Article No : a23_525
Selenium and Selenium Compounds
BERND E. LANGNER, Norddeutsche Affinerie AG, Hamburg, Federal Republic
of Germany
1. Introduction. . . . . . . . . . . . . . . . . . . .....
2. Properties . . . . . . . . . . . . . . . . . . . . .....
3. Occurrence and Raw Materials . . . . .....
4. Production . . . . . . . . . . . . . . . . . . . . .....
4.1. Primary Production . . . . . . . . . . . . . .....
4.2. Secondary Production . . . . . . . . . . . .....
4.3. Refining . . . . . . . . . . . . . . . . . . . . . .....
5. Environmental Protection . . . . . . . . .....
1. Introduction
Selenium [7782-49-2], atomic number 34, Ar
78.96, is a member of group 16 of the periodic
table and thus belongs to the chalcogens. Conso-
nant with its position between the nonmetal
sulfur and the metalloid tellurium, it has mainly
nonmetallic properties.
Naturally occurring selenium consists of six
stable isotopes: 74Se (0.9 %), 76Se (9.0 %), 77Se
(7.6 %), 78Se (23.5 %), 80Se (49.8 %), and 82Se
(9.2 %). Selenium is 66th in order of natural
abundance in the earth’s crust, with an average
concentration of 0.05 ppm.
Selenium was discovered in 1817 by BERZE-
LIUS in deposits in lead chambers used for the
production of sulfuric acid from copper pyrites.
The name selenium is derived from the Greek
word for moon and reflects the close resem-
blance between selenium and tellurium (¼
earth), which was discovered about 20 years
earlier.
Selenium is a byproduct of the extraction of
metals such as copper, zinc, and lead, and has
many industrial applications based on its
chemical and physical properties. Its semicon-
ducting properties and the light-induced
variation of its electrical conductivity are of
particular importance.

2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
DOI: 10.1002/14356007.a23_525
. 343 6. Uses . . . . . . . . . . . . . . . . . . . . . . . . ..... . 349
. 343 7. Quality Specifications and Analysis . ..... . 351
. 345 8. Selenium Compounds . . . . . . . . . . . ..... . 352
. 346 9. Economic Aspects . . . . . . . . . . . . . . ..... . 353
. 346 10. Biological Activity and Toxicology. . ..... . 354
. 348 References . . . . . . . . . . . . . . . . . . . . ..... . 354
. 349
. 349
2. Properties [1–4]
Like sulfur, selenium exists in several allotropic
forms. The structures of these and the mechanism
of transformation of one into another are not
completely understood. Red selenium is a
thermodynamically unstable, high-energy mod-
ification produced by precipitation at low tem-
perature, crystallization of selenium from solu-
tion, or quenching of selenium vapor or molten
selenium. The three modifications of monoclinic
selenium (a-, b-, and g-selenium) consist of Se8
rings and differ only in the packing of these in the
crystal (Fig. 1). The red, amorphous form con-
sists of chains in an irregular arrangement. It is
soluble in carbon disulfide and to some extent in
benzene, giving red solutions from which it can
be crystallized. Red selenium is an electrical
nonconductor. In the vapor phase, selenium ex-
ists mainly as Se8 rings. At higher temperature
these decompose into smaller units, eventually
forming Se2 molecules.
Thermodynamically unstable vitreous or
amorphous forms are obtained by rapid cooling
of molten selenium. The structure of these mod-
ifications is not yet fully understood. Presum-
ably, high molecular mass selenium rings of
various sizes are present, which explains the
poorly defined melting point of industrial-grade
344 Selenium and Selenium Compounds Vol. 32

often erroneous. Also, the previous history of the

material (e.g., high-temperature treatment) plays
an important role in the transformations between
various allotropic forms. The thermal properties
of selenium can be conveniently investigated by
differential thermal analysis [8]. Figure 2 shows
the various transformations of distilled selenium
on melting. The brittle vitreous form is trans-
formed at 50
C into the ductile vitreous form
(glass transition). Above ca. 120
C, vitreous
selenium changes into the stable hexagonal crys-
talline form, which melts at 220
C.
Important physical properties of selenium are
given below [1], [4]:

Atomic number 34
Electronic structure [Ar]3d104s24p4
Relative atomic mass 78.96
Oxidation states II,0,þIV,þVI
Atomic radius, nm 0.140
Ionic radii, nm
Se2 0.191
Se4þ 0.050
Se6þ 0.042
Ionization energy, kJ/mol 940
Ionization potential, eV
I 9.75
II 21.5
Electronegativity (Pauling) 2.4
Density at 25
C, g/cm3
Figure 1. Structures of selenium a) Se8 molecule in red a-, Hexagonal 4.189
b-, and g-selenium; b) Helical chains in hexagonal gray a-Monoclinic 4.389
selenium [4] Vitreous 4.285
Liquid (490 K) 3.975
vitreous selenium. This product softens at ca. Melting point,
C 217
Boiling point,
C (101.3 kPa;
50
C to a rubberlike state and is transformed at 760 mm Hg) 684.7 (0.03)
> 100
C into the gray, crystalline form, with Vapor pressure, kPa
release of the heat of crystallization. The black, 344.6
C 0.133 (1 mm Hg)
nonconducting form is slightly soluble in carbon 431.5
C 1.333 (10 mm Hg)
547.4
C 13.33 (100 mm Hg)
disulfide. Structures similar to those in vitreous 636.5
C 53.32 (400 mm Hg)
selenium are present in molten selenium. Electrical resistivity, W/cm*
On heating to > 100
C, both the red and the 25
C 1010
400
C 1.3105
black forms are transformed into the stable, gray,
Glass transition temperature,
C 30.2**
hexagonal (‘‘metallic’’) form in an exothermic (vitreous modification)
reaction. This modification is also produced by
reducing selenous acid with sulfur dioxide at high *
Strongly dependent on purity and light intensity.
