Bismuth compounds
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Bismuth compounds are compounds containing the element
bismuth Bismuth is a chemical element with the Symbol (chemistry), symbol Bi and atomic number 83. It is a post-transition metal and one of the pnictogens, with chemical properties resembling its lighter group 15 siblings arsenic and antimony. Elemental ...
(Bi). Bismuth forms trivalent and pentavalent compounds, the trivalent ones being more common. Many of its chemical properties are similar to those of
arsenic Arsenic is a chemical element with the symbol As and atomic number 33. Arsenic occurs in many minerals, usually in combination with sulfur and metals, but also as a pure elemental crystal. Arsenic is a metalloid. It has various allotropes, but ...
and
antimony Antimony is a chemical element with the symbol Sb (from la, stibium) and atomic number 51. A lustrous gray metalloid, it is found in nature mainly as the sulfide mineral stibnite (Sb2S3). Antimony compounds have been known since ancient time ...
, although they are less toxic than derivatives of those lighter elements.


Oxides and sulfides

At elevated temperatures, the vapors of the metal combine rapidly with oxygen, forming the yellow trioxide, . Wiberg, p. 768. Greenwood, p. 553. When molten, at temperatures above 710 °C, this oxide corrodes any metal oxide and even platinum. Krüger, p. 185 On reaction with a base, it forms two series of
oxyanion An oxyanion, or oxoanion, is an ion with the generic formula (where A represents a chemical element and O represents an oxygen atom). Oxyanions are formed by a large majority of the chemical elements. The formulae of simple oxyanions are determine ...
s: , which is polymeric and forms linear chains, and . The anion in is a cubic octameric anion, , whereas the anion in is tetrameric. The dark red bismuth(V) oxide, , is unstable, liberating gas upon heating. The compound NaBiO3 is a strong oxidising agent. Greenwood, p. 578. Bismuth sulfide, , occurs naturally in bismuth ores. It is also produced by the combination of molten bismuth and sulfur. Greenwood, pp. 559–561.
Bismuth oxychloride Bismuth oxychloride is an inorganic compound of bismuth with the formula Bi O Cl. It is a lustrous white solid used since antiquity, notably in ancient Egypt. Light wave interference from its plate-like structure gives a pearly iridescent light ...
(BiOCl, see figure at right) and bismuth oxynitrate (BiONO3) stoichiometrically appear as simple anionic salts of the bismuthyl(III) cation (BiO+) which commonly occurs in aqueous bismuth compounds. However, in the case of BiOCl, the salt crystal forms in a structure of alternating plates of Bi, O, and Cl atoms, with each oxygen coordinating with four bismuth atoms in the adjacent plane. This mineral compound is used as a pigment and cosmetic (see below). Krüger, p. 184.


