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Minggu, 07 Juli 2013

Francium

Francium is a chemical element with symbol Fr and atomic number 87. It was formerly known as eka-caesium and actinium K.[note 1] It is one of the two least electronegativeelements, the other being caesium. Francium is a highly radioactive metal that decays into astatineradium, and radon. As an alkali metal, it has one valence electron.
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 reflective metal, if enough could be collected together to be viewed as a bulk solid or liquid. However preparing such a sample is impossible, since the extreme heat of decay (the half-life of its longest-lived isotope is only 22 minutes) 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 discovered in nature, rather than by synthesis.[note 2] 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 are entirely synthetic. The largest amount produced in the laboratory was a cluster of more than 300,000 atoms.[1]


Francium is the most unstable of the naturally occurring elements: its most stable isotope, francium-223, has a
 half-life of only 22 minutes. In contrast, astatine, the second-least stable naturally occurring element, has a half-life of 8.5 hours.[2] All isotopes of francium decay into either astatine, radium, or radon.[2] Francium is also less stable than all synthetic elements up to element 105.[3]

Characteristics[edit]

Francium is an alkali metal whose chemical properties mostly resemble those ofcaesium.[3] A heavy element with a single valence electron,[4] it has the highestequivalent weight of any element.[3] Liquid francium—if such a substance were to be created—should have a surface tension of 0.05092 N/m at its melting point.[5] Francium's melting point was claimed to have been calculated to be around 27 °C (80 °F, 300 K).[6]However, the melting point is uncertain because of the element's extreme rarity and radioactivity. Thus, the estimated boiling point value of 677 °C (1250 °F, 950 K) is also uncertain.
Linus Pauling estimated the electronegativity of francium at 0.7 on the Pauling scale, the same as caesium;[7] the value for caesium has since been refined to 0.79, although there are no experimental data to allow a refinement of the value for francium.[8] Francium has a slightly higher ionization energy than caesium,[9] 392.811(4) kJ/mol as opposed to 375.7041(2) kJ/mol for caesium, as would be expected from relativistic effects, and this would imply that caesium is the less electronegative of the two.
Francium coprecipitates with several caesium salts, such as caesium perchlorate, which results in small amounts of francium perchlorate. This coprecipitation can be used to isolate francium, by adapting the radiocaesium coprecipitation method of Glendenin andNelson. It will additionally coprecipitate with many other caesium salts, including theiodate, the picrate, the tartrate (also rubidium tartrate), the chloroplatinate, and thesilicotungstate. It also coprecipitates with silicotungstic acid, and with perchloric acid, without another alkali metal as a carrier, which provides other methods of separation.[10][11] Nearly all francium salts are water-soluble.[12]

Applications[edit]

Due to its instability and rarity, there are no commercial applications for francium.[13][14][15][16] It has been used for research purposes in the fields of biology[17]and of atomic structure. Its use as a potential diagnostic aid for various cancers has also been explored,[2] but this application has been deemed impractical.[14]
Francium's ability to be synthesized, trapped, and cooled, along with its relatively simpleatomic structure have made it the subject of specialized spectroscopy experiments. These experiments have led to more specific information regarding energy levels and thecoupling constants between subatomic particles.[18] Studies on the light emitted by laser-trapped francium-210 ions have provided accurate data on transitions between atomic energy levels which are fairly similar to those predicted by quantum theory.[19]

History[edit]

As early as 1870, chemists thought that there should be an alkali metal beyond caesium, with an atomic number of 87.[2] It was then referred to by the provisional name eka-caesium.[20] Research teams attempted to locate and isolate this missing element, and at least four false claims were made that the element had been found before an authentic discovery was made.

Erroneous and incomplete discoveries[edit]

Soviet chemist D. K. Dobroserdov was the first scientist to claim to have found eka-caesium, or francium. In 1925, he observed weak radioactivity in a sample of potassium, another alkali metal, and incorrectly concluded that eka-caesium was contaminating the sample (the radioactivity from the sample was actually the naturally occurring potassium radioisotope, potassium-40).[21] He then published a thesis on his predictions of the properties of eka-caesium, in which he named the element russium after his home country.[22] Shortly thereafter, Dobroserdov began to focus on his teaching career at the Polytechnic Institute of Odessa, and he did not pursue the element further.[21]
The following year, English chemists Gerald J. F. Druce and Frederick H. Loring analyzed X-ray photographs of manganese(II) sulfate.[22] They observed spectral lines which they presumed to be of eka-caesium. They announced their discovery of element 87 and proposed the name alkalinium, as it would be the heaviest alkali metal.[21]
In 1930, Fred Allison of the Alabama Polytechnic Institute claimed to have discovered element 87 when analyzing pollucite and lepidoliteusing his magneto-optical machine. Allison requested that it be named virginium after his home state of Virginia, along with the symbols Vi and Vm.[22][23] In 1934, however, H.G. MacPherson of UC Berkeley disproved the effectiveness of Allison's device and the validity of this false discovery.[24]
In 1936, Romanian physicist Horia Hulubei and his French colleague Yvette Cauchois also analyzed pollucite, this time using their high-resolution X-ray apparatus.[21] They observed several weak emission lines, which they presumed to be those of element 87. Hulubei and Cauchois reported their discovery and proposed the name moldavium, along with the symbol Ml, after Moldavia, the Romanian province where Hulubei was born.[22] In 1937, Hulubei's work was criticized by American physicist F. H. Hirsh Jr., who rejected Hulubei's research methods. Hirsh was certain that eka-caesium would not be found in nature, and that Hulubei had instead observed mercury orbismuth X-ray lines. Hulubei, however, insisted that his X-ray apparatus and methods were too accurate to make such a mistake. Because of this, Jean Baptiste PerrinNobel Prize winner and Hulubei's mentor, endorsed moldavium as the true eka-caesium overMarguerite Perey's recently discovered francium. Perey, however, continuously criticized Hulubei's work until she was credited as the sole discoverer of element 87.[21]

Perey's analysis[edit]