temperature. Unlike the ring structure of the unsta- **
Strongly dependent on purity.
ble forms, it consists of helical chains in which the
structure is repeated at every third atom (Fig. 1). The electrical conductivity is strongly depen-
Gray selenium is a semiconductor whose electrical dent on purity. Thus, the conductivity of seleni-
conductivity increases by a factor > 1000 under um, including the poorly conducting amorphous
the influence of light (photoconductivity). form, can be increased considerably by traces (a
Impurities have a great influence on crystalliz- few parts per million) of halide ions or by alloying
ing properties, so results given in earlier research elements such as tellurium or arsenic. Because the
work, where impurity content is not quoted, are electrical properties are sensitive to the presence
Vol. 32
Figure 2. Differential thermal analysis of distilled high-purity selenium after 3 h at 450
C to give a material of uniform
structure [8]
of crystal defects, the purity of selenium, which
can be deliberately controlled by doping or alloy-
ing with other elements, plays an important role in
its use in electrical and electronic applications.
The chemical properties of selenium are in-
termediate between those of sulfur and those of
the metalloid tellurium. In its compounds, it
mainly exhibits the oxidation states II, þIV,
and þVI. The oxidation state þVI is consider-
ably less stable than for sulfur, and in acid
solutions is attained only by the action of strong
oxidizing agents such as chlorine or hydrogen
peroxide. Selenate(VI) is more easily obtained
by oxidation in alkaline solution. The redox
potentials of selenium in acid and alkaline solu-
tion are as follows [4], [7]:
Selenium burns in air to form selenium diox-
ide, which has the smell of rotten radishes.
Selenium is oxidized by nitric acid to selenous
acid. No reaction occurs with nonoxidizing acids
such as hydrochloric acid. Hot, concentrated
Selenium and Selenium Compounds 345
sulfuric acid dissolves selenium, giving a green
color and forming polymeric selenium cations,
for example:
Se8 þ3 H2 SO4 !Se2þ 
8 þ2 HSO4 þSO2 þ2 H2 O
With chlorine, vigorous oxidation to selenium
tetrachloride occurs. Selenium reacts with elec-
tropositive elements (e.g., many metals) to form
selenides and is therefore strongly corrosive,
especially at high temperature. With hydrogen,
the toxic gas hydrogen selenide is formed. Sele-
nium combines with sulfur to form nonstoichio-
metric alloys.
Selenium dissolves in solutions of strong
alkali, disproportionating into selenide and sele-
nite. It dissolves in alkali-metal sulfides, sulfites,
and cyanides, with formation of addition
compounds.
3. Occurrence and Raw Materials
Pure selenium minerals are very rare. Thus,
berzelianite (Cu2Se), tiemannite (HgS), and nau-
mannite (Ag2Se) are never processed simply to
obtain selenium. However, selenium occurs in
various concentrations as an accompanying ele-
ment in many sulfidic ores, although isomorphic
substitution in copper pyrites, iron pyrites, or
zinc blende cannot exceed a theoretical maxi-
mum of 0.5 % because of the larger ionic radius
of selenium (Se2: 0.191 nm, S2: 0.174 nm).
346 Selenium and Selenium Compounds
The selenium content of pyrites, zinc blende,
galena, and molybdenite is too low for economic
recovery. However, most copper concentrates
from ore flotation contain ca. 100 – 400 g/t
selenium and are hence the most important
sources of selenium. Selenium production is
therefore closely linked to copper production.
Selenium occurs in low concentrations (ca.
1 – 5 g/t) in some types of coal and mineral oil.
In addition to extraction of selenium from
copper ore, the recycling of photocopying drums
and rectifiers is becoming an important source.
4. Production
4.1. Primary Production
Selenium is an accompanying element obtained
during copper production (! Copper). The sul-
fidic copper concentrate (e.g., chalcopyrite) is
smelted in an oxidizing atmosphere to give a
copper matte containing 40 – 70 % Cu. This is
then blown in a converter to yield crude copper.
After reduction of excess copper oxide, the crude
copper is cast into anodes. Along with other
impurities, these copper anodes contain 25 –
70 % of the selenium, depending on the smelting
process. The rest of the selenium vaporizes dur-
ing smelting, mainly as selenium dioxide. This is
reduced to the element by the sulfur dioxide
produced during smelting and collects in the
slime formed in the gas purification equipment.
However, recovery is generally uneconomical
due to the complex composition of the slime.
Likewise, in the roasting of pyrites and zinc or
lead ore, most of the selenium volatilizes and
concentrates in the slime in the gas purification
equipment.
The selenium remaining in the copper anodes
is mainly in the form of Cu2Se, or sometimes
CuAgSe and Ag2Se, depending on the silver
content. Because they are insoluble in the sulfuric
acid electrolyte, these selenides remain in the
anode slime during electrolytic refining of
the copper, as do the noble metals. As a result
of the high stability of noble-metal selenides, the
copper selenides initially present in the anodes
can be converted to silver selenide or gold sele-
nide under the influence of the electrolyte, de-
pending on the noble-metal content. The seleni-
um in the anode slime is therefore in the form of
Vol. 32
various compounds, depending on the silver con-
tent. The selenium content of the anode slime
varies with the raw material and can reach > 20 %.