Bismuthine and bismuthides

Unlike the lighter
pnictogen A pnictogen ( or ; from grc, πνῑ́γω "to choke" and -gen, "generator") is any of the chemical elements in group 15 of the periodic table. Group 15 is also known as the nitrogen group or nitrogen family. Group 15 consists of the el ...
s nitrogen, phosphorus, and arsenic, but similar to
antimony Antimony is a chemical element with the symbol Sb (from la, stibium) and atomic number 51. A lustrous gray metalloid, it is found in nature mainly as the sulfide mineral stibnite (Sb2S3). Antimony compounds have been known since ancient time ...
, bismuth does not form a stable
hydride In chemistry, a hydride is formally the anion of hydrogen( H−). The term is applied loosely. At one extreme, all compounds containing covalently bound H atoms are called hydrides: water (H2O) is a hydride of oxygen, ammonia is a hydride ...
. Bismuth hydride,
bismuthine Bismuthine (IUPAC name: bismuthane) is the chemical compound with the formula BiH3. As the heaviest analogue of ammonia (a pnictogen hydride), BiH3 is unstable, decomposing to bismuth metal well below 0 °C. This compound adopts the expected ...
(), is an
endothermic In thermochemistry, an endothermic process () is any thermodynamic process with an increase in the enthalpy (or internal energy ) of the system.Oxtoby, D. W; Gillis, H.P., Butler, L. J. (2015).''Principle of Modern Chemistry'', Brooks Cole. ...
compound that spontaneously decomposes at room temperature. It is stable only below −60 °C.
Bismuthide The bismuthide ion is Bi3−. Bismuthides are compounds of bismuth with more electropositive elements. They are intermetallic compounds, containing partially metallic and partially ionic bonds. The majority of bismuthides adopt efficient pac ...
s are
intermetallic An intermetallic (also called an intermetallic compound, intermetallic alloy, ordered intermetallic alloy, and a long-range-ordered alloy) is a type of metallic alloy that forms an ordered solid-state compound between two or more metallic eleme ...
compounds between bismuth and other metals. In 2014 researchers discovered that sodium bismuthide can exist as a form of matter called a “three-dimensional topological Dirac semi-metal” (3DTDS) that possess 3D
Dirac fermion In physics, a Dirac fermion is a spin-½ particle (a fermion) which is different from its antiparticle. The vast majority of fermions – perhaps all – fall under this category. Description In particle physics, all fermions in the standard model ...
s in bulk. It is a natural, three-dimensional counterpart to
graphene Graphene () is an allotrope of carbon consisting of a single layer of atoms arranged in a hexagonal lattice nanostructure.
with similar electron mobility and velocity. Graphene and
topological insulator A topological insulator is a material whose interior behaves as an electrical insulator while its surface behaves as an electrical conductor, meaning that electrons can only move along the surface of the material. A topological insulator is an ...
s (such as those in 3DTDS) are both crystalline materials that are electrically insulating inside but conducting on the surface, allowing them to function as
transistor upright=1.4, gate (G), body (B), source (S) and drain (D) terminals. The gate is separated from the body by an insulating layer (pink). A transistor is a semiconductor device used to Electronic amplifier, amplify or electronic switch, switch e ...
s and other electronic devices. While sodium bismuthide () is too unstable to be used in devices without packaging, it can demonstrate potential applications of 3DTDS systems, which offer distinct efficiency and fabrication advantages over planar graphene in
semiconductor A semiconductor is a material which has an electrical resistivity and conductivity, electrical conductivity value falling between that of a electrical conductor, conductor, such as copper, and an insulator (electricity), insulator, such as glas ...
and
spintronics Spintronics (a portmanteau meaning spin transport electronics), also known as spin electronics, is the study of the intrinsic spin of the electron and its associated magnetic moment, in addition to its fundamental electronic charge, in solid-st ...
applications.


