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Caesium

Element with the atomic number of 55

Top 10 Caesium related articles

Caesium, 55Cs
Caesium
Pronunciation/ˈsziəm/ (SEE-zee-əm)
Alternative namecesium (US, informal)
Appearancepale gold
Standard atomic weight Ar, std(Cs)132.90545196(6)[1]
Caesium in the periodic table
Hydrogen Helium
Lithium Beryllium Boron Carbon Nitrogen Oxygen Fluorine Neon
Sodium Magnesium Aluminium Silicon Phosphorus Sulfur Chlorine Argon
Potassium Calcium Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper Zinc Gallium Germanium Arsenic Selenium Bromine Krypton
Rubidium Strontium Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium Palladium Silver Cadmium Indium Tin Antimony Tellurium Iodine Xenon
Caesium Barium Lanthanum Cerium Praseodymium Neodymium Promethium Samarium Europium Gadolinium Terbium Dysprosium Holmium Erbium Thulium Ytterbium Lutetium Hafnium Tantalum Tungsten Rhenium Osmium Iridium Platinum Gold Mercury (element) Thallium Lead Bismuth Polonium Astatine Radon
Francium Radium Actinium Thorium Protactinium Uranium Neptunium Plutonium Americium Curium Berkelium Californium Einsteinium Fermium Mendelevium Nobelium Lawrencium Rutherfordium Dubnium Seaborgium Bohrium Hassium Meitnerium Darmstadtium Roentgenium Copernicium Nihonium Flerovium Moscovium Livermorium Tennessine Oganesson
Rb

Cs

Fr
xenoncaesiumbarium
Atomic number (Z)55
Groupgroup 1: H and alkali metals
Periodperiod 6
Block  s-block
Electron configuration[Xe] 6s1
Electrons per shell2, 8, 18, 18, 8, 1
Physical properties
Phase at STPsolid
Melting point301.7 K ​(28.5 °C, ​83.3 °F)
Boiling point944 K ​(671 °C, ​1240 °F)
Density (near r.t.)1.93 g/cm3
when liquid (at m.p.)1.843 g/cm3
Critical point1938 K, 9.4 MPa[2]
Heat of fusion2.09 kJ/mol
Heat of vaporization63.9 kJ/mol
Molar heat capacity32.210 J/(mol·K)
Vapour pressure
P (Pa) 1 10 100 1 k 10 k 100 k
at T (K) 418 469 534 623 750 940
Atomic properties
Oxidation states−1, +1[3] (a strongly basic oxide)
ElectronegativityPauling scale: 0.79
Ionization energies
  • 1st: 375.7 kJ/mol
  • 2nd: 2234.3 kJ/mol
  • 3rd: 3400 kJ/mol
Atomic radiusempirical: 265 pm
Covalent radius244±11 pm
Van der Waals radius343 pm
Spectral lines of caesium
Other properties
Natural occurrenceprimordial
Crystal structurebody-centred cubic (bcc)
Thermal expansion97 µm/(m·K) (at 25 °C)
Thermal conductivity35.9 W/(m·K)
Electrical resistivity205 nΩ·m (at 20 °C)
Magnetic orderingparamagnetic[4]
Young's modulus1.7 GPa
Bulk modulus1.6 GPa
Mohs hardness0.2
Brinell hardness0.14 MPa
CAS Number7440-46-2
History
Namingfrom Latin caesius, sky blue, for its spectral colours
DiscoveryRobert Bunsen and Gustav Kirchhoff (1860)
First isolationCarl Setterberg (1882)
Main isotopes of caesium
Iso­tope Abun­dance Half-life (t1/2) Decay mode Pro­duct
133Cs 100% stable
134Cs syn 2.0648 y ε 134Xe
β 134Ba
135Cs trace 2.3×106 y β 135Ba
137Cs syn 30.17 y[5] β 137Ba
 Category: Caesium
| references

Caesium (IUPAC spelling[6]) (also spelled cesium in American English)[note 1] is a chemical element with the 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.

Caesium Intro articles: 25

Characteristics

Physical properties

High-purity caesium-133 stored in argon.

Of all elements that are solid at room temperature, caesium is the softest: 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.[11][12][13] 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 stable elemental metal with a known melting point lower than caesium.[note 3][15] In addition, the metal has a rather low boiling point, 641 °C (1,186 °F), the lowest of all metals other than mercury.[16] Its compounds burn with a blue[17][18] or violet[18] colour.

Caesium crystals (golden) compared to rubidium crystals (silvery)

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.[11] 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).[15][19] 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.[20]

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.[21]

Chemical properties

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

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).[11] It reacts with ice at temperatures as low as −116 °C (−177 °F).[15] 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.[22] 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.[11]

The chemistry of caesium is similar to that of other alkali metals, in particular rubidium, the element above caesium in the periodic table.[23] 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.[25] Caesium is the most electropositive chemical element.[note 5][15] The caesium ion is also larger and less "hard" than those of the lighter alkali metals.