Selenium contents ( %) of anode slimes (from
which residual copper has not been removed)
from various copper tankhouses are as follows
[9]:
CCR (Noranda), Canada 10.0
Chuquicamata, Chile 4,0
Copper Refineries Pty, Australia 0.7
IMI Refiners, United Kingdom 2.0
Inco, Canada 8.4
Kidd Creek, Canada 19.5
MHO, Belgium 5.1
Norddeutsche Affinerie, Germany 7.5
Palabora, South Africa 3.6
Phelps Dodge, United States 8.8
Southwire, United States 0.6
The precious metals can be recovered only by
decomposing the very stable selenides with very
strong acid or alkali, or by roasting. Selenium
must be removed from the anode slime before the
noble metals can be recovered. The important
processes are [10]:
1. Fusion with sodium carbonate
2. Roasting with sodium carbonate
3. Direct oxidation (roasting)
4. Oxidative leaching with sodium hydroxide
solution under pressure
5. Roasting with concentrated sulfuric acid
6. A hydrometallurgical process of chlorination
in hydrochloric acid
In roasting with sodium carbonate, the anode
slime is first treated with sulfuric acid solution to
remove the copper and then mixed with sodium
carbonate and water to give a stiff paste. The
paste is extruded or pelletized, and dried. It is
then roasted at 530 – 650
C in a stream of
oxygen – air. Sodium carbonate prevents vapor-
ization of the selenium as selenium dioxide by
converting it completely into sodium selenate.
The roasted pellets are ground and leached with
water to dissolve sodium selenate. The precious
metals remain in the solid residue, which also
contains tellurium in the form of sodium tellurate
if higher roasting temperatures are used. The
selenate is crystallized from solution and reduced
with active carbon to sodium selenide, which is
redissolved in water and oxidized with air to
Vol. 32
elemental selenium. However, this process leads
to the formation of large amounts of wastewater.
Elemental selenium can also be precipitated
from selenate solution by strongly acidifying
with hydrochloric acid and reducing with iron
(II) salts or sulfur dioxide. Alternatively, the
sodium carbonate solution can be decomposed
by adding acid to precipitate impurities such as
tellurium. After filtration and further acidifica-
tion,selenium is precipitated by reduction
(Fig. 3).
In the direct oxidation process, copper is
removed first from the anode slime by sulfuric
acid. The slime is then dried and mixed with inert
materials that prevent sintering, and the selenium
is volatilized as selenium dioxide vapor at 600 –
Figure 3. Recovery of selenium from copper anode slime by
roasting with sodium carbonate
Selenium and Selenium Compounds 347
900
C. Silver selenite is formed initially at
< 400
C
Ag2 Seþ1:5 O2 !Ag2 SeO3
and decomposes at higher temperature
Ag2 SeO3 !2 AgþSeO2 þ0:5 O2
Selenium dioxide and some of the sulfur
dioxide formed from the sulfate fraction of the
anode slime are removed from the gas phase by
scrubbing with water or sodium hydroxide solu-
tion. After acidifying the wash liquor, the seleni-
um is reduced with sulfur dioxide (Fig. 4). Very
high volatilization rates are achieved at < 600
C
if the oxidative roasting is carried out in the
presence of sulfur dioxide. The reaction is be-
lieved to occur via the intermediate formation of
sulfur trioxide, which reacts with silver selenite:
Ag2 SeO3 þSO3 !Ag2 SO4 þSeO2
Figure 4. Recovery of selenium from copper anode slime by
acidic roasting
348 Selenium and Selenium Compounds
Figure 5. Recovery of selenium from copper anode slime by
the Dor
e process
This method is used by Outokumpu [11]. The
selenium dioxide produced is absorbed in dilute
sulfuric acid and immediately precipitated as
elemental selenium by the excess sulfur dioxide
in the scrubbing equipment.
Whereas roasting is carried out below the
melting point of the anode slime, in the classical
Dor
e process (Fig. 5) the anode slime is melted
after addition of fluxes. A matte consisting main-
ly of silver selenide and a high-lead slag contain-
ing precious metals are formed. The slag can be
processed in a lead smelting works, or the noble
metals can be recovered by flotation. The seleni-
um- containing matte is oxidized in the molten
state in a second stage, and selenium is vaporized
as its dioxide and absorbed in a scrubbing stage.
In a process operated by the Canadian copper
producer Noranda, these two stages are carried
out in succession in a top blown rotary converter
(TBRC) [12].
Alternatively, roasting with sulfation is car-
ried out in the presence of concentrated sulfuric
acid at 500 – 600
C after removal of tellurium
[9], although the large quantities of sulfur dioxide
and sulfur trioxide aerosols formed can present
environmental problems, and the severely corro-
sive properties of sulfuric acid at high tempera-
ture are difficult to deal with.
Apart from the widely used high-temperature
processes, hydrometallurgical extraction of sele-
nium from copper anode slimes is of some
importance in small plants [13–15]. For example,
in the copper refinery Austria-Metall [14], the
Vol. 32
anode slime is leached with hydrochloric acid
and chlorine, whereby the gold, platinum metals,
and selenium (as selenous acid) dissolve, and
silver remains in the residue as silver chloride.