Eka-caesium was discovered in 1939 by Marguerite Perey of the Curie Institute in Paris, France when she purified a sample of actinium-227 which had been reported to have a decay energy of 220 keV. However, Perey noticed decay particles with an energy level below 80 keV. Perey thought this decay activity might have been caused by a previously unidentified decay product, one which was separated during purification, but emerged again out of the pure actinium-227. Various tests eliminated the possibility of the unknown element being thorium, radium, lead, bismuth, or thallium. The new product exhibited chemical properties of an alkali metal (such as coprecipitating with caesium salts), which led Perey to believe that it was element 87, caused by the alpha decay of actinium-227.[20]Perey then attempted to determine the proportion of beta decay to alpha decay in actinium-227. Her first test put the alpha branching at 0.6%, a figure which she later revised to 1%.[25]
Perey named the new isotope actinium-K (now referred to as francium-223)[20] and in 1946, she proposed the name catium for her newly discovered element, as she believed it to be the most electropositive cation of the elements. Irène Joliot-Curie, one of Perey's supervisors, opposed the name due to its connotation of cat rather than cation.[20] Perey then suggested francium, after France. This name was officially adopted by the International Union of Pure and Applied Chemistry in 1949,[2] becoming the second element aftergallium to be named after France. It was assigned the symbol Fa, but this abbreviation was revised to the current Fr shortly thereafter.[26] Francium was the last element discovered in nature, rather than synthesized, following rhenium in 1925.[20] Further research into francium's structure was carried out by, among others, Sylvain Lieberman and his team at CERN in the 1970s and 1980s.[27]

Occurrence[edit]

A shiny gray 5-centimeter piece of matter with a rough surface.
This sample of uraninite contains about 100,000 atoms (3.3×10−20 g) of francium-223 at any given time.[14]

Natural[edit]

Francium-223 is the result of the alpha decay of actinium-227 and can be found in trace amounts in uranium and thorium minerals.[3] In a given sample of uranium, there is estimated to be only one francium atom for every 1 × 1018 uranium atoms.[14] It is also calculated that there is at most 30 g of francium in the Earth's crust at any time.[28]

Synthesis[edit]

A complex experimental setup featuring a horizontal glass tube placed between two copper coils.
Neutral francium atoms can be trapped in the MOT using a magnetic field and laser beams.[29]
A round ball of red light surrounded by a green glowA small white spot in the middle surrounded by a red circle. There is a yellow ring outside the red circle, a green circle beyond the yellow ring and a blue circle surrounding all the other circles.
Image of light emitted by a sample of 200,000 francium atoms in a magneto-optical trap
Heat image of 300,000 francium atoms in a magneto-optical trap
Francium can be synthesized in the nuclear reaction:
197Au + 18O → 210Fr + 5 n
This process, developed by Stony Brook Physics, yields francium isotopes with masses of 209, 210, and 211,[30] which are then isolated by the magneto-optical trap (MOT).[29] The production rate of a particular isotope depends on the energy of the oxygen beam. An 18O beam from the Stony Brook LINAC creates 210Fr in the gold target with the nuclear reaction 197Au + 18O →210Fr + 5n. The production required some time to develop and understand. It was critical to operate the gold target very close to its melting point and to make sure that its surface was very clean. The nuclear reaction imbeds the francium atoms deep in the gold target, and they must be removed efficiently. The atoms diffuse fast to the surface of the gold target and are released as ions; however, this does not happen every time. The francium ions are guided by electrostatic lenses until they land into a surface of hot yttrium and become neutral again. The francium is then injected into a glass bulb. A magnetic field and laser beams cool and confine the atoms. Although the atoms remain in the trap for only about 20 seconds before escaping (or decaying), a steady stream of fresh atoms replaces those lost, keeping the number of trapped atoms roughly constant for minutes or longer. Initially, about 1000 francium atoms were trapped in the experiment. This was gradually improved and the setup is capable of trapping over 300,000 neutral atoms of francium a time.[1] Although these are neutral "metallic" atoms ("francium metal"), they are in a gaseous unconsolidated state. Enough francium is trapped that a video camera can capture the light given off by the atoms as they fluoresce. The atoms appear as a glowing sphere about 1 millimeter in diameter. This was the very first time that anyone had ever seen francium. The researchers can now make extremely sensitive measurements of the light emitted and absorbed by the trapped atoms, providing the first experimental results on various transitions between atomic energy levels in francium. Initial measurements show very good agreement between experimental values and calculations based on quantum theory. Other synthesis methods include bombarding radium with neutrons, and bombarding thorium with protons, deuterons, or heliumions.[25] Francium has not, as of 2012, been synthesized in amounts large enough to weigh.[2][6][14]

Isotopes[edit]

There are 34 known isotopes of francium ranging in atomic mass from 199 to 232.[3] Francium has seven metastable nuclear isomers.[3]Francium-223 and francium-221 are the only isotopes that occur in nature, though the former is far more common.[31]
Francium-223 is the most stable isotope with a half-life of 21.8 minutes,[3] and it is highly unlikely that an isotope of francium with a longer half-life will ever be discovered or synthesized.[25] Francium-223 is the fifth product of the actinium decay series as the daughter isotope of actinium-227.[16] Francium-223 then decays into radium-223 by beta decay (1149 keV decay energy), with a minor (0.006%)alpha decay path to astatine-219 (5.4 MeV decay energy).[32]
Francium-221 has a half-life of 4.8 minutes.[3] It is the ninth product of the neptunium decay series as a daughter isotope of actinium-225.[16] Francium-221 then decays into astatine-217 by alpha decay (6.457 MeV decay energy).[3]
The least stable ground state isotope is francium-215, with a half-life of 0.12 μs. (9.54 MeV alpha decay to astatine-211):[3] Itsmetastable isomer, francium-215m, is less stable still, with a half-life of only 3.5 ns

Caesium



Caesium or cesium[note 1] is a chemical element with symbol Cs and atomic number 55. It is a soft, silvery-gold alkali metal with a melting point of 28 °C (82 °F), which makes it one of only five elemental metals that are liquid at or near room temperature.[note 2]Caesium is an alkali metal and has physical and chemical properties similar to those ofrubidium and potassium. The metal is extremely reactive and pyrophoric, reacting with water even at −116 °C (−177 °F). It is the least electronegative element having a 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.

