Thiosulfate
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Thiosulfate ( IUPAC-recommended spelling; sometimes thiosulphate in British English) is an oxyanion of sulfur with the chemical formula . Thiosulfate also refers to the compounds containing this anion, which are the salts of thiosulfuric acid, e.g.
sodium thiosulfate Sodium thiosulfate (sodium thiosulphate) is an inorganic compound with the formula . Typically it is available as the white or colorless pentahydrate, . The solid is an efflorescent (loses water readily) crystalline substance that dissolves well in ...
. Thiosulfate also refers to the
esters In chemistry, an ester is a compound derived from an oxoacid (organic or inorganic) in which at least one hydroxyl group () is replaced by an alkoxy group (), as in the substitution reaction of a carboxylic acid and an alcohol. Glycerides ar ...
of thiosulfuric acid, e.g. ''O'',''S''-dimethyl thiosulfate . The prefix
thio- The prefix thio-, when applied to a chemical, such as an ion, means that an oxygen atom in the compound has been replaced by a sulfur atom. This term is often used in organic chemistry. For example, from the word ''ether,'' referring to an ox ...
indicates that the thiosulfate is a
sulfate The sulfate or sulphate ion is a polyatomic anion with the empirical formula . Salts, acid derivatives, and peroxides of sulfate are widely used in industry. Sulfates occur widely in everyday life. Sulfates are salts of sulfuric acid and many ...
with one
oxygen Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements as ...
replaced by sulfur. Thiosulfate is
tetrahedral In geometry, a tetrahedron (plural: tetrahedra or tetrahedrons), also known as a triangular pyramid, is a polyhedron composed of four triangular faces, six straight edges, and four vertex corners. The tetrahedron is the simplest of all the ...
at the central S atom. Thiosulfate salts occur naturally. Thiosulfate ion has C3v symmetry, and is produced by certain biochemical processes. It rapidly dechlorinates water and is notable for its use to halt bleaching in the paper-making industry. Thiosulfate salts are mainly used in dying in textiles and the bleaching of natural substances.
Sodium thiosulfate Sodium thiosulfate (sodium thiosulphate) is an inorganic compound with the formula . Typically it is available as the white or colorless pentahydrate, . The solid is an efflorescent (loses water readily) crystalline substance that dissolves well in ...
, commonly called ''hypo'' (from "hyposulfite"), was widely used in photography to fix black and white negatives and prints after the developing stage; modern 'rapid' fixers use
ammonium thiosulfate Ammonium thiosulfate (ammonium thiosulphate in British English) is an inorganic compound with the formula . It is white crystalline solid with ammonia odor, readily soluble in water, slightly soluble in acetone and insoluble in ethanol and diethyl ...
as a fixing salt because it acts three to four times faster. Some bacteria can metabolise thiosulfates.


Formation

Thiosulfate ion is produced by the reaction of sulfite ion with elemental sulfur, and by incomplete
oxidation Redox (reduction–oxidation, , ) is a type of chemical reaction in which the oxidation states of substrate change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is the gain of electrons or a ...
of sulfides (e.g.
pyrite The mineral pyrite (), or iron pyrite, also known as fool's gold, is an iron sulfide with the chemical formula Fe S2 (iron (II) disulfide). Pyrite is the most abundant sulfide mineral. Pyrite's metallic luster and pale brass-yellow hue giv ...
oxidation).
Sodium thiosulfate Sodium thiosulfate (sodium thiosulphate) is an inorganic compound with the formula . Typically it is available as the white or colorless pentahydrate, . The solid is an efflorescent (loses water readily) crystalline substance that dissolves well in ...
can be formed by
disproportionation In chemistry, disproportionation, sometimes called dismutation, is a redox reaction in which one compound of intermediate oxidation state converts to two compounds, one of higher and one of lower oxidation states. More generally, the term can ...
of sulfur dissolving in sodium hydroxide (similar to
phosphorus Phosphorus is a chemical element with the symbol P and atomic number 15. Elemental phosphorus exists in two major forms, white phosphorus and red phosphorus, but because it is highly reactive, phosphorus is never found as a free element on Ear ...
).


