Caesium - Wikipedia

03.11.
22, 14:30 Caesium - Wikipedia
Caesium
Caesium (IUPAC spelling[6]) (or cesium
Caesium, 55Cs
in American English)[note 1] is a chemical
element with the symbol Cs and atomic
number 55. It is a soft, silvery-golden alkali
metal with a melting point of 28.5 °C
(83.3 °F), which makes it one of only five
elemental metals that are liquid at or near
room temperature.[note 2] Caesium has
physical and chemical properties similar to
those of rubidium and potassium. It is
pyrophoric and reacts with water even at
−116 °C (−177 °F). It is the least Caesium
electronegative element, with a value of Pronunciation /ˈsiːziəm/ (SEE-zee-əm)
0.79 on the Pauling scale. It has only one
Alternative name cesium (US)
stable isotope, caesium-133. Caesium is
mined mostly from pollucite. The element Appearance pale gold
has 40 known isotopes, making it, along Standard atomic 132.905 451 96 ± 0.000 000 06
with barium and mercury, one of the weight Ar°(Cs) 132.91 ± 0.01 (abridged)[1]
elements with the most isotopes.[11]
Caesium-137, a fission product, is extracted Caesium in the periodic table
from waste produced by nuclear reactors.
Rb
The German chemist Robert Bunsen and Cs
physicist Gustav Kirchhoff discovered ↓
Fr
caesium in 1860 by the newly developed xenon ← caesium → barium
method of flame spectroscopy. The first
small-scale applications for caesium were Atomic number (Z) 55
as a "getter" in vacuum tubes and in Group group 1: hydrogen and alkali metals
photoelectric cells. In 1967, acting on
Einstein's proof that the speed of light is the Period period 6
most constant dimension in the universe, Block s-block

the International System of Units used two Electron [Xe] 6s1
specific wave counts from an emission
configuration
spectrum of caesium-133 to co-define the
second and the metre. Since then, caesium Electrons per shell 2, 8, 18, 18, 8, 1
has been widely used in highly accurate Physical properties
atomic clocks.
Phase at STP solid
Since the 1990s, the largest application of Melting point 301.7 K (28.5 °C, 83.3 °F)
the element has been as caesium formate
Boiling point 944 K (671 °C, 1240 °F)
for drilling fluids, but it has a range of
applications in the production of electricity, Density (near r.t.) 1.93 g/cm3
in electronics, and in chemistry. The when liquid 1.843 g/cm3
radioactive isotope caesium-137 has a half- (at m.p.)
life of about 30 years and is used in medical
Critical point 1938 K, 9.4 MPa[2]
applications, industrial gauges, and
hydrology. Nonradioactive caesium Heat of fusion 2.09 kJ/mol
compounds are only mildly toxic, but the
https://en.wikipedia.org/wiki/Caesium 1/23
03.11.22, 14:30 Caesium - Wikipedia
pure metal's tendency to react explosively Heat of 63.9 kJ/mol

with water means that caesium is vaporization
considered a hazardous material, and the
Molar heat 32.210 J/(mol·K)
radioisotopes present a significant health
capacity
and ecological hazard in the environment.
Vapour pressure
P (Pa) 1 10 100 1 k 10 k 100 k
Contents at T (K) 418 469 534 623 750 940
Characteristics Atomic properties

Physical properties
Oxidation states −1, +1[3] (a strongly basic oxide)
Chemical properties
Compounds Electronegativity Pauling scale: 0.79
Complexes Ionization 1st: 375.7 kJ/mol
Halides energies 2nd: 2234.3 kJ/mol
Oxides
3rd: 3400 kJ/mol
Isotopes
Occurrence Atomic radius empirical: 265 pm
Production Covalent radius 244±11 pm
History Van der Waals 343 pm

radius
Applications
Petroleum exploration
Atomic clocks
Definition of the second Spectral lines of caesium
Electric power and electronics Other properties

