Caesium (IUPAC spelling) or cesium (American spelling)[note 1] is a chemical element with symbol Cs and atomic number 55. It is a soft, silvery-golden alkali metal with a melting point of 28.5 °C (83.3 °F), which makes it one of only five elemental metals that are liquid at or near room temperature.[note 2] Caesium has physical and chemical properties similar to those of rubidium and potassium. The most reactive of all metals, it is pyrophoric and reacts with water even at −116 °C (−177 °F). It is the least electronegative 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, while the radioisotopes, especially caesium-137, a fission product, are extracted from waste produced by nuclear reactors.
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 vacuum tubes and in photoelectric cells. In 1967, acting on Einstein's proof that the speed of light is the most constant dimension in the universe, the International System of Units used two specific wave counts from an emission spectrum of caesium-133 to co-define the second and the metre. Since then, caesium has been widely used in highly accurate atomic clocks.
Since the 1990s, the largest application of the element has been as caesium formate for drilling fluids, 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 toxic, 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 ecological hazard in the environment.
|Alternative name||cesium (US, informal)|
|Standard atomic weight Ar, std(Cs)||132.90545196(6)|
|Caesium in the periodic table|
|Atomic number (Z)||55|
|Group||group 1 (alkali metals)|
|Element category||alkali metal|
|Electron configuration||[Xe] 6s1|
Electrons per shell
|2, 8, 18, 18, 8, 1|
|Phase at STP||solid|
|Melting point||301.7 K (28.5 °C, 83.3 °F)|
|Boiling point||944 K (671 °C, 1240 °F)|
|Density (near r.t.)||1.93 g/cm3|
|when liquid (at m.p.)||1.843 g/cm3|
|Critical point||1938 K, 9.4 MPa|
|Heat of fusion||2.09 kJ/mol|
|Heat of vaporization||63.9 kJ/mol|
|Molar heat capacity||32.210 J/(mol·K)|
|Oxidation states||−1, +1 (a strongly basic oxide)|
|Electronegativity||Pauling scale: 0.79|
|Atomic radius||empirical: 265 pm|
|Covalent radius||244±11 pm|
|Van der Waals radius||343 pm|
Spectral lines of caesium
|Crystal structure|| body-centred cubic (bcc)|
|Thermal expansion||97 µm/(m·K) (at 25 °C)|
|Thermal conductivity||35.9 W/(m·K)|
|Electrical resistivity||205 nΩ·m (at 20 °C)|
|Young's modulus||1.7 GPa|
|Bulk modulus||1.6 GPa|
|Brinell hardness||0.14 MPa|
|Naming||from Latin caesius, sky blue, for its spectral colours|
|Discovery||Robert Bunsen and Gustav Kirchhoff (1860)|
|First isolation||Carl Setterberg (1882)|
|Main isotopes of caesium|
Caesium is the softest element (it has a hardness of 0.2 Mohs). It is a very ductile, pale metal, which darkens in the presence of trace amounts of oxygen. When in the presence of mineral oil (where it is best kept during transport), it loses its metallic lustre and takes on a duller, grey appearance. It has a melting point of 28.5 °C (83.3 °F), making it one of the few elemental metals that are liquid near room temperature. Mercury is the only elemental metal with a known melting point lower than caesium.[note 3] In addition, the metal has a rather low boiling point, 641 °C (1,186 °F), the lowest of all metals other than mercury. Its compounds burn with a blue or violet colour.
Caesium forms alloys with the other alkali metals, gold, and mercury (amalgams). At temperatures below 650 °C (1,202 °F), it does not alloy with cobalt, iron, molybdenum, nickel, platinum, tantalum, or tungsten. It forms well-defined intermetallic compounds 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 −78 °C (−108 °F). A few amalgams have been studied: CsHg
2 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.
Caesium metal is highly reactive and very pyrophoric. It ignites spontaneously in air, and reacts explosively with water even at low temperatures, more so than the other alkali metals (first group of the periodic table). It reacts with solid water at temperatures as low as −116 °C (−177 °F). Because of this high reactivity, caesium metal is classified as a hazardous material. It is stored and shipped in dry, saturated hydrocarbons such as mineral oil. It can be handled only under inert gas, such as argon. However, a caesium-water explosion is often less powerful than a sodium-water explosion with a similar amount of sodium. This is because caesium explodes instantly upon contact with water, leaving little time for hydrogen to accumulate. Caesium can be stored in vacuum-sealed borosilicate glass ampoules. In quantities of more than about 100 grams (3.5 oz), caesium is shipped in hermetically sealed, stainless steel containers.
