Cesium and Cesium Compounds 1

Cesium and Cesium Compounds

Manfred Bick, Chemetall GmbH, Frankfurt/Main, Federal Republic of Germany

Horst Prinz, Chemetall GmbH, Frankfurt/Main, Federal Republic of Germany

1. Physical and Chemical Properties . . . 1 7. Storage and Transportation . . . . . . . 3

2. Resources . . . . . . . . . . . . . . . . . . . 2 8. Uses . . . . . . . . . . . . . . . . . . . . . . . 3
3. Production . . . . . . . . . . . . . . . . . . 2
9. Economic Aspects . . . . . . . . . . . . . 4
4. Cesium Compounds . . . . . . . . . . . . 3
5. Quality Specifications . . . . . . . . . . . 3 10. Toxicology and Occupational Health . 4
6. Chemical Analysis . . . . . . . . . . . . . 3 11. References . . . . . . . . . . . . . . . . . . 5

1. Physical and Chemical Properties cesium is strictly monovalent, and its chemistry
is typical of an alkali metal. Because of its ex-
Cesium [7440-46-2] (from the Latin word cae- tremely low ionization potential, cesium is usu-
sius, gray blue, which characterizes the pale blue ally far more reactive than lithium, sodium, or
color of the emissionof thermally excited cesium potassium and still pronouncedly more reactive
atoms) is a soft, gold-colored metal, which melts than rubidium. When cesium is exposed to air, an
slightly above room temperature. Table 1 sum- explosion-like oxidation to form cesium super-
marizes the physical properties of elemental ce- oxide, CsO2 , occurs; contact with water results
sium. in a vigorous reaction to form cesium hydrox-
Table 1. Physical properties of cesium [4], [5]
ide and hydrogen gas, which may ignite sponta-
neously.
Property Value Naturally occurring cesium consists only of
Atomic number 55 the stable isotope 133 Cs. Radioactive cesium iso-
Relative atomic mass Ar 132.90543 topes, such as 137 Cs (half-life of 30.1 a), are gen-
Melting point mp 28.7 ◦ C erated in fuel rods during operation of nuclear
Boiling point bp 685 ◦ C
Atomic radius ∗ 0.274 nm power plants.
Ionic radius ∗∗ 0.165 nm
Density
at 20 ◦ C 1.873 g/cm3
Specific heat, liquid 0.236 J g−1 K−1
Heat of fusion 2.13 kJ/mol 2. Resources
Heat of vaporization at 0.1 MPa 65.9 J/mol
Ionization potential 3.87 eV
Standard electrode potential −2.923 V Cesium is the 40th most abundant among the
Work function 1.91 eV elements, occurring about as frequently as ger-
Electrical conductivity
solid, 25 ◦ C 4.9 × 104 Ω−1 cm−1 manium. Resources can be categorized into two
vapor, 1250 ◦ C 2.0 × 102 Ω−1 cm−1 groups. One, of no commercial importance, con-
Vapor pressure P, kPa sists of the diffuse occurrence of the few grams
logP = −0.2185 A T +B
of cesium per ton contained in potassium salt
T, K A B deposits, sedimentary rocks, and seawater [3].
200 – 350 17543.0 6.0739
279 – 690 17070.7 5.8889 The only sources of cesium of commer-
cial importance originated during the solidifi-
∗ 12-Coordinate metal. cation of residual melts of silicate magmas. Af-
∗∗ 6-Coordinate salt, empirical.
ter the initial formation of huge granite masses,
the remaining melt rich in rare elements like
Cesium belongs to the alkali-metal group. lithium, rubidium, cesium, tantalum, niobium,
The metal reacts with most elements, to form beryllium, and tin then crystallized to form a
alloys when reacted with metals or to form typi- type of ore body well-known under the name
cal salts when reacted with halogens. In the salts, pegmatite. Under favorable conditions, which

