Caesium

Caesium (IUPAC spelling;[9] cesium in

Caesium, 55Cs
American English)[note 1] 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.[note 2]
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 Caesium
element, with a value of 0.79 on the Pauling Pronunciation /ˈsiːziəm/ ​(SEE -zee-əm)
scale. It has only one stable isotope, caesium- Alternative name cesium (US)
133. Caesium is mined mostly from pollucite.
Appearance pale gold
Caesium-137, a fission product, is extracted
from waste produced by nuclear reactors. It has Standard atomic weight Ar°(Cs)
the largest atomic radius of all elements whose 132.905 451 96 ± 0.000 000 06[1]
radii have been measured or calculated, at about
132.91 ± 0.01 (abridged)[2]
260 picometers.
Caesium in the periodic table
The German chemist Robert Bunsen and
Rb
physicist Gustav Kirchhoff discovered caesium ↑
Cs
in 1860 by the newly developed method of ↓
Fr
flame spectroscopy. The first small-scale
xenon ← caesium → barium
applications for caesium were as a "getter" in
vacuum tubes and in photoelectric cells. Atomic number (Z) 55
Caesium is widely used in highly accurate Group group 1: hydrogen and alkali
atomic clocks. In 1967, the International System metals
of Units began using a specific hyperfine
Period period 6
transition of neutral caesium-133 atoms to define
the basic unit of time, the second. Block s-block
Electron [Xe] 6s1
Since the 1990s, the largest application of the configuration
element has been as caesium formate for drilling Electrons per 2, 8, 18, 18, 8, 1
fluids, but it has a range of applications in the shell
production of electricity, in electronics, and in
Physical properties
chemistry. The radioactive isotope caesium-137
has a half-life of about 30 years and is used in Phase at STP solid
medical applications, industrial gauges, and Melting point 301.7 K ​(28.5 °C, ​83.3 °F)
hydrology. Nonradioactive caesium compounds Boiling point 944 K ​(671 °C, ​1240 °F)
are only mildly toxic, but the pure metal's
Density (at 20° C) 1.886 g/cm3 [3]
tendency to react explosively with water means when liquid 1.843 g/cm3
that caesium is considered a hazardous material, (at m.p.)
and the radioisotopes present a significant health Critical point 1938 K, 9.4 MPa[4]
and environmental hazard.
Heat of fusion 2.09 kJ/mol
Heat of 63.9 kJ/mol
Characteristics vaporization
Molar heat 32.210 J/(mol·K)
Physical properties capacity
Vapour pressure
P (Pa) 1 10 100 1k 10 k 100 k

at T (K) 418 469 534 623 750 940

Atomic properties
Oxidation states −1, +1[5] (a strongly basic oxide)
Electronegativity Pauling scale: 0.79
Ionization 1st: 375.7 kJ/mol
High-purity caesium-133 stored in
argon. energies 2nd: 2234.3 kJ/mol
3rd: 3400 kJ/mol
Of all elements that are solid at room
Atomic radius empirical: 265 pm
temperature, caesium is the softest: it has a
hardness of 0.2 Mohs. It is a very ductile, pale Covalent radius 244±11 pm
metal, which darkens in the presence of trace Van der Waals 343 pm
amounts of oxygen.[14][15][16] When in the radius
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 Spectral lines of caesium
melting point of 28.5 °C (83.3 °F), making it Other properties
one of the few elemental metals that are liquid
Natural primordial
near room temperature. Mercury is the only
occurrence
stable elemental metal with a known melting
Crystal structure ​body-centred cubic (bcc) (cI2)
point lower than caesium.[note 3][18] In addition,
the metal has a rather low boiling point, 641 °C Lattice constant a = 616.2 pm
(1,186 °F), the lowest of all metals other than (at 20 °C)[3]
mercury.[19] Its compounds burn with a
blue[20][21] or violet[21] colour. Thermal 92.6 × 10−6/K (at 20 °C)[3]
expansion
Caesium forms alloys with the other alkali Thermal 35.9 W/(m⋅K)
metals, gold, and mercury (amalgams). At conductivity
temperatures below 650 °C (1,202 °F), it does
Electrical 205 nΩ⋅m (at 20 °C)
not alloy with cobalt, iron, molybdenum, nickel,
resistivity
platinum, tantalum, or tungsten. It forms well-
defined intermetallic compounds with antimony, Magnetic ordering paramagnetic[6]
gallium, indium, and thorium, which are Young's modulus 1.7 GPa
photosensitive.[14] It mixes with all the other Bulk modulus 1.6 GPa
 alkali Mohs hardness 0.2
metals Brinell hardness 0.14 MPa
(except
CAS Number 7440-46-2
lithium);
the alloy History
with a Naming from Latin caesius 'bluish grey',
molar for its spectral colours

