Sulfide

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Sulfide
Sulfidion.svg
Names
Systematic IUPAC name
Sulfanediide [1] (substitutive)
Sulfide(2−) [1] (additive)
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
PubChem CID
Properties
S2−
Molar mass 32.06 g·mol−1
Conjugate acid Bisulfide
Related compounds
Other anions
Telluride
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

Sulfide (British English also sulphide) [2] is an inorganic anion of sulfur with the chemical formula S2− or a compound containing one or more S2− ions. Solutions of sulfide salts are corrosive. Sulfide also refers to chemical compounds large families of inorganic and organic compounds, e.g. lead sulfide and dimethyl sulfide. Hydrogen sulfide (H2S) and bisulfide (SH) are the conjugate acids of sulfide.

Contents

Chemical properties

The sulfide ion, S2−, does not exist in aqueous alkaline solutions of Na2S. [3] [4] Instead sulfide converts to hydrosulfide:

S2− + H2O → SH + OH

Upon treatment with an acid, sulfide salts convert to hydrogen sulfide:

S2− + H+ → SH
SH + H+ → H2S

Oxidation of sulfide is a complicated process. Depending on the conditions, the oxidation can produce elemental sulfur, polysulfides, polythionates, sulfite, or sulfate. Metal sulfides react with halogens, forming sulfur and metal salts.

8 MgS + 8 I2 → S8 + 8 MgI2

Metal derivatives

Aqueous solutions of transition metals cations react with sulfide sources (H2S, NaHS, Na2S) to precipitate solid sulfides. Such inorganic sulfides typically have very low solubility in water, and many are related to minerals with the same composition (see below). One famous example is the bright yellow species CdS or "cadmium yellow". The black tarnish formed on sterling silver is Ag2S. Such species are sometimes referred to as salts. In fact, the bonding in transition metal sulfides is highly covalent, which gives rise to their semiconductor properties, which in turn is related to the deep colors. Several have practical applications as pigments, in solar cells, and as catalysts. The fungus Aspergillus niger plays a role in the solubilization of heavy metal sulfides. [5]

Geology

Many important metal ores are sulfides. [6] Significant examples include: argentite (silver sulfide), cinnabar (mercury sulfide), galena (lead sulfide), molybdenite (molybdenum sulfide), pentlandite (nickel sulfide), realgar (arsenic sulfide), and stibnite (antimony), sphalerite (zinc sulfide), and pyrite (iron disulfide), and chalcopyrite (iron-copper sulfide).

Corrosion induced by sulfide

Dissolved free sulfides (H2S, HS and S2−) are very aggressive species for the corrosion of many metals such as steel, stainless steel, and copper. Sulfides present in aqueous solution are responsible for stress corrosion cracking (SCC) of steel, and is also known as sulfide stress cracking. Corrosion is a major concern in many industrial installations processing sulfides: sulfide ore mills, deep oil wells, pipelines transporting soured oil, Kraft paper factories.

Microbially-induced corrosion (MIC) or biogenic sulfide corrosion are also caused by sulfate reducing bacteria producing sulfide that is emitted in the air and oxidized in sulfuric acid by sulfur oxidizing bacteria. Biogenic sulfuric acid reacts with sewerage materials and most generally causes mass loss, cracking of the sewer pipes and ultimately, structural collapse. This kind of deterioration is a major process affecting sewer systems worldwide and leading to very high rehabilitation costs.

Oxidation of sulfide can also form thiosulfate (S
2
O2−
3
) an intermediate species responsible for severe problems of pitting corrosion of steel and stainless steel while the medium is also acidified by the production of sulfuric acid when oxidation is more advanced.

Organic chemistry

In organic chemistry, "sulfide" usually refers to the linkage C–S–C, although the term thioether is less ambiguous. For example, the thioether dimethyl sulfide is CH3–S–CH3. Polyphenylene sulfide (see below) has the empirical formula C6H4S. Occasionally, the term sulfide refers to molecules containing the –SH functional group. For example, methyl sulfide can mean CH3–SH. The preferred descriptor for such SH-containing compounds is thiol or mercaptan, i.e. methanethiol, or methyl mercaptan.