Centrifugation fluids Natural primordial
Chemical and medical use occurrence
Nuclear and isotope applications Crystal structure body-centred cubic (bcc)
Other uses
Health and safety hazards
Thermal 97 µm/(m⋅K) (at 25 °C)
See also
expansion
Notes
Thermal 35.9 W/(m⋅K)
References conductivity
External links Electrical 205 nΩ⋅m (at 20 °C)
resistivity
Magnetic ordering paramagnetic[4]
Characteristics
Young's modulus 1.7 GPa
Bulk modulus 1.6 GPa
Physical properties
Mohs hardness 0.2
Of all elements that are solid at room Brinell hardness 0.14 MPa
temperature, caesium is the softest: it has a CAS Number 7440-46-2
hardness of 0.2 Mohs. It is a very ductile,
pale metal, which darkens in the presence History
of trace amounts of oxygen.[12][13][14] When Naming from Latin caesius, sky blue, for its
in the presence of mineral oil (where it is spectral colours
best kept during transport), it loses its Discovery Robert Bunsen and Gustav
metallic Kirchhoff (1860)

lustre First isolation Carl Setterberg (1882)
and
takes on Main isotopes of caesium
a duller, Iso- Abun- Half-life Decay Pro-
grey
tope dance (t1/2) mode duct
133Cs 100% stable
ε 134Xe
High-purity caesium-133 stored in 134Cs syn 2.0648 y
argon. β− 134Ba
135Cs trace 2.3×106 y β− 135Ba

appearance. It has a melting point of
28.5 °C (83.3 °F), making it one of the few 137Cs syn 30.17 y[5] β− 137Ba
elemental metals that are liquid near room
temperature. Mercury is the only stable
elemental metal with a known melting point lower than caesium.[note 3][16] In addition, the metal
has a rather low boiling point, 641 °C (1,186 °F), the lowest of all metals other than mercury.[17] Its
compounds burn with a blue[18][19] or violet[19] colour.
Caesium forms alloys with the other alkali metals, gold, and
mercury (amalgams). At temperatures below 650 °C
(1,202 °F), it does not alloy with cobalt, iron, molybdenum,
nickel, platinum, tantalum, or tungsten. It forms well-defined
intermetallic compounds with antimony, gallium, indium, and
thorium, which are photosensitive.[12] It mixes with all the
other alkali metals (except lithium); the alloy with a molar
distribution of 41% caesium, 47% potassium, and 12% sodium
Caesium crystals (golden) has the lowest melting point of any known metal alloy, at
compared to rubidium crystals −78 °C (−108 °F).[16][20] A few amalgams have been studied:
(silvery) 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]
Chemical properties
Caesium metal is highly reactive and very pyrophoric. It ignites spontaneously in air, and reacts
explosively with water even at low temperatures, more so than the other alkali metals (first group
of the periodic table).[12] 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.[23] 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.[12]
The chemistry of caesium is similar to that of other alkali

metals, in particular rubidium, the element above caesium in
the periodic table.[24] 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.[26]
Caesium is the most electropositive chemical
0:15 element.[note 5][16] The caesium ion is also larger and less
"hard" than those of the lighter alkali metals.
Addition of a small amount of
caesium to cold water is explosive.
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 ),[3] 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.[28] This prediction needs to be validated by
further experiments.[29]
Ball-and-stick model of the
Salts of Cs+ are usually colourless unless the anion itself is coloured.
cubic coordination of Cs
Many of the simple salts are hygroscopic, but less so than the
and Cl in CsCl
corresponding salts of lighter alkali metals. The phosphate,[30]
acetate, carbonate, halides, oxide, nitrate, and sulfate salts are water-
soluble. Double salts are often less soluble, and the low solubility of caesium aluminium sulfate is
exploited in refining Cs from ores. The double salt with antimony (such as CsSbCl
4), bismuth,
cadmium, copper, iron, and lead are also poorly soluble.[12]
Caesium hydroxide (CsOH) is hygroscopic and strongly basic.[24] It rapidly etches the surface of
semiconductors such as silicon.[31] CsOH has been previously regarded by chemists as the
"strongest base", reflecting the relatively weak attraction between the large Cs+ ion and OH−;[18] 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.[24]
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.[32]
Complexes
Like all metal cations, Cs+ forms complexes with Lewis bases in solution. Because of its large size,
Cs+ usually adopts coordination numbers greater than 6, the number typical for the smaller alkali
metal cations. This difference is apparent in the 8-coordination of CsCl. This high coordination
number and softness (tendency to form covalent bonds) are properties exploited in separating Cs+
from other cations in the remediation of nuclear wastes, where 137Cs+ must be separated from
large amounts of nonradioactive K+.[33]
Halides
Caesium fluoride (CsF) is a hygroscopic white solid that is widely used

in organofluorine chemistry as a source of fluoride anions.[35]
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.[24] 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",[26] 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.[26] The CsCl structure is preferred because
−
Cs+ has an ionic radius of 174 pm and Cl 181 pm.[36]