Caesium crystals (golden) compared

Discovery Robert Bunsen and Gustav
to rubidium crystals (silvery) Kirchhoff (1860)
First isolation Carl Setterberg (1882)
distribution of 41% caesium, 47% potassium, Isotopes of caesium
and 12% sodium has the lowest melting point of
any known metal alloy, at −78 °C Main isotopes[7] Decay

(−108 °F).[18][22] A few amalgams have been abun­dance half-life (t1/2) mode pro­duct
studied: CsHg2 is black with a purple metallic 131
Cs synth 9.7 d ε 131
Xe
lustre, while CsHg is golden-coloured, also with
133
a metallic lustre.[23] Cs 100% stable

134 134
Cs synth 2.0648 y ε Xe
The golden colour of caesium comes from the
decreasing frequency of light required to excite β− 134
Ba
electrons of the alkali metals as the group is
descended. For lithium through rubidium this
135
Cs trace 1.33 × 106 y β− 135
Ba

frequency is in the ultraviolet, but for caesium it 137

Cs synth 30.17 y[8] β− 137
Ba
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.[24]

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

Chemical properties
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.[14] It reacts with
ice at temperatures as low as −116 °C (−177 °F).[18] 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
Addition of a small amount of sodium-water explosion with a similar amount of sodium. This is
caesium to cold water is explosive. 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.[14]

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.[note 4] 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.[note 5][18] The caesium ion is also larger and less "hard" than those of the lighter alkali metals.

Compounds
+
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 ),[28] and others are the several suboxides (see section on
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., CsFn with n > 1) under high pressure.[32] This prediction needs
to be validated by further experiments.[33]

Ball-and-stick model of the Salts of Cs+ are usually colourless unless the anion itself is coloured. Many
cubic coordination of Cs and of the simple salts are hygroscopic, but less so than the corresponding salts
Cl in CsCl of lighter alkali metals. The phosphate,[34] 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 CsSbCl4 ), bismuth, cadmium,
copper, iron, and lead are also poorly soluble.[14]

Caesium hydroxide (CsOH) is hygroscopic and strongly basic.[27] It rapidly etches the surface of
semiconductors such as silicon.[35] CsOH has been previously regarded by chemists as the "strongest
base", reflecting the relatively weak attraction between the large Cs+ ion and OH−;[20] 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; 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.[36]

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 137 Cs+ must be separated from large amounts of nonradioactive
K+.[37]

Halides
Caesium fluoride (CsF) is a hygroscopic white solid that is widely used in
organofluorine chemistry as a source of fluoride anions.[39] 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.[40]

Oxides Monatomic caesium halide

wires grown inside double-
More so than the other alkali metals, caesium
wall carbon nanotubes (TEM
forms numerous binary compounds with
image).[38]
oxygen. When caesium burns in air, the
superoxide CsO2 is the main product.[41] The
"normal" caesium oxide (Cs2 O) forms yellow-orange hexagonal crystals,[42]
and is the only oxide of the anti-CdCl2 type.[43] It vaporizes at 250 °C
(482 °F), and decomposes to caesium metal and the peroxide Cs2 O2 at
Cs11O3 cluster
temperatures above 400 °C (752 °F). In addition to the superoxide and the
ozonide CsO3 ,[44][45] several brightly coloured suboxides have also been
studied.[46] These include Cs7 O, Cs4 O, Cs11 O3 , Cs3 O (dark-green[47]), CsO,
Cs3 O2 ,[48] as well as Cs7 O2 .[49][50] The latter may be heated in a vacuum to generate Cs2 O.[43] Binary
compounds with sulfur, selenium, and tellurium also exist.[14]

Isotopes
Caesium has 41 known isotopes, ranging in mass number (i.e. number of nucleons in the nucleus) from 112
to 152. Several of these are synthesized from lighter elements by the slow neutron capture process (S-
process) inside old stars[51] and by the R-process in supernova explosions.[52] The only stable caesium
7
isotope is 133 Cs, with 78 neutrons. Although it has a large nuclear spin ( 2 +), nuclear magnetic resonance
studies can use this isotope at a resonating frequency of 11.7 MHz.[53]
The radioactive 135 Cs has a very long half-life of about 2.3 million
years, the longest of all radioactive isotopes of caesium. 137 Cs and
134 Cs have half-lives of 30 and two years, respectively. 137 Cs

decomposes to a short-lived 137mBa by beta decay, and then to

nonradioactive barium, while 134 Cs transforms into 134 Ba 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 Decay of caesium-137
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.[54][55]