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.[note 4] Some small differences arise from the fact that it has a higher atomic mass and is more electropositive than other (nonradioactive) alkali metals. Caesium is the most electropositive chemical element.[note 5] The caesium ion is also larger and less "hard" than those of the lighter alkali metals.
Most caesium compounds contain the element as the cation Cs+
, which binds ionically to a wide variety of anions. One noteworthy exception is the caeside anion (Cs−
), and others are the several suboxides (see section on oxides below).
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, acetate, carbonate, halides, oxide, nitrate, and sulfate salts are water-soluble. Double salts are often less soluble, and the low solubility of caesium aluminium sulfate is exploited in refining Cs from ores. The double salt with antimony (such as CsSbCl
4), bismuth, cadmium, copper, iron, and lead are also poorly soluble.
Caesium hydroxide (CsOH) is hygroscopic and strongly basic. It rapidly etches the surface of semiconductors 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, but a number of compounds that do not dissolve in water, such as n-butyllithium and sodium amide, are more basic.
A stoichiometric 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 (Cs2Pt), contains the platinide ion that behaves as a pseudochalcogen.
Like all metal cations, Cs+ forms complexes with Lewis bases in solution. Because of its large size, Cs+ usually adopts coordination numbers greater than 6, the number typical for the smaller alkali metal cations. This difference is apparent in the 8-coordination of CsCl. This high coordination number and softness (tendency to form covalent bonds) are properties exploited in separating Cs+ from other cations in the remediation of nuclear wastes, where 137Cs+ must be separated from large amounts of nonradioactive K+.
Caesium fluoride (CsF) is a hygroscopic white solid that is widely used in organofluorine chemistry as a source of fluoride anions. Caesium fluoride has the halite structure, which means that the Cs+ and F− pack in a cubic closest packed array as do Na+ and Cl− in sodium chloride. Notably, caesium and fluorine have the lowest and highest electronegativities, respectively, among all the known elements.
Caesium chloride (CsCl) crystallizes in the simple cubic crystal system. Also called the "caesium chloride structure", this structural motif is composed of a primitive 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 CsBr and CsI, 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 pm and Cl−
More so than the other alkali metals, caesium forms numerous binary compounds with oxygen. When caesium burns in air, the superoxide CsO
2 is the main product. The "normal" caesium oxide (Cs
2O) forms yellow-orange hexagonal crystals, and is the only oxide of the anti-CdCl
2 type. It vaporizes at 250 °C (482 °F), and decomposes to caesium metal and the peroxide Cs
2 at temperatures above 400 °C (752 °F). In addition to the superoxide and the ozonide CsO
3, several brightly coloured suboxides have also been studied. These include Cs
3O (dark-green), CsO, Cs
2, as well as Cs
2. The latter may be heated in a vacuum to generate Cs
2O. Binary compounds with sulfur, selenium, and tellurium also exist.
Caesium has 39 known isotopes, ranging in mass number (i.e. number of nucleons in the nucleus) from 112 to 151. Several of these are synthesized from lighter elements by the slow neutron capture process (S-process) inside old stars and by the R-process in supernova explosions. The only stable caesium isotope is 133Cs, with 78 neutrons. Although it has a large nuclear spin (7/+), nuclear magnetic resonance studies can use this isotope at a resonating frequency of 11.7 MHz.
The radioactive 135Cs has a very long half-life of about 2.3 million years, the longest of all radioactive isotopes of caesium. 137Cs and 134Cs have half-lives of 30 and two years, respectively. 137Cs decomposes to a short-lived 137mBa by beta decay, and then to nonradioactive barium, while 134Cs transforms into 134Ba directly. The isotopes with mass numbers of 129, 131, 132 and 136, have half-lives between a day and two weeks, while most of the other isotopes have half-lives from a few seconds to fractions of a second. At least 21 metastable nuclear isomers exist. Other than 134mCs (with a half-life of just under 3 hours), all are very unstable and decay with half-lives of a few minutes or less.