Halides

The halides of bismuth in low oxidation states have been shown to adopt unusual structures. What was originally thought to be bismuth(I) chloride, BiCl, turns out to be a complex compound consisting of Bi cations and BiCl and BiCl anions. The Bi cation has a distorted tricapped
trigonal prism In chemistry, octahedral molecular geometry, also called square bipyramidal, describes the shape of compounds with six atoms or groups of atoms or ligands symmetrically arranged around a central atom, defining the vertices of an octahedron. The oc ...
atic molecular geometry and is also found in , which is prepared by reducing a mixture of
hafnium(IV) chloride Hafnium(IV) chloride is the inorganic compound with the formula HfCl4. This colourless solid is the precursor to most hafnium organometallic compounds. It has a variety of highly specialized applications, mainly in materials science and as a ca ...
and
bismuth chloride Bismuth chloride (or butter of bismuth) is an inorganic compound with the chemical formula BiCl3. It is a covalent compound and is the common source of the Bi3+ ion. In the gas phase and in the crystal, the species adopts a pyramidal structure, ...
with elemental bismuth, having the structure . Other polyatomic bismuth cations are also known, such as Bi, found in . Bismuth also forms a low-valence bromide with the same structure as "BiCl". There is a ''true'' monoiodide, BiI, which contains chains of units. BiI decomposes upon heating to the triiodide, , and elemental bismuth. A monobromide of the same structure also exists. In oxidation state +3, bismuth forms trihalides with all of the halogens: , , , and . All of these except are
hydrolyze Hydrolysis (; ) is any chemical reaction in which a molecule of water breaks one or more chemical bonds. The term is used broadly for substitution, elimination, and solvation reactions in which water is the nucleophile. Biological hydrolysis ...
d by water.
Bismuth(III) chloride Bismuth chloride (or butter of bismuth) is an inorganic compound with the chemical formula BiCl3. It is a covalent compound and is the common source of the Bi3+ ion. In the gas phase and in the crystal, the species adopts a pyramidal structure, i ...
reacts with
hydrogen chloride The compound hydrogen chloride has the chemical formula and as such is a hydrogen halide. At room temperature, it is a colourless gas, which forms white fumes of hydrochloric acid upon contact with atmospheric water vapor. Hydrogen chloride ga ...
in
ether In organic chemistry, ethers are a class of compounds that contain an ether group—an oxygen atom connected to two alkyl or aryl groups. They have the general formula , where R and R′ represent the alkyl or aryl groups. Ethers can again be c ...
solution to produce the acid . The oxidation state +5 is less frequently encountered. One such compound is , a powerful oxidizing and fluorinating agent. It is also a strong fluoride acceptor, reacting with
xenon tetrafluoride Xenon tetrafluoride is a chemical compound with chemical formula . It was the first discovered binary compound of a noble gas. It is produced by the chemical reaction of xenon with fluorine: : Xe + 2  → This reaction is exothermic, rele ...
to form the cation:
Suzuki is a Japan, Japanese multinational corporation headquartered in Minami-ku, Hamamatsu, Japan. Suzuki manufactures automobiles, motorcycles, All-terrain vehicle, all-terrain vehicles (ATVs), outboard motor, outboard marine engines, wheelchairs ...
, p. 8.
: + →


Aqueous species

In
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 ...
solution, the Bi ion is solvated to form the aqua ion in strongly acidic conditions. At pH > 0 polynuclear species exist, the most important of which is believed to be the octahedral complex [].


