Thallium | Wikipedia audio article


Thallium is a chemical element with 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 “a 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
oxidize to the +3 and +1 oxidation states as ionic salts. 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, recalls the chemistry of alkali metals, and 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. Approximately 60–70% of thallium production
is used in the electronics industry, and the remainder is used in the pharmaceutical industry
and in glass manufacturing. It is also used in infrared detectors. The radioisotope thallium-201 (as the soluble
chloride TlCl) is used in small, nontoxic amounts as an agent in a nuclear medicine
scan, during one type of nuclear cardiac stress test. Soluble thallium salts (many of which are
nearly tasteless) are toxic, and they were historically used in rat poisons and insecticides. Use of these compounds has been restricted
or banned in many countries, because of their nonselective toxicity. Thallium poisoning usually results in hair
loss, although this characteristic symptom does not always surface. Because of its historic popularity as a murder
weapon, thallium has gained notoriety as “the poisoner’s poison” and “inheritance powder”
(alongside arsenic).==Characteristics==
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 them involved in
chemical bonding than for the heavier elements. Thus, very few electrons are available for
metallic bonding, similar to the neighboring elements mercury and lead, and hence thallium,
like its congeners, is a soft, highly electrically conducting metal with a low melting point
of 304 °C.A number of standard electrode potentials, depending on the reaction under
study, are reported for thallium, reflecting the greatly decreased stability of the +3
oxidation state: Thallium is the first element in group 13
where the reduction of the +3 oxidation state to the +1 oxidation state is spontaneous under
standard conditions. Since bond energies decrease down the group,
by thallium, the energy released in forming two additional bonds and attaining the +3
state is not always enough to outweigh the energy needed to involve the 6s-electrons. Accordingly, thallium(I) oxide and hydroxide
are more basic and thallium(III) oxide and hydroxide are more acidic, showing that thallium
conforms to the general rule of elements being more electropositive in their lower oxidation
states.Thallium is malleable and sectile enough to be cut with a knife at room temperature. It has a metallic luster that, when exposed
to air, quickly tarnishes to a bluish-gray tinge, resembling lead. It may be preserved by immersion in oil. A heavy layer of oxide builds up on thallium
if left in air. In the presence of water, thallium hydroxide
is formed. Sulfuric and nitric acid dissolve thallium
rapidly to make the sulfate and nitrate salts, while hydrochloric acid forms an insoluble
thallium(I) chloride layer.===Isotopes===Thallium has 25 isotopes which have atomic
masses that range from 184 to 210. 203Tl and 205Tl are the only stable isotopes
and make up nearly all of natural thallium. 204Tl is the most stable radioisotope, with
a half-life of 3.78 years. It is made by the neutron activation of stable
thallium in a nuclear reactor. The most useful radioisotope, 201Tl (half-life
73 hours), decays by electron capture, emitting X-rays (~70–80 keV), and photons of 135
and 167 keV in 10% total abundance; therefore, it has good imaging characteristics without
excessive patient radiation dose. It is the most popular isotope used for thallium
nuclear cardiac stress tests.==Compounds=====Thallium(III)===
Thallium(III) compounds resemble the corresponding aluminium(III) compounds. They are moderately strong oxidizing agents
and are usually unstable, as illustrated by the positive reduction potential for the Tl3+/Tl
couple. Some mixed-valence compounds are also known,
such as Tl4O3 and TlCl2, which contain both thallium(I) and thallium(III). Thallium(III) oxide, Tl2O3, is a black solid
which decomposes above 800 °C, forming the thallium(I) oxide and oxygen.The simplest
possible thallium compound, thallane (TlH3), is too unstable to exist in bulk, both due
to the instability of the +3 oxidation state as well as poor overlap of the valence 6s
and 6p orbitals of thallium with the 1s orbital of hydrogen. The trihalides are more stable, although they
are chemically distinct from those of the lighter group 13 elements and are still the
least stable in the whole group. For instance, thallium(III) fluoride, TlF3,
has the β-BiF3 structure rather than that of the lighter group 13 trifluorides, and
does not form the TlF−4 complex anion in aqueous solution. The trichloride and tribromide disproportionate
just above room temperature to give the monohalides, and thallium triiodide contains the linear
triiodide anion (I−3) and is actually a thallium(I) compound. Thallium(III) sesquichalcogenides do not exist.===Thallium(I)===
The thallium(I) halides are stable. In keeping with the large size of the Tl+
cation, the chloride and bromide have the caesium chloride structure, while the fluoride
and iodide have distorted sodium chloride structures. Like the analogous silver compounds, TlCl,
TlBr, and TlI are photosensitive. The stability of thallium(I) compounds demonstrates
its differences from the rest of the group: a stable oxide, hydroxide, and carbonate are