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 is a strong emission of gamma radiation. 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 radioactive fallout. It is a ready marker of the movement of soil and sediment from those times.
Caesium is a relatively rare element, estimated to average 3 parts per million in the Earth's crust. It is the 45th most abundant element and the 36th among the metals. Nevertheless, it is more abundant than such elements as antimony, cadmium, tin, and tungsten, and two orders of magnitude more abundant than mercury and silver; it is 3.3% as abundant as rubidium, with which it is closely associated, chemically.
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 (KMgCl
2O) may contain only 0.002% caesium. Consequently, Cs is found in few minerals. Percentage amounts of caesium may be found in beryl (Be
6) and avogadrite ((K,Cs)BF
4), up to 15 wt% Cs2O in the closely related mineral pezzottaite (Cs(Be2Li)Al2Si6O18), up to 8.4 wt% Cs2O in the rare mineral londonite ((Cs,K)Al
28), and less in the more widespread rhodizite. The only economically important ore for caesium is pollucite Cs(AlSi
6), 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.
One of the world's most significant and richest sources of caesium is the Tanco Mine at Bernic Lake in Manitoba, Canada, estimated to contain 350,000 metric tons 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 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 Karibib Desert, Namibia. At the present rate of world mine production of 5 to 10 metric tons per year, reserves will last for thousands of years.
Mining and refining pollucite ore is a selective process and is conducted on a smaller scale than for most other metals. The ore is crushed, hand-sorted, but not usually concentrated, and then ground. Caesium is then extracted from pollucite primarily by three methods: acid digestion, alkaline decomposition, and direct reduction.
In the acid digestion, the silicate pollucite rock is dissolved with strong acids, such as hydrochloric (HCl), sulfuric (H
4), hydrobromic (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 (Cs
7), caesium iodine chloride (Cs
2ICl), or caesium hexachlorocerate (Cs
6)). 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 (CsAl(SO
2O). 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 Cs
Roasting pollucite with calcium carbonate and calcium chloride yields insoluble calcium silicates and soluble caesium chloride. Leaching with water or dilute ammonia (NH
4OH) 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 can produce caesium metal directly.
Most of the mined caesium (as salts) is directly converted into caesium 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 12,000 barrels (1,900 m3) per year of caesium formate solution. The primary smaller-scale commercial compounds of caesium are caesium chloride and 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 700 to 800 °C (1,292 to 1,472 °F) 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 390 °C (734 °F) thermal decomposition of caesium azide CsN
3, 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 US$10 per gram ($280 per ounce), but the compounds are significantly cheaper.
In 1860, Robert Bunsen and Gustav Kirchhoff discovered caesium in the mineral water from Dürkheim, Germany. Because of the bright blue lines in the emission spectrum, they derived the name from the Latin word caesius, meaning sky-blue.[note 6] Caesium was the first element to be discovered with a spectroscope, which had been invented by Bunsen and Kirchhoff only a year previously.
To obtain a pure sample of caesium, 44,000 litres (9,700 imp gal; 12,000 US gal) of mineral water had to be evaporated to yield 240 kilograms (530 lb) of concentrated salt solution. The alkaline earth metals were precipitated either as sulfates or oxalates, leaving the alkali metal in the solution. After conversion to the nitrates 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 ((Cs,Rb)2PtCl6) 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 9.2 grams (0.32 oz) of rubidium chloride and 7.3 grams (0.26 oz) 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 (Cs
2Cl). In reality, the product was probably a colloidal 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 German 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 vacuum tubes, 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 photoelectric cells, photomultiplier tubes, optical components of infrared spectrophotometers, catalysts for several organic reactions, crystals for scintillation counters, and in magnetohydrodynamic power generators. Caesium also was, and still is, 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 energy levels 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 largest present-day use of nonradioactive caesium is in caesium formate drilling fluids for the extractive oil industry. Aqueous solutions of caesium formate (HCOO−Cs+)—made by reacting caesium hydroxide with formic acid—were developed in the mid-1990s for use as oil well drilling and completion fluids. The function of a drilling fluid is to lubricate drill bits, to bring rock cuttings to the surface, and to maintain pressure on the formation during drilling of the well. Completion fluids assist the emplacement of control hardware after drilling but prior to production by maintaining the pressure.