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a06 153
2 Cesium and Cesium Compounds
seem to have existed only in relatively few
cases, these pegmatites differentiated into sep-
arate bodies. Sodium, potassium, and rubidium
formed feldspar-type minerals of considerable
mutual solubility, while lithium and cesium, be-
cause of the considerable difference in ionic radii
from the other alkali metals, formed separate
minerals. In the case of cesium, this seems to
have occurred in far fewer cases than for lithium,
yielding the only commercial cesium mineral,
pollucite [1308-53-8] [6], [7].
Pollucite is a cesium aluminum silicate,
which typically contains 18 – 26 % cesium ox-
ide. The theoretical content is 42 %, but usu-
ally pollucite contains considerable quantities
of quartz. Its appearance is also very similar to
that of quartz. For this reason and because the
demand for cesium has not been great enough
to result in any systematic exploration for ce-
sium minerals, possibly further deposits may be
discovered. Well known are the large deposits
at Bernic Lake in Canada, at Bikita in Zim-
babwe, and in South-West Africa. In the for-
mer Soviet Union a new mineral, cestibtantite, a
mixed cesium – antimony – tantalum oxide, has
been reported [8], and pollucite has been found
in some deposits of lithium, niobium, and tan-
talum minerals [9], [10]. Apparently, pollucite
also occurs in Afghanistan [11]. Small concen-
trations of cesium, less than one percent, are
found in lepidolite, a lithium mineral.
3. Production
For any of the production methods described,
pollucite must be powdered first. Production
processes can be categorized as (1) decompo-
sition with bases and (2) acid digestion. The
second category includes the group of processes
used industrially.
Alkaline decomposition can be carried out
either by mixing ore with lime and calcium
chloride and heating to 800 – 900 ◦ C followed
by leaching of the residue [12] or by heating
pollucite with sodium chloride and soda ash
to 600 – 800 ◦ C followed by leaching [13]. In
both cases, solutions of impure cesium chlo-
ride result. Hydrothermal alkaline leaching with
Ca(OH)2 at 200 – 280 ◦ C under high pressure
[14] has been developed as an industrial process
to yield a low-purity cesium hydroxide directly
from pollucite [15], [16].
Acid digestion can be carried out with hy-
drochloric acid, sulfuric acid, or hydrobromic
acid. Treatment of pollucite with hydrochloric
acid at elevated temperature produces a solu-
tion of chlorides of cesium, aluminum, and al-
kali metals, which is separated from the silica
residue. The cesium is precipitated as mixed
chloride with lead, antimony, or tin. Hydroly-
sis precipitates the auxiliary metal [17]. Alterna-
tives are precipitation with hydrogen sulfide or
recovery of cesium by solvent extraction from
the leach liquor [18] or ion exchange from ce-
sium chloride solution.
Treatment of pollucite with sulfuric acid [12,
p. 5] yields sparingly soluble cesium alum, ce-
sium aluminum sulfate [7784-17-0], which is
roasted with carbon to convert the aluminumto
alumina and the sulfate sulfur to SO2 . The
residue is leached to obtain a cesium sulfate so-
lution, which can be converted to the desired
salts by ion exchange, treatment with ammo-
nia or lime (to precipitate aluminum), or sol-
vent extraction [19]. Hydrobromic acid converts
pollucite into a solution of bromides of cesium,
aluminum, and impurity metals, from which ce-
sium can be precipitated by addition of alco-
hol. Leaching the precipitate with bromine se-
lectively extracts cesium as CsBr3 [20].
Cesium metal can be produced as an amal-
gam by electrolyzing concentrated cesium salt
solutions on a mercury cathode [21], but reduc-
tion of solid cesium salts, especially the halides,
with calcium or barium at elevated temperature
and removal of cesium by vacuum distillation is
the usual method [22].
4. Cesium Compounds
Cesium carbonate [534-17-8], Cs2 CO3 , M r
325.82, 81.58 % Cs, is a colorless, hygroscopic
powder, decomp. at 610 ◦ C,
4.07 g/cm3 , solu-
bility of 261.5 g in 100 g of water, basic solution.
Cesium hydrogen carbonate [15519-28-5],
CsHCO3 , M r 193.92, 68.54 % Cs, colorless crys-
talline powder, decomp. at 175 ◦ C, solubility of
209 g in 100 g of water, basic solution.
Cesium chloride [7647-17-8], CsCl,
M r 168.36, 78.9 % Cs, colorless, crystalline,