Two German chemists, Robert Bunsen and 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, a specific frequency from the emission spectrum of caesium-133 was chosen to be used in the definition of the second by the International System of Units. Since then, caesium has been widely used in atomic clocks.

Since the 1990s, the largest application of the element has been as caesium formate fordrilling fluids. 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. Although the element is only mildly toxic, it is a hazardous material as a metal and its radioisotopes present a high health risk if released into the environment.

Physical properties[edit]

Characteristics
[edit]

High-purity caesium-133 preserved under argon

Caesium is a very soft (it has the lowest hardness of all elements, 0.2 Mohs), veryductile, pale metal, which darkens in the presence of trace amounts of oxygen.[8][9][10]It has a melting point of 28.4 °C (83.1 °F), making it one of the few elemental metals which are liquid near room temperature.Mercury is the only elemental metal with a known melting point lower than caesium.[note 3][12] In addition, the metal has a rather low boiling point, 641 °C (1,186 °F), thelowest of all metals other than mercury.[13] Its compounds burn with a blue[14][15] or violet[15]color.

Secure caesium sample for teaching

Caesium forms alloys with the other alkali metals, as well as with gold, and amalgamswith mercury. At temperatures below 650 °C(1,202 °F), it does not alloy with cobalt, iron,molybdenum, nickel, platinum, tantalum ortungsten. It forms well-defined intermetallic compounds with antimony, gallium, indiumand thorium, which are photosensitive.[8] It mixes with the other alkali metals (except with lithium), and 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).[12][16]A few amalgams have been studied: CsHg
2 is black with a purple metallic luster, while CsHg is golden-colored, also with a metallic luster.[17]
Chemical properties[edit]

Addition of a small amount of caesium to cold water is explosive.

Caesium metal is highly reactive and verypyrophoric. In addition to igniting spontaneously in air, it reacts explosively with water even at low temperatures, more so than other members of the first group of the periodic table.[8] The reaction with solid water occurs at temperatures as low as −116 °C(−177 °F).[12] Because of its high reactivity, the metal is classified as a hazardous material. It is stored and shipped in dry saturated hydrocarbons such as mineral oil. Similarly, it must be handled under inert gassuch 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.[18] Caesium can be stored in vacuum-sealedborosilicate glass ampoules. In quantities of more than about 100 grams (3.5 oz), caesium is shipped in hermetically sealed, stainless steel containers.[8]

The chemistry of caesium is similar to that of other alkali metals, but is more closely similar to that of rubidium, the element above caesium in the periodic table.[19] Some small differences arise from the fact that it has a higher atomic mass and is more electropositivethan other (nonradioactive) alkali metals.[20] Caesium is the most electropositive stable chemical element.[note 4][12] The caesium ion is also larger and less "hard" than those of the lighter alkali metals.
Compounds[edit]

Ball-and-stick model of the cubic coordination of Cs and Cl in CsCl

The vast majority of caesium compounds contain the element as the cation Cs+
, which binds ionically to a wide variety of anions. One noteworthy exception is provided by the caeside anion (Cs−
).[22] Other exceptions include the several suboxides (see section on oxides below).

Returning to more normal compounds, salts of Cs+ are almost invariably colorless unless the anion itself is colored. Many of the simple salts are hygroscopic, but less so than the corresponding salts of the lighter alkali metals. The phosphate,[23] 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 the purification of Cs from its ores. The double salt with antimony (such as CsSbCl
4),bismuth, cadmium, copper, iron, and lead are also poorly soluble.[8]

Caesium hydroxide (CsOH) is hygroscopic and a very strong base.[19] It rapidly etches the surface ofsemiconductors such as silicon.[24] CsOH has been previously regarded by chemists as the "strongest base", reflecting the relatively weak attraction between the large Cs+ ion and OH–.;[14] it is indeed the strongest Arrhenius base, but a number of compounds that cannot exist in aqueous solution, such as n-butyllithium and sodium amide,[19] are more basic.

A stoichiometric mixture of caesium and gold will react to form caesium auride.
Complexes[edit]

Like all metal cations, Cs+ forms complexes with Lewis bases in solution. Because of its large size, Cs+ usually adopts coordination numbers greater than six-coordination, which is typical for the lighter alkali metal cations. This trend is already apparent by the 8-coordination in CsCl, vs the halite motif adopted by the other alkali metal chlorides. Its high coordination number and softness (tendency to form covalent bonds) are the basis of the separation of Cs+ from other cations, as is practiced in the remediation of nuclear wastes, where 137Cs+ is separated from large amounts of nonradioactive K+.[25]
Halides[edit]

Caesium chloride (CsCl) crystallizes in the simple cubic crystal system. Also called the "caesium chloride structure",[20] 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 center of the cubes. This structure is shared withCsBr and CsI, and many other compounds that do not contain Cs. In contrast, most other alkaline halides adopt the sodium chloride(NaCl) structure.[20] The CsCl structure is preferred because Cs+ has an ionic radius of 174 pm and Cl−
181 pm.[26]
Oxides[edit]

Cs
11O
3 cluster

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.[27] The "normal" caesium oxide (Cs
2O) forms yellow-orange hexagonal crystals,[28] and is the only oxide of the anti-CdCl
2 type.[29] It vaporizes at 250 °C (482 °F), and decomposes to caesium metal and the peroxide Cs
2O
2 at temperatures above400 °C (752 °F).[30] Aside from the superoxide and the ozonide CsO
3,[31][32] several brightly coloredsuboxides have also been studied.[33] These include Cs
7O, Cs
4O, Cs
11O
3, Cs
3O (dark-green[34]), CsO,Cs
3O
2,[35] as well as Cs
7O
2.[36][37] The latter may be heated under vacuum to generate Cs
2O.[29] Binary compounds with sulfur, selenium, and tellurium also exist.[8]
Isotopes[edit]
Main article: Isotopes of caesium