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 ZnBr
2 solutions) sometimes do; they also require less cleanup and reduce disposal costs.
Caesium-based atomic clocks use the electromagnetic transitions in the hyperfine structure of caesium-133 atoms as a reference point. The first accurate caesium clock was built by Louis Essen in 1955 at the National Physical Laboratory in the UK. Caesium clocks have improved over the past half-century and are regarded as "the most accurate realization of a unit that mankind has yet achieved." These clocks measure frequency with an error of 2 to 3 parts in 1014, which corresponding to an accuracy of 2 nanoseconds per day, or one second in 1.4 million years. The latest versions are more accurate than 1 part in 1015, about 1 second in 20 million years. The Caesium standard is the primary standard for standards-compliant time and frequency measurements. Caesium clocks regulate the timing of cell phone networks and the Internet.
It is currently (2018) being proposed by the International Committee for Weights and Measures (CIPM) that the second, symbol s, the SI unit of time, be defined using the fixed numerical value of the caesium frequency ΔνCs, the unperturbed ground-state hyperfine transition frequency of the caesium 133 atom.
Caesium vapour thermionic generators are low-power devices that convert heat energy to electrical energy. In the two-electrode vacuum tube converter, caesium neutralizes the space charge near the cathode and enhances the current flow.
Caesium is also important for its photoemissive properties, converting light to electron flow. It is used in photoelectric cells because caesium-based cathodes, such as the intermetallic compound K
2CsSb, have a low threshold voltage for emission of electrons. The range of photoemissive devices using caesium include optical character recognition devices, photomultiplier tubes, 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), bromide (CsBr) and caesium fluoride (CsF) crystals are employed for scintillators in scintillation counters widely used in mineral exploration and particle physics research to detect gamma 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).
The element is used as an internal standard in spectrophotometry. Like other alkali metals, caesium has a great affinity for oxygen and is used as a "getter" in vacuum tubes. Other uses of the metal include high-energy lasers, vapour glow lamps, and vapour rectifiers.
The high density of the caesium ion makes solutions of caesium chloride, caesium sulfate, and caesium trifluoroacetate (Cs(O
3)) useful in molecular biology for density gradient ultracentrifugation. This technology is used primarily in the isolation of viral particles, subcellular organelles and fractions, and nucleic acids from biological samples.
Relatively few chemical applications use caesium. Doping with caesium compounds enhances the effectiveness of several metal-ion catalysts for chemical synthesis, such as acrylic acid, anthraquinone, ethylene oxide, methanol, phthalic anhydride, styrene, methyl methacrylate monomers, and various olefins. It is also used in the catalytic conversion of sulfur dioxide into sulfur trioxide in the production of sulfuric acid.
Caesium fluoride enjoys a niche use in organic chemistry as a base and as an anhydrous source of fluoride ion. Caesium salts sometimes replace potassium or sodium salts in organic synthesis, such as cyclization, 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 is a radioisotope commonly used as a gamma-emitter in industrial applications. Its advantages include a half-life of roughly 30 years, its availability from the nuclear fuel cycle, and having 137Ba as a stable end product. The high water solubility is a disadvantage which makes it incompatible with large pool irradiators for food and medical supplies. It has been used in agriculture, cancer treatment, and the sterilization of food, sewage sludge, and surgical equipment. Radioactive isotopes of caesium in radiation devices were used in the medical field to treat certain types of cancer, but emergence of better alternatives and the use of water-soluble caesium chloride in the sources, which could create wide-ranging contamination, gradually put some of these caesium sources out of use. Caesium-137 has been employed in a variety of industrial measurement gauges, including moisture, density, levelling, and thickness gauges. It has also been used in well logging devices for measuring the electron density of the rock formations, which is analogous to the bulk density of the formations.
