Bisulfide

Bisulfide
Names
	IUPAC name Hydrosulfide
	Systematic IUPAC name Sulfanide (rarely used, not common)
	Other names hydrosulfide; hydrogenosulfide;
Identifiers
CAS Number	15035-72-0;
3D model (JSmol)	Interactive image;
ChEBI	CHEBI:29919;
ChEMBL	ChEMBL38703;
ChemSpider	4224877;
Gmelin Reference	24766
PubChem CID	5047209;
CompTox Dashboard (EPA)	DTXSID30893785 ;
	InChI InChI=1S/H2S/h1H2/p-1 Key: RWSOTUBLDIXVET-UHFFFAOYSA-M;
	SMILES [SH-];
Properties
Chemical formula	HS−;
Molar mass	33.07 g·mol−1
Conjugate acid	Hydrogen sulfide
Conjugate base	Sulfide
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). Infobox references

Bisulfide (or bisulphide in British English) is an inorganic anion with the chemical formula HS⁻ (also written as SH⁻). It contributes no color to bisulfide salts, and its salts may have a distinctive putrid smell. It is a strong base. Bisulfide solutions are corrosive and attack the skin.

It is an important chemical reagent and an industrial chemical, mainly used in paper pulp industry (Kraft process), textiles, synthetic flavors, coloring brasses, and iron control.

Properties

A variety of salts are known, including sodium hydrosulfide and potassium hydrosulfide. Ammonium hydrosulfide, a component of "stink bombs" has not been isolated as a pure solid. Some compounds described as salts of the sulfide dianion contain primarily hydrosulfide. For example, the hydrated form of sodium sulfide, nominally with the formula Na₂S · 9 H₂O, is better described as NaSH · NaOH · 8 H₂O.

The UV–visible spectrum of septic sewage from three different sites. The absorption of bisulfide is observed around 230 nm in each case.

Aqueous bisulfide absorbs light at around 230 nm in the UV–visible spectrum.^[1] Using this approach, bisulfide has been detected in the ocean^[2]^[3] and in sewage.^[4] Bisulfide should not be confused with the disulfide dianion, S2−2, or ⁻S–S⁻.

Basicity

The bisulfide anion can accept a proton:

HS⁻ + H⁺ → H₂S

(1)

Because of its affinity to accept a proton (H⁺), bisulfide has a basic character. In aqueous solution, it has a corresponding pK_a value of 6.9. Its conjugate acid is hydrogen sulfide (H₂S). However, bisulfide's basicity stems from its behavior as an Arrhenius base. A solution containing spectator-only counter ions, has a basic pH according to the following acid-base reaction:

HS⁻ + H₂O

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H₂S + OH⁻

(2)

Chemical reactions

Upon treatment with an acid, bisulfide converts to hydrogen sulfide. With strong acids, it can be doubly protonated to give H
₃S⁺
. Oxidation of bisulfide gives sulfate. When strongly heated, bisulfide salts decompose to produce sulfide salts and hydrogen sulfide.

2 HS⁻ → H₂S + S²⁻

(3)

Biochemistry

At physiological pH, hydrogen sulfide is usually fully ionized to bisulfide (HS⁻). Therefore, in biochemical settings, "hydrogen sulfide" is often used to mean, bisulfide. Hydrosulfide has been identified as the third gasotransmitter along with nitric oxide and carbon monoxide.^[5]

Other derivatives

SH⁻ is a soft anionic ligand that forms complexes with most metal ions. Examples include [Au(SH)₂]⁻ and (C₅H₅)₂Ti(SH)₂, derived from gold(I) chloride and titanocene dichloride, respectively.^[6]

Safety

Bisulfide salts are corrosive, strongly alkaline and release toxic hydrogen sulfide upon acidification.

References

^ Goldhaber, M.B.; Kaplan, I.R. (1975), "Apparent dissociation constants of hydrogen sulfide in chloride solutions", Marine Chemistry, 3 (1): 83–104, doi:10.1016/0304-4203(75)90016-X
^ Johnson, K.S.; Coletti, L.S. (2001), "In situ ultraviolet spectrophotometry for high resolution and long-term monitoring of nitrate, bromide and bisulfide in the ocean.", Deep-Sea Research, 49 (7): 1291–1305, Bibcode:2002DSRI...49.1291J, doi:10.1016/s0967-0637(02)00020-1
^ Guenther, E.A.; Johnson, K.S.; Coale, K.H. (2001), "Direct ultraviolet spectrophotometric determination of total sulfide and iodide in natural waters", Analytical Chemistry, 73 (14): 3481–3487, doi:10.1021/ac0013812, PMID 11476251
^ Sutherland-Stacey, L.; Corrie, S.; Neethling, A.; Johnson, I.; Gutierrez, O.; Dexter, R.; Yuan, Z.; Keller, J.; Hamilton, G. (2007), "Continuous measurement of dissolved sulfide in sewer systems", Water Science and Technology
^ J. W. Pavlik, B. C. Noll, A. G. Oliver, C. E. Schulz, W. R. Scheidt, “Hydrosulfide (HS⁻) Coordination in Iron Porphyrinates”, Inorganic Chemistry, 2010, vol. 49(3), 1017-1026.
^ Peruzzini, M.; de los Rios, I. & Romerosa, A. (2001), "Coordination Chemistry of Transition Metals with Hydrogen Chalcogenide and Hydrogen Chalcogenido Ligands", Progress in Inorganic Chemistry, 49: 169–543, doi:10.1002/9780470166512.ch3, ISBN 978-0-470-16651-2

[1] Goldhaber, M.B.; Kaplan, I.R. (1975), "Apparent dissociation constants of hydrogen sulfide in chloride solutions", Marine Chemistry, 3 (1): 83–104, doi:10.1016/0304-4203(75)90016-X

[2] Johnson, K.S.; Coletti, L.S. (2001), "In situ ultraviolet spectrophotometry for high resolution and long-term monitoring of nitrate, bromide and bisulfide in the ocean.", Deep-Sea Research, 49 (7): 1291–1305, Bibcode:2002DSRI...49.1291J, doi:10.1016/s0967-0637(02)00020-1

[3] Guenther, E.A.; Johnson, K.S.; Coale, K.H. (2001), "Direct ultraviolet spectrophotometric determination of total sulfide and iodide in natural waters", Analytical Chemistry, 73 (14): 3481–3487, doi:10.1021/ac0013812, PMID 11476251

[4] Sutherland-Stacey, L.; Corrie, S.; Neethling, A.; Johnson, I.; Gutierrez, O.; Dexter, R.; Yuan, Z.; Keller, J.; Hamilton, G. (2007), "Continuous measurement of dissolved sulfide in sewer systems", Water Science and Technology

[5] J. W. Pavlik, B. C. Noll, A. G. Oliver, C. E. Schulz, W. R. Scheidt, “Hydrosulfide (HS⁻) Coordination in Iron Porphyrinates”, Inorganic Chemistry, 2010, vol. 49(3), 1017-1026.

[6] Peruzzini, M.; de los Rios, I. & Romerosa, A. (2001), "Coordination Chemistry of Transition Metals with Hydrogen Chalcogenide and Hydrogen Chalcogenido Ligands", Progress in Inorganic Chemistry, 49: 169–543, doi:10.1002/9780470166512.ch3, ISBN 978-0-470-16651-2

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