Selenium is then precipitated from the hydro-
chloric acid solution by reduction with SO2.
4.2. Secondary Production
Although most selenium comes from primary
production, recycling of the selenium in used
rectifiers and photocopying drums is becoming
increasingly important for environmental rea-
sons. An older recovery process involves fusion
with sodium hydroxide to dissolve the selenium,
forming polyselenides:
6 NaOHþð2xþ1ÞSe!2 Na2 Sex þNa2 SeO3 þ3 H2 O
Selenium is obtained by acidifying the solu-
tion, but toxic hydrogen selenide may be formed.
This can be prevented if an alkaline solution of
sodium sulfite is used in the treatment process.
This dissolves selenium selectively, forming
sodium selenosulfate:
Na2 SO3 þSe!Na2 SeSO3
Selenium can be recovered by acidification,
which produces SO2.
In another process, selenium is treated with
sodium hydroxide solution and hydrogen per-
oxide to give a mixture of sodium selenite and
sodium selenate. The solution is acidified,
and selenium is precipitated by sulfur dioxide
[16].
Selenium can also be removed mechanically
from photocopying drums by using a water jet.
The aluminum drum can be reused whether
selenium is removed chemically or mechanical-
ly; the selenium on photocopying drums is thus
100 % recyclable without any deterioration of its
quality. Recycling of photocopying drums is
performed on a large scale (e.g., by the company
Retorte).
Selenium can be dissolved selectively from
residues by leaching with ammonia or amines in
an aprotic solvent in the presence of carbon
monoxide, to form amine salts of selenocarbamic
acid. It can then be precipitated in a pure state by
heating, with recovery of carbon monoxide and
the amine [17].
Vol. 32
4.3. Refining [3]
The roasting processes, followed by precipitation
with sulfur dioxide, gives selenium with a purity
usually exceeding 99 %, which is adequate for
many chemical applications. However, for elec-
tronic applications or xerography, selenium must
be purified further, because of the sensitivity of
its physical properties to the presence of
impurities.
The simplest method of purification is distil-
lation at atmospheric pressure and ca. 650
C,
which gives a purity up to 99.99 %. All the
nonvolatile elements, such as copper, nickel, iron,
and tellurium (if present as the dioxide), remain in
the distillation vessel. However, sulfur and mer-
cury (as HgSe) also distill over and are thus not
removed. Therefore, the crude selenium should
not contain mercury. A sufficiently pure product
is obtained if some of the selenium is not distilled,
ca. 50 % being left behind in the distillation vessel
to be returned later to the recovery process. The
corrosive properties of selenium vapor cause
problems during distillation, and purified seleni-
um that is collected in cast iron vessels sometimes
becomes contaminated with iron. Improved sep-
aration is obtained by vacuum distillation at
0.7 – 1.3 kPa and 360 – 400
C, or at 0.1 Pa and
260
C, which also reduces corrosivity [18]. A
further improvement in quality is obtained if the
melt is selectively oxidized by atmospheric oxy-
gen before distillation. This gives better separa-
tion of the more readily oxidized impurities.
An alternative to distillation for producing
high-quality selenium is vaporization with oxi-
dation, the selenium dioxide vapor formed being
absorbed in pure water. Mercury can be removed
from the solution by adsorption, and the other
metallic ions by ion exchangers. Elemental sele-
nium is then precipitated with high-purity sulfur
dioxide. Purities > 99.99 % can be achieved in
this way [19]. After precipitation, the selenium
powder is washed and can be remelted if desired
(e.g., to produce granules or to homogenize the
structure).
High-purity selenium is also obtained by the
hydride process. Impure selenium is treated with
hydrogen at ca. 550 – 685
C to form hydrogen
selenide, which is then decomposed at 1000
C.
Alternatively, it can be cooled to remove gaseous
impurities before thermal decomposition is car-
ried out [20].
Selenium and Selenium Compounds 349
5. Environmental Protection
Selenium is toxic at high concentration and must
therefore be effectively removed from off-gases
and wastewater. Since oxidizing processes are
used, selenium is present in the off-gas as seleni-
um dioxide. After cooling, it can be removed
either by dust filters or, because of its high
solubility, by absorption in water or sodium
hydroxide solution in gas-scrubbing equipment.
Because selenium dioxide is readily reduced by
organic compounds or sulfur dioxide, the off-gas
always contains a small amount of elemental
selenium. The selenium- containing dust filtered
out thus generally has a reddish color.
The wastewater treatment process and the
minimum attainable selenium content both de-
pend on the form in which selenium is present and
on the other components in the wastewater.
Although selenites in acid solution are reduced
readily to insoluble selenium, complete removal
is often difficult, because the selenium sometimes
precipitates as a colloid and the reduction is very
slow, especially in dilute solution. Therefore,
precipitation aids such as hydroxides of alumi-
num or iron must be added usually. Adsorptive
precipitation then enables a final content of <10
mg/L Se to be achieved in the wastewater.
Selenium- containing wastewater, as pro-
duced in the sour waters from petroleum refining,
can be purified by ion exchange [21].