Caesium-137 has been used in hydrologic 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 and mercury were used as a propellant in early ion engines designed for spacecraft propulsion on very long interplanetary or extraplanetary missions. The fuel was ionized by contact with a charged tungsten electrode. But corrosion by caesium on spacecraft components has pushed development in the direction of inert gas propellants, such as xenon, which are easier to handle in ground-based tests and do less potential damage to the spacecraft. Xenon was used in the experimental spacecraft Deep Space 1 launched in 1998. Nevertheless, field-emission electric propulsion thrusters that accelerate liquid metal ions such as caesium have been built.
Caesium nitrate is used as an oxidizer and pyrotechnic colorant to burn silicon in infrared flares, such as the LUU-19 flare, because it emits much of its light in the near infrared spectrum. Caesium is used to reduce the radar signature of exhaust plumes in the SR-71 Blackbird military aircraft. Caesium and rubidium have been added as a carbonate to glass because they reduce electrical conductivity and improve stability and durability of fibre optics and night vision devices. Caesium fluoride or caesium aluminium fluoride are used in fluxes formulated for brazing aluminium alloys that contain magnesium.
Magnetohydrodynamic (MHD) power-generating systems were researched, but failed to gain widespread acceptance. Caesium metal has also been considered as the working fluid in high-temperature Rankine cycle turboelectric generators.
Caesium salts have been evaluated as antishock reagents following the administration of arsenical drugs. 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 cooled and used to probe fundamental and technological problems in quantum physics. It has a particularly convenient Feshbach spectrum to enable studies of ultracold atoms requiring tunable interactions.
|GHS signal word||Danger|
|P223, P231+232, P280, P305+351+338, P370+378, P422|
Nonradioactive caesium compounds are only mildly toxic, and nonradioactive caesium is not a significant environmental hazard. Because biochemical processes can confuse and substitute caesium with potassium, excess caesium can lead to hypokalemia, arrhythmia, and acute cardiac arrest. But such amounts would not ordinarily be encountered in natural sources.
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 drilling fluids because it is much less toxic than alternatives, though it is more costly.
Caesium metal 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 pyrophoric: the autoignition temperature of caesium is −116 °C, 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 isotopes 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. Experiments with dogs showed that a single dose of 3.8 millicuries (140 MBq, 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 "dirty bombs".
The alkali metals are a group (column) in the periodic table consisting of the chemical elements lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), and francium (Fr). This group lies in the s-block of the periodic table of elements as all alkali metals have their outermost electron in an s-orbital: this shared electron configuration results in their having very similar characteristic properties. Indeed, the alkali metals provide the best example of group trends in properties in the periodic table, with elements exhibiting well-characterised homologous behaviour.
The alkali metals are all shiny, soft, highly reactive metals at standard temperature and pressure and readily lose their outermost electron to form cations with charge +1. They can all be cut easily with a knife due to their softness, exposing a shiny surface that tarnishes rapidly in air due to oxidation by atmospheric moisture and oxygen (and in the case of lithium, nitrogen). Because of their high reactivity, they must be stored under oil to prevent reaction with air, and are found naturally only in salts and never as the free elements. Caesium, the fifth alkali metal, is the most reactive of all the metals. In the modern IUPAC nomenclature, the alkali metals comprise the group 1 elements, excluding hydrogen (H), which is nominally a group 1 element but not normally considered to be an alkali metal as it rarely exhibits behaviour comparable to that of the alkali metals. All the alkali metals react with water, with the heavier alkali metals reacting more vigorously than the lighter ones.
All of the discovered alkali metals occur in nature as their compounds: in order of abundance, sodium is the most abundant, followed by potassium, lithium, rubidium, caesium, and finally francium, which is very rare due to its extremely high radioactivity; francium occurs only in the minutest traces in nature as an intermediate step in some obscure side branches of the natural decay chains. Experiments have been conducted to attempt the synthesis of ununennium (Uue), which is likely to be the next member of the group, but they have all met with failure. However, ununennium may not be an alkali metal due to relativistic effects, which are predicted to have a large influence on the chemical properties of superheavy elements; even if it does turn out to be an alkali metal, it is predicted to have some differences in physical and chemical properties from its lighter homologues.