The isotope 135 Cs is one of the long-lived fission products of uranium produced in nuclear reactors.[56]
However, this fission product yield is reduced in most reactors because the predecessor, 135 Xe, is a potent
neutron poison and frequently transmutes to stable 136 Xe before it can decay to 135 Cs.[57][58]

The beta decay from 137 Cs to 137mBa results in gamma radiation as the 137mBa relaxes to ground state
137 Ba, with the emitted photons having an energy of 0.6617 MeV.[59] 137 Cs and 90 Sr 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.[60] Those two isotopes are the largest source of
residual radioactivity in the area of the Chernobyl disaster.[61] 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.[62]

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.[63] 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.[64] 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. It is a
ready marker of the movement of soil and sediment from those times.[14]

Occurrence
Caesium is a relatively rare element, estimated to average 3 parts
per million in the Earth's crust.[65] It is the 45th most abundant
element and 36th among the metals.[66] Caesium is 30 times less
abundant than rubidium, with which it is closely associated,
chemically.[14]

Due to its large ionic radius, caesium is one of the "incompatible

elements".[67] During magma crystallization, caesium is Pollucite, a caesium mineral
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 (KMgCl3 ·6H2 O) may contain only 0.002% caesium.
Consequently, caesium is found in few minerals. Percentage amounts of caesium may be found in beryl
(Be3 Al2 (SiO3 )6 ) and avogadrite ((K,Cs)BF4 ), up to 15 wt% Cs2 O in the closely related mineral pezzottaite
(Cs(Be2 Li)Al2 Si6 O18 ), up to 8.4 wt% Cs2 O in the rare mineral londonite ((Cs,K)Al4 Be4 (B,Be)12 O28 ),
and less in the more widespread rhodizite.[14] The only economically important ore for caesium is pollucite
Cs(AlSi2 O6 ), 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.[68]

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.[68][69] 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%.[69] Commercial pollucite contains more than 19% caesium.[70] 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.[69] At the present rate of world mine production of 5
to 10 metric tons per year, reserves will last for thousands of years.[14]

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.[14][71]

In the acid digestion, the silicate pollucite rock is dissolved with strong acids, such as hydrochloric (HCl),
sulfuric (H2 SO4 ), 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 (Cs4 SbCl7 ), caesium iodine chloride (Cs2 ICl), or caesium hexachlorocerate
(Cs2 (CeCl6 )). 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(SO4 )2 ·12H2 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 Cs2 SO4 solution.[14]

Roasting pollucite with calcium carbonate and calcium chloride yields insoluble calcium silicates and
soluble caesium chloride. Leaching with water or dilute ammonia (NH4 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.[14]

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.[72] The primary smaller-scale commercial compounds of caesium are
caesium chloride and nitrate.[73]
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.[14]

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 CsN3 ,
which can be produced from aqueous caesium sulfate and barium azide.[71] In vacuum applications,
caesium dichromate can be reacted with zirconium to produce pure caesium metal without other gaseous
products.[73]

Cs2Cr2O7 + 2 Zr → 2 Cs + 2 ZrO2+ Cr2O3

The price of 99.8% pure caesium (metal basis) in 2009 was about $10 per gram ($280/oz), but the
compounds are significantly cheaper.[69]

History
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 6][74][75][76] Caesium was the first element to be
discovered with a spectroscope, which had been invented by
Bunsen and Kirchhoff only a year previously.[18]

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 Gustav Kirchhoff (left) and Robert
Bunsen (centre) discovered caesium
chloroplatinic acid, but these salts show a slight difference in
with their newly invented
solubility in hot water, and the less-soluble caesium and rubidium
spectroscope.
hexachloroplatinate ((Cs,Rb)2 PtCl6 ) 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.[75]

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).[75] 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 (Cs2 Cl). In reality, the product was probably a
colloidal mixture of the metal and caesium chloride.[77] The electrolysis of the aqueous solution of chloride
with a mercury cathode produced a caesium amalgam which readily decomposed under the aqueous
conditions.[75] The pure metal was eventually isolated by the Swedish chemist Carl Setterberg while
working on his doctorate with Kekulé and Bunsen.[76] In 1882, he produced caesium metal by
electrolysing caesium cyanide, avoiding the problems with the chloride.[78]

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.[79] 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.[14] Caesium is also used as a source of positive ions in secondary
ion mass spectrometry (SIMS).

