The term 'sulfide' (also spelled 'sulphide', see
spelling) refers to several types of
chemical compounds containing
sulfur in its lowest
oxidation number of −2.
Formally, "sulfide" is the di
anion, S
2−, which exists in strongly
alkaline aqueous solutions formed from H
2S or alkali metal salts such as Li
2S, Na
2S, and K
2S. Sulfide is exceptionally basic and, with a pK
a > 14, it does not exist in appreciable concentrations even in highly alkaline water, being undetectable at pH < ~15 (8 M
NaOH). Instead, sulfide combines with protons to form HS
−, which is variously called 'hydrogen sulfide' ion, 'hydrosulfide' ion, 'sulfhydryl' ion, or 'bisulfide' ion. At still lower pH's (<7), HS
− converts to H
2S,
hydrogen sulfide. Thus, the exact sulfur species obtained upon dissolving sulfide salts depends on the pH of the final solution.
Aqueous solutions of
transition metal cations react with sulfide sources (H
2S, NaSH, Na
2S) to precipitate solid sulfides. Such
inorganic sulfides typically have very low solubility in water and many are related to minerals. One famous example is the bright yellow species CdS or "
cadmium yellow". The black tarnish formed on sterling silver is Ag
2S. 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 practical applications of many sulfide materials.
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 CH
3-S-CH
3.
Polyphenylene sulfide (see below) has the empirical formula C
6H
4S. Occasionally, the term sulfide refers to molecules containing the -SH
functional group. For example, methyl suflide can mean CH
3-SH. The preferred descriptor for such SH-containing compounds is
thiol or mercaptan, i.e. methanethiol or methyl mercaptan.
Confusion arises from the different meanings of the term "
disulfide". Molybdenum disulfide consists of separated sulfide centers, in association with molybdenum in the formal 4+ oxidation state. Iron disulfide on the other hand consists of S
22−, or S
−-S
−, in association with iron in the formal 2+ oxidation state. Dimethyldisulfide has the connectivity CH
3-S-S-CH
3, whereas
carbon disulfide has no S-S linkages, being S=C=S.
Examples
★
hydrogen sulfide (H
2S)
Uses
★
Cadmium sulfide (CdS) can be used in
photocells.
★
Calcium polysulfide ("
lime sulfur") is a traditional
fungicide in
gardening.
★
Carbon disulfide (CS
2) is sometimes used as a
solvent in industrial chemistry.
★
Lead sulfide (PbS) is used in
infra-red sensors.
★
Molybdenum disulfide (MoS
2), the mineral
molybdenite, is used as a catalyst to remove suflur from fossil fuels.
★
Silver sulfide (Ag
2S) is formed on
silver electrical contacts operating in an atmosphere rich in
hydrogen sulfide.
★
Sodium sulfide (Na
2S) is an important industrial chemical, used in manufacture of
kraft paper,
dyes,
leather tanning,
crude petroleum processing, treatment of
heavy metal pollution, and others.
★
Zinc sulfide (ZnS) is used for
lenses and other
optical devices in the
infrared part of the
spectrum.
★
Zinc sulfide with a trace of copper is used for
photoluminescent strips for emergency lighting and luminous watch dials.
★ Several metal sulfides are used as
pigments in art, although their use has declined somewhat due to their toxicity. Sulfide pigments include cadmium, mercury, and arsenic.
★
Polyphenylene sulfide is a polymer commonly called
Sulfar. Its repeating units are bonded together by sulfide (thioether) linkages.
Natural occurrence
Many important
metal ores are sulfides. Significant sulfide
minerals include:
★
arsenopyrite (
arsenic and
iron)
★
argentite (
silver)
★
chalcopyrite (
iron and
copper)
★
cinnabar (
mercury)
★
galena (
lead)
★
molybdenite (
molybdenum)
★
pentlandite (
nickel)
★
pyrite (
iron)
★
realgar (
arsenic)
★
sphalerite (
zinc) and
★
stibnite (
antimony).
Safety
Many metal sulfides are so insoluble 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, the fumes usually include toxic
sulfur dioxide (SO
2) gas.
Hydrogen sulfide, some of its salts, and almost all organic sulfides have a strong and putrid stench, as rotting biomass releases these.
Mercaptans, in particular, are the strongest-smelling substances known.
References
★ Meyer B, Ward K, Koshlap K, Peter L (1983). Second dissociation constant of hydrogen sulfide. ''Inorg Chem, 22:2345''.
See also
★
sulfate
★
sulfite
★
thioether
★
sulfidation