Disulfides

Confusion arises from the different meanings of the term "disulfide". Molybdenum disulfide (MoS2) consists of separated sulfide centers, in association with molybdenum in the formal +4 oxidation state (that is, Mo4+ and two S2−). Iron disulfide (pyrite, FeS2) on the other hand consists of S2−
2
, or S–S dianion, in association with divalent iron in the formal +2 oxidation state (ferrous ion: Fe2+). Dimethyldisulfide has the chemical binding CH3–S–S–CH3, whereas carbon disulfide has no S–S bond, being S=C=S (linear molecule analog to CO2). Most often in sulfur chemistry and in biochemistry, the disulfide term is commonly ascribed to the sulfur analogue of the peroxide –O–O– bond. The disulfide bond (–S–S–) plays a major role in the conformation of proteins and in the catalytic activity of enzymes.

Examples

FormulaMelting point (°C)Boiling point (°C)CAS number
H2S Hydrogen sulfide is a very toxic and corrosive gas characterised by a typical odour of "rotten egg".−85.7−60.20 7783-06-4
CdS Cadmium sulfide can be used in photocells.1750 1306-23-6
Calcium polysulfide ("lime sulfur") is a traditional fungicide in gardening.
CS2 Carbon disulfide is a precursor to organosulfur compounds.−111.646 75-15-0
PbS Lead sulfide is used in infra-red sensors.1114 1314-87-0
MoS2 Molybdenum disulfide, the mineral molybdenite, is used as a catalyst to remove sulfur from fossil fuels; also as lubricant for high-temperature and high-pressure applications. 1317-33-5
Cl–CH2CH2–S–CH2CH2–Cl Sulfur mustard (mustard gas) is an organosulfur compound (thioether) that was used as a chemical weapon in the First World War.13–14217 505-60-2
Ag2S Silver sulfide is a component of silver tarnish. 21548-73-2
Na2S Sodium sulfide, as the hydrate, is used in manufacture of kraft paper and as a precursor to organosulfur compounds.9201180 1313-82-2
ZnS Zinc sulfide is used for lenses and other optical devices in the infrared part of the spectrum. ZnS-doped with silver is used in alpha detectors while zinc sulfide with traces of copper has applications in photoluminescent strips for emergency lighting and luminous watch dials.1185 1314-98-3
C6H4S Polyphenylene sulfide is a polymer commonly called "Sulfar". Its repeating units are bonded together by sulfide (thioether) linkages. 26125-40-6
25212-74-2
SeS2 Selenium disulfide is an antifungal used in anti-dandruff preparations, such as Selsun Blue. The presence of the highly toxic selenium in healthcare and cosmetics products represents a general health and environmental concern.<100 7488-56-4
FeS2Known as "fool's gold", pyrite, is a common mineral.600 1317-66-4

Preparation

Sulfide compounds can be prepared in several different ways: [7]

  1. Direct combination of elements:
    Example: Fe(s) + S(s) → FeS(s)
  2. Reduction of a sulfate:
    Example: MgSO4(s) + 4C(s) → MgS(s) + 4CO(g)
  3. Precipitation of an insoluble sulfide:
    Example: M2+ + H2S(g) → MS(s) + 2H+(aq)

Safety

Many metal sulfides are so insoluble in water that they are probably not very toxic. Some metal sulfides, when exposed to a strong mineral acid, including gastric acids, will release toxic hydrogen sulfide.

Organic sulfides are highly flammable. When a sulfide burns it produces sulfur dioxide (SO2) gas.

Hydrogen sulfide, some of its salts, and almost all organic sulfides have a strong and putrid stench; rotting biomass releases these.

Nomenclature

The systematic names sulfanediide and sulfide(2−), valid IUPAC names, are determined according to the substitutive and additive nomenclatures, respectively. However, the name sulfide is also used in compositional IUPAC nomenclature which does not take the nature of bonding involved. Examples of such naming are selenium disulfide and titanium sulfide, which contains no sulfide ions whatsoever.

Related Research Articles

Hydroxide family of the hydroxide salts

Hydroxide is a diatomic anion with chemical formula OH. It consists of an oxygen and hydrogen atom held together by a covalent bond, and carries a negative electric charge. It is an important but usually minor constituent of water. It functions as a base, a ligand, a nucleophile, and a catalyst. The hydroxide ion forms salts, some of which dissociate in aqueous solution, liberating solvated hydroxide ions. Sodium hydroxide is a multi-million-ton per annum commodity chemical. A hydroxide attached to a strongly electropositive center may itself ionize, liberating a hydrogen cation (H+), making the parent compound an acid.

