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Caesium
Caesium
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Caesium, 55Cs
Some pale gold metal, with a liquid-like texture and lustre, sealed in a glass ampoule
Caesium
Pronunciation/ˈsziəm/ (SEE-zee-əm)
Alternative namecesium (US)
Appearancepale gold
Standard atomic weight Ar°(Cs)
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: hydrogen 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 (at 20° C)1.886 g/cm3[3]
when liquid (at m.p.)1.843 g/cm3
Critical point1938 K, 9.4 MPa[4]
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 statescommon: +1
−1[5]
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
Color lines in a spectral range
Spectral lines of caesium
Other properties
Natural occurrenceprimordial
Crystal structurebody-centred cubic (bcc) (cI2)
Lattice constant
Bodycentredcubic crystal structure for caesium
a = 616.2 pm (at 20 °C)[3]
Thermal expansion92.6×10−6/K (at 20 °C)[3]
Thermal conductivity35.9 W/(m⋅K)
Electrical resistivity205 nΩ⋅m (at 20 °C)
Magnetic orderingparamagnetic[6]
Young's modulus1.7 GPa
Bulk modulus1.6 GPa
Mohs hardness0.2
Brinell hardness0.14 MPa
CAS Number7440-46-2
History
Namingfrom Latin caesius 'bluish grey', for its spectral colours
DiscoveryGustav Kirchhoff and Robert Bunsen (1860)
First isolationCarl Setterberg (1882)
Isotopes of caesium
Main isotopes[7] Decay
Isotope abun­dance half-life (t1/2) mode pro­duct
131Cs synth 9.69 d ε 131Xe
133Cs 100% stable
134Cs synth 2.0650 y β 134Ba
ε 134Xe
135Cs trace 1.33×106 y β 135Ba
137Cs synth 30.04 y β 137Ba
 Category: Caesium
| references

Caesium (IUPAC spelling;[8] also spelled cesium in American English) is a chemical element; it has symbol Cs and atomic number 55. It is a soft, silvery-golden alkali metal with a melting point of 28.5 °C (83.3 °F; 301.6 K), which makes it one of only five elemental metals that are liquid at or near room temperature. Caesium has physical and chemical properties similar to those of rubidium and potassium. It is pyrophoric and reacts with water even at −116 °C (−177 °F). It is the least electronegative stable element, with a value of 0.79 on the Pauling scale. It has only one stable isotope, caesium-133. Caesium is mined mostly from pollucite. Caesium-137, a fission product, is extracted from waste produced by nuclear reactors. It has the largest atomic radius of all elements whose radii have been measured or calculated, at about 260 picometres.

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 the light-sensitive anodes of photoelectric cells. Caesium is widely used in highly accurate atomic clocks. In 1967, the International System of Units began using a specific hyperfine transition of neutral caesium-133 atoms to define the basic unit of time, the second.

Since the 1990s, the largest application of the element has been as caesium formate for 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 it is considered a hazardous material, and the radioisotopes present a significant health and environmental hazard.

Spelling

[edit]

Caesium is the spelling recommended by the International Union of Pure and Applied Chemistry (IUPAC).[9] The American Chemical Society (ACS) has used the spelling cesium since 1921,[10][11] following Webster's New International Dictionary. The element was named after the Latin word caesius, meaning "bluish grey".[12] In medieval and early modern writings caesius was spelled with the ligature æ as cæsius; hence, an alternative but now old-fashioned orthography is cæsium. More spelling explanation at ae/oe vs e.

Characteristics

[edit]

Physical properties

[edit]
Y-shaped yellowish crystal in glass ampoule, looking like the branch of a pine tree
High-purity caesium stored in argon

Of all elements that are solid at room temperature, caesium is the softest: it has a hardness of Mohs 0.2. It is a very ductile, pale metal, which darkens in the presence of trace amounts of oxygen.[13][14][15] 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. The others are rubidium (39 °C [102 °F]), francium (estimated at 27 °C [81 °F]), mercury (−39 °C [−38 °F]), and gallium (30 °C [86 °F]); bromine is also liquid at room temperature (melting at −7.2 °C [19.0 °F]), but it is a halogen and not a metal. Mercury is the only stable elemental metal with a known melting point lower than caesium.[16] In addition, the metal has a rather low boiling point, 641 °C (1186 °F), the lowest of all stable metals other than mercury.[17] Copernicium and flerovium have been predicted to have lower boiling points than mercury and caesium, but they are extremely radioactive and it is not certain that they are metals.[18][19]

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 (1202 °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.[13] 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).[16][20] 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.[21]

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.[22] Its compounds burn with a blue[23][24] or violet[24] colour.

Allotropes

[edit]

Caesium exists in the form of different allotropes; one of them is a dimer, called dicaesium.[25]

Chemical properties

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

Caesium metal is highly reactive and pyrophoric. It ignites spontaneously in air, and reacts explosively with water even at low temperatures, more so than the other alkali metals.[13] It reacts with ice at temperatures as low as −116 °C (−177 °F).[16] 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.[26] 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.[13]

The chemistry of caesium is similar to that of other alkali metals, in particular rubidium, the element above caesium in the periodic table.[27] As expected for an alkali metal, the only common oxidation state is +1. It differs from this value in caesides, which contain the Cs
anion and thus have caesium in the −1 oxidation state.[5] Under conditions of extreme pressure (greater than 30 GPa), theoretical studies indicate that the inner 5p electrons could form chemical bonds, where caesium would behave as the seventh 5p element, suggesting that higher caesium fluorides with caesium in oxidation states from +2 to +6 could exist under such conditions.[28][29] Some slight differences arise from the fact that it has a higher atomic mass and is more electropositive than other (nonradioactive) alkali metals.[30] Caesium is the most electropositive chemical element.[16] The caesium ion is also larger and less "hard" than those of the lighter alkali metals.