known, as are many chalcogenides.The double salt Tl4(OH)2CO3 has been shown to have hydroxyl-centred
triangles of thallium, [Tl3(OH)]2+, as a recurring motif throughout its solid structure.===Organothallium compounds===
Organothallium compounds tend to be thermally unstable, in concordance with the trend of
decreasing thermal stability down group 13. The chemical reactivity of the Tl–C bond
is also the lowest in the group, especially for ionic compounds of the type R2TlX. Thallium forms the stable [Tl(CH3)2]+ ion
in aqueous solution; like the isoelectronic Hg(CH3)2 and [Pb(CH3)2]2+, it is linear. Trimethylthallium and triethylthallium are,
like the corresponding gallium and indium compounds, flammable liquids with low melting
points. Like indium, thallium cyclopentadienyl compounds
contain thallium(I), in contrast to gallium(III).==History==
Thallium (Greek θαλλός, thallos, meaning “a green shoot or twig”) was discovered by
flame spectroscopy in March 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. William Crookes and Claude-Auguste Lamy both
started to use the new method. William 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. Lamy had received this material from the sulfuric
acid plant of his friend Fréd Kuhlmann and this by-product was available in large quantities. Lamy started to isolate the new element from
that source. The fact that Lamy was able to work ample
quantities of thallium enabled him to determine the properties of several compounds and in
addition he prepared a small ingot of metallic thallium which he prepared by remelting thallium
he had obtained by electrolysis of thallium salts. As both scientists discovered thallium independently
and a large part of the work, especially the isolation of the metallic thallium was done
by Lamy, Crookes tried to secure his own priority on the work. Lamy was awarded a medal at the International
Exhibition in London 1862: For the discovery of a new and abundant source of thallium and
after heavy protest Crookes also received a medal: thallium, for the discovery of the
new element. The controversy between both scientists continued
through 1862 and 1863. Most of the discussion ended after Crookes
was elected Fellow of the Royal Society in June 1863.The dominant use of thallium was
the use as poison for rodents. After several accidents the use as poison
was banned in the United States by Presidential Executive Order 11643 in February 1972. In subsequent years several other countries
also banned its use.==Occurrence and production==
Although thallium is a modestly abundant element in the Earth’s crust, with a concentration
estimated to be about 0.7 mg/kg, mostly in association with potassium-based minerals
in clays, soils, and granites, thallium is not generally economically recoverable from
these sources. 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, but the collection of these nodules has been prohibitively expensive. There is also the potential for damaging the
oceanic environment. 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/or silver. These minerals are rare, and they have had
no commercial importance as sources of thallium. The Allchar deposit in southern 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 about 10 metric tonnes as a by-product from the smelting of
copper, zinc, and lead ores. Thallium is either extracted from the dusts
from the smelter flues or from residues such as slag that are collected at the end of the
smelting process. The raw materials used for thallium production
contain large amounts of other materials and therefore a purification is the first step. The thallium is leached either by the use
of a base or sulfuric acid from the material. The thallium is precipitated several times
from the solution to remove impurities. At the end it is converted to thallium sulfate
and the thallium is extracted by electrolysis on platinum or stainless steel plates. The production of thallium decreased by about
33% in the period from 1995 to 2009 – from about 15 metric tonnes to about 10 tonnes. Since there are several small deposits or
ores with relatively high thallium content, it would be possible to increase the production
if a new application, such as a hypothetical thallium-containing high-temperature superconductor,
becomes practical for widespread use outside of the laboratory.==Applications=====
Historic uses===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
in subsequent years. 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.===Optics===
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 °C. These glasses have room temperature properties that
are similar to ordinary glasses and are durable, insoluble in water and have unique refractive
indices.===Electronics===Thallium(I) sulfide’s electrical conductivity
changes with exposure to infrared light therefore making this compound useful in photoresistors. Thallium selenide has been used in a bolometer
for infrared detection. Doping selenium semiconductors with thallium
improves their performance, thus it is used in trace amounts in selenium rectifiers. Another application of thallium doping is
the sodium iodide crystals in gamma radiation detection devices. In these, the sodium iodide crystals are doped
with a small amount of thallium to improve their efficiency as scintillation generators. Some of the electrodes in dissolved oxygen