Inorganic chemistry deals with the synthesis and behavior of inorganic and organometallic compounds. This field covers all chemical compounds except the myriad organic compounds, which are the subjects of organic chemistry. The distinction between the two disciplines is far from absolute, as there is much overlap in the subdiscipline of organometallic chemistry. It has applications in every aspect of the chemical industry, including catalysis, materials science, pigments, surfactants, coatings, medications, fuels, and agriculture.

Compounds of carbon are defined as chemical substances containing carbon. More compounds of carbon exist than any other chemical element except for hydrogen. Organic carbon compounds are far more numerous than inorganic carbon compounds. In general bonds of carbon with other elements are covalent bonds. Carbon is tetravalent but carbon free radicals and carbenes occur as short-lived intermediates. Ions of carbon are carbocations and carbanions are also short-lived. An important carbon property is catenation as the ability to form long carbon chains and rings.

Sulfur Chemical element with atomic number 16

Sulfur (in British English, sulphur) is a chemical element with the symbol S and atomic number 16. It is abundant, multivalent, and nonmetallic. Under normal conditions, sulfur atoms form cyclic octatomic molecules with a chemical formula S8. Elemental sulfur is a bright yellow, crystalline solid at room temperature.

In chemistry, a disulfide refers to a functional group with the structure R−S−S−R′. The linkage is also called an SS-bond or sometimes a disulfide bridge and is usually derived by the coupling of two thiol groups. In biology, disulfide bridges formed between thiol groups in two cysteine residues are an important component of the secondary and tertiary structure of proteins. The connection is a persulfide, in analogy to its congener, peroxide (R−O−O−R′), but this terminology is rarely used, except in reference to hydrodisulfides.

Sulfate Anion

The sulfate or sulphate ion is a polyatomic anion with the empirical formula SO2−
4
. Sulfate is the spelling recommended by IUPAC, but sulphate is used in British English. 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 are prepared from that acid.

Hydrogen sulfide Poisonous, corrosive and flammable gas

Hydrogen sulfide is the chemical compound with the formula H
2
S
. It is a colorless chalcogen hydride gas with the characteristic foul odor of rotten eggs. It is very poisonous, corrosive, and flammable.

The Brønsted–Lowry theory is an acid–base reaction theory which was proposed independently by Johannes Nicolaus Brønsted and Thomas Martin Lowry in 1923. The fundamental concept of this theory is that when an acid and a base react with each other, the acid forms its conjugate base, and the base forms its conjugate acid by exchange of a proton (the hydrogen cation, or H+). This theory is a generalization of the Arrhenius theory.

Acidic oxides, or acid anhydride, are oxides that react with water to form an acid, or with a base to form a salt. They are oxides of either nonmetals or of metals in high oxidation states. Their chemistry can be systematically understood by taking an oxoacid and removing water from it, until only an oxide remains. The resulting oxide belongs to this group of substances. For example, sulfurous acid (SO2), sulfuric acid (SO3), and carbonic acid (CO2) are acidic oxides. An inorganic anhydride (a somewhat archaic term) is an acid anhydride without an organic moiety.

Bisulfide is an inorganic anion with the chemical formula HS. It contributes no color to bisulfide salts, and its salts may have a distinctive putrid smell. It is classified as a strong base, bisulfide solutions are corrosive and attack the skin.

Molybdenum trioxide is chemical compound with the formula MoO3. This compound is produced on the largest scale of any molybdenum compound. It is an intermediate in the production of molybdenum metal. It is also an important industrial catalyst. Molybdenum trioxide occurs as the rare mineral molybdite.

Calcium sulfide chemical compound

Calcium sulfide is the chemical compound with the formula CaS. This white material crystallizes in cubes like rock salt. CaS has been studied as a component in a process that would recycle gypsum, a product of flue-gas desulfurization. Like many salts containing sulfide ions, CaS typically has an odour of H2S, which results from small amount of this gas formed by hydrolysis of the salt.

