Book:

Standard methods of chemical analysis

Volumen 1
Frank Johnson Welcher

SELENIUM AND TELLURIUM.

Selenium, which was discovered in 1817 by Berzelius in the fue dust of pyrite burnes, is found in
cooper and iron pyrites, meteoric iron, and in the minerals clausthalite, PbSe; tiemannite, HgSe;
guanajuatite, Bi2Se3, klockmannite, CuSe; eucairite, CuAgSe; crookesite (Cu,Tl,Ag)2Se. The
commercial source of selenium (and tellarium) is the slimes in the electrolytic copper refining
cells.
Tellurium, which was discovered in 1782 by Muller, occurs in tellurides and arsenical iron pyrites
and is frequently associated with gold, silver, lead, bismuth, and iron Minerals in which tellurium
is found include altaite, PbT; calaverite, AuTe2; coloradoite, HgTe; rickardite, Cu 4Te8; petzite,
Ag3AuTe2 sylvanite, (Ag,Au)Te2, tellurite, TeO2 (tellurium ochre): tetradymite Bi 2Te3S. Tellurium
has also been found as the native metal.
Selenium is used as a decolorizer of glass to counteract the green ferrous shade; as selenium or
sodium selenite to produce clear red glass and for red enamels on ceramic ware and steel ware: in
vulcanied rubber-the presence of 1-3% selenium notably increases the resistance to abrasion. The
allotropie red crystalline form of selenium is used in microscopy as an imbedding substance.
Selenium is used in the xerographic process (photo-printing). It is also used in photoelectric cells,
Electrical rectifierand as a stabilizer di lubricating oils. Many selenium compounds are extremely
toxic.
Tellurium also fonds uses as a coloring substance in the glass and ceramic industries, and as a
(secondary) vulcanizing agent for rubber. It is also used in certain alloys of lead, iron and steel,
one of which is a variety of stainless steel.

DETECTION
Selenium and tellurium are commonly detected by precipitation with sufurdioxide in hydrochloric
acid solution.
A solution of tetravalent or hexavalent selenium containing strong hydrochloric acid in the cold
gives with either sufur dioxide or an aqueous solution of the gas red amorphous selenium which,
on warming, goes over to the gray, crystalline form. Solutions of tellurous or telluric tellurium in
the presence of dilute hydrochloric acid when gassed with sulfur dioxide yield black, elementary
tellurium.
Hydrogen sulfide gives with selenious acid solution a leo on yellow precipitate of selenium sulfide
which on standing dissociates into sulfur and red amorphous selenium. Similarly the red brown
tellurium sulfide, which is formed when hydrogen sulfide reacts with tellurous acid, dissociates
into tellurium and sulfur, Both of the sulfides are soluble in alkaline sulfide solutions.
Stannous chloride, ferrous sulfate, hydroxylamine hydrochloride, hydrazine sulfate, phosphorous

acid, or hypophosphorous acid added in the cold to solutions of tetravalent selenium give red
elementary selenium. Selenite is reduced to elemental tetravalent selenium by thiocyanate in 6 N
hydrochloric acid solution. As little as 0.05 . p. m of selenium can be detected by this reaction.
Potassium iodide added in excess to a hydrochloric acid solution of a selenate or selenite gives in
the cold red selenium together with iodine. On warming the iodine distills and the red selenium
goes over to the gray form.
A solution of Te(M or TeM) yields black elementary tellurium when treated with stannous
chloride, hypophosphorous acid, hydrazine hydrochloride or with aluminum amalgam, zinc or
magnesium.
Neutral selenious solutions give with barium chloride a precipitate of barium selenite which is
soluble in hydrochloric acid. Neutral selenates yield with barium chloride insoluble barium
selenate, which, like all selenates, is decomposed on heating with the evolution of oxygen and
subsequent reduction to the selenite.
Precipitations of silver selenite and mercuric selenite have been employed for the quanatative
estimation of selenium.
The few soluble alkaline tellurites give with barium chloride a white precipitate of barium tellurite
which is soluble in hydrochloric acid. Barium tellurate is analagous to barium selenate in its
formation and decomposition.
Sulfuric Acid Test-Selenium or a selenide with concentrated sulfuric acid, gently warmed, or with
fuming sulfuric acid in the cold gives a green color the intensity of which varies from a light green
to an almost opaque greenish black depending on the amount of selenium present. When the green
solution is added to water, red elementary selenium is precipitated. The green color in the concen
trated sulfuric acid is destroyed by warming the solution a few minutes The test is not applicable
to an oxidized selenium compound.
Tellurium or a telluride, but not oxidized tellurium compounds, gives in the cold with fuming
sulfuric acid or with warm concentrated sulfuric acid a red color, the intensity of which depends
on the amount of tellurium present when the red solution is poured into water, black elementary
tellurium is precipitated.
When the red solution is warmed, sulfur dioxide is evolved, the red color disappears, and if much
tellurium is present, white crystals of basic tellurium sulfate separate out. The sulfuric acid test has
been applied to the spectrophotometric determination of selenium and tellurium, and to the
detection of tellurium in minerals.

