Product Code Database
Caesium (IUPAC spelling; also spelled cesium in American English) is a chemical element; it has symbol Cs and atomic number 55. It is a soft, silvery-golden alkali metal with a melting point of , which makes it one of only five elemental that are liquid at or near room temperature. Caesium has physical and chemical properties similar to those of rubidium and potassium. It is pyrophoricity and reacts with water even at . It is the least electronegative stable element, with a value of 0.79 on the Pauling scale. It has only one stable isotope, caesium-133. Caesium is mined mostly from pollucite. Caesium-137, a fission product, is extracted from waste produced by nuclear reactors. It has the largest atomic radius of all elements whose radii have been measured or calculated, at about 260 .
The German chemist Robert Bunsen and physicist Gustav Kirchhoff discovered caesium in 1860 by the newly developed method of flame spectroscopy. The first small-scale applications for caesium were as a "getter" in and in solar cell. Caesium is widely used in highly accurate . In 1967, the International System of Units began using a specific hyperfine transition of neutral caesium-133 atoms to define the basic unit of time, the second.
Since the 1990s, the largest application of the element has been as caesium formate for , but it has a range of applications in the production of electricity, in electronics, and in chemistry. The radioactive isotope caesium-137 has a half-life of about 30 years and is used in medical applications, industrial gauges, and hydrology. Nonradioactive caesium compounds are only mildly toxicity, but the pure metal's tendency to react explosively with water means that caesium is considered a hazardous material, and the radioisotopes present a significant health and environmental hazard.
Caesium forms with the other alkali metals, gold, and mercury (amalgams). At temperatures below , it does not alloy with cobalt, iron, molybdenum, nickel, platinum, tantalum, or tungsten. It forms well-defined intermetallics with antimony, gallium, indium, and thorium, which are photosensitive. It mixes with all the other alkali metals (except lithium); the alloy with a molar distribution of 41% caesium, 47% potassium, and 12% sodium has the lowest melting point of any known metal alloy, at . A few amalgams have been studied: is black with a purple metallic lustre, while CsHg is golden-coloured, also with a metallic lustre.
The golden colour of caesium comes from the decreasing frequency of light required to excite electrons of the alkali metals as the group is descended. For lithium through rubidium this frequency is in the ultraviolet, but for caesium it enters the blue–violet end of the spectrum; in other words, the plasmonic frequency of the alkali metals becomes lower from lithium to caesium. Thus caesium transmits and partially absorbs violet light preferentially while other colours (having lower frequency) are reflected; hence it appears yellowish. Its compounds burn with a blue or violet colour.
The chemistry of caesium is similar to that of other alkali metals, in particular rubidium, the element above caesium in the periodic table. As expected for an alkali metal, the only common oxidation state is +1. It differs from this value in caesides, which contain the Cs− anion and thus have caesium in the −1 oxidation state. Under conditions of extreme pressure (greater than 30 GPa), theoretical studies indicate that the inner 5p electrons could form chemical bonds, where caesium would behave as the seventh 5p element, suggesting that higher caesium fluorides with caesium in oxidation states from +2 to +6 could exist under such conditions. Some slight differences arise from the fact that it has a higher atomic mass and is more electropositive than other (nonradioactive) alkali metals. (1985). 9783110075113, Walter de Gruyter. ISBN 9783110075113 Caesium is the most electropositive chemical element. The caesium ion is also larger and HSAB theory than those of the lighter alkali metals.
Salts of Cs+ are usually colourless unless the anion itself is coloured. Many of the simple salts are hygroscopic, but less so than the corresponding salts of lighter alkali metals. The phosphate,Hogan, C. M. (2011). in Encyclopedia of Earth. Jorgensen, A. and Cleveland, C.J. (eds.). National Council for Science and the Environment. Washington DC acetate, carbonate, , oxide, nitrate, and sulfate salts are water-soluble. Its are often less soluble, and the low solubility of caesium aluminium sulfate is exploited in refining Cs from ores. The double salts with antimony (such as ), bismuth, cadmium, copper, iron, and lead are also poorly soluble.