Caesium has a total of 39 known isotopes that range in their mass number (i.e. number of nucleons in its nucleus) from 112 to 151. Several of these are synthesized from lighter elements by the slow neutron capture process (S-process) inside old stars,[38] as well as inside supernova explosions (R-process).[39] However, the only stable isotope is 133Cs, which has 78 neutrons. Although it has a largenuclear spin (7/2+), nuclear magnetic resonance studies can be done with this isotope at a resonating frequency of 11.7 MHz.[40]

Decay of caesium-137

The radioactive 135Cs has a very long half-life of about 2.3 million years, while 137Csand 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-times between a day and two weeks, while most of the other isotopes have half-lives from a few seconds to fractions of a second. There are at least 21 metastable nuclear isomers. 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.[41][42]

The isotope 135Cs is one of the long-lived fission products of uranium which form innuclear reactors.[43] However, its fission product yield is reduced in most reactors because its predecessor, 135Xe, is an extremely potent neutron poison and transmutes frequently to stable 136Xe before it can decay to135Cs.[44][45]

Because of its beta decay (to 137mBa), 137Cs is a strong emitter of gamma radiation.[46] Its half-life makes it the principal medium-lived fission product along with 90Sr—both are responsible for radioactivity of spent nuclear fuel after several years of cooling up to several hundred years after use.[47] For example 137Cs together with 90Sr currently generate the largest source of radioactivity generated in the area around the Chernobyl disaster.[48] It is not feasible to dispose of 137Cs through neutron capture (due to the low capture rate) and as a result it must be allowed to decay.[49]

Almost all caesium produced from nuclear fission comes from beta decay of originally more neutron-rich fission products, passing through various isotopes of iodine and of xenon.[50] 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.[51] With the commencement of nuclear weapons testing around 1945, 137Cs was released into the atmosphere and then returned to the surface of the earth as a component of radioactive fallout.[8]
Occurrence[edit]

Pollucite, a caesium mineral
See also: Caesium minerals

Caesium is a relatively rare element as it is estimated to average approximately 3 parts per million in the Earth's crust.[52] This makes it the 45th most abundant of all elements and the 36th of all 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 orsilver, but 3.3% as abundant as rubidium—with which it is so closely chemically associated.[8]

Due to its large ionic radius, caesium is one of the "incompatible elements".[53] Duringmagma 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 does rubidium, the alkali evaporite mineralssylvite (KCl) and carnallite (KMgCl
3·6H
2O) may contain only 0.002% caesium. Consequently, Cs is found in few minerals. Percentage amounts of caesium may be found in beryl (Be
3Al
2(SiO
3)
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
4Be
4(B,Be)
12O
28), and less in the more widespread rhodizite.[8] The only economically important source mineral for caesium is pollucite Cs(AlSi
2O
6), which is found in a few places around the world in zoned pegmatites, and is associated with the more commercially important lithium minerals lepidoliteand petalite. Within the pegmatites, the large grain size and the strong separation of the minerals create high-grade ore for mining.[54]

One of the world's most significant and richest sources of the metal is the Tanco mine at Bernic Lake in Manitoba, Canada. The deposits there are estimated to contain 350,000 metric tons of pollucite ore, which represent more than two-thirds of the world's reserve base.[54][55] 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%.[55] Commercial pollucite contains over 19% caesium.[56] The Bikita pegmatite deposit in Zimbabwe is mined for its petalite, but it also contains a significant amount of pollucite. Notable amounts of pollucite are also mined in the Karibib Desert, Namibia.[55] At the present rate of world mine production of 5 to 10 metric tons per year, reserves will last for thousands of years.[8]
Production[edit]

The mining of pollucite ore is a selective process and is conducted on a small scale in comparison with most metal mining operations. The ore is crushed, hand-sorted, but not usually concentrated, and then ground. Caesium is then extracted from pollucite mainly by three methods: acid digestion, alkaline decomposition, and direct reduction.[8][57]

In the acid digestion, the silicate pollucite rock is dissolved with strong acids such as hydrochloric (HCl), sulfuric (H
2SO
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
4SbCl
7), caesium iodine chloride (Cs
2ICl), or caesium hexachlorocerate (Cs
2(CeCl
6)). After separation, the pure precipitated double salt is decomposed, and pure CsCl is obtained after evaporating the water. The method using sulfuric acid yields the insoluble double salt directly as caesium alum (CsAl(SO
4)
2·12H
2O). The aluminium sulfate in it is converted to the insoluble aluminium oxide by roasting the alum with carbon, and the resulting product isleached with water to yield a Cs
2SO
4 solution.[8]

The roasting of pollucite with calcium carbonate and calcium chloride yields insoluble calcium silicates and soluble caesium chloride. Leaching with water or dilute ammonia (NH
4OH) yields then a dilute chloride (CsCl) solution. This solution can be evaporated to produce caesium chloride or transformed into caesium alum or caesium carbonate. Albeit not commercially feasible, direct reduction of the ore with potassium, sodium or calcium in vacuum can produce caesium metal directly.[8]

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.[58] The primary smaller-scale commercial compounds of caesium are caesium chloride and its nitrate.[59]

Alternatively, caesium metal may be obtained from the purified compounds derived from the ore. Caesium chloride, and the other caesium halides, as well, can be reduced at 700 to 800 °C (1,292 to 1,472 °F) with calcium or barium, followed by distillation of the caesium metal. In the same way, the aluminate, carbonate, or hydroxide may be reduced by magnesium.[8] The metal can also be isolated by electrolysis of fused caesium cyanide (CsCN). Exceptionally pure and gas-free caesium can be made by the thermal decomposition at 390 °C (734 °F) of caesium azide CsN
3, which is produced from aqueous caesium sulfate and barium azide.[57] In vacuum applications, caesium dichromate can be reacted with zirconium forming pure caesium metal without other gaseous products.[59]Cs
2Cr
2O
7 + 2 Zr → 2 Cs + 2 ZrO
2+ Cr
2O
3

The price of 99.8% pure caesium (metal basis) in 2009 was about US$10 per gram ($280 per ounce), but its compounds are significantly cheaper.[55]
History[edit]

Gustav Kirchhoff (left) and Robert Bunsen (center) discovered caesium spectroscopically.