Compounds

[edit]
27 small grey spheres in 3 evenly spaced layers of nine. 8 spheres form a regular cube and 8 of those cubes form a larger cube. The grey spheres represent the caesium atoms. The center of each small cube is occupied by a small green sphere representing a chlorine atom. Thus, every chlorine is in the middle of a cube formed by caesium atoms and every caesium is in the middle of a cube formed by chlorine.
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
),[5] and others are the several suboxides (see section § Oxides below). More recently, caesium is predicted to behave as a p-block element and capable of forming higher fluorides with higher oxidation states (i.e., CsF
n
with n > 1) under high pressure.[31] This prediction needs to be validated by further experiments.[32]

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,[33] acetate, carbonate, halides, oxide, nitrate, and sulfate salts are water-soluble. Its double salts are often less soluble, and the low solubility of caesium aluminium sulfate is exploited in refining Cs from ores. The double salts with antimony (such as CsSbCl
4
), bismuth, cadmium, copper, iron, and lead are also poorly soluble.[13]

Caesium hydroxide (CsOH) is hygroscopic and strongly basic.[27] It rapidly etches the surface of semiconductors such as silicon.[34] CsOH has been previously regarded by chemists as the "strongest base", reflecting the relatively weak attraction between the large Cs+
ion and OH
;[23] 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.[27]

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; it dissolves in liquid ammonia and then 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.[35]

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 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 137
Cs+
must be separated from large amounts of nonradioactive K+
.[36]

Halides

[edit]
Monatomic caesium halide wires grown inside double-wall carbon nanotubes (TEM image).[37]

Caesium fluoride (CsF) is a hygroscopic white solid that is widely used in organofluorine chemistry as a source of fluoride anions.[38] 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.[27] 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",[30] 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.[30] The CsCl structure is preferred because Cs+
has an ionic radius of 174 pm and Cl
181 pm.[39]

Oxides

[edit]
The stick and ball diagram shows three regular octahedra, which are connected to the next one by one surface and the last one shares one surface with the first. All three have one edge in common. All eleven vertices are purple spheres representing caesium, and at the center of each octahedron is a small red sphere representing oxygen.
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.[40] The "normal" caesium oxide (Cs
2
O
) forms yellow-orange hexagonal crystals,[41] and is the only oxide of the anti-CdCl
2
type.[42] 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
,[43][44] several brightly coloured suboxides have also been studied.[45] These include Cs
7
O
, Cs
4
O
, Cs
11
O
3
, Cs
3
O
(dark-green[46]), CsO, Cs
3
O
2
,[47] as well as Cs
7
O
2
.[48][49] The latter may be heated in a vacuum to generate Cs
2
O
.[42] Binary compounds with sulfur, selenium, and tellurium also exist.[13]

Isotopes

[edit]
A graph showing the energetics of caesium-137 (nuclear spin: I=⁠7/2⁠+, half-life about 30 years) decay. With a 94.6% probability, it decays by a 512 keV beta emission into barium-137m (I=11/2-, t=2.55min); this further decays by a 662 keV gamma emission with an 85.1% probability into barium-137 (I=⁠3/2⁠+). Alternatively, caesium-137 may decay directly into barium-137 by a 0.4% probability beta emission.
Decay of caesium-137

Caesium has 41 known isotopes, ranging in mass number from 112 to 152. The only stable caesium isotope is 133
Cs
, with 78 neutrons. The radioactive 135Cs has a very long half-life of about 1.33 million years, the longest of all radioactive isotopes of caesium. 137Cs and 134Cs have half-lives of 30.04 and 2.065 years, respectively. 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.[50]

The isotope 135Cs is one of the long-lived fission products of uranium produced in nuclear reactors.[51] 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.[52][53]

The beta decay from 137Cs to 137mBa results in gamma radiation as the 137mBa relaxes to ground state 137Ba, with the emitted photons having an energy of 0.6617 MeV.[54] 137
Cs
and 90Sr are the principal medium-lived products of nuclear fission, and the prime sources of radioactivity from spent nuclear fuel from several years to several hundred years after removal.[55] Those two isotopes are the largest source of residual radioactivity in the area of the Chernobyl disaster.[56] Because of the low capture rate, disposing of 137
Cs
through neutron capture is not feasible and the only current solution is to allow it to decay over time.[57]

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.[58] 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.[59] With nuclear weapons testing in the 1950s through the 1980s, 137
Cs
was released into the atmosphere and returned to the surface of the earth as a component of radioactive fallout, becoming a marker of the movement of soil and sediment from those times.[13]

Although it has a large nuclear spin (7/2+), nuclear magnetic resonance can use the stable 133
Cs
isotope.[60]

Occurrence

[edit]
A white mineral, from which white and pale pink crystals protrude
Pollucite, a caesium mineral

Caesium is a relatively rare element, estimated to average 3 parts per million in the Earth's crust.[61] It is the 45th most abundant element and 36th among the metals.[62] Caesium is 30 times less abundant than rubidium, with which it is closely associated, chemically.[13]

Due to its large ionic radius, caesium is one of the "incompatible elements".[63] 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.[13] 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.[64]

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.[64][65] 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%.[65] Commercial pollucite contains more than 19% caesium.[66] 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.[65] At the present rate of world mine production of 5 to 10 metric tons per year, reserves will last for thousands of years.[13]

Production

[edit]

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.[13][67]

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.[13]

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 to produce caesium metal directly.[13]

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.[68] The primary smaller-scale commercial compounds of caesium are caesium chloride and nitrate.[69]

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.[13]

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.[67] In vacuum applications, caesium dichromate can be reacted with zirconium to produce pure caesium metal without other gaseous products.[69]

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.[65]

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.
The German scientists 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 'bluish grey'.[note 1][70][71][72] Caesium was the first element to be discovered with a spectroscope, which had been invented by Bunsen and Kirchhoff only a year previously.[16]

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.[71]

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).[71] 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.[73] The electrolysis of the aqueous solution of chloride with a mercury cathode produced a caesium amalgam which readily decomposed under the aqueous conditions.[71] The pure metal was eventually isolated by the Swedish chemist Carl Setterberg while working on his doctorate with Kekulé and Bunsen.[72] In 1882, he produced caesium metal by electrolysing caesium cyanide, avoiding the problems with the chloride.[74]

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.[75] 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.[13] Caesium is also used as a source of positive ions in secondary ion mass spectrometry (SIMS).

