to the inert pair effect, the 6s electron pair is relativistically stabilised and it is more difficult to get these involved in chemical bonding than it is for the heavier elements. Thus, very few electrons are available for metallic bonding, similar to the neighboring elements mercury and lead. Thallium, then, like its congeners, is a soft, highly electrically conducting metal with a low melting point, of 304 °C. …
Thallium concentration in the Earth's crust is estimated to be 0.7 mg/kg, mostly in association with potassium-based minerals in clays, soils, and granites. The major source of thallium for practical purposes is the trace amount that is found in copper, lead, zinc, and other heavy-metal-sulfide ores.
Thallium is found in the minerals crookesite TlCu7Se4, hutchinsonite TlPbAs5S9, and lorándite TlAsS2. Thallium also occurs as a trace element in iron pyrite, and thallium is extracted as a by-product of roasting this mineral for the production of sulfuric acid.
Thallium can also be obtained from the smelting of lead and zinc ores. Manganese nodules found on the ocean floor contain some thallium. In addition, several other thallium minerals, containing 16% to 60% thallium, occur in nature as complexes of sulfides or selenides that primarily contain antimony, arsenic, copper, lead, and silver. These minerals are rare, and have had no commercial importance as sources of thallium. The Allchar deposit in southern North Macedonia was the only area where thallium was actively mined. This deposit still contains an estimated 500 tonnes of thallium, and it is a source for several rare thallium minerals, for example lorándite.
The United States Geological Survey (USGS) estimates that the annual worldwide production of thallium is 10 metric tonnes as a by-product from the smelting of copper, zinc, and lead ores. …
The odorless and tasteless thallium sulfate was once widely used as rat poison and ant killer. Since 1972 this use has been prohibited in the United States due to safety concerns. Many other countries followed this example. Thallium salts were used in the treatment of ringworm, other skin infections and to reduce the night sweating of tuberculosis patients. This use has been limited due to their narrow therapeutic index, and the development of improved medicines for these conditions.
Thallium(I) bromide and thallium(I) iodide crystals have been used as infrared optical materials, because they are harder than other common infrared optics, and because they have transmission at significantly longer wavelengths. The trade name KRS-5 refers to this material. Thallium(I) oxide has been used to manufacture glasses that have a high index of refraction. Combined with sulfur or selenium and arsenic, thallium has been used in the production of high-density glasses that have low melting points in the range of 125 and 150 Celsius°. These glasses have room-temperature properties that are similar to ordinary glasses and are durable, insoluble in water and have unique refractive indices.
Thallium(I) sulfide's electrical conductivity changes with exposure to infrared light, making this compound useful in photoresistors. Thallium selenide has been used in bolometers for infrared detection. …
Thallium has 41 known isotopes with atomic masses from 176 to 216. 203Tl and 205Tl are the only stable isotopes and make up all natural thallium. The five short-lived isotopes 206Tl through 210Tl inclusive occur in nature, but only as part of the natural decay chains of heavier elements. 204Tl is the most stable radioisotope, with a half-life of 3.78 years; the next most stable are 202Tl (half-life 12.31 days) and 201Tl (half-life 3.0421 days). It is made by the neutron activation of stable thallium in a nuclear reactor.
The isotope 201Tl is useful in nuclear medicine; it decays by electron capture, emitting X-rays (~70–80 keV), and gamma rays of 135 and 167 keV; therefore, it has good imaging characteristics without an excessive patient-radiation dose. It is the most popular isotope used for thallium nuclear cardiac stress tests.
Thallium and its compounds are extremely toxic, with numerous recorded cases of fatal thallium poisoning. The Occupational Safety and Health Administration (OSHA) has set the legal limit (permissible exposure limit) for thallium exposure in the workplace as 0.1 mg/m3 skin exposure over an eight-hour workday. The National Institute for Occupational Safety and Health (NIOSH) also set a recommended exposure limit (REL) of 0.1 mg/m3 skin exposure over an eight-hour workday. At levels of 15 mg/m3, thallium is immediately dangerous to life and health.
Contact with skin is dangerous, and adequate ventilation is necessary when melting this metal. Thallium(I) compounds have a high aqueous solubility and are readily absorbed through the skin, and care should be taken to avoid this route of exposure, as cutaneous absorption can exceed the absorbed dose received by inhalation at the permissible exposure limit (PEL). Exposure by inhalation cannot safely exceed 0.1 mg/m3 in an eight-hour time-weighted average (40-hour work week). The Centers for Disease Control and Prevention (CDC) states, "Thallium is not classifiable as a carcinogen, and it is not suspected to be a carcinogen. It is unknown whether chronic or repeated exposure to thallium increases the risk of reproductive toxicity or developmental toxicity. …