Thiosulfate

Thiosulfate
Names
IUPAC names
  • Sulfurothioate
  • Trioxidosulfidosulfate(2−)
  • Trioxido-1κ3O-disulfate(S—S)(2−)[1]
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
UNII
  • InChI=1S/H2O3S2/c1-5(2,3)4/h(H2,1,2,3,4)/p-2
    Key: DHCDFWKWKRSZHF-UHFFFAOYSA-L
  • [O-]S(=O)(=O)[S-]
Properties
S2O2−3
Molar mass 112.12 g·mol−1
Conjugate acid Thiosulfuric acid
Related compounds
Related compounds
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

Thiosulfate (IUPAC-recommended spelling; sometimes thiosulphate in British English) is an oxyanion of sulfur with the chemical formula S2O2−3. Thiosulfate also refers to the compounds containing this anion, which are the salts of thiosulfuric acid, such as sodium thiosulfate (Na2S2O3) and ammonium thiosulfate ((NH4)2S2O3). Thiosulfate salts occur naturally. Thiosulfate rapidly dechlorinates water, and is used to halt bleaching in the paper-making industry. Thiosulfate salts are mainly used for dyeing in textiles, and bleaching of natural substances.[2]

Structure and bonding

The thiosulfate ion is tetrahedral at the central S atom. The thiosulfate ion has C3v symmetry. 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. The S-S distance of about 201 pm in sodium thiosulfate is appropriate for a single bond. The S-O distances are slightly shorter than the S-O distances in sulfate.

For many years, the oxidation states of the sulfur atoms in the thiosulfate ion were considered to be +6 as in sulfate and −2 as in sulfide for the central and terminal atoms, respectively. This view precluded the disproportionation reaction of thiosulfate into sulfate and sulfide as a redox mechanism for providing energy to bacteria under anaerobic conditions in sediments because there is no change in oxidation state for either S atom. However, X-ray absorption near edge structure (XANES) spectroscopy measurements have revealed that the charge densities of the sulfur atoms point towards +5 and −1 oxidation states for the central and terminal S atoms, respectively. This observation is consistent with the disproportionation of thiosulfate into sulfate and sulfide as a redox mechanism freeing up energy from microbial fermentation.[3]

Formation

Thiosulfate ion is produced by the reaction of sulfite ion with elemental sulfur, and by incomplete oxidation of sulfides (e.g. pyrite oxidation). Sodium thiosulfate can be formed by disproportionation of sulfur dissolving in sodium hydroxide.

Reactions

Thiosulfate ions reacts with acids to give sulfur dioxide and various sulfur rings:[4]

8 S2O2−3 + 16 H+ → 8 SO2 + S8 + 8 H2O

This reaction may be used to generate sulfur colloids and demonstrate the Rayleigh scattering of light. 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 and dusk.

Thiosulfate ions react with iodine to give tetrathionate ions:

2 S2O2−3 + I2 → S4O2−6 + 2 I−

This reaction is key for iodometry. With bromine (X = Br) and chlorine (X = Cl), thiosulfate ions are oxidized to sulfate ions:

S2O2−3 + 4 X2 + 5 H2O → 2 SO2−4 + 8 X− + 10 H+

Reactions with metals and metal ions

Thiosulfate ion extensively forms diverse complexes with transition metals.

Also reflecting its affinity for metals, thiosulfate ion rapidly corrodes metals in acidic conditions. Steel and stainless steel are particularly sensitive to pitting corrosion induced by thiosulfate ions. Molybdenum improves the resistance of stainless steel toward pitting. In alkaline aqueous conditions and medium temperature (60 °C (140 °F)), carbon steel and stainless steel are not attacked, even at high concentration of base (30%/w potassium hydroxide), thiosulfate ion (10%/w) and in the presence of fluoride ion (5%/w potassium fluoride).

In film photography, thiosulfate salts are consumed on a large scale as a fixer reagent. This application exploits thiosulfate ion's ability to form coordination complexes with silver. Sodium thiosulfate, 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 as a fixing salt because it acts three to four times faster.[5]

Thiosulfate salts have been used to extract or leach gold and silver from their ores as a less toxic alternative to cyanide ion.[2]

Reactions with other salts

Inorganic nitrites detonate violently when heated with thiosulfates. This combination is notably used in emergency medicine in the cyanide antidote kit, though as separate medicines.[6][7]

Biochemistry

The enzyme rhodanase (thiosulfate sulfurtransferase) catalyzes the detoxification of cyanide ion by thiosulfate ion by transforming them into thiocyanate ion and sulfite ion:

CN− + S2O2−3 → SCN− + SO2−3

Sodium thiosulfate is used as a combination with amyl nitrite and sodium nitrite, along with hydroxocobalamin. 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, at complex IV.[7][8]

It activates thiosulfate sulfurtransferase (TST) in mitochondria. TST is associated with protection against obesity and type II (insulin resistant) diabetes.[9][10]

Thiosulfate can also work as electron donor for growth of bacteria oxidizing sulfur, such as Chlorobium limicola forma thiosulfatophilum. These bacteria use electrons from thiosulfate (and other sources) and carbon from carbon dioxide to synthesize carbon compounds through reverse Krebs cycle.[11]

Some bacteria can metabolise thiosulfates.[12]

Minerals

Thiosulfate ion is a component of the very rare mineral sidpietersite Pb4(S2O3)O2(OH)2.[13]

Nomenclature

Thiosulfate is an acceptable common name and almost always used.