Since 1967, the International System of Measurements has based the primary unit of time, the second, on the properties of caesium. The International System of Units (SI) defines the second as the duration of 9192631770 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.[76] The 13th General Conference on Weights and Measures of 1967 defined a second as: "the duration of 9192631770 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 present-day use of nonradioactive caesium is in caesium formate drilling fluids for the extractive oil industry.[13] 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.[13]

The high density of the caesium formate brine (up to 2.3 g/cm3, or 19.2 pounds per gallon),[77] 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.[77] 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).[78] 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.[13]

Atomic clocks

[edit]
A room with a black box in the foreground and six control cabinets with space for five to six racks each. Most, but not all, of the cabinets are filled with white boxes.
Atomic clock ensemble at the U.S. Naval Observatory

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.[79] 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."[76] These clocks measure frequency with an error of 2 to 3 parts in 1014, which corresponds 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.[13] The caesium standard is the primary standard for standards-compliant time and frequency measurements.[80] Caesium clocks regulate the timing of cell phone networks and the Internet.[81]

Definition of the second

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The second, symbol s, is the SI unit of time. The BIPM restated its definition at its 26th conference in 2018: "[The second] is defined by taking the fixed numerical value of the caesium frequency ΔνCs, the unperturbed ground-state hyperfine transition frequency of the caesium-133 atom, to be 9192631770 when expressed in the unit Hz, which is equal to s−1."[82]

Electric power and electronics

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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.[83]

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
2
CsSb
, have a low threshold voltage for emission of electrons.[84] The range of photoemissive devices using caesium include optical character recognition devices, photomultiplier tubes, and video camera tubes.[85][86] Nevertheless, germanium, rubidium, selenium, silicon, tellurium, and several other elements can be substituted for caesium in photosensitive materials.[13]

Caesium iodide (CsI), bromide (CsBr) and 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).

Caesium vapour is used in many common magnetometers.[87]

The element is used as an internal standard in spectrophotometry.[88] Like other alkali metals, caesium has a great affinity for oxygen and is used as a "getter" in vacuum tubes.[89] Other uses of the metal include high-energy lasers, vapour glow lamps, and vapour rectifiers.[13]

Centrifugation fluids

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The high density of the caesium ion makes solutions of caesium chloride, caesium sulfate, and caesium trifluoroacetate (Cs(O
2
CCF
3
)
) useful in molecular biology for density gradient ultracentrifugation.[90] This technology is used primarily in the isolation of viral particles, subcellular organelles and fractions, and nucleic acids from biological samples.[91]

Chemical and medical use

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Some fine white powder on a laboratory watch glass
Caesium chloride powder

Relatively few chemical applications use caesium.[92] 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.[13]

Caesium fluoride enjoys a niche use in organic chemistry as a base[27] and as an anhydrous source of fluoride ion.[93] 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.

Nuclear and isotope applications

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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.[94] It has been used in agriculture, cancer treatment, and the sterilization of food, sewage sludge, and surgical equipment.[13][95] Radioactive isotopes of caesium in radiation devices were used in the medical field to treat certain types of cancer,[96] 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.[97][98] Caesium-137 has been employed in a variety of industrial measurement gauges, including moisture, density, levelling, and thickness gauges.[99] 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.[100]

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.[101]

Other uses

[edit]
Electrons beamed from an electron gun hit and ionize neutral fuel atoms; in a chamber surrounded by magnets, the positive ions are directed toward a negative grid that accelerates them. The force of the engine is created by expelling the ions from the rear at high velocity. On exiting, the positive ions are neutralized from another electron gun, ensuring that neither the ship nor the exhaust is electrically charged and are not attracted.
Schematics of an electrostatic ion thruster developed for use with caesium or mercury fuel

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.[13] Xenon was used in the experimental spacecraft Deep Space 1 launched in 1998.[102][103] Nevertheless, field-emission electric propulsion thrusters that accelerate liquid metal ions such as caesium have been built.[104]

Caesium nitrate is used as an oxidizer and pyrotechnic colorant to burn silicon in infrared flares,[105] such as the LUU-19 flare,[106] because it emits much of its light in the near infrared spectrum.[107] Caesium compounds may have been used as fuel additives to reduce the radar signature of exhaust plumes in the Lockheed A-12 CIA reconnaissance aircraft.[108] 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.[13]

Magnetohydrodynamic (MHD) power-generating systems were researched, but failed to gain widespread acceptance.[109] Caesium metal has also been considered as the working fluid in high-temperature Rankine cycle turboelectric generators.[110]

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.[13]

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.[111]

Health and safety hazards

[edit]
Caesium
Hazards
GHS labelling:[112]
GHS02: Flammable GHS05: Corrosive
Danger
H260, H314
P223, P231+P232, P280, P305+P351+P338, P370+P378, P422
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasFlammability 4: Will rapidly or completely vaporize at normal atmospheric pressure and temperature, or is readily dispersed in air and will burn readily. Flash point below 23 °C (73 °F). E.g. propaneInstability 3: Capable of detonation or explosive decomposition but requires a strong initiating source, must be heated under confinement before initiation, reacts explosively with water, or will detonate if severely shocked. E.g. hydrogen peroxideSpecial hazard W: Reacts with water in an unusual or dangerous manner. E.g. sodium, sulfuric acid
3
4
3
Graph of percentage of the radioactive output by each nuclide that form after a nuclear fallout vs. logarithm of time after the incident. In curves of various colours, the predominant source of radiation are depicted in order: Te-132/I-132 for the first five or so days; I-131 for the next five; Ba-140/La-140 briefly; Zr-95/Nb-95 from day 10 until about day 200; and finally Cs-137. Other nuclides producing radioactivity, but not peaking as a major component are Ru, peaking at about 50 days, and Cs-134 at around 600 days.
The portion of the total radiation dose (in air) contributed by each isotope plotted against time after the Chernobyl disaster. Caesium-137 became the primary source of radiation about 200 days after the accident.[113]