Reactions

Thiosulfate ions are stable only in neutral or alkaline solutions, but not in
acidic In computer science, ACID ( atomicity, consistency, isolation, durability) is a set of properties of database transactions intended to guarantee data validity despite errors, power failures, and other mishaps. In the context of databases, a ...
solutions, due to
disproportionation In chemistry, disproportionation, sometimes called dismutation, is a redox reaction in which one compound of intermediate oxidation state converts to two compounds, one of higher and one of lower oxidation states. More generally, the term can ...
to sulfite ions and sulfur, the sulfite ions being dehydrated to sulfur dioxide: : This reaction may be used to generate an
aqueous An aqueous solution is a solution in which the solvent is water. It is mostly shown in chemical equations by appending (aq) to the relevant chemical formula. For example, a solution of table salt, or sodium chloride (NaCl), in water would be re ...
suspension Suspension or suspended may refer to: Science and engineering * Suspension (topology), in mathematics * Suspension (dynamical systems), in mathematics * Suspension of a ring, in mathematics * Suspension (chemistry), small solid particles suspende ...
of sulfur and demonstrate the
Rayleigh scattering Rayleigh scattering ( ), named after the 19th-century British physicist Lord Rayleigh (John William Strutt), is the predominantly elastic scattering of light or other electromagnetic radiation by particles much smaller than the wavelength of th ...
of
light Light or visible light is electromagnetic radiation that can be perceived by the human eye. Visible light is usually defined as having wavelengths in the range of 400–700 nanometres (nm), corresponding to frequencies of 750–420 te ...
in
physics Physics is the natural science that studies matter, its fundamental constituents, its motion and behavior through space and time, and the related entities of energy and force. "Physical science is that department of knowledge which r ...
. If white light is shone from below, blue light is seen from sideways and orange light from above, due to the same mechanisms that color the sky at
midday Noon (or midday) is 12 o'clock in the daytime. It is written as 12 noon, 12:00 m. (for meridiem, literally 12:00 noon), 12 p.m. (for post meridiem, literally "after noon"), 12 pm, or 12:00 (using a 24-hour clock) or 1200 (military time). Solar ...
and
dusk Dusk occurs at the darkest stage of twilight, or at the very end of astronomical twilight after sunset and just before nightfall.''The Random House College Dictionary'', "dusk". At predusk, during early to intermediate stages of twilight, enou ...
. Thiosulfate ions react with iodine to give
tetrathionate The tetrathionate anion, , is a sulfur oxoanion derived from the compound tetrathionic acid, H2S4O6. Two of the sulfur atoms present in the ion are in oxidation state 0 and two are in oxidation state +5. Alternatively, the compound can be viewed ...
ions: : This reaction is key for iodometry. With
bromine Bromine is a chemical element with the symbol Br and atomic number 35. It is the third-lightest element in group 17 of the periodic table ( halogens) and is a volatile red-brown liquid at room temperature that evaporates readily to form a simi ...
(X = Br) and
chlorine Chlorine is a chemical element with the symbol Cl and atomic number 17. The second-lightest of the halogens, it appears between fluorine and bromine in the periodic table and its properties are mostly intermediate between them. Chlorine i ...
(X = Cl), thiosulfate ions are
oxidized Redox (reduction–oxidation, , ) is a type of chemical reaction in which the oxidation states of substrate change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is the gain of electrons or a ...
to
sulfate The sulfate or sulphate ion is a polyatomic anion with the empirical formula . Salts, acid derivatives, and peroxides of sulfate are widely used in industry. Sulfates occur widely in everyday life. Sulfates are salts of sulfuric acid and many ...
ions: :


Reactions with metals and metal ions

Thiosulfate ion extensively forms diverse complexes with
transition metal In chemistry, a transition metal (or transition element) is a chemical element in the d-block of the periodic table (groups 3 to 12), though the elements of group 12 (and less often group 3) are sometimes excluded. They are the elements that ca ...
s. In the era of silver-based
photography Photography is the art, application, and practice of creating durable images by recording light, either electronically by means of an image sensor, or chemically by means of a light-sensitive material such as photographic film. It is employe ...
, thiosulfate ion was consumed on a large scale as a "fixer" reagent. This application exploits thiosulfate ion's ability to dissolve silver halides. Thiosulfate ion (as
sodium thiosulfate Sodium thiosulfate (sodium thiosulphate) is an inorganic compound with the formula . Typically it is available as the white or colorless pentahydrate, . The solid is an efflorescent (loses water readily) crystalline substance that dissolves well in ...
) is also used to extract or leach
gold Gold is a chemical element with the symbol Au (from la, aurum) and atomic number 79. This makes it one of the higher atomic number elements that occur naturally. It is a bright, slightly orange-yellow, dense, soft, malleable, and ductile me ...
and
silver Silver is a chemical element with the symbol Ag (from the Latin ', derived from the Proto-Indo-European ''h₂erǵ'': "shiny" or "white") and atomic number 47. A soft, white, lustrous transition metal, it exhibits the highest electrical ...
from their ores as a less toxic alternative to
cyanide Cyanide is a naturally occurring, rapidly acting, toxic chemical that can exist in many different forms. In chemistry, a cyanide () is a chemical compound that contains a functional group. This group, known as the cyano group, consists of ...
ion. Also reflecting its affinity for
metals A metal (from Greek μέταλλον ''métallon'', "mine, quarry, metal") is a material that, when freshly prepared, polished, or fractured, shows a lustrous appearance, and conducts electricity and heat relatively well. Metals are typical ...
, thiosulfate ion rapid corrodes metals in
acidic In computer science, ACID ( atomicity, consistency, isolation, durability) is a set of properties of database transactions intended to guarantee data validity despite errors, power failures, and other mishaps. In the context of databases, a ...
conditions. Steel and stainless steel are particularly sensitive to pitting corrosion induced by thiosulfate ions. Molybdenum improves the resistance of stainless steel toward pitting (AISI 316L hMo). In alkaline aqueous conditions and medium temperature (60 °C), carbon steel and stainless steel (AISI 304L, 316L) are not attacked, even at high concentration of base (30%w  KOH), thiosulfate ion (10%w) and in presence of fluoride ion (5%w  KF).