The functional replacement IUPAC name is sulfurothioate; the systematic additive IUPAC name is trioxidosulfidosulfate(2−) or trioxido-1κ3O-disulfate(S—S)(2−).[1]

Thiosulfate also refers to the esters of thiosulfuric acid, e.g. O,S-dimethyl thiosulfate CH3−O−S(=O)2−S−CH3. Such species are rare.

References

  1. ^ a b International Union of Pure and Applied Chemistry (2005). Nomenclature of Inorganic Chemistry (IUPAC Recommendations 2005). Cambridge (UK): RSC–IUPAC. ISBN 0-85404-438-8. pp. 139,329. Electronic version.
  2. ^ a b Barberá, J.J.; Metzger, A.; Wolf, M. "Sulfites, Thiosulfates, and Dithionites". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a25_477. ISBN 978-3-527-30673-2.
  3. ^ Vairavamurthy, A.; Manowitz, B.; Luther, G.W.; Jeon, Y. (1993). "Oxidation state of sulfur in thiosulfate and implications for anaerobic energy metabolism". Geochimica et Cosmochimica Acta. 57 (7). Elsevier BV: 1619–1623. doi:10.1016/0016-7037(93)90020-w. ISSN 0016-7037.
  4. ^ Steudel, Ralf (1982). "Homocyclic Sulfur Molecules". Inorganic Ring Systems. Topics in Current Chemistry. Vol. 102. pp. 149–176. doi:10.1007/3-540-11345-2_10. ISBN 978-3-540-11345-4.
  5. ^ Sowerby, A. L. M., ed. (1961). Dictionary of Photography: A Reference Book for Amateur and Professional Photographers (19th ed.). London: Illife Books Ltd.
  6. ^ Kaye, Seymour M. (1 January 1978). "N - Nitrites". Encyclopedia of Explosives and Related Items (PDF) (Technical report). Vol. 8, M1 Thickener through Pyruvonitrolic Acid. Dover, NJ: Army Armament Research And Development Center - Large Caliber Weapon Systems Lab. p. N107. LCCN 61-61759. ADA057762, PATR 2700.
  7. ^ a b Hamel, J. (2011). "A Review of Acute Cyanide Poisoning with a Treatment Update" (PDF). Critical Care Nurse. 31 (1): 72–81, quiz 82. doi:10.4037/ccn2011799. PMID 21285466. Retrieved 2014-08-18.
  8. ^ Miles, Bryant (February 24, 2003). "Inhibitors & Uncouplers" (PDF). Texas A&M University. Archived from the original (PDF) on 4 March 2016. Retrieved 25 November 2015.
  9. ^ Stylianou, I. M. (2005). "Microarray gene expression analysis of the Fob3b obesity QTL identifies positional candidate gene Sqle and perturbed cholesterol and glycolysis pathways". Physiological Genomics. 20 (3): 224–232. CiteSeerX 10.1.1.520.5898. doi:10.1152/physiolgenomics.00183.2004. PMID 15598878.
  10. ^ Morton, N. M.; Beltram, J.; Carter, R. N. (2016). "Genetic identification of thiosulfate sulfurtransferase as an adipocyte-expressed antidiabetic target in mice selected for leanness". Nature Medicine. 22 (7): 771–779. doi:10.1038/nm.4115. PMC 5524189. PMID 27270587.
  11. ^ Buchanan, Bob B.; Arnon, Daniel I. (1990-04-01). "A reverse KREBS cycle in photosynthesis: consensus at last". Photosynthesis Research. 24 (1): 47–53. Bibcode:1990PhoRe..24...47B. doi:10.1007/BF00032643. ISSN 1573-5079. PMID 24419764. S2CID 2753977.
  12. ^ Hogan, C.M.; Nodvin, S.C. (10 May 2011) [25 March 2007]. Cleveland, C.J.; Jorgensen, A. (eds.). "Sulfur". The Encyclopedia of Earth. Washington, D.C.: Environmental Information Coalition - National Council for Science and the Environment. Archived from the original on 9 September 2011. Retrieved 29 November 2025.
  13. ^ Roberts, A.C.; Cooper, M.A.; Hawthorne, F.C.; Stanley, C.J.; Key, C.L.; Jambor, J.L. (1999). "Sidpietersite, Pb4(S6+O3S2-)O2(OH)2, a new thiosulfate-bearing mineral species from Tsumeh, Namibia". The Canadian Mineralogist. 37: 1269-1273.
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