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.[114][115]

The median lethal dose (LD50) for caesium chloride in mice is 2.3 g/kg, which is comparable to the LD50 values of potassium chloride and sodium chloride.[116] 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.[77]

Elemental caesium is one of the most reactive elements and is highly explosive in the presence of water. The hydrogen gas produced by the reaction is heated by the thermal energy released at the same time, causing ignition and a violent explosion. This can occur with other alkali metals, but caesium is so potent that this explosive reaction can be triggered even by cold water.[13]

It is highly pyrophoric: the autoignition temperature of caesium is −116 °C (−177 °F), 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.[17]

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.[117] Radiocaesium follows potassium and tends to accumulate in plant tissues, including fruits and vegetables.[118][119][120] 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.[121] Accumulation of caesium-137 in lakes has been a great concern after the Chernobyl disaster.[122][123] 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;[124] smaller amounts may cause infertility and cancer.[125] 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".[126]

See also

[edit]

Notes

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References

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[edit]
Revisions and contributorsEdit on WikipediaRead on Wikipedia
from Grokipedia
Caesium is a with the symbol Cs and 55. It belongs to the alkali metals, exhibiting extreme reactivity as the most electropositive element, with a soft, ductile, pale appearance and the lowest (28.5 °C) among all metals, rendering it liquid under slightly elevated temperatures. Its density is 1.873 g/cm³, and it boils at 671 °C. Caesium reacts violently with water, exploding to form and gas, and ignites spontaneously upon exposure to air due to rapid oxidation. Discovered in 1860 by and at through spectrographic analysis of Dürkheim , which revealed unique blue emission lines, caesium was the first element identified by this method. The stable caesium-133 serves as the basis for atomic clocks, where the second is defined by 9,192,631,770 oscillations of the hyperfine transition frequency in its , enabling unprecedented timekeeping precision essential for GPS, , and scientific measurements. Industrially, it finds applications in drilling fluids, scintillators, and ion propulsion, though its radioactive caesium-137, a byproduct with a 30-year , poses persistent environmental contamination risks from events like reactor accidents and weapons testing.

Properties

Physical Properties

Caesium is a soft, ductile, pale golden-yellow that exhibits the lowest among metallic elements at 28.5 °C (83.3 °F). Its is 671 °C (1240 °F), and it has a of 1.93 g/cm³ (solid) at , making it denser than other but still low compared to transition metals. In comparison, melts at 39.31 °C with a of 1.532 g/cm³, while melts at 63.28 °C with a of 0.862 g/cm³, highlighting caesium's increasing softness and liquidity trend down the group. The element adopts a body-centered cubic , with an empirical of 265 pm and a calculated atomic radius of 298 pm, larger than 's 248 pm and 's 231 pm, consistent with in atomic size. Caesium's Mohs hardness is approximately 0.2, underscoring its extreme malleability; it can be cut with a knife and deformed easily at , more so than rubidium (Mohs ~0.3) or potassium (Mohs ~0.4). Thermal conductivity of solid caesium is 35.9 /(m·) at 25 °C, and electrical conductivity is about 5 × 10⁶ S/m, both values lower than those of lighter metals due to increased from larger atomic size. is 0.24 J/(g·). follows the parameters from NIST data, rising rapidly above the ; for instance, at 300 , it is approximately 10⁻⁶ mmHg, enabling significant even near under .

Chemical Properties

Caesium, positioned as the heaviest in group 1 of the periodic table, possesses the lowest first of any element at 3.8939 eV, facilitating facile loss of its to achieve a +1 exclusively under standard conditions. This low energy barrier, combined with an of 0.79 on the Pauling scale—the minimum value recorded—renders caesium the most electropositive element, predisposing it toward highly and extreme reactivity as a potent . Its standard of -3.026 V for the Cs⁺/Cs couple underscores this, exceeding the negativity of other metals and driving spontaneous oxidation in ambient environments. The element's reactivity manifests profoundly with water, where even trace exposure yields explosive evolution and formation via 2Cs(s) + 2H₂O(l) → 2CsOH(aq) + H₂(g), with the liberated heat often igniting the hydrogen gas. This vigor stems from the large exothermic release, amplified by caesium's low in products and high of Cs⁺ ions, contrasting milder responses from lighter congeners. With atmospheric oxygen, caesium ignites spontaneously above -116 °C, forming primarily caesium superoxide (CsO₂) through 4Cs + 3O₂ → 2Cs₂O₃ or related oxides, reflecting its affinity for higher oxygen stoichiometries due to large cation size accommodating or anions. elicit similarly vigorous responses, as caesium reduces F₂, Cl₂, Br₂, or I₂ exothermically to yield colorless, highly ionic halides like CsF or CsCl, often with incandescence. In non-aqueous media, caesium dissolves in liquid to produce intensely solutions of solvated (Cs → Cs⁺ + e⁻(NH₃)_solv), enabling reducing chemistry akin to amalgams but with enhanced conductivity and reactivity toward organic substrates. These solutions persist indefinitely in inert conditions, underscoring caesium's predisposition to electron donation without covalent character, a direct consequence of its electronic configuration [Xe] 6s¹ and minimal on the valence shell. Such behavior exemplifies first-principles dominance of entropic and enthalpic factors favoring dissociation over metallic cohesion in polar solvents.