6. Uses [5], [6]
The uses of selenium and selenium compounds
can be divided into the following categories [22]:
Electronic applications ca. 25 %
Pigments ca. 10 %
Glass ca. 40 %
Metallurgy ca. 10 %
Agricultural and biological applications 5%
Other uses (e.g., additives for rubber
vulcanization, oxidation catalysts) ca. 10 %
Rectifiers. Selenium conducts electricity
preferentially in one direction, and this property
has been utilized since 1920 for converting alter-
nating to direct current. A selenium rectifier
consists of a steel or aluminum plate coated with
nickel, with an additional coating of selenium,
350 Selenium and Selenium Compounds
50 – 60 mm thick. A sprayed cadmium alloy is
used as a counterelectrode. Several of these
rectifiers can be stacked in series. The efficiency
of rectification is ca. 85 %. Although selenium
rectifiers have been increasingly replaced by
germanium and silicon diode rectifiers, selenium
is still used where the performance of the rectifier
must be maintained even in the presence of high
countervoltage peaks.
Xerography (! Imaging Technology, 2.
Copying and Nonimpact Printing Processes, Sec-
tion 1.1.) [23]. The use of selenium in photo-
copying technology is based on its sensitivity to
light. Selenium, which may be highly pure,
doped, or alloyed, is deposited by a vaporization
process to form a film, ca. 50 mm thick, on an
aluminum drum. In the copying process, the
selenium surface is first charged by a high-volt-
age corona discharge. The drum is then exposed
to the projected light from the picture. Where the
light falls on the drum, the charge on the selenium
flows away, and a latent picture is thereby
formed. After the illumination stage, the thermo-
plastic toner powder is applied to the drum,
attracted electrostatically to the charged parts
(not illuminated), and then fixed by heat. A
photograph of a used photocopier drum after
60 000 photocopying runs is shown in Figure
6. The pure, amorphous selenium originally used
to coat the drums is very fragile and crystallizes at
Figure 6. Selenium-coated photocopier drums after 60 000
copies
Vol. 32
high temperature. Therefore, selenium stabilized
with tellurium or arsenic is now often used
(selenium – tellurium alloys or arsenic trisele-
nide), generally doped with small amounts of
chlorine. The alloys containing high-purity tel-
lurium enable copying rates to be increased and
light of a wider spectral range to be used. A still-
higher copying rate and wider spectral range are
possible with arsenic triselenide, which has been
used increasingly despite its toxicity and pro-
blems in manufacture. The drums also have a
considerably longer life. The selenium-based
system is now being replaced by organic photo-
conductors and amorphous silicon in low- cost
applications. However, selenium is maintaining
its position in industrial applications because of
its long life and high photocopying capacity.
Whereas a drum with organic photoconductors
has a lifetime of ca. 10 000 – 30 000 copies,
drums coated with selenium can withstand more
than 100 000 copying operations.
A potential application of xerography with
selenium as the photoconductor is in medicine.
Here, X-rays are used instead of visible light to
form the latent image. The advantage of this
process lies in the possibility for direct digitiza-
tion without producing a copy or a film, so that the
X-ray image is generated directly by a computer
on a visual display unit, and can be stored and
processed. Although several patents exist and
comprehensive research has been carried out, the
process is not yet in general use [24], [25].
Glass Manufacture. Selenium and seleni-
um compounds are used in silicate glass both in
decolorization and as a colorant for producing
intense yellow to red glass for special applica-
tions (selenium pink glass).
The main application in glass manufacture is in
the decolorization of glass, which is always col-
ored green to yellow green by traces of iron(II) and
iron(III). The addition of 30 – 150 g/t selenium
compensates for this color by adding the pink of
the selenium, with no apparent reduction in trans-
parency [26]. Formerly, selenium was added main-
ly as the element. However, elemental selenium
volatilizes below the melting temperature of glass,
so the yields were usually < 50 %. Therefore,
selenium compounds such as sodium selenite,
sodium selenate, barium selenite, or zinc selenite
are now increasingly used. Even so, some volatili-
zation losses are unavoidable. If an excess of
Vol. 32
selenium is used, pink glasses are obtained that
used to be important for artistic purposes.
The addition of cadmium sulfoselenide to
glass gives intense colors such as those required
for signal technology (e.g., traffic lights). The
colors vary from yellow to red, depending on the
CdSe content and melting conditions. Because of
the volatility of selenium compounds, reproduc-
ible color control is difficult.
Pigments (! Pigments, Inorganic, 3. Col-
ored Pigments, Chap. 2.). Selenium is used as a
pigment in the form of cadmium sulfoselenide.
Replacement of part of the sulfur in cadmium
sulfide by selenium changes the yellow color to an
intense red. The pigment has good brightness and
high stability. It is an important colorant for
plastics, because the addition of up to 1.5 %
cadmium sulfoselenide does not significantly af-
fect their physical properties; it is also stable at the
temperatures used for injection molding and
extrusion. However, the importance of these pig-
ments has declined considerably because of the
toxicity of cadmium compounds. In some areas,
the use of cadmium sulfoselenide is prohibited.
Metallurgy. The addition of selenium to
steel improves its machinability, resulting in
higher cutting speeds, lower energy consump-
tion, and a longer lifetime for the machine tool.
Although this is often achieved by adding sulfur,
selenium is always used where good hot and cold
formability, corrosion resistance, and surface
finish are also required. For stainless steel, the
addition rate is ca. 0.1 – 0.3 % Se. The machin-
ability of copper can also be improved by addi-
tion of selenium, but tellurium is used more
often. Addition of up to 0.1 % selenium to mag-
netic silicon steels improves their magnetic prop-
erties for use in transformer cores. Selenium is
also used in lead accumulators to improve the
casting and mechanical properties of lead –
antimony alloys with low antimony content.