hygroscopic powder, mp 642 ◦ C,
3.983 g/cm3 ,
solubility of 186 g in 100 g of water.
Cesium hydroxide [21351-79-1], CsOH,
M r 149.91, 88.66 % Cs, anhydrous, colorless,
lumpy solid, mp 272 ◦ C,
3.68 g/cm3 , solubil-
ity of ca. 400 g in 100 g of water. The solution
is a strong base and very caustic.
Cesium hydroxide monohydrate [35103-79-8],
CsOH · H2 O, M r 167.93, 79.14 % Cs, col-
orless, crystalline, hygroscopic powder, mp
205 – 208 ◦ C,
3.5 g/cm3 , solubility of ca. 860 g
in 100 g of water. The solution is a strong base
and very caustic.
Cesium iodide [7789-17-5], CsI, M r 259.81,
51.2 % Cs, colorless, slightly hygroscopic pow-
der, mp 621 ◦ C,
4.51 g/cm3 , solubility of 74 g
in 100 g of water.
Cesium nitrate [7789-18-6], CsNO3 ,
M r 194.91, 68.19 % Cs, colorless crystalline
powder, mp 414 ◦ C,
3.69 g/cm3 , oxidant.
Cesium sulfate [10294-54-9], Cs2 SO4 ,
M r 361.87, 73.46 % Cs, colorless hygroscopic
powder, mp 1010 ◦ C,
4.243 g/cm3 .
5. Quality Specifications
Cesium metal and cesium salts are marketed
in purities from 99 % for technical grades to
99.999 % for high-purity compounds. For some
applications, a crude form with ca. 85 % purity
can also be produced.
6. Chemical Analysis
Assays and purities of commercial products are
derived by subtracting the sum of analyzed im-
purity levels from unity. Alkali-metal impurities
are analyzed by emission spectroscopy, whereas
alkaline-earth metals are determined by atomic
absorption. Other metals and anions, such as
phosphate and sulfate, can be determined by
photometric methods; chloride is established ar-
gentometrically.
7. Storage and Transportation
Special precautions are necessary for cesium
metal, which is shipped in evacuated glass am-
pules or steel containers with an appropriate
Cesium and Cesium Compounds 3
outer packing to ensure that the metal is kept
from air and moisture under any conditions.
Many cesium salts, especially halides, are hy-
groscopic and must be stored dry. Transportation
regulations, where they exist, are governed by
the anion, i.e., the hydroxide being caustic, the
nitrate being an oxidant, because nothing inher-
ent in the cesium cation calls for special precau-
tions.
8. Uses
Cesium metal is used in frequency standards,
especially the time standards known as atomic
clocks, which lock in on one frequency of ex-
cited gas-phase cesium. The metal is also used
in the production of various types of vacuum
tubes, where it acts as a scavenger to reduce
residual gaseous impurities after the tubes have
been sealed. The cesium is normally generated
in situ by firing the tube to convert a pellet of
cesium chromate mixed with a metal powder to
elemental cesium vapor.
In ion thrusters, cesium metal is the propel-
lant. It is ionized in a vacuum chamber, and ce-
sium ions are then accelerated through a field
and ejected through a nozzle, producing a high
specific impulse because of their high atomic
mass. Devices of this type are used in satellites
for orientation control.
Recognition that the reserves of fossil fuels
are limited has focused considerable research on
conversion of solar energy into electricity. One
approach to achieve this uses thermionic con-
verters, which require cesium. Direct conversion
of heat from nuclear reactors into electricity by
generating a voltage difference across a cesium
vapor-filled vacuum tube between hot and cold
electrodes has been proposed [23]. Another po-
tential use of cesium metal for energy generation
is its use as a plasma seeding agent in closed-
cycle magnetohydrodynamic generators that use
high-temperature nuclear reactors as their heat
source.
Of the compounds, the halides (especially
the chloride), the trifluoroacetate, and the sul-
fate are used in ultracentrifuges, where aqueous
solutions of high-purity grades are a medium
for separation and purification of nucleic acids
(DNA and RNA) for biochemical research. At
4 Cesium and Cesium Compounds
high rates of rotation, these solutions form a den-
sity gradient that separates nucleic acids accord-
ing to their densities [24].
Various catalysts can be doped with cesium
salts as activators, much like the corresponding
potassium salts. High-purity cesium halides are
transparent to infrared radiation; therefore, they
are used for cuvettes, prisms, and windows for
spectroscopic equipment. Cesium iodide can be
doped to make it a scintillator [25]; single crys-
tals are used in scintillation counting equipment.
Cesium fluoride is used for fluorination in or-
ganic chemistry.
Open-cycle magnetohydrodynamic genera-
tors could offer a considerable potential for ce-
sium compounds as a plasma seeding agent.
These devices are under development, especially
in North America and the former Soviet Union,
with the hope that they can boost the overall ef-
ficiency of power plants that depend on fossil
fuels from ca. 35 to ca. 45 %. Hot combustion
gas is seeded with potassium or cesium carbon-
ate to make a highly conductive plasma, which
is passed through a magnetic field. At right an-
gles to both the field and the direction of plasma
flow, there is a voltage difference [26]. Never-
theless, the higher seeding efficiency of cesium
compounds must compete with the lower price
of potassium compounds.
The very low toxicity of the cesium cation
and the pronounced physical and chemical prop-
erties of cesium formate to form clear solutions
of high density (up to 2.3 t/m3 ), have led to the
suggestion to use these solutions as brines in oil
and gas well drilling [27], alone or in mixtures
with sodium or potassium formate.
As an environmentally friendly alternative,
cesium formate (and the other alkali metal for-
mates) could potentially replace large quantities
of the toxic, hazardous, corrosive heavy metal
compound zinc bromide in this application. This
is most likely in areas where environmental reg-
ulations are strict, for example, in the off-shore
North Sea fields.
9. Economic Aspects
The producers do not publish production or con-
sumption figures. The U.S. Bureau of Mines es-
timated world consumption in 1978 at about 20 t
of cesium, as metal and in compounds. At that
time prices for cesium salts were 64 – 81 $/kg
for technical grades and 147 – 170 $/kg for high-
purity products.
The price levels in 1996 were 35 – 85 $/kg for
technical and pure grades and 85 – 150 $/kg for
high-purity salts.
10. Toxicology and
Occupational Health
The cesium ion itself is only very slightly toxic,
more toxic than the sodium ion, but less toxic
than the potassium ion. Typical LD50 values
of cesium salts are 1400 mg/kg (rat, intraperi-
toneal) and 1000 mg/kg (rat, oral) [28]. Excep-
tions are caused by the toxicity of the particular
anion. Cesium hydroxide is strongly caustic, ce-
sium nitrate is an oxidant, and cesium fluoride
exhibits the typical toxicity of fluoride.
Special precautions are necessary when han-
dling the metal because exposure to this sub-
stance results in severe caustic burns.
11. References
General References
1. Gmelin, system no. 25, Caesium (1938).
2. Kirk-Othmer, 3rd ed., vol. 5, pp. 327 – 338.
3. C. A. Hampel: Rare Metals Handbook, 2nd
ed., Reinhold Publ. Co., New York 1969.
Specific References
4. W. Peek, Chem.-Ztg. 87 (1963) 315 – 318.
5. Handbook of Chemistry and Physics, 53rd ed.,
CRC Press, Cleveland 1972 – 1973.
6. V. M. Goldschmidt: Geochemistry, Clarendon
Press, Oxford 1954.
7. V. V. Gordiyenko, Int. Geol. Rev. 13 (1970)
no. 2, 134.
8. P. Černý: “Mineralogy of Rubidium and
Cesium,” Short Course Handb. Mineral.
Assoc. Can. 8 1982 , 149 – 161.
9. V. F. Durnev, G. B. Melentyev, V. A. Sokolov,
Y. N. Pokrovskiy, G. A. Cherepivskaya, Dokl.
Akad. Nauk SSSR 213 (1973) no. 1, 180 – 183.
10. L. G. Kuznetsova, B. M. Shmakin, Zap. Vses.
Mineral. O-va. 110 (1981) no. 1, 59 – 70.
11. L. N. Rossovskii, Dokl. Akad. Nauk SSSR 236
(1977) no. 1, 216 – 219.
12. K. C. Dean, P. H. Johnson, I. L. Nichols, Rep.
Invest. U.S. Bur. Mines 6387 (1964) .