Isotopes and Allotropes

Caesium occurs naturally as a single stable , ^{133}Cs, which constitutes 100% of its elemental abundance in the , with a standard atomic mass of 132.905 u. This isotope has a nuclear spin of 7/2^+ and is the reference for defining the unit in some contexts due to its prevalence. Caesium has over 40 known isotopes, spanning mass numbers from 112 to 152, all others being radioactive with half-lives ranging from microseconds to years. Among the radioactive isotopes, ^{134}Cs and ^{137}Cs are particularly significant due to their production in nuclear reactions and relatively long half-lives. ^{134}Cs decays primarily by beta emission to stable ^{134}Ba, with a half-life of 2.065 years. ^{137}Cs, with a half-life of 30.17 years, undergoes beta-minus decay (94.6% to excited ^{137m}Ba, which emits a 662 keV gamma ray, and 5.4% directly to ground-state ^{137}Ba). These isotopes arise mainly from neutron-induced fission of heavy nuclei like ^{235}U, where the cumulative fission yield for ^{137}Cs is approximately 6.15% under thermal neutron conditions. At , metallic caesium adopts a body-centered cubic (BCC) crystal structure, characterized by a nearest-neighbor Cs-Cs of 532 pm. This is the only allotrope stable under ambient conditions. Under elevated pressures, caesium exhibits polymorphism, including a distinct phase (Cs-V) identified via and a narrow-range polymorph between 42.2 and 42.7 kbar at . Theoretical models predict additional high-pressure phases driven by s-to-d electronic transitions.

Occurrence and Production

Natural Occurrence

Caesium occurs naturally in trace amounts in the Earth's crust at an average concentration of approximately 3 parts per million (ppm), making it one of the rarer alkali metals. Its primary mineral source is pollucite, with the chemical formula Cs(Na)AlSi₂O₆·0.5H₂O, typically found in zoned lithium-rich pegmatites. Significant deposits are located at Bernic Lake in Manitoba, Canada, and the Bikita pegmatite in Zimbabwe, where pollucite forms through late-stage magmatic differentiation processes involving volatile-rich fluids. In aqueous environments, caesium maintains low concentrations, such as about 0.3 parts per billion (ppb) in seawater, reflecting its high solubility and mobility as a monovalent cation akin to potassium. Plants readily absorb caesium from soil solutions, bioaccumulating it in tissues with transfer factors influenced by soil clay content, potassium availability, and species-specific uptake mechanisms, often leading to higher concentrations in edible parts of crops like rice and vegetables. Extraterrestrially, caesium has been detected in lunar samples returned by Apollo missions, with concentrations correlating to content and exhibiting Cs/U ratios around 0.23, lower than in chondritic meteorites. In chondritic meteorites, which serve as proxies for solar system abundances, caesium abundances align with primitive material compositions, typically on the order of 0.1–0.2 ppm in CI chondrites, underscoring its geochemical consistency across cosmic reservoirs despite depletion patterns in differentiated bodies.

Commercial Production Methods

Caesium is commercially extracted primarily from ore (CsNaAlSi₂O₆·0.5H₂O), sourced mainly from the Tanco pegmatite mine in , , operated by Sinomine Resource Group since its acquisition from in 2019. The process begins with acid to solubilize caesium, yielding impure solutions of caesium salts amid silica and alumina residues. involves or leaching at 200–300°C, forming soluble caesium hydrogen sulfate, followed by cooling to precipitate caesium alum (CsAl(SO₄)₂·12H₂O) at efficiencies exceeding 90%; the alum is then redissolved and treated to isolate caesium sulfate (Cs₂SO₄) via fractional crystallization or solvent extraction. , alternatively, employs concentrated HCl at boiling temperatures (around 100–150°C) to produce caesium chloride solutions, with yields up to 93% after impurity removal via double salt formation (e.g., caesium tetraphenylborate ). processes achieve comparable high recoveries (>95%) by complexing aluminum silicates but are limited commercially due to HF's corrosivity and handling hazards. Purified caesium salts, typically CsCl or Cs₂SO₄, are converted to metal via thermal reduction rather than , as the latter risks vaporization losses given caesium's low (671°C) versus CsCl's (645°C). The standard method heats anhydrous CsCl with excess calcium metal under vacuum at 750–850°C: 2CsCl + Ca → 2Cs + CaCl₂, distilling the caesium vapor for into ingots; this yields high-purity metal (>99.5%) with minimal energy input beyond heating, though exact consumption figures are proprietary. Global caesium metal production remains low at 9–20 tonnes annually, constrained by availability and fluctuating demand, particularly for caesium fluids that surged post-2020 amid oil sector recovery from lows. Sinomine dominates supply, processing Tanco's high-grade (up to 30% Cs₂O equivalent), while minor outputs come from Chinese operations; no significant electrolytic commercial routes are reported due to technical inefficiencies.

History

Discovery and Early Research

![Color lines in a spectral range](./assets/55_CsICs_I Caesium was discovered on 10 May 1860 by German chemists and through applied to mineral water residues from Dürkheim, . Employing their prism spectroscope, they identified two prominent blue lines in the , characteristic of a new ; these lines correspond to wavelengths of 852.1 nm and 894.3 nm in the near-infrared, though perceived as blue in early qualitative observations due to the overall spectral signature. The element was named caesium from the Latin caesius ("sky-blue"), reflecting these distinctive lines, and its salts were isolated as and sulfate for further verification. The isolation of elemental caesium occurred in 1882, when Carl Setterberg, a graduate student under Bunsen at , performed electrolysis on molten caesium cyanide (CsCN) using platinum electrodes. This process yielded beads of the soft, ductile metal, confirming its nature through observed properties such as high reactivity, low (approximately 1.9 g/cm³), and near 28°C. Early handling revealed caesium's extreme sensitivity to moisture and oxygen, igniting spontaneously in air, which aligned it below in the periodic table as the heaviest stable . Subsequent research in the late 19th and early 20th centuries characterized caesium's chemical behavior, including its formation of soluble salts and strong basicity, surpassing other metals in electropositivity. By the 1940s, amid studies during the , radioactive caesium isotopes like (discovered in 1941) were recognized as key fission products, with yields around 6% per fission event, linking the element to atomic processes though stable caesium dominated initial non-nuclear investigations.