Most alkali metals have many different applications. One of the best-known applications of the pure elements is the use of rubidium and caesium in atomic clocks, of which caesium atomic clocks are the most accurate and precise representation of time. A common application of the compounds of sodium is the sodium-vapour lamp, which emits light very efficiently. Table salt, or sodium chloride, has been used since antiquity. Lithium finds use as a psychiatric medication. Sodium and potassium are also essential elements, having major biological roles as electrolytes, and although the other alkali metals are not essential, they also have various effects on the body, both beneficial and harmful.Atomic clock
An atomic clock is a clock device that uses an electron transition frequency in the microwave, optical, or ultraviolet region of the electromagnetic spectrum of atoms as a frequency standard for its timekeeping element. Atomic clocks are the most accurate time and frequency standards known, and are used as primary standards for international time distribution services, to control the wave frequency of television broadcasts, and in global navigation satellite systems such as GPS.
The principle of operation of an atomic clock is based on atomic physics; it uses the electromagnetic signal that electrons in atoms emit when they change energy levels. Early atomic clocks were based on masers at room temperature. Since 2004, more accurate atomic clocks first cool the atoms to near absolute zero temperature by slowing them with lasers and probing them in atomic fountains in a microwave-filled cavity. An example of this is the NIST-F1 atomic clock, one of the national primary time and frequency standards of the United States.
The accuracy of an atomic clock depends on two factors. The first factor is temperature of the sample atoms—colder atoms move much more slowly, allowing longer probe times. The second factor is the frequency and intrinsic width of the electronic transition. Higher frequencies and narrow lines increase the precision.
National standards agencies in many countries maintain a network of atomic clocks which are intercompared and kept synchronized to an accuracy of 10−9 seconds per day (approximately 1 part in 1014). These clocks collectively define a continuous and stable time scale, the International Atomic Time (TAI). For civil time, another time scale is disseminated, Coordinated Universal Time (UTC). UTC is derived from TAI, but has added leap seconds from UT1, to account for variations in the rotation of the Earth with respect to the solar time.Avogadrite
Avogadrite ((K,Cs)BF4) is a potassium-caesium tetrafluoroborate in the halide class. Avogadrite crystallizes in the orthorhombic system (space group Pnma) with cell parameters a 8.66 Å, b 5.48 Å and c Å 7.03.Caesium-137
Caesium-137 (13755Cs), or radiocaesium, is a radioactive isotope of caesium which is formed as one of the more common fission products by the nuclear fission of uranium-235 and other fissionable isotopes in nuclear reactors and nuclear weapons. It is among the most problematic of the short-to-medium-lifetime fission products because it easily moves and spreads in nature due to the high water solubility of caesium's most common chemical compounds, which are salts.Caesium bromide
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 a melting point a 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.Caesium chloride
Caesium chloride or cesium chloride is the inorganic compound with the formula CsCl. This colorless solid 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 chlorine ions. Caesium chloride dissolves in water. CsCl changes to NaCl structure on heating. Caesium chloride occurs naturally as impurities in carnallite (up to 0.002%), sylvite and kainite. Less than 20 tonnes of CsCl is produced annually worldwide, mostly from a caesium-bearing mineral pollucite.Caesium chloride is widely used medicine structure in isopycnic centrifugation for separating various types of DNA. It is a reagent in analytical chemistry, where it is used to identify ions by the color and morphology of the precipitate. When enriched in radioisotopes, such as 137CsCl or 131CsCl, caesium chloride is used in nuclear medicine applications such as treatment of cancer and diagnosis of myocardial infarction. Another form of cancer treatment was studied using conventional non-radioactive CsCl. Whereas conventional caesium chloride has a rather low toxicity to humans and animals, the radioactive form easily contaminates the environment due to the high solubility of CsCl in water. Spread of 137CsCl powder from a 93-gram container in 1987 in Goiânia, Brazil, resulted in one of the worst-ever radiation spill accidents killing four and directly affecting more than 100,000 people.Caesium fluoride
Caesium fluoride or cesium fluoride is an inorganic compound usually encountered as a hygroscopic white solid. It is used in organic synthesis as a source of the fluoride anion.Caesium hydride
Caesium hydride or cesium hydride (CsH) is a compound of caesium and hydrogen. It is an alkali metal hydride.
It was the first substance to be created by light-induced particle formation in metal vapor, and showed promise in early studies of an ion propulsion system using caesium. It is the most reactive stable alkaline metal hydride of all. It reacts with water extremely vigorously.