Since 1967, the International System of Measurements has based the primary unit of time, the second, on
the properties of caesium. The International System of Units (SI) defines the second as the duration of
9,192,631,770 cycles at the microwave frequency of the spectral line corresponding to the transition
between two hyperfine energy levels of the ground state of caesium-133.[80] The 13th General Conference
on Weights and Measures of 1967 defined a second as: "the duration of 9,192,631,770 cycles of microwave
light absorbed or emitted by the hyperfine transition of caesium-133 atoms in their ground state undisturbed
by external fields".

Applications

Petroleum exploration
The largest present-day use of nonradioactive caesium is in caesium formate drilling fluids for the extractive
oil industry.[14] 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.[14]

The high density of the caesium formate brine (up to 2.3 g/cm3 , or 19.2 pounds per gallon),[81] 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.[81] 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).[82]
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 ZnBr2 solutions) sometimes do; they also
require less cleanup and reduce disposal costs.[14]

Atomic clocks
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.[83] 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."[80] These clocks measure frequency with an error of 2 to
3 parts in 1014 , which corresponds to an accuracy of 2 nanoseconds Atomic clock ensemble at the U.S.
Naval Observatory
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.[14] The caesium standard is the primary standard for standards-compliant time and frequency
measurements.[84] Caesium clocks regulate the timing of cell phone networks and the Internet.[85]

Definition of the second

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 9 192 631 770
when expressed in the unit Hz, which is equal to s−1 ."[86]

Electric power and electronics

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.[87]

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 K2 CsSb, have a
low threshold voltage for emission of electrons.[88] The range of photoemissive devices using caesium
include optical character recognition devices, photomultiplier tubes, and video camera tubes.[89][90]
Nevertheless, germanium, rubidium, selenium, silicon, tellurium, and several other elements can be
substituted for caesium in photosensitive materials.[14]

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.[91]

The element is used as an internal standard in spectrophotometry.[92] Like other alkali metals, caesium has a
great affinity for oxygen and is used as a "getter" in vacuum tubes.[93] Other uses of the metal include high-
energy lasers, vapour glow lamps, and vapour rectifiers.[14]

Centrifugation fluids
The high density of the caesium ion makes solutions of caesium chloride, caesium sulfate, and caesium
trifluoroacetate (Cs(O2 CCF3 )) useful in molecular biology for density gradient ultracentrifugation.[94] This
technology is used primarily in the isolation of viral particles, subcellular organelles and fractions, and
nucleic acids from biological samples.[95]

Chemical and medical use

Relatively few chemical applications use caesium.[96] 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.[14]

Caesium fluoride enjoys a niche use in organic chemistry as a

base[27] and as an anhydrous source of fluoride ion.[97] Caesium
salts sometimes replace potassium or sodium salts in organic Caesium chloride powder
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

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 137 Ba 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.[98] It has been used in agriculture, cancer treatment, and the
sterilization of food, sewage sludge, and surgical equipment.[14][99] Radioactive isotopes of caesium in
radiation devices were used in the medical field to treat certain types of cancer,[100] 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.[101][102] Caesium-137 has been
employed in a variety of industrial measurement gauges, including moisture, density, levelling, and
thickness gauges.[103] 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.[104]

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.[105]

Other uses
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.[14] Xenon
was used in the experimental spacecraft Deep Space
1 launched in 1998.[106][107] Nevertheless, field- Schematics of an electrostatic ion thruster
emission electric propulsion thrusters that accelerate developed for use with caesium or mercury fuel
liquid metal ions such as caesium have been
built.[108]

Caesium nitrate is used as an oxidizer and pyrotechnic colorant to burn silicon in infrared flares,[109] such
as the LUU-19 flare,[110] because it emits much of its light in the near infrared spectrum.[111] 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.[112] 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.[14]

Magnetohydrodynamic (MHD) power-generating systems were researched, but failed to gain widespread
acceptance.[113] Caesium metal has also been considered as the working fluid in high-temperature Rankine
cycle turboelectric generators.[114]

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.[14]

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.[115]