Caesium hydroxide (CsOH) is hygroscopic and strongly basic. It rapidly etching the surface of such as silicon. CsOH has been previously regarded by chemists as the "strongest base", reflecting the relatively weak attraction between the large Cs+ ion and OH−; it is indeed the strongest Arrhenius base; however, a number of compounds such as n-butyllithium, sodium amide, sodium hydride, caesium hydride, etc., which cannot be dissolved in water as reacting violently with it but rather only used in some anhydrous polar aprotic solvents, are far more basic on the basis of the Brønsted–Lowry acid–base theory.
A stoichiometry mixture of caesium and gold will react to form yellow caesium auride (Cs+Au−) upon heating. The auride anion here behaves as a pseudohalogen. The compound reacts violently with water, yielding caesium hydroxide, metallic gold, and hydrogen gas; in liquid ammonia it can be reacted with a caesium-specific ion exchange resin to produce tetramethylammonium auride. The analogous platinum compound, red caesium platinide (), contains the platinide ion that behaves as a .
Caesium chloride (CsCl) crystallizes in the simple cubic crystal system. Also called the "caesium chloride structure", this structural motif is composed of a primitive cell cubic lattice with a two-atom basis, each with an eightfold coordination; the chloride atoms lie upon the lattice points at the edges of the cube, while the caesium atoms lie in the holes in the centre of the cubes. This structure is shared with caesium bromide and caesium iodide, and many other compounds that do not contain Cs. In contrast, most other alkaline halides have the sodium chloride (NaCl) structure. The CsCl structure is preferred because Cs+ has an ionic radius of 174 picometer and 181 pm.
The isotope 135Cs is one of the long-lived fission products of uranium produced in nuclear reactors. However, this fission product yield is reduced in most reactors because the predecessor, 135Xe, is a potent neutron poison and frequently transmutes to stable 136Xe before it can decay to 135Cs.
The beta decay from 137Cs to 137mBa results in gamma ray as the 137mBa relaxes to ground state 137Ba, with the emitted photons having an energy of 0.6617 MeV. 137Cs and 90Sr are the principal medium-lived products of nuclear fission, and the prime sources of radioactivity from spent nuclear fuel after several years of cooling, lasting several hundred years. Those two isotopes are the largest source of residual radioactivity in the area of the Chernobyl disaster. Because of the low capture rate, disposing of 137Cs through neutron capture is not feasible and the only current solution is to allow it to decay over time.
Almost all caesium produced from nuclear fission comes from the beta decay of originally more neutron-rich fission products, passing through various isotopes of iodine and xenon. Because iodine and xenon are volatile and can diffuse through nuclear fuel or air, radioactive caesium is often created far from the original site of fission. With nuclear weapons testing in the 1950s through the 1980s, 137Cs was released into the atmosphere and returned to the surface of the earth as a component of nuclear fallout. It is a ready marker of the movement of soil and sediment from those times.
Due to its large ionic radius, caesium is one of the "incompatible elements". During magma crystallization, caesium is concentrated in the liquid phase and crystallizes last. Therefore, the largest deposits of caesium are zone pegmatite ore bodies formed by this enrichment process. Because caesium does not substitute for potassium as readily as rubidium does, the alkali evaporite minerals sylvite (KCl) and carnallite () may contain only 0.002% caesium. Consequently, caesium is found in few minerals. Percentage amounts of caesium may be found in beryl () and avogadrite (), up to 15 wt% Cs2O in the closely related mineral pezzottaite (), up to 8.4 wt% Cs2O in the rare mineral londonite (), and less in the more widespread rhodizite. The only economically important ore for caesium is pollucite , which is found in a few places around the world in zoned pegmatites, associated with the more commercially important lithium minerals, lepidolite and petalite. Within the pegmatites, the large grain size and the strong separation of the minerals results in high-grade ore for mining.