Development of Key Applications

The first practical applications of caesium emerged in the , primarily in photoelectric cells and as a getter in radio vacuum tubes, leveraging its low of approximately 1.95 eV to facilitate emission and remove residual gases for improved vacuum performance. These uses capitalized on caesium's high reactivity and ease of , enabling early advancements in light-sensitive devices and electron tubes before broader industrial scalability. In the 1950s, significant progress occurred with the development of caesium-based atomic clocks at the U.S. National Bureau of Standards (now NIST), where Harold Lyons and Jesse Sherwood constructed the first caesium clock utilizing the hyperfine transition of caesium-133 atoms, measuring its frequency at around 9,192,631,770 Hz by 1952. This beam-frequency standard marked a pivotal shift from oscillators to atomic timekeeping, with the UK's National Physical Laboratory achieving a practical caesium-beam clock in 1955, paving the way for the redefinition of the second based on this transition. The saw caesium's role expand into thermionic energy converters, where its vapor served as a plasma bridge to neutralize , enhancing efficiency in high-temperature devices powered by nuclear sources, as explored in U.S. and Soviet programs for space applications. By the late , caesium brines were developed as high-density fluids for high-pressure, high-temperature and gas wells, offering superior and formation stability compared to traditional brines, with initial commercialization by Shell in the early . Post-2000 refinements in technology introduced techniques, which excite more caesium atoms for improved stability and holdover, as demonstrated in Adtran's Oscilloquartz OSA 3200 SP and OSA 3250 ePRC models released in June 2025, reducing costs and enabling wider adoption in and defense . These advancements build on the hyperfine standard while addressing limitations in traditional magnetic-state selection methods.

Applications

Atomic Clocks and Timekeeping

The (SI) defines the second as the duration of 9,192,631,770 periods of the radiation corresponding to the transition between the two hyperfine levels of the of the caesium-133 atom, unperturbed by external fields, at rest relative to the laboratory, and at a temperature of 0 K. This definition, adopted by the 13th General Conference on Weights and Measures in 1967, replaced earlier ephemeris-based standards and established caesium atomic clocks as the primary realization of the SI second. Caesium was selected due to its suitable hyperfine splitting frequency in the range, around 9.192 GHz, which allows precise measurement using established microwave technology. Caesium atomic clocks operate by interrogating ensembles of caesium-133 atoms with tuned to the hyperfine transition . In traditional beam clocks, a thermal beam of caesium atoms passes through a and interacts with a resonant , where state selection and Ramsey separate and detect atoms in the desired hyperfine state. Modern caesium clocks enhance precision by cooling atoms to microkelvin temperatures via , launching them vertically in a within a , which extends time and reduces . Key components include caesium vapour sources or dispensers, lasers for state preparation, synthesizers for , and detectors for readout; active oscillators may stabilize the local oscillator . Fractional frequency stability in caesium fountain clocks reaches levels of 10^{-16} or better after averaging over hours, with systematic uncertainties as low as 2 × 10^{-16}, equivalent to a time error of less than 1 second over 150 million years. Major sources include the second-order Doppler shift from atomic motion, gravitational redshifts, collisions in dense atom clouds, and the (BBR) Stark shift, where thermal photons induce electric field perturbations on the atomic levels; BBR effects are mitigated through precise and shielding, but remain a limiting factor at the 10^{-16} level. While caesium fountain clocks maintain the current SI second standard, optical lattice clocks using transitions in ions or neutral atoms like or achieve stabilities and accuracies up to 100 times superior, with uncertainties below 10^{-18}. These optical systems probe higher-frequency visible or transitions, enabling longer coherence times and reduced sensitivities to certain perturbations, though they face challenges in across labs. Recent efforts integrate optical referencing with caesium clocks to leverage short-term optical stability for improved synthesis, as demonstrated in 2025 commercial upgrades enhancing short-term Allan deviation for precision timing networks. Ongoing international comparisons evaluate optical clocks for potential redefinition of the second, but caesium remains the benchmark due to its established global network and metrological maturity.

Oil and Gas Exploration

Caesium brines are employed in oil and gas operations primarily for , completing, and workover activities in high-pressure, high-temperature (HPHT) wells, where they provide hydrostatic control to manage formation pressures without compromising productivity. These solids-free fluids, derived from caesium (CsHCO₂), enable precise density adjustments essential for narrow-margin environments, as demonstrated in field trials where they maintained well stability during HPHT operations. The brines offer a density range extending to 2.3 g/cm³ through blending with lower-density s like and sodium variants, allowing tailored formulations for specific well conditions; for instance, densities around 2.19 g/cm³ have been used effectively in over 20 HPHT workovers for . Unlike traditional oil-based muds or brines, caesium formate systems exhibit low equivalent circulating (ECD) and minimal formation damage, preserving permeability in sections during drill-in and completion phases, with and field data confirming reduced dispersion and screen plugging compared to alternatives. By gross weight, the predominant use of caesium is in these brines for HPHT applications in and production, accounting for the majority of global consumption due to their stability under extreme conditions (up to 29 ultra-HPHT wells documented in deployments). Post-2020, demand has aligned with broader oil and gas recovery trends, including plays, driven by the fluids' recyclability—up to 85% retrieval rates—and return on investment in deepwater and complex wells, where performance gains offset high costs relative to brines. Environmentally, caesium brines are biodegradable, non-hazardous, and exhibit low aquatic toxicity, serving as a preferable substitute for zinc-based systems that pose greater risks to personnel and ecosystems.

Electronics and Power Sources

Caesium's low of approximately 1.95 eV enables its use in photoelectric cells, where it facilitates emission with relatively low-energy photons, extending sensitivity into the near- up to wavelengths around 637 nm. These devices, historically employed in detection applications such as spectrometers, leverage caesium coatings on cathodes to achieve high quantum efficiency for red and . In thermionic energy converters, caesium vapor serves as a to lower the effective of the collector electrode and neutralize effects, improving across the interelectrode gap. Soviet TOPAZ-I and TOPAZ-II space nuclear reactors incorporated multicell thermionic converters operating with caesium, achieving overall system efficiencies of about 6-10% at emitter temperatures around 1700-1900 K and optimized caesium pressures of 0.4-1 . Caesium contact ionization thrusters generate ions by thermal vaporization and surface ionization on hot porous emitters, producing high specific impulses exceeding 2000 seconds due to the low of caesium atoms (3.89 eV). Early prototypes, such as those tested in the , demonstrated impulses up to 8050 seconds at power levels of 0.6 kW, though challenges with caesium handling and erosion limited operational lifetimes. For magnetohydrodynamic (MHD) generators, seeding combustion gases with caesium vapor enhances plasma electrical conductivity by providing easily ionizable electrons, with conductivities reaching 20 S/m at temperatures around 2350 K in air-methane mixtures. This seeding, preferred over due to caesium's lower potential, more than doubles conductivity compared to other alkalis, enabling efficient direct conversion of to in high-temperature flows.