Health and safety hazards

Nonradioactive caesium compounds are only mildly toxic, and
Caesium
nonradioactive caesium is not a significant environmental hazard.
Because biochemical processes can confuse and substitute caesium Hazards
GHS labelling:[116]
with potassium, excess caesium can lead to hypokalemia, Pictograms
arrhythmia, and acute cardiac arrest, but such amounts would not
ordinarily be encountered in natural sources.[118][119]
Signal word Danger
The median lethal dose (LD50 ) for caesium chloride in mice is Hazard H260, H314
2.3 g per kilogram, which is comparable to the LD50 values of statements
potassium chloride and sodium chloride.[120] The principal use of Precautionary P223, P231+P232,
nonradioactive caesium is as caesium formate in petroleum drilling statements P280,
fluids because it is much less toxic than alternatives, though it is P305+P351+P338,
more costly.[81] P370+P378, P422
NFPA 704
Caesium is one of the most reactive elements and is highly (fire diamond)
4
explosive in the presence of water. The hydrogen gas produced by 3 3
the reaction is heated by the thermal energy released at the same W
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.[14]

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.[19]

The isotopes 134 and 137 are present in the

The portion of the total radiation dose (in air)
biosphere in small amounts from human activities, contributed by each isotope plotted against time
differing by location. Radiocaesium does not after the Chernobyl disaster. Caesium-137 became
accumulate in the body as readily as other fission the primary source of radiation about 200 days after
products (such as radioiodine and radiostrontium). the accident.[117]
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.[121] Radiocaesium follows potassium
and tends to accumulate in plant tissues, including fruits and vegetables.[122][123][124] 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.[125] Accumulation of caesium-137 in lakes has been a great concern after the Chernobyl
disaster.[126][127] 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;[128] smaller amounts may cause infertility and
cancer.[129] 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".[130]

See also
Caesium-137 § Incidents and accidents
Acerinox accident, a caesium-137 contamination accident in 1998
Goiânia accident, a major radioactive contamination incident in 1987 involving caesium-137
 Kramatorsk radiological accident, a 137Cs lost-source incident between 1980 and 1989

Notes
1. Caesium is the spelling recommended by the International Union of Pure and Applied
Chemistry (IUPAC).[10] The American Chemical Society (ACS) has used the spelling cesium
since 1921,[11][12] following Webster's New International Dictionary. The element was
named after the Latin word caesius, meaning "bluish grey".[13] 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.
2. Along with 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. Preliminary work with copernicium and
flerovium suggests that they are gaseous metals at room temperature.
3. The radioactive element francium may also have a lower melting point, but its radioactivity
prevents enough of it from being isolated for direct testing.[17] Copernicium and flerovium
may also have lower melting points.
4. It differs from this value in caesides, which contain the Cs− anion and thus have caesium in
the −1 oxidation state.[28] Additionally, 2013 calculations by Mao-sheng Miao indicate that
under conditions of extreme pressure (greater than 30 GPa), the inner 5p electrons could
form chemical bonds, where caesium would behave as the seventh 5p element. This
discovery indicates that higher caesium fluorides with caesium in oxidation states from +2 to
+6 could exist under such conditions.[29]
5. Francium's electropositivity has not been experimentally measured due to its high
radioactivity. Measurements of the first ionization energy of francium suggest that its
relativistic effects may lower its reactivity and raise its electronegativity above that expected
from periodic trends.[31]
6. Bunsen quotes Aulus Gellius Noctes Atticae II, 26 by Nigidius Figulus: Nostris autem
veteribus caesia dicts est quae Graecis, ut Nigidus ait, de colore coeli quasi coelia.

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External links
Caesium or Cesium (https://www.periodicvideos.com/videos/055.htm) at The Periodic Table
of Videos (University of Nottingham)
View the reaction of Caesium (most reactive metal in the periodic table) with Fluorine (most
reactive non-metal) (https://web.archive.org/web/20171104215850/http://richannel.org/the-m
 odern-alchemist-reacting-fluorine-with-caesium) courtesy of The Royal Institution.
Rogachev, Andrey Yu.; Miao, Mao-Sheng; Merino, Gabriel; Hoffmann, Roald (2015).
"Molecular CsF5and CsF2+". Angewandte Chemie. 127 (28): 8393–8396.
Bibcode:2015AngCh.127.8393R (https://ui.adsabs.harvard.edu/abs/2015AngCh.127.8393
R). doi:10.1002/ange.201500402 (https://doi.org/10.1002%2Fange.201500402).

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