Detection of selenium and Tellurium in Complex Mixtures-The substance in question is treated

with aqua regia or with a mixture of hydrochloric acid and potassium chlorate, and the free
chlorine expelled at a temperature below boiling in order to avoid loss of volatile chlorides.
(Materials not decomposed in any acid or combination of acids may require fusion with an
alkaline oxidizing flux. For this purpose nickel crucibles should be used since platinum vessels are
seriously attacked.) The solution is then diluted and filtered to remove insoluble matter.
Should tellurous acid precipitate on diluting with water, it can be redissolved by hydrochloric acid.
The acid solution is treated with sulfur dioxide gas, the formation of a precipitate indicating the
possible of selenium, tellurium, or gold. If the precipitate is allowed to settle, the liquid decanted,
and the precipitate warmed with concentrated nitric acid, selenium and tellurium will aissive
leaving the gold insoluble. The nitric acid solution can be carefully evaporated with hydrochloric
acid to destroy the nitric acid and then treated in concentrated hydrochloric acid solution with
sulfur dioxide gas. If selenium is present it will appear as a red precipitate. The solution is then
filtered through asbestos and the filtrate diluted with water and gassed with sulfur dioxide. A black
precipitate indicates the presence of tellurium. The sulfur dioxide precipitate containing possible
selenium, tellurium, and gold can, after washing, be treated directly with hot concentrated sulfuric
acid in order to obtain, if possible, the characteristic selenium or tellurium colors.

ESTIMATION
In the determination of selenium and tellurium where special precautions are not taken in regard to
these elements, losses may occur due to coprecipitation or volatilization. Both elements may be
coprecipitated with hydrous oxides of bismuth, antimony, iron, zinc, zirconium, titanium: hence
such impurities should be solubilized. Volatilization loss is most pronounced with selenium which
will distill in various acid vapors. With nitric acid solutions the loss may be prevented by
oxidation to selenate with excess potassium bromate. With hydrochloric acid the loss is intensified
in solutions greater than 6 N. Fortunately in most cases volatilization may be greatly minimized by
a refluxing action made possible by the use of covered beakers or by evaporation below 100 oC.
Sulfuric acid fuming may be used to eliminate selenium from a selenium-tellurium mixture.
However, dry tellurium sulfate is slowly volatile above 400oC and should not be heated strongly
in the absence of an alkali bisulfate.
The presence of organic matter in a solution from which selenium is to be precipitated may cause
either a colloidal precipitate that cannot be filtered or a precipitate contaminated by organic matter.
If there is a dificult organic component in the sample, it should be completely destroyed by the use
of nitric acid and potassium chlorate or following nitric acid treatment by evaporation at 100C
with a l:l sulfuric-perchloric acid mixture.

SEPARATION
Volatilization in halogen or hydrohlide vapors may be employed to effect separations of selenium
and tellurium from other elements not volatile in this manner.
Thus selenides or tellurides may be distilled in chlorine. Heating selenites or tellurites in a stream
of hydrogen chloride gas results in the formation of volatile SeO 2.2l or O2.2l while
selenates and tellurates give chlorine in addition.
Alternatively a sulfuric acid solution containing selenium may be distilled with hydrobromic acid
to give a distillate of selenium relatively free from tellurium, iron, and copper but containing
usually all the arsenic, antimony and gemanium impurities.
In solution selenium and tellurium may be separated from a large number of elements first by
reduction to the tetravalent form and then to the elements by certain reducing agents in
hydrochloric acid medium. Sulfur dioxide is the preferred reducing agent. If the solution is very
impure, the elements are generally precipitated together and separated later. When solutions are
highly impure and the amount of selenium and tellurium low, separation of the selenium and
tellurium can be realized conveniently by precipitating basic zirconium selenite and tellurite along
with zirconium hydroxide at pH 2. By this means a concentrate may be obtained which is
remarkably free from iron, copper, and most other metals but containing all the arsenic and
antimony present in the original solution.