Monatomic caesium halide
Oxides wires grown inside double-
wall carbon nanotubes
(TEM image).[34]
More so than the other alkali metals,
caesium forms numerous binary compounds
with oxygen. When caesium burns in air, the

superoxide CsO2 is the main product.[37] The "normal" caesium oxide

(Cs2O) forms yellow-orange hexagonal crystals,[38] and is the only oxide

of the anti-CdCl2 type.[39] It vaporizes at 250 °C (482 °F), and

decomposes to caesium metal and the peroxide Cs
2O2 at temperatures
Cs
11O
3 cluster above 400 °C (752 °F). In addition to the superoxide and the ozonide

CsO3,[40][41] several brightly coloured suboxides have also been

studied.[42] These include Cs
7O, Cs
4O, Cs
11O
3, Cs
3O (dark-green[43]),
CsO, Cs
3O
2,[44] as well as Cs
7O
2.[45][46] The latter may be heated in a vacuum to generate Cs
2O.[39]
Binary compounds with sulfur, selenium, and tellurium also exist.[12]
Isotopes
Caesium has 40 known isotopes, ranging in mass number (i.e. number of nucleons in the nucleus)
from 112 to 151. Several of these are synthesized from lighter elements by the slow neutron capture
process (S-process) inside old stars[47] and by the R-process in supernova explosions.[48] The only
7
stable caesium isotope is 133Cs, 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.[49]
The radioactive 135Cs has a very long half-life of about

2.3 million years, the longest of all radioactive isotopes of
caesium. 137Cs and 134Cs have half-lives of 30 and two years,
respectively. 137Cs decomposes to a short-lived 137mBa by beta
decay, and then to nonradioactive barium, while 134Cs
transforms into 134Ba directly. The isotopes with mass
numbers of 129, 131, 132 and 136, have half-lives between a day
and two weeks, while most of the other isotopes have half-lives Decay of caesium-137
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][51]
The isotope 135Cs is one of the long-lived fission products of uranium produced in nuclear
reactors.[52] 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.[53][54]
The beta decay from 137Cs to 137mBa is a strong emission of gamma radiation.[55] 137Cs and 90Sr
are the principal medium-lived products of nuclear fission, and the prime sources of radioactivity
from spent nuclear fuel after several years of cooling, lasting several hundred years.[56] Those two
isotopes are the largest source of residual radioactivity in the area of the Chernobyl disaster.[57]
Because of the low capture rate, disposing of 137Cs through neutron capture is not feasible and the
only current solution is to allow it to decay over time.[58]
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.[59] 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.[60] With nuclear weapons testing in the 1950s
through the 1980s, 137Cs was released into the atmosphere and returned to the surface of the earth
as a component of radioactive fallout. It is a ready marker of the movement of soil and sediment
from those times.[12]
Occurrence
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 the 36th among the metals.
Nevertheless, it is more abundant than such elements as
antimony, cadmium, tin, and tungsten, and two orders of
magnitude more abundant than mercury and silver; it is 3.3%
as abundant as rubidium, with which it is closely associated,
chemically.[12] Pollucite, a caesium mineral
Due to its large ionic radius, caesium is one of the

"incompatible elements".[62] 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 (KMgCl3·6H2O)
may contain only 0.002% caesium. Consequently, caesium is found in few minerals. Percentage
amounts of caesium may be found in beryl (Be
3Al
2(SiO
3)
6) and avogadrite ((K,Cs)BF
4), up to