The world's most significant and richest known source of caesium is the Tanco Mine at Bernic Lake in Manitoba, Canada, estimated to contain 350,000 tonne of pollucite ore, representing more than two-thirds of the world's reserve base. Although the stoichiometric content of caesium in pollucite is 42.6%, pure pollucite samples from this deposit contain only about 34% caesium, while the average content is 24 wt%. Commercial pollucite contains more than 19% caesium. The Bikita District pegmatite deposit in Zimbabwe is mined for its petalite, but it also contains a significant amount of pollucite. Another notable source of pollucite is in the Erongo Region, Namibia. At the present rate of world mine production of 5 to 10 metric tons per year, reserves will last for thousands of years.
In the acid digestion, the silicate pollucite rock is dissolved with strong acids, such as hydrochloric (HCl), sulfuric acid (), hydrobromic acid (HBr), or hydrofluoric (HF) acids. With hydrochloric acid, a mixture of soluble chlorides is produced, and the insoluble chloride double salts of caesium are precipitated as caesium antimony chloride (), caesium iodine chloride (), or caesium hexachlorocerate (). After separation, the pure precipitated double salt is decomposed, and pure CsCl is precipitated by evaporating the water.
The sulfuric acid method yields the insoluble double salt directly as caesium alum (). The aluminium sulfate component is converted to insoluble aluminium oxide by roasting the alum with carbon, and the resulting product is leached with water to yield a solution.
Roasting pollucite with calcium carbonate and calcium chloride yields insoluble calcium silicates and soluble caesium chloride. Leaching with water or dilute ammonia () yields a dilute chloride (CsCl) solution. This solution can be evaporated to produce caesium chloride or transformed into caesium alum or caesium carbonate. Though not commercially feasible, the ore can be directly reduced with potassium, sodium, or calcium in vacuum to produce caesium metal directly.
Most of the mined caesium (as salts) is directly converted into formate (HCOO−Cs+) for applications such as oil drilling. To supply the developing market, Cabot Corporation built a production plant in 1997 at the Tanco mine near Bernic Lake in Manitoba, with a capacity of per year of caesium formate solution. The primary smaller-scale commercial compounds of caesium are caesium chloride and caesium nitrate.
Alternatively, caesium metal may be obtained from the purified compounds derived from the ore. Caesium chloride and the other caesium halides can be reduced at with calcium or barium, and caesium metal distilled from the result. In the same way, the aluminate, carbonate, or hydroxide may be reduced by magnesium.
The metal can also be isolated by electrolysis of fused caesium cyanide (CsCN). Exceptionally pure and gas-free caesium can be produced by thermal decomposition of caesium azide , which can be produced from aqueous caesium sulfate and barium azide. In vacuum applications, caesium dichromate can be reacted with zirconium to produce pure caesium metal without other gaseous products.
The price of 99.8% pure caesium (metal basis) in 2009 was about , but the compounds are significantly cheaper.
To obtain a pure sample of caesium, of mineral water had to be evaporated to yield of concentrated salt solution. The alkaline earth metals were precipitated either as sulfates or , leaving the alkali metal in the solution. After conversion to the and extraction with ethanol, a sodium-free mixture was obtained. From this mixture, the lithium was precipitated by ammonium carbonate. Potassium, rubidium, and caesium form insoluble salts with chloroplatinic acid, but these salts show a slight difference in solubility in hot water, and the less-soluble caesium and rubidium hexachloroplatinate () were obtained by fractional crystallization. After reduction of the hexachloroplatinate with hydrogen, caesium and rubidium were separated by the difference in solubility of their carbonates in alcohol. The process yielded of rubidium chloride and of caesium chloride from the initial 44,000 litres of mineral water.
From the caesium chloride, the two scientists estimated the atomic weight of the new element at 123.35 (compared to the currently accepted one of 132.9). They tried to generate elemental caesium by electrolysis of molten caesium chloride, but instead of a metal, they obtained a blue homogeneous substance which "neither under the naked eye nor under the microscope showed the slightest trace of metallic substance"; as a result, they assigned it as a subchloride (). In reality, the product was probably a mixture of the metal and caesium chloride. The electrolysis of the aqueous solution of chloride with a mercury cathode produced a caesium amalgam which readily decomposed under the aqueous conditions. The pure metal was eventually isolated by the Swedish chemist Carl Setterberg while working on his doctorate with Kekulé and Bunsen. In 1882, he produced caesium metal by electrolysing caesium cyanide, avoiding the problems with the chloride.