Occurrence

The very rare
mineral In geology and mineralogy, a mineral or mineral species is, broadly speaking, a solid chemical compound with a fairly well-defined chemical composition and a specific crystal structure that occurs naturally in pure form.John P. Rafferty, ed. (2 ...
sidpietersite, , as the presence of this anion in the mineral bazhenovite was recently disputed.


Nomenclature

Thiosulfate is an acceptable common name (but used almost always); functional replacement
IUPAC The International Union of Pure and Applied Chemistry (IUPAC ) is an international federation of National Adhering Organizations working for the advancement of the chemical sciences, especially by developing nomenclature and terminology. It is ...
name is sulfurothioate; the systematic additive IUPAC name is trioxidosulfidosulfate(2−) or trioxido-1''κ''3''O''-disulfate(''S''—''S'')(2−). The external sulfur atom has an
oxidation state In chemistry, the oxidation state, or oxidation number, is the hypothetical charge of an atom if all of its bonds to different atoms were fully ionic. It describes the degree of oxidation (loss of electrons) of an atom in a chemical compound. C ...
of –1 while the central sulfur atom has an oxidation state of +5. The oxygen atoms have an oxidation state of –2. On the other hand, the external sulfur atom has a valence of 2 while the central sulfur atom has a valence of 6. The oxygen atoms have a valence of 2.


Biochemistry

The enzyme
rhodanase Rhodanese, also known as rhodanase, thiosulfate sulfurtransferase, thiosulfate cyanide transsulfurase, and thiosulfate thiotransferase, ...
(thiosulfate sulfurtransferase) catalyzes the detoxification of
cyanide Cyanide is a naturally occurring, rapidly acting, toxic chemical that can exist in many different forms. In chemistry, a cyanide () is a chemical compound that contains a functional group. This group, known as the cyano group, consists of ...
ion by thiosulfate ion by transforming them into
thiocyanate Thiocyanate (also known as rhodanide) is the anion . It is the conjugate base of thiocyanic acid. Common derivatives include the colourless salts potassium thiocyanate and sodium thiocyanate. Mercury(II) thiocyanate was formerly used in pyr ...
ion and sulfite ion: : Sodium thiosulfate has been considered as an empirical treatment for cyanide poisoning, along with
hydroxocobalamin Hydroxocobalamin, also known as vitamin B12a and hydroxycobalamin, is a vitamin found in food and used as a dietary supplement. As a supplement it is used to treat vitamin B12 deficiency including pernicious anemia. Other uses include treatment ...
. It is most effective in a pre-hospital setting, since immediate administration by emergency personnel is necessary to reverse rapid intracellular hypoxia caused by the inhibition of
cellular respiration Cellular respiration is the process by which biological fuels are oxidised in the presence of an inorganic electron acceptor such as oxygen to produce large amounts of energy, to drive the bulk production of ATP. Cellular respiration may be des ...
, at
complex IV The enzyme cytochrome c oxidase or Complex IV, (was , now reclassified as a translocasEC 7.1.1.9 is a large transmembrane protein complex found in bacteria, archaea, and mitochondria of eukaryotes. It is the last enzyme in the respiratory electr ...
. It activates thiosulfate sulfurtransferase ( TST) in mitochondria. TST is associated with protection against obesity and type II (insulin resistant) diabetes.


References


External links


''Thiosulfate ion'' General Chemistry Online, Frostburg State University
{{Antidotes * Corrosion Corrosive substances Sulfur oxyanions