15 wt% Cs2O in the closely related mineral pezzottaite (Cs(Be2Li)Al2Si6O18), up to 8.4 wt% Cs2O in

the rare mineral londonite ((Cs,K)Al4Be4(B,Be)12O28), and less in the more widespread
rhodizite.[12] The only economically important ore for caesium is pollucite Cs(AlSi
2O
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.[63]
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.[63][64] 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%.[64] Commercial pollucite contains more than 19%
caesium.[65] 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.[64] At the present rate of world mine production of 5 to 10 metric tons per year, reserves
will last for thousands of years.[12]
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.[12][66]
In the acid digestion, the silicate pollucite rock is dissolved with strong acids, such as hydrochloric
(HCl), sulfuric (H
2SO
4), hydrobromic (HBr), or hydrofluoric (HF) acids. With hydrochloric acid, a
mixture of soluble chlorides is produced, and the insoluble chloride double salts of caesium are
precipitated as caesium antimony chloride (Cs
4SbCl
7), caesium iodine chloride (Cs
2ICl), or
caesium hexachlorocerate (Cs
2(CeCl
6)). After separation, the pure precipitated double salt is
decomposed, and pure CsCl is precipitated by evaporating the water.
The sulfuric acid method yields the insoluble double salt directly as caesium alum

(CsAl(SO4)2·12H2O). 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
2SO4
solution.[12]
Roasting pollucite with calcium carbonate and calcium chloride yields insoluble calcium silicates
and soluble caesium chloride. Leaching with water or dilute ammonia (NH
4OH) yields a dilute
chloride (CsCl) solution. This solution can be evaporated to produce caesium chloride or
transformed into caesium alum or caesium carbonate. Though not commercially feasible, the ore
can be directly reduced with potassium, sodium, or calcium in vacuum to produce caesium metal
directly.[12]
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.[67] The primary smaller-scale
commercial compounds of caesium are caesium chloride and nitrate.[68]
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.[12]
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.[66] In vacuum
applications, caesium dichromate can be reacted with zirconium to produce pure caesium metal
without other gaseous products.[68]
Cs
2Cr
2O
7 + 2 Zr → 2 Cs + 2 ZrO
2+ Cr
2O
3
The price of 99.8% pure caesium (metal basis) in 2009 was about $10 per gram ($280/oz), but the
compounds are significantly cheaper.[64]
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 sky-
blue.[note 6][69][70][71] 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 Gustav Kirchhoff (left) and Robert
Bunsen (centre) discovered
acid, but these salts show a slight difference in solubility in hot
caesium with their newly invented
water, and the less-soluble caesium and rubidium
spectroscope.
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.[70]
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).[70] They tried to generate elemental
caesium by electrolysis of molten caesium chloride, but instead of a metal, they obtained a blue
homogeneous substance which "neither under the naked eye nor under the microscope showed the
slightest trace of metallic substance"; as a result, they assigned it as a subchloride (Cs
2Cl). In
reality, the product was probably a colloidal mixture of the metal and caesium chloride.[72] The
electrolysis of the aqueous solution of chloride with a mercury cathode produced a caesium
amalgam which readily decomposed under the aqueous conditions.[70] The pure metal was
eventually isolated by the German chemist Carl Setterberg while working on his doctorate with
Kekulé and Bunsen.[71] In 1882, he produced caesium metal by electrolysing caesium cyanide,
avoiding the problems with the chloride.[73]
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.[74] 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.[12] 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.[75] 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.[12] 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.[12]
The high density of the caesium formate brine (up to 2.3 g/cm3, or 19.2 pounds per gallon),[76]
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.[76] 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).[77] 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.[12]
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.[78] 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."[75] 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.[12] The caesium
standard is the primary standard for standards-compliant time

and frequency measurements.[79] Caesium clocks regulate the
timing of cell phone networks and the Internet.[80]
Definition of the second
The second, symbol s, is the SI unit of time. It is defined by