Historically, the most important use for caesium has been in research and development, primarily in chemical and electrical fields. Very few applications existed for caesium until the 1920s, when it came into use in radio , where it had two functions; as a getter, it removed excess oxygen after manufacture, and as a coating on the heated cathode, it increased the electrical conductivity. Caesium was not recognized as a high-performance industrial metal until the 1950s. Applications for nonradioactive caesium included solar cell, photomultiplier tubes, optical components of infrared spectrophotometers, catalysts for several organic reactions, crystals for scintillation counters, and in MHD generator. Caesium is also used as a source of positive ions in secondary ion mass spectrometry (SIMS).
Since 1967, the International System of Measurements has based the primary unit of time, the second, on the properties of caesium. The International System of Units (SI) defines the second as the duration of 9,192,631,770 cycles at the microwave frequency of the spectral line corresponding to the transition between two hyperfine of the ground state of caesium-133. The 13th General Conference on Weights and Measures of 1967 defined a second as: "the duration of 9,192,631,770 cycles of microwave light absorbed or emitted by the hyperfine transition of caesium-133 atoms in their ground state undisturbed by external fields".
The high density of the caesium formate brine (up to 2.3 g/cm3, or 19.2 pounds per gallon), coupled with the relatively benign nature of most caesium compounds, reduces the requirement for toxic high-density suspended solids in the drilling fluid—a significant technological, engineering and environmental advantage. Unlike the components of many other heavy liquids, caesium formate is relatively environment-friendly. Caesium formate brine can be blended with potassium and sodium formates to decrease the density of the fluids to that of water (1.0 g/cm3, or 8.3 pounds per gallon). Furthermore, it is biodegradable and may be recycled, which is important in view of its high cost (about $4,000 per barrel in 2001). Alkali formates are safe to handle and do not damage the producing formation or downhole metals as corrosive alternative, high-density brines (such as zinc bromide solutions) sometimes do; they also require less cleanup and reduce disposal costs.
Caesium is also important for its photoemissive properties, converting light to electron flow. It is used in solar cell because caesium-based cathodes, such as the intermetallic compound , have a low threshold voltage for emission of . The range of photoemissive devices using caesium include optical character recognition devices, photomultiplier, and video camera tubes. Nevertheless, germanium, rubidium, selenium, silicon, tellurium, and several other elements can be substituted for caesium in photosensitive materials.
Caesium iodide (CsI), caesium bromide (CsBr) and caesium fluoride (CsF) crystals are employed for in scintillation counters widely used in mineral exploration and particle physics research to detect gamma ray and X-ray radiation. Being a heavy element, caesium provides good stopping power with better detection. Caesium compounds may provide a faster response (CsF) and be less hygroscopic (CsI).
Caesium vapour is used in many common .
The element is used as an internal standard in spectrophotometry. (1994). 9780471285724, John Wiley and Sons. ISBN 9780471285724 Like other , caesium has a great affinity for oxygen and is used as a "getter" in . Other uses of the metal include high-energy , fluorescent lamp, and vapour .
Caesium fluoride enjoys a niche use in organic chemistry as a base (1984). 9780080220574, Pergamon Press. ISBN 9780080220574 and as an anhydrous source of fluoride ion.
Friestad, Gregory K.; Branchaud, Bruce P.; Navarrini, Walter and Sansotera, Maurizio (2007) "Cesium Fluoride" in Encyclopedia of Reagents for Organic Synthesis, John Wiley & Sons. Caesium salts sometimes replace potassium or sodium salts in organic synthesis, such as cyclic compound, esterification, and polymerization. Caesium has also been used in thermoluminescent radiation dosimetry (TLD): When exposed to radiation, it acquires crystal defects that, when heated, revert with emission of light proportionate to the received dose. Thus, measuring the light pulse with a photomultiplier tube can allow the accumulated radiation dose to be quantified.