Chalcogenide class of chemical compounds

A chalcogenide is a chemical compound consisting of at least one chalcogen anion and at least one more electropositive element. Although all group 16 elements of the periodic table are defined as chalcogens, the term chalcogenide is more commonly reserved for sulfides, selenides, tellurides, and polonides, rather than oxides. Many metal ores exist as chalcogenides. Photoconductive chalcogenide glasses are used in xerography. Some pigments and catalysts are also based on chalcogenides. The metal dichalcogenide MoS2 is a common solid lubricant.

Copper monosulfide chemical compound

Copper monosulfide is a chemical compound of copper and sulfur. It occurs in nature as the dark indigo blue mineral covellite. It is a moderate conductor of electricity. A black colloidal precipitate of CuS is formed when hydrogen sulfide, H2S, is bubbled through solutions of Cu(II) salts. It is one of a number of binary compounds of copper and sulfur (see copper sulfide for an overview of this subject), and has attracted interest because of its potential uses in catalysis and photovoltaics.

Thiocarbonate describes a family of anions with the general chemical formula CS
3−x
O2−
x
. Like the carbonate dianion, the thiocarbonates are planar, with carbon at the center. The average bond order from C to S or O is ​1 13. The state of protonation is usually not specified. These anions are good nucleophiles and good ligands.

Compounds of zinc are chemical compounds containing the element zinc which is a member of the group 12 of the periodic table. The oxidation state of most compounds is the group oxidation state of +2. Zinc may be classified as a post-transition main group element with zinc(II). Zinc compounds are noteworthy for their nondescript behavior, they are generally colorless, do not readily engage in redox reactions, and generally adopt symmetrical structures.

Thiosulfurous acid chemical compound

Thiosulfurous acid is a low oxidation state (+1) sulfur acid. It is the equivalent acid for disulfur monoxide. Thiosulfurous acid is formed by reacting hydrogen sulfide and sulfur dioxide at room temperature. The thiosulfurous acid molecule is unstable when condensed, reacting with itself.

Evolution of metal ions in biological systems refers to the incorporation of metallic ions into living organisms and how it has changed over time. Metal ions have been associated with biological systems for billions of years, but only in the last century have scientists began to truly appreciate the scale of their influence. Major and minor metal ions have become aligned with living organisms through the interplay of biogeochemical weathering and metabolic pathways involving the products of that weathering. The associated complexes have evolved over time.

Hydrogen chalcogenides are binary compounds of hydrogen with chalcogen atoms. Water, the first chemical compound in this series, contains one oxygen atom and two hydrogen atoms, and is the most common compound on the Earth's surface.

Sulfoxylic acid chemical compound

Sulfoxylic acid (H2SO2) (also known as hyposulfurous acid or sulfur dihydroxide) is an unstable oxoacid of sulfur in an intermediate oxidation state between hydrogen sulfide and dithionous acid. It consists of two hydroxy groups attached to a sulfur atom. Sulfoxylic acid contains sulfur in an oxidation state of +2. Sulfur monoxide (SO) can be considered as a theoretical anhydride for sulfoxylic acid, but it is not actually known to react with water.

References

  1. 1 2 "sulfide(2−) (CHEBI:15138)". Chemical Entities of Biological Interest (ChEBI). UK: European Bioinformatics Institute.
  2. https://www.lexico.com/en/definition/sulphide
  3. May, P.M.; Batka, D.; Hefter, G.; Könignberger, E.; Rowland, D. (2018). "Goodbye to S2-". Chem. Comm. 54: 1980–1983. doi:10.1039/c8cc00187a. PMID   29404555.
  4. Meyer, B; Ward, K; Koshlap, K; Peter, L (1983). "Second dissociation constant of hydrogen sulfide". Inorganic Chemistry. 22: 2345. doi:10.1021/ic00158a027.
  5. Harbhajan Singh. Mycoremediation: Fungal Bioremediation. p. 509.
  6. Vaughan, D. J.; Craig, J. R. “Mineral chemistry of metal sulfides" Cambridge University Press, Cambridge: 1978. ISBN   0-521-21489-0.
  7. Atkins; Shriver (2010). Inorganic Chemistry (5th ed.). New York: W. H. Freeman & Co. p. 413.