analyzers contain thallium.===High-temperature superconductivity===
Research activity with thallium is ongoing to develop high-temperature superconducting
materials for such applications as magnetic resonance imaging, storage of magnetic energy,
magnetic propulsion, and electric power generation and transmission. The research in applications started after
the discovery of the first thallium barium calcium copper oxide superconductor in 1988. Thallium cuprate superconductors have been
discovered that have transition temperatures above 120 K. Some mercury-doped thallium-cuprate superconductors
have transition temperatures above 130 K at ambient pressure, nearly as high as the world-record-holding
mercury cuprates.===Medical===
Before the widespread application of technetium-99m in nuclear medicine, the radioactive isotope
thallium-201, with a half-life of 73 hours, was the main substance for nuclear cardiography. The nuclide is still used for stress tests
for risk stratification in patients with coronary artery disease (CAD). This isotope of thallium can be generated
using a transportable generator, which is similar to the technetium-99m generator. The generator contains lead-201 (half-life
9.33 hours), which decays by electron capture to the thallium-201. The lead-201 can be produced in a cyclotron
by the bombardment of thallium with protons or deuterons by the (p,3n) and (d,4n) reactions.====Thallium stress test====
A thallium stress test is a form of scintigraphy, where the amount of thallium in tissues correlates
with tissue blood supply. Viable cardiac cells have normal Na+/K+ ion-exchange
pumps. The Tl+ cation binds the K+ pumps and is transported
into the cells. Exercise or dipyridamole induces widening
(vasodilation) of arteries in the body. This produces coronary steal by areas where
arteries are maximally dilated. Areas of infarct or ischemic tissue will remain
“cold”. Pre- and post-stress thallium may indicate
areas that will benefit from myocardial revascularization. Redistribution indicates the existence of
coronary steal and the presence of ischemic coronary artery disease.===Other uses===
A mercury–thallium alloy, which forms a eutectic at 8.5% thallium, is reported to
freeze at −60 °C, some 20 °C below the freezing point of mercury. This alloy is used in thermometers and low-temperature
switches. In organic synthesis, thallium(III) salts,
as thallium trinitrate or triacetate, are useful reagents for performing different transformations
in aromatics, ketones and olefins, among others. Thallium is a constituent of the alloy in
the anode plates of magnesium seawater batteries. Soluble thallium salts are added to gold plating
baths to increase the speed of plating and to reduce grain size within the gold layer.A
saturated solution of equal parts of thallium(I) formate (Tl(CHO2)) and thallium(I) malonate
(Tl(C3H3O4)) in water is known as Clerici solution. It is a mobile, odorless liquid which changes
from yellowish to colourless upon reducing the concentration of the thallium salts. With a density of 4.25 g/cm3 at 20 °C, Clerici
solution is one of the heaviest aqueous solutions known. It was used in the 20th century for measuring
the density of minerals by the flotation method, but its use has discontinued due to the high
toxicity and corrosiveness of the solution.Thallium iodide is frequently used as an additive in
metal-halide lamps, often together with one or two halides of other metals. It allows optimization of the lamp temperature
and color rendering, and shifts the spectral output to the green region, which is useful
for underwater lighting.==Toxicity==Thallium and its compounds are extremely toxic,
and should be handled with care. There are 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 8-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 8-hour workday. At levels of 15 mg/m3, thallium is immediately
dangerous to life and health.Contact with skin is dangerous, and adequate ventilation
should be provided when melting this metal. Thallium(I) compounds have a high aqueous
solubility and are readily absorbed through the skin. Exposure by inhalation should not exceed 0.1
mg/m3 in an 8-hour time-weighted average (40-hour work week). Thallium will readily absorb 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). Thallium is a suspected human carcinogen. For a long time thallium compounds were readily
available as rat poison. This fact and that it is water-soluble and
nearly tasteless led to frequent intoxication caused by accident or criminal intent.One
of the main methods of removing thallium (both radioactive and normal) from humans is to
use Prussian blue, a material which absorbs thallium. Up to 20 grams per day of Prussian blue is
fed by mouth to the person, and it passes through their digestive system and comes out
in the stool. Hemodialysis and hemoperfusion are also used
to remove thallium from the blood serum. At later stage of the treatment additional
potassium is used to mobilize thallium from the tissue.According to the United States
Environmental Protection Agency (EPA), man-made sources of thallium pollution include gaseous
emission of cement factories, coal-burning power plants, and metal sewers. The main source of elevated thallium concentrations
in water is the leaching of thallium from ore processing operations.==See also==Myocardial perfusion imaging