In 1860, Robert Bunsen and Gustav Kirchhoff discovered caesium in the mineral water fromDürkheim, Germany. Due to the bright blue lines in its emission spectrum, they chose a name derived from the Latin word caesius, meaning sky-blue.[note 5][60][61][62] Caesium was the first element to be discovered spectroscopically, only one year after the invention of thespectroscope by Bunsen and Kirchhoff.[12]

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. Thealkaline 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. Therefore, the less-soluble caesium and rubidium hexachloroplatinate ((Cs,Rb)2PtCl6) could be obtained by fractional crystallization. After reduction of the hexachloroplatinate with hydrogen, caesium and rubidium could be 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 liters of mineral water.[61]

The two scientists used the caesium chloride thus obtained to estimate the atomic weight of the new element at 123.35 (compared to the currently accepted one of 132.9).[61] They tried to generate elemental caesium by electrolysis of molten caesium chloride, but instead of a metal, they obtained a blue homogenous 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 colloidalmixture of the metal and caesium chloride.[63] The electrolysis of the aqueous solution of chloride with a mercury anode produced a caesium amalgam which readily decomposed under the aqueous conditions.[61] The pure metal was eventually isolated by the German chemist Carl Setterberg while working on his doctorate with Kekulé and Bunsen.[62] In 1882, he produced caesium metal by electrolyzing caesium cyanide, and thus avoiding the problems with the chloride.[64]

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 to be used in radio vacuum tubes. It had two functions; as a getter, it removed excess oxygen after manufacture, and as a coating on the heated cathode, it increased its electrical conductivity. Caesium did not become recognized as a high-performance industrial metal until the 1950s.[65] Applications of nonradioactive caesium includedphotoelectric cells, photomultiplier tubes, optical components of infrared spectrophotometers, catalysts for several organic reactions, crystals for scintillation counters, and in magnetohydrodynamic power generators.[8]

Since 1967, the International System of Measurements has based its unit of time, the second, on the properties of caesium. The International System of Units (SI) defines the second as 9,192,631,770 cycles of the radiation, which corresponds to the transition between two hyperfine energy levels of the ground state of the caesium-133 atom.[66] 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".
Applications[edit]
Petroleum exploration[edit]

The largest current end-use of nonradioactive caesium is in caesium formate-based drilling fluids for the extractive oil industry.[8]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 caesium formate as 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. As completion fluid, which assists the emplacement of control hardware after drilling but prior to production, the function of caesium formate is to maintain the pressure.[8]

The high density of the caesium formate brine (up to 2.3 g·cm−3, or 19.2 pounds per gallon),[67] 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.[67] The caesium formate brine can be blended with potassium and sodium formates to decrease the density of the fluids down to that of water (1.0 g·cm−3, or 8.3 pounds per gallon). Furthermore, it is biodegradable and reclaimable, and may be recycled, which is important in view of its high cost (about $4,000 per barrel in 2001).[68] Alkali formates are safe to handle and do not damage the producing formation or downhole metals as their corrosive alternative, high-density brines (such as zinc bromideZnBr
2 solutions),sometimes do; they also require less cleanup and disposal costs.[8]
Atomic clocks[edit]

Atomic clock ensemble at the U.S. Naval Observatory

FOCS-1, a continuous cold caesium fountain atomic clock in Switzerland, started operating in 2004 at an uncertainty of one second in 30 million years

Caesium-based atomic clocks observe electromagnetic transitions in the hyperfine structure of caesium-133 atoms and use it as a reference point. The first accurate caesium clock was built by Louis Essen in 1955 at the National Physical Laboratory in the UK.[69] Since then, they have been improved repeatedly over the past half-century, and form the basis for standards-compliant time and frequency measurements. These clocks measure frequency with an error of 2 to 3 parts in 1014, which would correspond to a time measurement accuracy of 2 nanoseconds per day, or one second in 1.4 million years. The latest versions are accurate to better than 1 part in 1015, which means they would be off by about 2 seconds since the extinction of the dinosaurs65 million years ago,[8] and has been regarded as "the most accurate realization of a unit that mankind has yet achieved."[66]

Caesium clocks are also used in networks that oversee the timing of cell phone transmissions and the information flow on the Internet.[70]
Electric power and electronics[edit]

Caesium vapor thermionic generators are low-power devices that convert heat energy to electrical energy. In the two-electrode vacuum tube converter, it neutralizes the space charge that builds up near the cathode, and in doing so, it enhances the current flow.[71]

Caesium is also important for its photoemissive properties by which light energy is converted to electron flow. It is used in photoelectric cells because caesium-based cathodes such as the intermetallic compound K
2CsSb have low threshold voltage for emission of electrons.[72]The range of photoemissive devices using caesium include optical character recognitiondevices, photomultiplier tubes, and video camera tubes.[73][74] Nevertheless, germanium, rubidium, selenium, silicon, tellurium, and several other elements can substitute caesium in photosensitive materials.[8]

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, as they are well-suited for the detection of gamma and X-ray radiation. Caesium, being a heavy element, provides good stopping power, contributing to better detectivity. Caesium compounds may also provide a faster response (CsF) and be less hygroscopic (CsI).

Caesium vapor is used in many common magnetometers.[75] The element is also used as an internal standard in spectrophotometry.[76]Like other alkali metals, caesium has a great affinity for oxygen and is used as a "getter" in vacuum tubes.[77] Other uses of the metal include high-energy lasers, vapor glow lamps, and vapor rectifiers.[8]
Centrifugation fluids[edit]

Because of their high density, solutions of caesium chloride, caesium sulfate, and caesium trifluoroacetate (Cs(O
2CCF
3)) are commonly used in molecular biology for density gradient ultracentrifugation.[78] This technology is primarily applied to the isolation of viral particles, subcellular organelles and fractions, and nucleic acids from biological samples.[79]
Chemical and medical use[edit]

A sample of caesium chloride

Relatively few chemical applications exist for caesium.[80] Doping with caesium compounds is used to enhance the effectiveness of several metal-ion catalysts used in the production of chemicals, 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.[8]