Nuclear and Radiochemical Uses

Caesium-137, a radioactive isotope with a half-life of 30.17 years, undergoes beta decay primarily to metastable barium-137m, which subsequently emits a 662 keV gamma ray with an intensity of approximately 85%. This gamma emission makes ¹³⁷Cs a valuable source for radiochemical applications, including calibration of radiation detection instruments such as Geiger-Mueller counters. In larger quantities, sealed ¹³⁷Cs sources are employed for gamma irradiation in sterilization processes, such as treating medical supplies and food commodities to eliminate pathogens and insects without heat. As a fission product from uranium-235 thermal fission, ¹³⁷Cs exhibits a cumulative yield of about 6% per fission event, contributing significantly to the inventory in spent fuel. This yield informs calculations and management strategies, where ¹³⁷Cs accumulation helps estimate fuel exposure and predict over decades. In radiochemical tracing, ¹³⁷Cs from atmospheric nuclear testing fallout serves as an environmental marker for hydrological processes, particularly and redistribution. Its strong adsorption to fine particles and peak deposition around 1963 enables quantification of net soil loss rates by comparing depths at reference and eroded sites, with erosion rates derived from models incorporating and particle-bound coefficients. Post-nuclear test monitoring programs have utilized ¹³⁷Cs gamma signatures to track long-term atmospheric dispersion and ground deposition patterns.

Emerging Technologies

Researchers at the University of Wisconsin-Madison have advanced neutral-atom by developing stable two-dimensional arrays of caesium atom qubits trapped in , achieving coherence times exceeding 1 second as demonstrated in 2025 experiments. These hyperfine ground-state qubits leverage caesium's favorable atomic properties for individual optical addressing and nondestructive readout, with reported coherence durations up to 12.6 seconds in optical tweezer arrays, enabling progress toward fault-tolerant quantum processors. Such developments position optically trapped caesium atoms as a scalable alternative to superconducting qubits, with prototypes demonstrating over 6,000 ultracold caesium atoms in arrays for quantum simulation and computation tasks. In , caesium-doped nanostructures are emerging as catalysts for environmental applications, including pollutant degradation in . A 2024 study on caesium-doped hexagonal (MoO₃) nanostructures revealed enhanced photocatalytic performance under visible light, attributed to improved charge separation and surface reactivity, outperforming undoped variants in degrading organic dyes. nanoparticles are also under investigation for roles in and chemical , exploiting their high surface area and ionic conductivity, though scalability and stability remain challenges in peer-reviewed prototypes. Caesium formate brines have seen enhanced application in high-pressure, high-temperature (HPHT) fluids for extraction, providing superior thermal stability and compared to traditional brines. Post-2020 evaluations highlight their rheological advantages in maintaining wellbore stability under extreme conditions, as evidenced in challenges where densities up to 2.2 sg enable solids-free formulations for deeper reservoirs. These innovations support goals by reducing fluid loss and formation damage in HPHT environments.

Health Effects and Safety

Toxicity of Stable Caesium

Stable caesium compounds exhibit low in animal models, with oral LD50 values ranging from 800 to 2,000 mg Cs/kg body weight in rats and mice for and similar salts. This places caesium in the category of mildly toxic substances, far less potent than many common industrial chemicals. Due to its chemical similarity to , the caesium (Cs⁺) can substitute for K⁺ in biological systems, entering cells through potassium channels and disrupting membrane potentials, particularly in excitable tissues like . In humans, high-dose exposure to stable caesium, primarily from ingestion in unregulated alternative therapies, has been associated with severe cardiac effects including prolongation, , and ventricular tachyarrhythmias. Case reports document these arrhythmias resolving upon cessation of exposure and supportive treatment, such as correction, underscoring reversibility in non-fatal instances. Industrial exposures are rare and typically involve caesium salts in or settings, with limited documented cases beyond therapeutic misuse; primary risks manifest as cardiac instability rather than multi-organ failure. Stable caesium compounds are not classified as carcinogenic by the International Agency for Research on Cancer (IARC), lacking sufficient evidence for or tumor promotion in available studies. Occupational exposure guidelines reflect this low , with the American Conference of Governmental Industrial Hygienists (ACGIH) setting a (TLV) of 2 mg/m³ as an 8-hour time-weighted average for dust, primarily to prevent irritation rather than acute poisoning. Metabolic studies indicate rapid gastrointestinal absorption (up to 90%) and urinary excretion, mimicking kinetics without long-term in healthy individuals.

Hazards of Radioactive Isotopes

Radioactive isotopes of caesium, particularly (half-life 2.06 years) and (half-life 30.2 years), emit beta particles and s that pose acute and chronic health risks through . decays primarily by beta emission to stable barium-134, while undergoes (maximum energy 0.514 MeV) to metastable , which promptly emits a penetrating 662 keV . These emissions ionize biological tissues, causing DNA double-strand breaks and cellular damage via direct and indirect (free radical) mechanisms. External exposure to high levels of ^{137}Cs gamma can induce skin burns, , ulceration, , and death at doses exceeding 4-6 Gy, as gamma photons penetrate deeply and deposit energy uniformly. Beta particles from both isotopes contribute to superficial skin damage but are less hazardous externally unless is direct and prolonged. Internal exposure, via or of contaminated particles, results in systemic distribution mimicking , leading to prolonged whole-body , particularly in muscle tissue. The internal committed effective dose coefficient for adult ingestion of ^{137}Cs is 1.4 \times 10^{-8} Sv/Bq, reflecting efficient gastrointestinal absorption (approximately 90%) and of about 70 days in adults. Bioaccumulation amplifies risks, as radiocaesium exhibits high in , uptake by , and transfer to animal products; transfer coefficients to cow (F_m \approx 10^{-2} to 10^{-1} d kg L^{-1}) result in concentration factors exceeding 1000 relative to soil activity in low-potassium environments, facilitating magnification. Long-term stochastic effects include elevated cancer incidence, with from caesium isotopes causally linked to via epidemiological data from fallout-exposed cohorts showing dose-dependent increases (excess \approx 2-5 per Sv for ). The BEIR VII model extrapolates linear no-threshold risks, estimating lifetime cancer incidence of approximately 0.01 per Sv, applicable to gamma and beta exposures from these isotopes despite some institutional reports minimizing low-dose effects; from high-dose analogs prioritizes causal DNA over threshold assumptions.