taking the fixed numerical value of the caesium frequency Atomic clock ensemble at the U.S.
ΔνCs, the unperturbed ground-state hyperfine transition Naval Observatory
frequency of the caesium-133 atom, to be 9 192 631 770 when
expressed in the unit Hz, which is equal to s−1.
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.[81]
FOCS-1, a continuous cold caesium
fountain atomic clock in Switzerland,
Caesium is also important for its photoemissive properties,
started operating in 2004 at an
converting light to electron flow. It is used in photoelectric cells
uncertainty of one second in 30
because caesium-based cathodes, such as the intermetallic
million years
compound K
2CsSb, have a low threshold voltage for emission
of electrons.[82] The range of photoemissive devices using
caesium include optical character recognition devices, photomultiplier tubes, and video camera
tubes.[83][84] Nevertheless, germanium, rubidium, selenium, silicon, tellurium, and several other
elements can be substituted for caesium in photosensitive materials.[12]
Caesium iodide (CsI), bromide (CsBr) and caesium fluoride (CsF) crystals are employed for
scintillators in scintillation counters widely used in mineral exploration and particle physics
research to detect gamma and X-ray radiation. Being a heavy element, caesium provides good
stopping power with better detection. Caesium compounds may provide a faster response (CsF)
and be less hygroscopic (CsI).
Caesium vapour is used in many common magnetometers.[85]
The element is used as an internal standard in spectrophotometry.[86] Like other alkali metals,
caesium has a great affinity for oxygen and is used as a "getter" in vacuum tubes.[87] Other uses of
the metal include high-energy lasers, vapour glow lamps, and vapour rectifiers.[12]
Centrifugation fluids
The high density of the caesium ion makes solutions of caesium chloride, caesium sulfate, and
caesium trifluoroacetate (Cs(O
2CCF
3)) useful in molecular biology for density gradient
ultracentrifugation.[88] This technology is used primarily in the isolation of viral particles,
subcellular organelles and fractions, and nucleic acids from biological samples.[89]
Chemical and medical use
Relatively few chemical applications use caesium.[90] 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.[12]
Caesium fluoride enjoys a niche use in organic chemistry as a

base[24] and as an anhydrous source of fluoride ion.[91]
Caesium salts sometimes replace potassium or sodium salts in
organic synthesis, such as cyclization, esterification, and Caesium chloride powder
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 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.[92] It has been used in
agriculture, cancer treatment, and the sterilization of food, sewage sludge, and surgical
equipment.[12][93] Radioactive isotopes of caesium in radiation devices were used in the medical
field to treat certain types of cancer,[94] 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.[95][96] Caesium-137 has been employed in a variety
of industrial measurement gauges, including moisture, density, levelling, and thickness gauges.[97]
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.[98]
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.[99]
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.[12] Xenon was used in the
experimental spacecraft Deep Space 1 launched in 1998.[100][101] Nevertheless, field-emission
electric propulsion thrusters that accelerate liquid metal ions such as caesium have been built.[102]
Caesium nitrate is used as an oxidizer and

pyrotechnic colorant to burn silicon in infrared
flares,[103] such as the LUU-19 flare,[104] because
it emits much of its light in the near infrared
spectrum.[105] 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.[106] 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
Schematics of an electrostatic ion thruster
aluminium fluoride are used in fluxes formulated
developed for use with caesium or mercury fuel
for brazing aluminium alloys that contain
magnesium.[12]
Magnetohydrodynamic (MHD) power-generating systems were researched, but failed to gain

widespread acceptance.[107] Caesium metal has also been considered as the working fluid in high-
temperature Rankine cycle turboelectric generators.[108]
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.[12]
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.[109]
Health and safety hazards