Compounds

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

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
),[3] 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,[27] 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.[11]

Caesium hydroxide (CsOH) is hygroscopic and strongly basic.[23] It rapidly etches the surface of semiconductors such as silicon.[28] CsOH has been previously regarded by chemists as the "strongest base", reflecting the relatively weak attraction between the large Cs+ ion and OH;[17] it is indeed the strongest Arrhenius base; however, a number of compounds such as n-butyllithium, sodium amide, sodium hydride, caesium hydride, etc., which cannot be dissolved in water as reacting violently with it but rather only used in some anhydrous polar aprotic solvents, are far more basic on the basis of the Brønsted–Lowry acid–base theory.[23]

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.[29]

Complexes

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+.[30]

Halides

Monatomic caesium halide wires grown inside double-wall carbon nanotubes (TEM image).[31]

Caesium fluoride (CsF) is a hygroscopic white solid that is widely used in organofluorine chemistry as a source of fluoride anions.[32] 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.[23] 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",[25] 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.[25] The CsCl structure is preferred because Cs+ has an ionic radius of 174 pm and Cl
181 pm.[33]

Oxides

Cs
11
O
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.[34] The "normal" caesium oxide (Cs
2
O
) forms yellow-orange hexagonal crystals,[35] and is the only oxide of the anti-CdCl
2
type.[36] It vaporizes at 250 °C (482 °F), and decomposes to caesium metal and the peroxide Cs
2
O
2
at temperatures above 400 °C (752 °F). In addition to the superoxide and the ozonide CsO
3
,[37][38] several brightly coloured suboxides have also been studied.[39] These include Cs
7
O
, Cs
4
O
, Cs
11
O
3
, Cs
3
O
(dark-green[40]), CsO, Cs
3
O
2
,[41] as well as Cs
7
O
2
.[42][43] The latter may be heated in a vacuum to generate Cs
2
O
.[36] Binary compounds with sulfur, selenium, and tellurium also exist.[11]

Isotopes

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[44] and by the R-process in supernova explosions.[45] The only stable caesium isotope is 133Cs, with 78 neutrons. Although it has a large nuclear spin (7/2+), nuclear magnetic resonance studies can use this isotope at a resonating frequency of 11.7 MHz.[46]

Decay of caesium-137

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.[47][48]

The isotope 135Cs is one of the long-lived fission products of uranium produced in nuclear reactors.[49] 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.[50][51]

The beta decay from 137Cs to 137mBa is a strong emission of gamma radiation.[52] 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.[53] Those two isotopes are the largest source of residual radioactivity in the area of the Chernobyl disaster.[54] 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.[55]

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.[56] 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.[57] 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.[11]

Occurrence

Pollucite, a caesium mineral

Caesium is a relatively rare element, estimated to average 3 parts per million in the Earth's crust.[58] 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.[11]

Due to its large ionic radius, caesium is one of the "incompatible elements".[59] 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
3
·6H
2
O
) may contain only 0.002% caesium. Consequently, caesium is found in few minerals. Percentage amounts of caesium may be found in beryl (Be
3
Al
2
(SiO
3
)
6
) and avogadrite ((K,Cs)BF
4
), up to 15 wt% Cs2O in the closely related mineral pezzottaite (Cs(Be
2
Li)Al
2
Si
6
O
18
), up to 8.4 wt% Cs2O in the rare mineral londonite ((Cs,K)Al
4
Be
4
(B,Be)
12
O
28
), and less in the more widespread rhodizite.[11] The only economically important ore for caesium is pollucite Cs(AlSi
2
O
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.[60]

The world's most significant and richest known source of caesium is the Tanco Mine at Bernic Lake in Manitoba, Canada, estimated to contain 350,000 metric tons of pollucite ore, representing more than two-thirds of the world's reserve base.[60][61] 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%.[61] Commercial pollucite contains more than 19% caesium.[62] 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.[61] At the present rate of world mine production of 5 to 10 metric tons per year, reserves will last for thousands of years.[11]

Caesium Characteristics articles: 159

Production

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.[11][63]

In the acid digestion, the silicate pollucite rock is dissolved with strong acids, such as hydrochloric (HCl), sulfuric (H
2
SO
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
4
SbCl
7
), caesium iodine chloride (Cs
2
ICl
), or caesium hexachlorocerate (Cs
2
(CeCl
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
4
)
2
·12H
2
O
). 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
2
SO
4
solution.[11]

Roasting pollucite with calcium carbonate and calcium chloride yields insoluble calcium silicates and soluble caesium chloride. Leaching with water or dilute ammonia (NH
4
OH
) 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.[11]

Most of the mined caesium (as salts) is directly converted into caesium formate (HCOOCs+) 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.[64] The primary smaller-scale commercial compounds of caesium are caesium chloride and nitrate.[65]

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.[11]

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.[63] In vacuum applications, caesium dichromate can be reacted with zirconium to produce pure caesium metal without other gaseous products.[65]

Cs
2
Cr
2
O
7
+ 2 Zr → 2 Cs + 2 ZrO
2
+ Cr
2
O
3

The price of 99.8% pure caesium (metal basis) in 2009 was about $10 per gram ($280/oz), but the compounds are significantly cheaper.[61]

Caesium Production articles: 24

History

Gustav Kirchhoff (left) and Robert Bunsen (centre) discovered caesium with their newly invented spectroscope.

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][66][67][68] Caesium was the first element to be discovered with a spectroscope, which had been invented by Bunsen and Kirchhoff only a year previously.[15]

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.[67]

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).[67] 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
2
Cl
). In reality, the product was probably a colloidal mixture of the metal and caesium chloride.[69] The electrolysis of the aqueous solution of chloride with a mercury cathode produced a caesium amalgam which readily decomposed under the aqueous conditions.[67] The pure metal was eventually isolated by the German chemist Carl Setterberg while working on his doctorate with Kekulé and Bunsen.[68] In 1882, he produced caesium metal by electrolysing caesium cyanide, avoiding the problems with the chloride.[70]

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.[71] 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.[11] 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.[72] 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".

Caesium History articles: 31