Ferroselenium, copper selenide, and nickel
selenide are used in metallurgy.
Agriculture. Although the toxicity of soil
with high selenium content has long been known,
only much later was the need for selenium as an
essential trace element in low concentrations
discovered. A number of diseases formerly
thought to be due to vitamin E deficiency are in
Selenium and Selenium Compounds 351
fact the result of a deficiency of selenium. For
example, the addition of 0.1 – 0.3 ppm selenium
to the feed of chickens and pigs considerably
increases their growth rate and prevents certain
diseases, although the mechanism of this is not
fully understood. Selenium may act as an anti-
oxidant or free-radical trap.
The high rate of heart disease in Finland is
thought to be due to a selenium deficiency, the
soil being low in selenium, and the law now
requires that 6 – 16 g/t selenium be added to
fertilizers used there.
Selenium is added to fertilizers or animal feed
in the form of sodium selenite or sodium selenate,
which are absorbed more readily by plants.
Other Uses. Selenium and selenium com-
pounds (e.g., Selenac, dialkylselenium carba-
mates) are added with sulfur in rubber manufac-
ture. This improves the thermal stability of the
product and controls the vulcanization rate.
Selenium compounds are used to a small
extent as additives to oxidation catalysts for
hydrocarbons. Selenium dioxide is also used as
a selective oxidizing agent in organic chemistry.
Selenium acts as an absorbent for mercury,
forming stable mercury selenide, in gas purifica-
tion [27].
Addition of up to 5 % selenium has been
proposed in the preparation of dental amalgams
[28].
7. Quality Specifications and Analysis
Standard-grade selenium containing 99.5 % Se is
adequate for chemical and metallurgical use,
although many producers supply a 99.9 % Se
material. A special pigment grade containing
99.8 % Se is also marketed. The standard grades
are supplied as powders of various bulk densities,
depending on precipitation conditions. The stan-
dard grade is used mainly as starting material for
the production of high-purity selenium for photo-
copiers and electronic applications, which re-
quire a product containing > 99.999 % Se. Here,
the heavy-metal content must also be as low as
possible, and the oxygen content should be much
less than 5 ppm. Electronic-grade selenium is
supplied in the form of granules, which can be
produced by pouring molten selenium into deio-
nized water. In addition to chemical analysis, the
352 Selenium and Selenium Compounds
quality assessment of high-purity selenium in-
cludes measurement of electrical and especially
the photoelectrical properties [29]. The crystal-
lization temperature, determined by thermal
analysis, can give a useful indication of the
impurities in selenium (Fig. 2), although inter-
pretation of the results is not always
unambiguous.
The methods of analysis for selenium depend
on the matrix material. Direct spectroscopic de-
termination in raw materials and intermediate
products is usually impossible due to lack of
standards. Hence, selenium- containing materi-
als are first treated with nitric or sulfuric acid, for
example, to dissolve the selenium as selenous
acid. Most methods of determination involve
reduction of selenous acid with various reducing
agents, usually in solution in strong hydrochloric
acid. Selenium can be determined gravimetrical-
ly after reduction with iron(II), for example, if the
hydrochloric acid concentration is such that pre-
cipitation is complete and no loss of SeCl4 vapor
occurs [30]. The precipitated selenium is
weighed, or redissolved and determined by atom-
ic absorption spectroscopy, inductively coupled
plasma, or direct coupled plasma spectroscopy
[31]. In one of the oldest methods still in use,
selenous acid is titrated with thiosulfate accord-
ing to the equation:
Na2 SeO3 þ4 Na2 S2 O3 þ6 HCl!Na2 SeS4 O6 þNa2 S4 O6
þ6 NaClþ3 H2 O
Sodium monoselenopentathionate is formed,
and the excess of thiosulfate is back-titrated
iodometrically [32].
8. Selenium Compounds
Selenium forms a large number of chemical
compounds, some of which are of major indus-
trial importance.
Selenium Dioxide, Selenous Acid, Sele-
nites. Volatile selenium dioxide (sublimes at
315
C) is formed by the combustion of seleni-
um- containing materials. Selenium dioxide
[7446-08-4] dissolves readily in water (800 g/L
at 85
C) to form selenous acid [7783-07-5].
Unlike sulfur dioxide, selenium dioxide and se-
lenous acid are easily reduced to selenium by
reducing agents such as sulfur dioxide. Even
Vol. 32
traces of organic material reduce part of the
selenium dioxide to selenium, resulting in a
slightly reddish color of the SeO2. The sensitivity
to reduction is increased by the influence of light.
Selenium dioxide is used to oxidize alkyl groups
to carbonyl groups in organic chemistry, as a
lubricant additive, and as an additive in the elec-
trolysis of manganese. Selenous acid is more
stable than sulfurous acid and can be isolated in
the pure state in the form of colorless prisms.
Selenous acid decomposes above 70
C, forming
selenium dioxide and water. Sodium selenite
[10102-18-8], zinc selenite [13597-46-1], and
barium selenite [13718-59-7] are important ad-
ditives in glass manufacture. These salts are
prepared by the reaction of selenous acid with
the corresponding hydroxides or oxides, followed
by crystallization.