13. W. D. Arnold, D. J. Crouse, K. B. Brown, Ind.
Eng. Chem. 4 (1965) 249.
14. Y. G. Goroshchenko, E. B. Panasenko, V. A.
Roi, V. P. Izotov, Tsvetnye Metally 2 (1961)
no. 5, 57 – 59.
15. Metallgesellschaft AG, DE 42 37 954 C1 (M.
Wegner, K. Köbele, H. Hoffmann, H. Prinz).
16. Metallgesellschaft AG, DE 43 39 062.5-41 (K.
Schade, K. Köbele, H. Hoffmann, H. Prinz).
17. J. C. Bailor, Jr.: Inorganic Syntheses, vol. 4,
McGraw-Hill, New York 1965.
18. Chem. Eng. News 41 (1963) no. 51 (Dec. 23),
35.
19. H. W. Parsons, J. A. Vezina, R. Simard, H. W.
Smith, Can. Dept. Mines, Mineral Branch,
Tech. Bull. 50 (1963) , reprint of Can. Metall.
Q. 2 (1963) 1 – 13; Chem. Abstr. 58 (1963)
12 199c.
20. V. A. Stenger, US 2 481 455, 1949.
Cetyl Alcohol → Fatty Alcohols
Chalks → Drawing and Writing Materials
Cesium and Cesium Compounds 5
21. R. E. Davis: “Electrowinning of Rubidium and
Cesium,” Encyclopedia of Electrochemistry,
Reinhold Publ. Co., New York 1964.
22. L. Hackspill, Helv. Chim. Acta 11 (1928)
1003.
23. J. Raloff, Sci. News (Washington D.C.) 113
(1978) no. 13, 202.
24. J. Vinograd, J. E. Hearst: Equilibrium
Sedimentation of Macromolecules and Viruses
in a Density Gradient, Springer-Verlag, Wien
1962.
25. P. Brinckmann, US 3 446 745, 1966.
26. J. Melcher, Min. Eng. (Littleton, Colo.) 29
(1977) no. 12, 34.
27. Shell Internationale Research Maatschappij
B.V., EP-A 0 259 939 A3 (A. J.
Clarke-Sturman, P. L. Sturla).
28. K. W. Cochran et al., Arch. Ind. Hyg. Occup.
Med. 1 (1950) 637.