Caesium fluoride enjoys niche use in organic chemistry as a base,[19] or as an anhydroussource of fluoride ion.[81] Caesium salts sometimes replace potassium or sodium salts inorganic synthesis, such as cyclization, esterification, and polymerization.
Nuclear and isotope applications[edit]

Caesium-137 is a very common radioisotope used as a gamma-emitter in industrial applications. Its advantages include a half-life of roughly 30 years, its availability from thenuclear fuel cycle, and having 137Ba as stable end product. The high water solubility is a disadvantage which makes it incompatible with large pool irradiators for food and medical supplies.[82] It has been used in agriculture, cancer treatment, and the sterilization of food, sewage sludge, and surgical equipment.[8][83] Radioactive isotopes of caesium in radiation devices were used in the medical field to treat certain types of cancer,[84]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.[85][86] Caesium-137 has been employed in a variety of industrial measurement gauges, including moisture, density, leveling, and thickness gauges.[87] It has also been used in well loggingdevices for measuring the electron density of the rock formations, which is analogous to the bulk density of the formations.[88]

Isotope 137 has also been used in hydrologic studies analogous to those using tritium. It is a daughter product of nuclear fission reactions. With the commencement of nuclear testing around 1945, and continuing through the mid-1980s, caesium-137 was released into the atmosphere, where it is 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 as a measure of caesium output by the nuclear power industry. While they are less prevalent than either caesium-133 or caesium-137, these isotopes have the advantage of being produced solely from anthropogenic sources.[89]
Other uses[edit]

Schematics of an electrostatic ion thruster which was initially developed for use with caesium or mercury

Caesium and mercury were used as a propellant in early ion engines designed for spacecraft propulsion on very long interplanetary or extraplanetary missions. The ionization method was to strip the outer electron from the propellant upon contact with a tungsten electrode that had voltage applied. Concerns about the corrosive action of caesium on spacecraft components have pushed development in the direction of use of inert gas propellants such as xenon; this is easier to handle in ground-based tests and has less potential to interfere with the spacecraft.[8] Eventually, xenon was used in the experimental spacecraft Deep Space 1 launched in 1998.[90][91] Nevertheless, field emission electric propulsion thrusters which use a simple system of accelerating liquid metal ions such as of caesium to create thrust have been built.[92]

Caesium nitrate is used as an oxidizer and pyrotechnic colorant to burn siliconin infrared flares[93] such as the LUU-19 flare,[94] because it emits much of its light in the near infrared spectrum.[95] Caesium has been used to reduce theradar signature of exhaust plumes in the SR-71 Blackbird military aircraft.[96]Caesium, along with rubidium, has been added as a carbonate to glass because it reduces electrical conductivity and improves stability and durability of fiber optics and night vision devices. Caesium fluoride or caesium aluminium fluoride are used in fluxes formulated for the brazing of aluminium alloys that contain magnesium.[8]
Prognostications[edit]

Magnetohydrodynamic (MHD) power-generating systems were researched, but failed to gain widespread acceptance.[97] Caesium metal has also been considered as the working fluid in high-temperature Rankine cycle turboelectric generators.[98] Caesium salts have been evaluated as antishock reagents to be used 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.[8]
Health and safety hazards[edit]

The portion of the total radiation dose (in air) contributed by each isotope versus time after the Chernobyl disasterdepicting caesium-137 becoming the largest source of radiation about 200 days after the accident.[99]

Caesium compounds are rarely encountered by most people, but most are mildly toxic because of chemical similarity of caesium to potassium. Exposure to large amounts of caesium compounds can cause hyperirritability andspasms, but as such amounts would not ordinarily be encountered in natural sources, caesium is not a major chemical environmental pollutant.[100] Themedian lethal dose (LD50) value for caesium chloride in mice is 2.3 g per kilogram, which is comparable to the LD50 values of potassium chloride andsodium chloride.[101]

NFPA 704


3
4
3
W
The fire diamondhazard sign for caesium metal


Caesium metal is one of the most reactive elements and is highly explosive when it comes in contact with 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 even be triggered by cold water.[8] Theautoignition temperature of caesium is also −116 °C, so it is highly pyrophoric, and ignites explosively in air to form caesium hydroxide and various oxides. Caesium hydroxide is a very strong base, and will rapidly corrode glass.[13]

The isotopes 134 and 137 are present in the biosphere in small amounts from human activities and represent a radioactivity burden which varies depending on location. Radiocaesium does not accumulate in the body as effectively as many 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 half-life between 50 and 150 days.[102] Radiocaesium follows potassium and tends to accumulate in plant tissues, including fruits and vegetables.[103][104][105] It is also well-documented that mushrooms from contaminated forests accumulate radiocaesium (caesium-137) in their fungal sporocarps.[106] Accumulation of caesium-137 in lakes has been a high concern after the Chernobyl disaster.[107][108] 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;[109] smaller amounts may cause infertility and cancer.[110] TheInternational 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"

Rubidium

Rubidium is a chemical element with the symbol Rb and atomic number 37. Rubidium is a soft, silvery-white metallic element of the alkali metal group, with an atomic mass of 85.4678. Elemental rubidium is highly reactive, with properties similar to those of other elements in Group 1, such as very rapid oxidation in air. Rubidium has only one stable isotope, 85Rb. Another isotope, 87Rb, which composes almost 28% of naturally occurring rubidium, is slightly radioactive 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 method of flame spectroscopy.
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 known to be necessary for any living organisms. However, like caesium, rubidium ions are handled by living organisms in a manner similar to potassium ions, being actively taken up by plants and by animal cells.