Selenium Trioxide, Selenic Acid, Sele-
nates. Selenous acid is oxidized to selenic acid
[7783-08-6] by strong oxidizing agents such as
chlorine, chloric acid, ozone, or anodic oxida-
tion. Selenic acid is a hygroscopic solid that melts
at 59.9
C. It is a much stronger oxidizing agent
than sulfuric acid; for example, a mixture of
concentrated selenic acid with concentrated hy-
drochloric acid evolves chlorine. Selenic acid
can be dehydrated with phosphorus pentoxide
or by applying vacuum (200 Pa) at 160
C to
give the strongly oxidizing selenium trioxide
[13768-86-0] (mp 118
C). Above 185
C, sele-
nium trioxide decomposes into selenium dioxide
and oxygen. Selenates are formed by the reaction
of selenic acid with metal oxides or hydroxides,
and resemble the isomorphous sulfates in both
structure and solubility. Sodium selenate [13410-
01-0] has become an important fertilizer
additive.
Hydrogen Selenide, Selenides. Hydrogen
selenide [7783-07-5] can be obtained either
directly from the elements at ca. 400
C or by
decomposition of the selenides of iron, magne-
sium, or aluminum with hydrochloric acid. It is a
colorless gas (bp 41.3
C) smelling like rotten
radishes, is even more toxic than hydrogen sul-
fide, and has a very irritating effect on the mucous
membranes, causing bronchial and nasal irrita-
tion. Hydrogen selenide is less stable than hy-
drogen sulfide and can be oxidized to selenium by
air, especially in the presence of light. Heavy-
Vol. 32 Selenium and Selenium Compounds 353

metal selenides such as copper selenide form the sodium selenide:

basis of selenium extraction from ores. Cadmium
selenide [1306-24-7], produced from cadmium
and selenium, is used in the pigment industry
together with cadmium sulfide.
High-purity zinc selenide [1315-09-9] is an
important infrared optical material. Single crys-
tals can be produced by reacting zinc vapor with
hydrogen selenide (chemical vapor deposition,
CVD). Copper indium selenide could be the basis
for solar cells of the future; light efficiencies of
14 % at an energy flux density of > 100 W/m2
can be achieved. However, the manufacturing
process (CVD) is expensive [23], [33].
Selenium Disulfide [7488-56-4] is formed
by reaction of hydrogen sulfide with selenous
acid or by direct combination of the elements.
The red powder (mp ca. 100
C) is used in
concentrations of < 1 % in shampoos and hair
preparations for the treatment of dandruff.
Selenium Halides. The action of halogens
or halides on elemental selenium yields various
selenium halides, depending on the temperature
and stoichiometric ratio. Selenium monochloride
[14457-70-6], Se2Cl2 (r 2.774 g/cm3), and sele-
nium monobromide, Se2Br2 (r 3.604 g/cm3), are
intensely colored, heavy liquids. SeCl4 [10026-
2 RBrþNa2 Se!R2 Seþ2 NaBr
2 RBrþNa2 Se2 !R2 Se2 þ2 NaBr
9. Economic Aspects
The total consumption of selenium in 1989 – 1991
was ca. 2100 – 2300 t/a (Table 1) [22], [34].
Average consumption in previous years was ca.
1700 t/a, although the published figures are unreli-
able due to the lack of information from Eastern
European countries. Of the total, about one-third is
produced as high-purity selenium for electronic
applications. Since selenium is a byproduct of
copper production, its price is subject to very wide
variations due to over- or underproduction from
time to time. The price of selenium has decreased
considerably (see Table 1). However, most dealing
takes place not on the open market, but directly
between the producer and consumer, so the true
prices differ from the published prices. The price
for standard-grade selenium in 1990 was ca. $ 10/
kg, and for high-purity selenium ca. $ 30 – 50/kg
Table 1. Estimated production (t), consumption (t), and price ($/kg) of
selenium [22], [35]

03-6] and SeBr4 [7789-65-3] are crystalline sub- 1989 1990 1991 1995*
stances that readily form complexes with alkali-
Production
metal halides. Selenium exhibits the oxidation Belgium 275 260 260 250
state þVI only in SeF6 [7783-79-1], the corre- Canada 270 340 240 300
sponding chloride and bromide being unstable. Chile 40 40 40 45
Of the oxyhalides, seleninyl chloride [7791-23- Finland 10 25 25 31
Germany 110 110 100 120
3], SeOCl2, is liquid at room temperature and is Japan 534 550 631 595
remarkable for its extreme reactivity, combining South Korea 20 25 25
with almost all elements. Mexico 25 25 25
Peru 20 20 20
Philippines 120 120 120 40
Organic Selenium Compounds. Like sul- Sweden 60 30 30 50
fur, selenium forms a large number of organic United States 253 287 240 360
compounds and can be a component of aliphatic, Former Yugoslavia 50 60 40
aromatic, and heterocyclic compounds. From the Zambia 50 60 40
Others 100 100 100
simple selenols (RSeH), which correspond to the Total 1937 2052 1918 1791
alcohols, to the amino acids, enzymes, and pro- Consumption
teins, a large number of selenium- containing United States 560 530 500
organic compounds are known, several of which Japan 283 289 263
Europe 830 800 770
are of biological importance. The starting com- China 200 300 350
pounds for the introduction of selenium into Others 300 300 300
organic compounds are often dialkyl selenides Total 2173 2119 2283
(R2Se) or dialkyl diselenides (R2Se2), which are Average price 13.81 11.26 10.56
formed from the corresponding alkyl halide and *
[36]
354 Selenium and Selenium Compounds
[36]. Manufacturers of elemental selenium in the
Western world include the large copper producers
Noranda Mines (Canada); Norddeutsche Affinerie
AG (Germany), with its subsidiary Retorte produc-
ing selenium compounds and high-purity seleni-
um; Metallurgie Hoboken-Overpelt (Belgium);
Mitsubishi Metals, Nippon Mining, Sumitomo
(Japan); Outokumpu (Finland); ASARCO, Kenne-
cott, and Phelps Dodge (United States) [35]. Sele-
nium compounds are also produced by Degussa
(Germany).