Recent Contamination Incidents

In August 2025, Indonesian authorities detected elevated levels of (Cs-137) at multiple sites, including 22 facilities within the Cikande industrial estate in province near and a clove plantation in province. levels in affected areas reached thousands of times above normal , traced to a leak from industrial equipment containing Cs-137 sources, likely used for or processing at a steel-related facility such as Peter Metal. Nine workers exposed during site operations received medical treatment for effects and remained stable, out of 1,600 screened individuals. The incident prompted international scrutiny when the U.S. (FDA) identified Cs-137 traces in frozen imported from Indonesia's PT Bahari Makmur Sejati, detected in early August 2025 sampling. This , potentially from environmental exposure near affected industrial or agricultural sites, led to recalls of implicated products, including Walmart's Great Value brand frozen raw under lot codes 8005540-1, 8005538-1, and 8005539-1, with best-by dates of March 15, 2027. FDA assessments indicated that while acute risks were low, chronic low-dose exposure to Cs-137 could elevate cancer risks through DNA damage from beta and gamma emissions. Similar traces appeared in exported spices like cloves from , prompting FDA import alerts and certification requirements for and spices from and regions effective October 31, 2025. Post-Fukushima global monitoring by the (IAEA) has tracked persistent Cs-137 hotspots in Japanese soils, with airborne surveys and soil profiling confirming ongoing redistribution via natural processes like animal rooting, though no new widespread release incidents were reported beyond localized industrial cases like Indonesia's. IAEA-verified data on Fukushima's ALPS-treated water discharges through 2025 showed Cs-137 concentrations well below safety limits, underscoring that recent contaminations stem primarily from mishandled legacy sources rather than reactor emissions.

Environmental Impact

Release Mechanisms

Caesium enters the environment predominantly through , where isotopes like form as volatile fission products with a cumulative yield of approximately 6.2% in fission of , contributing to roughly 10% of the total fission product inventory in the by atomic number. These releases occur via atmospheric pathways during events such as or reactor accidents, with caesium aerosols depositing globally through wet and dry fallout mechanisms. Atmospheric transport models of fallout events, such as Chernobyl, estimate an effective removal half-life for aerosols of 6 to 9 days, driven by precipitation scavenging and gravitational settling rather than . Once deposited, stable and radioactive caesium disperses further through soil-water interactions; the Cs⁺ ion's high solubility leads to leaching, particularly in soils with low clay content, where the (Kd) ranges from <5 to low tens of mL/g, indicating weak sorption and facilitating downward migration via rainwater percolation. Kd variability arises from soil mineralogy—higher values (>1000 mL/g) occur in micaceous clays via fixation, but mobile fractions dominate initial transport in sandy or organic-rich soils. Minor industrial contributions arise from processing caesium ores like , where tailings retain residual caesium that can mobilize through or acid leaching if containment fails, though such releases are negligible compared to nuclear sources due to limited global production (historically <30 tonnes annually). In the , beyond fission, caesium volatilizes during fuel reprocessing or cladding failures, entering liquid effluents or stacks, with transport modeling emphasizing its partitioning into aqueous phases over solids.

Mitigation and Regulation

Prussian blue, an iron compound, is administered orally to bind caesium isotopes in the , preventing absorption and promoting fecal excretion, thereby reducing by approximately 43% and overall body burden in contaminated individuals. This decorporation therapy has demonstrated efficacy in post-accident scenarios, such as Chernobyl exposures, where it accelerated elimination without significant adverse effects. For remediation, mixes contaminated topsoil with deeper layers, diluting surface concentrations; in Fukushima, removing 5 cm of topsoil achieved up to 80% reduction in levels, though generating substantial waste volumes exceeding 20 million cubic meters by 2019. employs hyperaccumulating plants like Amaranthus species to uptake , with field trials yielding extraction efficiencies of 1-5% per crop cycle in moderately contaminated soils (10-100 Bq/g), limited by root adsorption and requiring multiple harvests over years for meaningful . These methods' empirical success varies with clay content and rainfall, often falling short in high-adsorption clays where caesium binds to minerals, necessitating integrated approaches. International standards guide remediation thresholds; the IAEA Basic Safety Standards set clearance levels for at 0.1 Bq/g in bulk materials for unrestricted release, assuming conservative exposure models. U.S. EPA derives site-specific action levels under CERCLA, typically targeting annual public doses below 25 mrem for in , prioritizing binding to silicates that limit leaching. High-level caesium-bearing wastes are immobilized via into , exhibiting normalized leach rates for below 10^{-6} g/cm²/day under static testing, with long-term repository performance confirmed over 16 years at averages of 2.2 × 10^{-7} g/cm²/day. Enforcement gaps persist in developing nations, as evidenced by Indonesia's 2025 caesium-137 crisis, where contaminated industrial scrap from imported sources led to widespread and pollution across 22 sites near , triggering U.S. FDA import alerts and recalls despite initial regulatory oversights. Delayed allowed migration into food chains, highlighting under-enforcement of IAEA-derived protocols in resource-limited settings, where monitoring lags behind developed nations' real-time spectrometry requirements. Data from such incidents underscore that policy efficacy hinges on proactive waste tracking, with failures amplifying transboundary risks absent stringent border controls.

References

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