Rubidium is a very soft,
 ductile, silvery-white metal.  It is the second mostelectropositive of the non-radioactive alkali metals and melts at a temperature of 39.3 °C(102.7 °F). Similar to other alkali metals, rubidium metal reacts violently with water, formsamalgams with mercury and alloys with gold, iron, caesium, sodium, and potassium, but not lithium (despite the fact that rubidium and lithium are in the same group).[3] As with potassium (which is slightly less reactive) and caesium (which is slightly more reactive), rubidium's reaction with water is usually vigorous enough to ignite the hydrogen gas it liberates. Rubidium has also been reported to ignite spontaneously in air.[2] Rubidium has a very low ionization energy of only 406 kJ/mol.[4] Rubidium and potassium show a very similar purple color in the flame test, which makes spectroscopy methods necessary to distinguish the two elements.Characteristics
[edit]

Compounds[edit]

 The ball-and-stick diagram shows two regular octahedra which are connected to each other by one face. All nine vertices of the structure are purple spheres representing rubidium, and at the centre of each octahedron is a small red sphere representing oxygen.
Rb
9
O
2
 cluster
Rubidium chloride (RbCl) is probably the most used rubidium compound; it is used in biochemistry to induce cells to take upDNA, and as a biomarker since it is readily taken up to replace potassium, and occurs in only small quantities in living organisms. Other common rubidium compounds are the corrosive rubidium hydroxide (RbOH), the starting material for most rubidium-based chemical processes; rubidium carbonate (Rb2CO3), which is used in some optical glasses, and rubidium copper sulfate, Rb2SO4·CuSO4·6H2O. Rubidium silver iodide (RbAg4I5) has the highest room temperature conductivity of any known ionic crystal, a property that is being exploited in thin film batteries and other applications.[5][6]
Rubidium has a number of oxides, including rubidium monoxide (Rb2O), Rb6O and Rb9O2, which form if rubidium metal is exposed to air; rubidium in excess oxygen gives the superoxide RbO2. Rubidium forms salts with halides, making rubidium fluoride, rubidium chloride, rubidium bromide, and rubidium iodide.

Isotopes[edit]

Although rubidium is monoisotopic, naturally occurring rubidium is composed of two isotopes: the stable 85Rb (72.2%) and the radioactive 87Rb (27.8%).[7] Natural rubidium is radioactive with specific activity of about 670 Bq/g, enough to significantly expose aphotographic film in 110 days.[8][9] Aside from 85Rb and 87Rb, another 24 synthetically produced isotopes or rubidium are known, with half times of under 3 months; most of these are highly radioactive and have few uses.
Rubidium-87 has a half-life of 48.8×109 years, which is more than three times the age of the universe of 13.798±0.037×109 years,[10] making it a primordial nuclide. It readily substitutes for potassium in minerals, and is therefore fairly widespread. Rb has been used extensively in dating rocks; 87Rb decays to stable 87Sr by emission of a negativebeta particle. During fractional crystallization, Sr tends to become concentrated inplagioclase, leaving Rb in the liquid phase. Hence, the Rb/Sr ratio in residual magma may increase over time, resulting in rocks with elevated Rb/Sr ratios due to progressingdifferentiation. The highest ratios (10 or more) occur in pegmatites. If the initial amount of Sr is known or can be extrapolated, then the age can be determined by measurement of the Rb and Sr concentrations and of the 87Sr/86Sr ratio. The dates indicate the true age of the minerals only if the rocks have not been subsequently altered (see rubidium-strontium dating).[11][12]
Rubidium-82, one of the element's non-natural isotopes, is produced by electron-capturedecay of strontium-82 with a half-life of 25.36 days. The subsequent decay of rubidium-82 with a half-life of 76 seconds to stable krypton-82 happens by positron emission.[7]

Occurrence[edit]

Rubidium is the twenty-third most abundant element in the Earth's crust, roughly as abundant as zinc and rather more common than copper.[13] It occurs naturally in the minerals leucite, pollucite, carnallite, and zinnwaldite, which contain up to 1% of itsoxide. Lepidolite contains between 0.3% and 3.5% rubidium, and is the commercial source of the element.[14] Some potassium minerals and potassium chlorides also contain the element in commercially significant amounts.[15]
Seawater contains an average of 125 µg/L of rubidium compared to the much higher value for potassium of 408 mg/L and the much lower value of 0.3 µg/L for caesium[16]
Because of its large ionic radius, rubidium is one of the "incompatible elements."[17]During magma crystallization, rubidium is concentrated together with its heavier analogue caesium in the liquid phase and crystallizes last. Therefore the largest deposits of rubidium and caesium are zone pegmatite ore bodies formed by this enrichment process. Because rubidium substitutes for potassium in the crystallization of magma, the enrichment is far less effective than in the case of caesium. Zone pegmatite ore bodies containing mineable quantities of caesium as pollucite or the lithium minerals lepidoliteare also a source for rubidium as a by-product.[13]
Two notable sources of rubidium are the rich deposits of pollucite at Bernic Lake,Manitoba, Canada, and the rubicline ((Rb,K)AlSi3O8) found as impurities in pollucite on the Italian island of Elba, with a rubidium content of 17.5%.[18] Both of these deposits are also sources of caesium.

Production[edit]

Although rubidium is more abundant in Earth's crust than caesium, the limited applications and the lack of a mineral rich in rubidium limits the production of rubidium compounds to 2 to 4 tonnes per year.[13] Several methods are available for separating potassium, rubidium, and caesium. The fractional crystallization of a rubidium and caesium alum (Cs,Rb)Al(SO4)2·12H2O yields after 30 subsequent steps pure rubidium alum. Two other methods are reported, the chlorostannate process and the ferrocyanide process.[13][19]
For several years in the 1950s and 1960s, a by-product of potassium production called Alkarb was a main source for rubidium. Alkarb contained 21% rubidium, with the rest being potassium and a small fraction of caesium.[20] Today the largest producers of caesium, such as the Tanco Mine, Manitoba, Canada, produce rubidium as by-product from pollucite.[13]

Flame test for Rubidium

History[edit]