Although the consumption of selenium com-
pounds in the glass industry and as a fertilizer
additive is increasing, the use of cadmium sele-
nide in pigments is decreasing, and selenium is
being replaced by organic photoconductors in
some types of xerography. Therefore the total
consumption of selenium is not expected to
increase in the near future. However, the supply
of selenium could decrease in the future if copper
is produced partly by hydrometallurgical pro-
cesses, which do not yield a selenium byproduct.
10. Biological Activity and
Toxicology
Although selenium is an important trace element
in low concentrations, it is toxic at higher con-
centrations. It is an essential trace element in the
selenoenzyme glutathione peroxidase. This en-
zyme, together with vitamin E, is important for
the protection of cells from oxidative attack. The
activity of glutathione peroxidase in red blood
corpuscles correlates well with the selenium
concentration up to 100 mg/L [37], [38]. Low
selenium levels in the blood cause heart disease.
For instance, in China, Keshan disease, a cardio-
myopathy, caused the deaths of a large number of
people, especially children, until the daily con-
sumption of selenium was found to be very low.
The transition from essential trace quantities to
toxic quantities of selenium in terms of intake in
food is summarized below [38]:
Low-selenium area with Keshan disease 11 mg/d
Selenium adequate area 116 mg/d
National Academy of Sciences, Food and 50 – 200 mg/d
Nutrition Board ‘‘safe and adequate’’ range
Lowest observed effect level (LOEL) 3200 mg/d
High-selenium area with chronic selenosis 4990 mg/d
Vol. 32
The concentration of selenium in the blood
should be 60 – 100 mg/L. Although small
amounts of selenium may reduce the risk of
cancer, as indicated by some investigative stud-
ies, this has not been proved conclusively.
A chronic high selenium intake of > 5 mg/d
gives rise to nonspecific symptoms such as hair
loss, changes to the fingernails, diarrhea, effects
on the central nervous system, and nonspecific
changes to the liver. Also, a loss of appetite and a
tendency to walk in a circle can occur. High
concentrations of selenium in the workplace can
cause headaches and ‘‘selenium catarrh.’’ Also,
the breath can have a garliclike smell due to the
formation of methyl selenide, although this
effect is much less pronounced than with
tellurium.
A few selenium compounds exhibit acute
toxicity. Irritation of the mucous membranes of
the digestive system, liver damage, and toxic
edema of the lungs have been observed. The
most toxic compound is hydrogen selenide, for
which the MAK is 0.05 ppm, the MAK value for
other selenium compounds being 0.1 ppm. In
the United States, the TLV is 0.2 mg/m3. In a
study carried out in Canada on people working
in selenium production, if the TLV was ex-
ceeded slightly (up to 0.8 mg/m3) for limited
periods, no symptoms resulted [39]. In Ger-
many, the limit in drinking water is 0.008 mg/L
[40], and in the United States, the EPA recom-
mends a maximum contamination level (MCL) of
0.01 mg/L.
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2 K. W. Bagnall: The Chemistry of Selenium, Tellurium and
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3 Gmelin, System no. 10, Teil A 1953, Teil B 1949, Erg€an-
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7 A. J. Bard (ed.): Encyclopedia of Electrochemistry of the
Elements, Dekker, New York 1975.
Vol. 32 Selenium and Selenium Compounds 355

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8 M. Nachtrab, Retorte Company, personal communication. 30 A. M. Scherfhaufer, Fresenius Z. Anal. Chem. 164 (1958)
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Chem. Abstr. (1957) 10 858.
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Sch€oning). 2nd ed., Springer, Boston, MA 2006.
21 P. J. Marcantonio, US 4 915 928, 1990. J. E. Hoffmann, M. J. King: Selenium and Selenium Com-
22 Gardener, Met. Miner. Rev. (1991) 91. pounds, ‘‘Kirk Othmer Encyclopedia of Chemical Tech-
23 M. Caffaray, Trans. Inst. Min. Metall. Sect. C 97 (1988) nology’’, 5th edition, John Wiley & Sons, Hoboken, NJ,
C 87. online DOI: 10.1002/0471238961.1905120508150606.
24 Siemens, DE-OS 3 236 137, 1984 (K. Kempter). a01.pub2.
25 U. Schiebel, T. Buchkremer, G. Frings, P. Quadflieg, A. Olin, F. J. Mompean (eds.): Chemical Thermodynamics of
J. Non Cryst. Solids 115 (1989) 216. Selenium, Vol. 7, Elsevier, Amsterdam 2005.
26 B. Simmingsk€old in [5], p. 274. C. Reilly: Selenium in Food and Health, 2nd ed., Springer,
27 K. Itagaki, A. Yazawa, Erzmetall 35 (1982) 358. New York 2006.
28 A. Sato, US 4 528 034, 1982.