Nonradioactive caesium compounds are only mildly toxic, and Caesium
nonradioactive caesium is not a significant environmental
Hazards
hazard. Because biochemical processes can confuse and
substitute caesium with potassium, excess caesium can lead to GHS labelling:[110]
hypokalemia, arrhythmia, and acute cardiac arrest, but such Pictograms
amounts would not ordinarily be encountered in natural
sources.[112][113]
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.[114] The principal use Precautionary P223, P231+P232,
of nonradioactive caesium is as caesium formate in petroleum statements P280,
drilling fluids because it is much less toxic than alternatives,
P305+P351+P338,
though it is more costly.[76]
P370+P378, P422
Caesium metal is one of the most reactive elements and is NFPA 704
highly explosive in the presence of water. The hydrogen gas (fire diamond) 4
produced by the reaction is heated by the thermal energy 3 3
released at the same time, causing ignition and a violent W
explosion. This can occur with other alkali metals, but caesium
is so potent that this explosive reaction can be triggered even by cold water.[12]
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
The portion of the total radiation dose (in air)
radiostrontium). About 10% of absorbed
contributed by each isotope plotted against time
radiocaesium washes out of the body relatively
after the Chernobyl disaster. Caesium-137 became
quickly in sweat and urine. The remaining 90%
the primary source of radiation about 200 days after
has a biological half-life between 50 and 150
the accident.[111]
days.[115] Radiocaesium follows potassium and
tends to accumulate in plant tissues, including
fruits and vegetables.[116][117][118] 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.[119] Accumulation of
caesium-137 in lakes has been a great concern after the Chernobyl disaster.[120][121] 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;[122] smaller amounts may cause infertility and cancer.[123]
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".[124]
See also
Goiânia accident, a major radioactive contamination incident in 1987 involving Caesium-137.
Kramatorsk radiological accident, another 137Cs incident between 1980 and 1989.
Acerinox accident, a Caesium-137 contamination accident in 1998.
Notes
1. Caesium is the spelling recommended by the International Union of Pure and Applied
Chemistry (IUPAC).[7] The American Chemical Society (ACS) has used the spelling cesium
since 1921,[8][9] following Webster's New International Dictionary. The element was named
after the Latin word caesius, meaning "bluish grey".[10] 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.[15] 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.[3] 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.[25]
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.[27]
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 (http://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-mod
ern-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.127.8393R).
doi:10.1002/ange.201500402 (https://doi.org/10.1002%2Fange.201500402).
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Caesium - Wikipedia

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03.11.

22, 14:30 Caesium - Wikipedia

The German chemist Robert Bunsen and Cs

physicist Gustav Kirchhoff discovered ↓

pure metal's tendency to react explosively Heat of 63.9 kJ/mol

Contents at T (K) 418 469 534 623 750 940

Characteristics Atomic properties

Production Covalent radius 244±11 pm

History Van der Waals 343 pm

Electric power and electronics Other properties

metallic Kirchhoff (1860)

135Cs trace 2.3×106 y β− 135Ba

The chemistry of caesium is similar to that of other alkali

Most caesium compounds contain the element as the cation Cs ,

Caesium fluoride (CsF) is a hygroscopic white solid that is widely used

Caesium chloride (CsCl) crystallizes in the simple cubic crystal

Cs+ has an ionic radius of 174 pm and Cl 181 pm.[36]

superoxide CsO2 is the main product.[37] The "normal" caesium oxide

(Cs2O) forms yellow-orange hexagonal crystals,[38] and is the only oxide

of the anti-CdCl2 type.[39] It vaporizes at 250 °C (482 °F), and

CsO3,[40][41] several brightly coloured suboxides have also been

The radioactive 135Cs has a very long half-life of about

Caesium is a relatively rare element, estimated to average

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

(CsAl(SO4)2·12H2O). The aluminium sulfate component is converted to insoluble aluminium oxide

To obtain a pure sample of caesium, 44,000 litres

standard is the primary standard for standards-compliant time

Definition of the second

The second, symbol s, is the SI unit of time. It is defined by

Electric power and electronics

Caesium vapour thermionic generators are low-power devices

Caesium vapour is used in many common magnetometers.[85]

Chemical and medical use

Relatively few chemical applications use caesium.[90] Doping

Caesium fluoride enjoys a niche use in organic chemistry as a

Nuclear and isotope applications

Caesium-137 is a radioisotope commonly used as a gamma-emitter in industrial applications. Its

Caesium nitrate is used as an oxidizer and

Magnetohydrodynamic (MHD) power-generating systems were researched, but failed to gain

Health and safety hazards

It is highly pyrophoric: the autoignition

The isotopes 134 and 137 are present in the

55. "Cesium | Radiation Protection" (https://web.archive.org/web/20110315034747/http://www.epa.

68. Eagleson, Mary, ed. (1994). Concise encyclopedia chemistry (https://books.google.com/book

82. "Cesium Supplier & Technical Information" (http://www.americanelements.com/cs.html).

111. Data from The Radiochemical Manual (https://archive.org/details/TheRadiochemicalManual)

Retrieved from "https://en.wikipedia.org/w/index.php?title=Caesium&oldid=1117553800"

This page was last edited on 22 October 2022, at 09:58 (UTC).

Text is available under the Creative Commons Attribution-ShareAlike License 3.0;

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