SEPARATION OF SELENIUM FROM TELLURIUM

Keller's method is to separate the selenium and tellurium from each other making use of the
principle that selenium is completely precipitated by sulfur dioxide from concentrated
hydrochloric acid solution while tellurium is not.
Procedure-The two elements are separated from the other elements by sulfur dioxide in dilute
hydrochloric acid solution. The washed precipitate is dissolved in nitric acid and the solution
evaporated to dryness on the water bath. The residue is dissolved in 200 mL of hydrochloric acid
and the solution warmed to expel all free nitric acid. The solution is then saturated with sulfur
dioxide gas at 15-20oC. The selenium is filtered off through a Gooch crucible, washed with water,
then alcohol, and dried at 105 oC. Following filtration the tellurium is precipitated in the filtrate by
diluting with water, adding more sulfur dioxide and hydrazine hydrochloride as in the gravimetric
method for tellurium. The tellurium is finally washed with water, then alcohol, dried at 90. and
weighed.
The foregoing method parallels that of Lenher and Kao.

Distillation Method of Len her and Smith-This method is based on the fact that selenium
chloride volatilizes from sulfuric acid solution when treated with hydrochloric acid gas while
tellurium chloride is nonvolatile under the same conditions. None of the common elements
naturally associated with selenium forms a volatile chloride under the conditions of the
determination.

GRAVIMETRIC METHODS FOR SELENTUM

Selenium is most commonly determined by precipitation as the element with sulfur dioxide.
Hydroxylamine and hydrazine are also employed as reductants. This reduction to the element at
the same time separates the selenium from most of the elements except gold, or in weaker
hydrochloric acid concentrations, tellurium, also. When hydroxylamine hydrochloride or
hydrazine hydrochloride is the precipitating agent, the material is usually most conveniently
brought into hydrochloric acid solution and the selenium converted into the selenious state.
From this selenious solution, which may be acid, neutral, or ammoniacal, these reducing agents on
boiling precipitate elementary selenium which can be transferred to Gooch crucible, was dried at
105oC, and weighed. Alternatively the crucible and precipitate be weighed, the selenium
volatilized and the crucible reweighed, the loss in weight being the weight of the selenium in the
sample. (Conversion of the primary red amorphous precipitate of selenium to the black granular
form by hot water is not recommended since a significant positive error may be introduced by
permanent water occlusion.)

SULFUR DIOXIDE METHOD

Procedure.-The addition of sulfur dioxide to a solution of selenious acid or a selenite wich is
stronger than 3.4 N 28% by volume in hydrochloric acid is one of the oldest and best methods of
precipitating elementary selenium.
A selenate or selenic acid must first be reduced to selenious acid by warming with hydrochloric
acid, after which sulfur dioxide can be introduced as the gas or as a saturated solution in water or
methyl alcohol.
The common sources of error in this method are: (1) the production of selenium monochloride as a
result of too slow gassing, too high a temperature during gassing, or the presence of nitric acid; (2)
the permanent enclosure of water or mother liquor in the precipitate brought about by too high a
solution temperature.
Where samples are prepared by evaporation to fumes with a sulfuric-nime mixture, it is desirable
to remove the residual nitric acid by the addition of solid sulfamic acid to the hot sulfuric acid.
Most of the emors are removed by rapid gassing of the solution, filtration as soon as possible after
gassing and preliminary drying at 50oC for 30 minutes before final treatment at 105. The
solution temperature during precipitation should be about 15-20C. A minimum of 6 N
hydrochloric acid is advisable to achieve the separation of selenium from tellurium present in
small amounts, but the maximum acid concentration is recommended when large amount are
involved. Utmost accuracy in this method is obtained by deposition of the selenium precipitate on
a base of suspended asbestos whereby the sources of error are still further reduced. It must not be
forgotten that the selenium precipitate is voluminous, and therefore coprecipitates finely divide

silica and organic Therefore the initial of the solution must be considered. As general principle,
the selenium should be filtered on an asbestos padded Gooch crucible and, drying at 105.,
weighed, ignited, and re-weighed. Any error from gold and most of the errors due to occlusions
are thus eliminated.

ITRIMETRIC METHODS FOR SELENIUM

Numerous direct and indirect titrimetric procedures have been advanced for the determination of
selenium. Many of these methods require conditions that are dificult to maintain and which render
them unsuitable for routine analysis. A commendable permanganate method is that of Gooch and
Clemons as extended by Schrenk and Browning and Barabas and Cooper. In this method selenium
and tellurium are oxidized in sulfuric acid medium from Se(IV) or Te(IV) to Se(IV) or Te(IV) by
an excess of permanganate, the excess being determined by back titration with ferrous ammonium
sulfate. Disodium phosphate is added to prevent the precipitation of manganese dioxide.

ITRIMETRIC PERMANGANATE METHOD

Schrenk and Browning's titrimetric permanganate method may be applied to the estimation of
selenium in refined selenium, sodium selenite and selenate, and iron selenide. Procedural details
for the first three determinations are given under "Determinations in specific substances."