The caesium nuclei in CsH can be hyperpolarized through interactions with an optically pumped caesium vapor in a process known as spin-exchange optical pumping (SEOP). SEOP can increase the nuclear magnetic resonance (NMR) signal of caesium nuclei by an order of magnitude.Caesium hydroxide
Caesium hydroxide or cesium hydroxide (CsOH) is a chemical compound consisting of caesium ions and hydroxide ions. It is a strong base (pKb=-1.76), much like the other alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. In fact, caesium hydroxide is corrosive enough to quickly corrode through glass.
Due to its high reactivity, caesium hydroxide is extremely hygroscopic. Laboratory caesium hydroxide is typically a hydrate.
It is an anisotropic etchant of silicon, exposing octahedral planes. This technique can form pyramids and regularly shaped etch pits for uses such as Microelectromechanical systems. It is known to have a higher selectivity to etch highly p-doped silicon than the more commonly used potassium hydroxide.
This compound is not commonly used in experiments due to the high extraction cost of caesium and its reactive behaviour. It acts in similar fashion to the compounds rubidium hydroxide and potassium hydroxide, although more reactive.Caesium iodide
Caesium iodide or cesium iodide (chemical formula CsI) 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.Caesium nitrate
Caesium nitrate or cesium nitrate is a chemical compound with the chemical formula CsNO3. An alkali metal nitrate, it is used in pyrotechnic compositions, as a colorant and an oxidizer, e.g. in decoys and illumination flares. The caesium emissions are chiefly due to two powerful spectral lines at 852.113 nm and 894.347 nm.
Caesium nitrate prisms are used in infrared spectroscopy, in x-ray phosphors, and in scintillation counters. It is also used in making optical glasses and lenses.
As with other alkali metal nitrates, caesium nitrate decomposes on gentle heating to give caesium nitrite:
2CsNO3 → 2CsNO2 + O2Caesium also forms two unusual acid nitrates, which can be described as CsNO3·HNO3 and CsNO3·2HNO3 (melting points 100 °C and 36–38 °C respectively).Caesium oxide
Caesium oxide (IUPAC name) or cesium oxide describes inorganic compounds composed of caesium and oxygen. The following binary (containing only Cs and O) oxides of caesium are known: Cs11O3, Cs4O, Cs7O, and Cs2O. Both the oxide and suboxides are brightly coloured. The species Cs2O forms yellow-orange hexagonal crystals.Caesium sulfate
Caesium sulfate or cesium sulfate is the inorganic compound and salt with the formula Cs2SO4. It is a white water-soluble solid that is used to prepare dense aqueous solutions for use in isopycnic (or "density-gradient") centrifugation. It is isostructural with potassium salt.Formate
Formate (IUPAC name: methanoate) is the anion derived from formic acid. Its formula is represented in various equivalent ways: HCOO− or CHOO− or HCO2−. It is the product of deprotonation of formic acid. It is the simplest carboxylate anion. A formate (compound) is a salt or ester of formic acid.Francium
Francium is a chemical element with symbol Fr and atomic number 87. It used to be known as eka-caesium. It is extremely radioactive; its most stable isotope, francium-223 (originally called actinium K after the natural decay chain it appears in), has a half-life of only 22 minutes. It is the second-most electropositive element, behind only caesium, and is the second rarest naturally occurring element (after astatine). The isotopes of francium decay quickly into astatine, radium, and radon. The electronic structure of a francium atom is [Rn] 7s1, and so the element is classed as an alkali metal.
Bulk francium has never been viewed. Because of the general appearance of the other elements in its periodic table column, it is assumed that francium would appear as a highly reactive metal, if enough could be collected together to be viewed as a bulk solid or liquid. Obtaining such a sample is highly improbable, since the extreme heat of decay caused by its short half-life would immediately vaporize any viewable quantity of the element.
Francium was discovered by Marguerite Perey in France (from which the element takes its name) in 1939. It was the last element first discovered in nature, rather than by synthesis. Outside the laboratory, francium is extremely rare, with trace amounts found in uranium and thorium ores, where the isotope francium-223 continually forms and decays. As little as 20–30 g (one ounce) exists at any given time throughout the Earth's crust; the other isotopes (except for francium-221) are entirely synthetic. The largest amount produced in the laboratory was a cluster of more than 300,000 atoms.Glossary of chemical formulas
This is a list of common chemical compounds with chemical formulas and CAS numbers, indexed by formula. This complements alternative listing at inorganic compounds by element. There is no complete list of chemical compounds since by nature the list would be infinite.