Caesium-137 has been used in hydrology studies analogous to those with tritium. As a daughter product of fission bomb testing from the 1950s through the mid-1980s, caesium-137 was released into the atmosphere, where it was absorbed readily into solution. Known year-to-year variation within that period allows correlation with soil and sediment layers. Caesium-134, and to a lesser extent caesium-135, have also been used in hydrology to measure the caesium output by the nuclear power industry. While they are less prevalent than either caesium-133 or caesium-137, these bellwether isotopes are produced solely from anthropogenic sources.
Caesium nitrate is used as an oxidizing agent and pyrotechnic colorant to burn silicon in infrared flares, such as the LUU-19 flare, because it emits much of its light in the infrared spectrum. Caesium compounds may have been used as fuel additives to reduce the radar signature of exhaust gas in the Lockheed A-12 CIA reconnaissance aircraft. Caesium and rubidium have been added as a carbonate to glass because they reduce electrical conductivity and improve stability and durability of optical fiber and night vision devices. Caesium fluoride or caesium aluminium fluoride are used in fluxes formulated for brazing aluminium alloys that contain magnesium.
MHD generator-generating systems were researched, but failed to gain widespread acceptance.National Research Council (U.S.) (2025). 9780309074483, National Academy Press. . ISBN 9780309074483 Caesium metal has also been considered as the working fluid in high-temperature Rankine cycle turboelectric generators.Roskill Information Services (1984). 9780862142506, Roskill Information Services. ISBN 9780862142506
Caesium salts have been evaluated as antishock reagents following the administration of arsenic toxicity. Because of their effect on heart rhythms, however, they are less likely to be used than potassium or rubidium salts. They have also been used to treat epilepsy.
Caesium-133 can be laser cooling and used to probe fundamental and technological problems in quantum physics. It has a particularly convenient Feshbach spectrum to enable studies of requiring tunable interactions.
The median lethal dose (LD50) for caesium chloride in mice is 2.3 g per kilogram, which is comparable to the LD50 values of potassium chloride and sodium chloride. The principal use of nonradioactive caesium is as caesium formate in petroleum because it is much less toxic than alternatives, though it is more costly.
Elemental caesium is one of the most reactive elements and is highly explosive in the presence of water. The hydrogen gas produced by the reaction is heated by the thermal energy released at the same time, causing ignition and a violent explosion. This can occur with other alkali metals, but caesium is so potent that this explosive reaction can be triggered even by cold water.
It is highly pyrophoricity: the autoignition temperature of caesium is , and it ignites explosively in air to form caesium hydroxide and various oxides. Caesium hydroxide is a very strong base, and will rapidly corrode glass.
The 134 and 137 are present in the biosphere in small amounts from human activities, differing by location. Radiocaesium does not accumulate in the body as readily as other fission products (such as radioiodine and radiostrontium). About 10% of absorbed radiocaesium washes out of the body relatively quickly in sweat and urine. The remaining 90% has a biological half-life between 50 and 150 days. Radiocaesium follows potassium and tends to accumulate in plant tissues, including fruits and vegetables. Plants vary widely in the absorption of caesium, sometimes displaying great resistance to it. It is also well-documented that mushrooms from contaminated forests accumulate radiocaesium (caesium-137) in the fungal sporocarps. Accumulation of caesium-137 in lakes has been a great concern after the Chernobyl disaster. (2025). 9783540238669, Springer. ISBN 9783540238669 Experiments with dogs showed that a single dose of 3.8 millicuries (140 Becquerel, 4.1 μg of caesium-137) per kilogram is lethal within three weeks; smaller amounts may cause infertility and cancer. The International Atomic Energy Agency and other sources have warned that radioactive materials, such as caesium-137, could be used in radiological dispersion devices, or "".
|
|