 Three middle-aged men, with the one in the middle sitting down. All wear long jackets, and the shorter man on the left has a beard.
Gustav Kirchhoff (left) and Robert Bunsen (center) discovered rubidium spectroscopically. (Henry Enfield Roscoe is on the right side.)
Rubidium was discovered in 1861 by Robert Bunsen and Gustav Kirchhoff, in Heidelberg, Germany, in the mineral lepidolite through the use of a spectroscope. Because of the bright red lines in its emission spectrum, they chose a name derived from the Latin word rubidus, meaning "dark red".[21][22]
Rubidium is present as a minor component in lepidolite. Kirchhoff and Bunsen processed 150 kg of a lepidolite containing only 0.24% rubidium oxide (Rb2O). Both potassium and rubidium form insoluble salts with chloroplatinic acid, but these salts show a slight difference in solubility in hot water. Therefore, the less-soluble rubidium hexachloroplatinate (Rb2PtCl6) could be obtained by fractional crystallization. After reduction of the hexachloroplatinate with hydrogen. This process yielded 0.51 grams of rubidium chloride for further studies. The first large scale isolation of caesium and rubidium compounds, performed from 44,000 liters of mineral water by Bunsen and Kirchhoff, yielded, besides 7.3 grams ofcaesium chloride, also 9.2 grams of rubidium chloride.[21][22] Rubidium was the second element, shortly after caesium, to be discovered spectroscopically, only one year after the invention of the spectroscope by Bunsen and Kirchhoff.[23]
The two scientists used the rubidium chloride thus obtained to estimate the atomic weight of the new element as 85.36 (the currently accepted value is 85.47).[21] They tried to generate elemental rubidium by electrolysis of molten rubidium 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." They assigned it as asubchloride (Rb
2
Cl
); however, the product was probably a colloidal mixture of the metal and rubidium chloride.[24] In a second attempt to produce metallic rubidium, Bunsen was able to reduce rubidium by heating charred rubidium tartrate. Although the distilled rubidium waspyrophoric, it was possible to determine the density and the melting point of rubidium. The quality of the research done in the 1860s can be appraised by the fact that their determined density differs less than 0.1 g/cm3 and the melting point by less than 1 °C from the presently accepted values.[25]
The slight radioactivity of rubidium was discovered in 1908 but before the theory of isotopes was established in the 1910s and the low activity due to the long half-life of above 1010 years made interpretation complicated. The now proven decay of 87Rb to stable 87Sr through beta decay was still under discussion in the late 1940s.[26][27]
Rubidium had minimal industrial value before the 1920s.[28] Since then, the most important use of rubidium has been in research and development, primarily in chemical and electronic applications. In 1995, rubidium-87 was used to produce a Bose–Einstein condensate,[29] for which the discoverers, Eric Allin Cornell, Carl Edwin Wieman and Wolfgang Ketterle, won the 2001 Nobel Prize in Physics.[30]

Applications[edit]


A rubidium fountain atomic clock at theUnited States Naval Observatory
Rubidium compounds are sometimes used in fireworks to give them a purple color.[31]Rubidium has also been considered for use in a thermoelectric generator using themagnetohydrodynamic principle, where rubidium ions are formed by heat at high temperature and passed through a magnetic field.[32] These conduct electricity and act like an armatureof a generator thereby generating an electric current. Rubidium, particularly vaporized 87Rb, is one of the most commonly used atomic species employed for laser cooling and Bose-Einstein condensation. Its desirable features for this application include the ready availability of inexpensive diode laser light at the relevant wavelength, and the moderate temperatures required to obtain substantial vapor pressures.[33][34]
Rubidium has been used for polarizing 3He, producing volumes of magnetized 3He gas, with the nuclear spins aligned toward a particular direction in space, rather than randomly.
Rubidium vapor is optically pumped by a laser and the polarized Rb polarizes 3He through the hyperfine interaction.[35]
Such spin-polarized 3He cells are becoming popular for neutron polarization measurements and for producing polarized neutron beams for other purposes.[36]
The resonant element in atomic clocks utilizes the hyperfine structure of rubidium's energy levels, making rubidium useful for high-precision timing, and is used as the main component of secondary frequency references (rubidium oscillators) to maintain frequency accuracy in cell site transmitters and other electronic transmitting, networking, and test equipment. These rubidium standards are often used with GPS to produce a "primary frequency standard" that has greater accuracy and is less expensive than caesium standards.[37][38] Such rubidium standards are often mass-produced for the telecommunicationindustry.[39]
Other potential or current uses of rubidium include a working fluid in vapor turbines, as a getter in vacuum tubes, and as a photocellcomponent.[40] Rubidium is also used as an ingredient in special types of glass, in the production of superoxide by burning in oxygen, in the study of potassium ion channels in biology, and as the vapor to make atomic magnetometers.[41] In particular, 87Rb is currently being used, with other alkali metals, in the development of spin-exchange relaxation-free (SERF) magnetometers.[41]
Rubidium-82 is used for positron emission tomography. Rubidium is very similar to potassium and therefore tissue with high potassium content will also accumulate the radioactive rubidium. One of the main uses is in myocardial perfusion imaging. The very short half-life of 76 seconds makes it necessary to produce the rubidium-82 from decay of strontium-82 close to the patient.[42] As a result of changes in the blood brain barrier in brain tumors, rubidium collects more in brain tumors than normal brain tissue, allowing the use of radioisotope rubidium-82 in nuclear medicine to locate and image brain tumors.[43]
Rubidium was tested for the influence on manic depression and depression.[44][45] Dialysis patients suffering from depression show a depletion in rubidium and therefore a supplementation may help during depression.[46] In some tests the rubidium was administered as rubidium chloride with up to 720 mg per day for 60 days.[47][48]

Precautions and biological effects[edit]

Rubidium reacts violently with water and can cause fires. To ensure safety and purity, this metal is usually kept under a dry mineral oilor sealed in glass ampoules in an inert atmosphere. Rubidium forms peroxides on exposure even to small amount of air diffusing into oil, and is thus subject to similar peroxide precautions as storage of metallic potassium.[49]
Rubidium, like sodium and potassium, almost always has +1 oxidation state when dissolved in water, including its presence in all biological systems. The human body tends to treat Rb+ ions as if they were potassium ions, and therefore concentrates rubidium in the body's intracellular fluid (i.e., inside cells).[50] The ions are not particularly toxic; a 70 kg person contains on average 0.36 g of rubidium, and an increase in this value by 50 to 100 times did not show negative effects in test persons.[51] The biological half-life of rubidium in humans was measured as 31–46 days.[44] Although a partial substitution of potassium by rubidium is possible, rats with more than 50% of their potassium substituted in the muscle tissue died.

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