Note: There are elements for which spellings may differ, such as aluminum/ aluminium, sulfur/ sulphur, and caesium/ cesium.Isotopes of caesium
Caesium (55Cs) has 40 known isotopes, making it, along with barium and mercury, the element with the most isotopes. The atomic masses of these isotopes range from 112 to 151. Only one isotope, 133Cs, is stable. The longest-lived radioisotopes are 135Cs with a half-life of 2.3 million years, 137Cs with a half-life of 30.1671 years and 134Cs with a half-life of 2.0652 years. All other isotopes have half-lives less than 2 weeks, most under an hour.
Beginning in 1945 with the commencement of nuclear testing, caesium isotopes were released into the atmosphere where caesium is absorbed readily into solution and is returned to the surface of the earth as a component of radioactive fallout. Once caesium enters the ground water, it is deposited on soil surfaces and removed from the landscape primarily by particle transport. As a result, the input function of these isotopes can be estimated as a function of time.Rubidium
Rubidium is a chemical element with symbol Rb and atomic number 37. Rubidium is a soft, silvery-white metallic element of the alkali metal group, with a standard atomic weight of 85.4678. Elemental rubidium is highly reactive, with properties similar to those of other alkali metals, including rapid oxidation in air. On Earth, natural rubidium comprises two isotopes: 72% is the stable isotope, 85Rb; 28% is the slightly radioactive 87Rb, with a half-life of 49 billion years—more than three times longer than the estimated age of the universe.
German chemists Robert Bunsen and Gustav Kirchhoff discovered rubidium in 1861 by the newly developed technique, flame spectroscopy. The name comes from the Latin word rubidus, meaning deep red, the color of its emission spectrum. Rubidium's compounds have various chemical and electronic applications. Rubidium metal is easily vaporized and has a convenient spectral absorption range, making it a frequent target for laser manipulation of atoms. Rubidium is not a known nutrient for any living organisms. However, rubidium ions have the same charge as potassium ions, and are actively taken up and treated by animal cells in similar ways.Second
The second is the base unit of time in the International System of Units (SI), commonly understood and historically defined as 1⁄86400 of a day – this factor derived from the division of the day first into 24 hours, then to 60 minutes and finally to 60 seconds each. Mechanical and electric clocks and watches usually have a face with 60 tickmarks representing seconds and minutes, traversed by a second hand and minute hand. Digital clocks and watches often have a two-digit counter that cycles through seconds. The second is also part of several other units of measurement like meters per second for velocity, meters per second per second for acceleration, and per second for frequency.
Although the historical definition of the unit was based on this division of the Earth's rotation cycle, the formal definition in the International System of Units (SI) is a much steadier timekeeper: 1 second is defined to be exactly "the duration of 9,192,631,770 periods of the radiation corresponding to the transition between the two hyperfine levels of the ground state of the caesium-133 atom" (at a temperature of 0 K).
Because the Earth's rotation varies and is also slowing ever so slightly, a leap second is periodically added to clock time to keep clocks in sync with Earth's rotation.
Multiples of seconds are usually counted in hours and minutes. Fractions of a second are usually counted in tenths or hundredths. In scientific work, small fractions of a second are counted in milliseconds (thousandths), microseconds (millionths), nanoseconds (billionths), and sometimes smaller units of a second.
An everyday experience with small fractions of a second is a 1-gigahertz microprocessor which has a cycle time of 1 nanosecond. Camera shutter speeds usually range from 1⁄60 second to 1⁄250 second.
Sexagesimal divisions of the day from a calendar based on astronomical observation have existed since the third millennium BC, though they were not seconds as we know them today. Small divisions of time could not be counted back then, so such divisions were figurative. The first timekeepers that could count seconds accurately were pendulum clocks invented in the 17th century. Starting in the 1950s, atomic clocks became better timekeepers than earth's rotation, and they continue to set the standard today.