Applications

* Bismuth is included in
BSCCO Bismuth strontium calcium copper oxide (BSCCO, pronounced ''bisko''), is a type of cuprate superconductor having the generalized chemical formula Bi2 Sr2 Ca''n''−1 Cu''n'' O2''n''+4+''x'', with ''n'' = 2 being the most commonly stud ...
(bismuth strontium calcium copper oxide) which is a group of similar superconducting compounds discovered in 1988 that exhibit the highest superconducting transition temperatures. *
Bismuth subnitrate Bismuth oxynitrate is the name applied to a number of compounds that contain Bi3+, nitrate ions and oxide ions and which can be considered as compounds formed from Bi2O3, N2O5 and H2O. Other names for bismuth oxynitrate include bismuth subnit ...
is a component of glazes that produces an iridescence and is used as a pigment in paint. *
Bismuth telluride Bismuth telluride (Bi2Te3) is a gray powder that is a compound of bismuth and tellurium also known as bismuth(III) telluride. It is a semiconductor, which, when alloyed with antimony or selenium, is an efficient thermoelectric material for refriger ...
is a semiconductor and an excellent
thermoelectric The thermoelectric effect is the direct conversion of temperature differences to electric voltage and vice versa via a thermocouple. A thermoelectric device creates a voltage when there is a different temperature on each side. Conversely, when ...
material. Bi2Te3 diodes are used in mobile refrigerators, CPU coolers, and as detectors in
infrared Infrared (IR), sometimes called infrared light, is electromagnetic radiation (EMR) with wavelengths longer than those of visible light. It is therefore invisible to the human eye. IR is generally understood to encompass wavelengths from around ...
spectrophotometers. *
Bismuth oxide Bismuth(III) oxide is perhaps the most industrially important compound of bismuth. It is also a common starting point for bismuth chemistry. It is found naturally as the mineral bismite (monoclinic) and sphaerobismoite (tetragonal, much more rare ...
, in its delta form, is a solid electrolyte for oxygen. This form normally breaks down below a high-temperature threshold, but can be electrodeposited well below this temperature in a highly alkaline solution. * Bismuth germanate is a scintillator, widely used in X-ray and gamma ray detectors. *
Bismuth vanadate Bismuth vanadate is the inorganic compound with the formula BiVO4. It is a bright yellow solid. It is widely studied as visible light photo-catalyst with a narrow band gap of less than 2.4 eV. It is a representative of "complex inorganic colored ...
is an opaque yellow pigment used by some artists' oil,
acrylic Acrylic may refer to: Chemicals and materials * Acrylic acid, the simplest acrylic compound * Acrylate polymer, a group of polymers (plastics) noted for transparency and elasticity * Acrylic resin, a group of related thermoplastic or thermosett ...
, and watercolor paint companies, primarily as a replacement for the more toxic
cadmium sulfide Cadmium sulfide is the inorganic compound with the formula CdS. Cadmium sulfide is a yellow solid.Egon Wiberg, Arnold Frederick Holleman (2001''Inorganic Chemistry'' Elsevier It occurs in nature with two different crystal structures as the rare mi ...
yellows in the greenish-yellow (lemon) to orange-toned yellow range. It performs practically identically to the cadmium pigments, such as in terms of resistance to degradation from UV exposure, opacity, tinting strength, and lack of reactivity when mixed with other pigments. The most commonly-used variety by artists' paint makers is lemon in color. In addition to being a replacement for several cadmium yellows, it also serves as a non-toxic visual replacement for the older chromate pigments made with zinc, lead, and strontium. If a green pigment and barium sulfate (for increased transparency) are added it can also serve as a replacement for
barium chromate Barium chromate, named barium tetraoxochromate(VI) by the IUPAC, is a yellow sand like powder with the formula BaCrO4. It is a known oxidizing agent and produces a green flame when heated, a result of the barium ions. History The first naturally o ...
, which possesses a more greenish cast than the others. In comparison with
lead chromates Lead is a chemical element with the symbol Pb (from the Latin ) and atomic number 82. It is a heavy metal that is denser than most common materials. Lead is soft and malleable, and also has a relatively low melting point. When freshly cut, ...
, it does not blacken due to
hydrogen sulfide Hydrogen sulfide is a chemical compound with the formula . It is a colorless chalcogen-hydride gas, and is poisonous, corrosive, and flammable, with trace amounts in ambient atmosphere having a characteristic foul odor of rotten eggs. The unde ...
in the air (a process accelerated by UV exposure) and possesses a particularly brighter color than them, especially the lemon, which is the most translucent, dull, and fastest to blacken due to the higher percentage of lead sulfate required to produce that shade. It is also used, on a limited basis due to its cost, as a vehicle paint pigment. * A
catalyst Catalysis () is the process of increasing the rate of a chemical reaction by adding a substance known as a catalyst (). Catalysts are not consumed in the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recyc ...
for making acrylic fibers. * As an
electrocatalyst An electrocatalyst is a catalyst that participates in electrochemical reactions. Electrocatalysts are a specific form of catalysts that function at electrode surfaces or, most commonly, may be the electrode surface itself. An electrocatalyst ...
in the conversion of CO2 to CO. * Ingredient in
lubricating Lubrication is the process or technique of using a lubricant to reduce friction and wear and tear in a contact between two surfaces. The study of lubrication is a discipline in the field of tribology. Lubrication mechanisms such as fluid-lubrica ...
greases. * In crackling microstars (
dragon's egg ''Dragon's Egg'' is a 1980 hard science fiction novel by American writer Robert L. Forward. In the story, Dragon's Egg is a neutron star with a surface gravity 67 billion times that of Earth, and inhabited by cheela, intelligent creatures ...
s) in
pyrotechnics Pyrotechnics is the science and craft of creating such things as fireworks, safety matches, oxygen candles, explosive bolts and other fasteners, parts of automotive airbags, as well as gas-pressure blasting in mining, quarrying, and demolition. ...
, as the
oxide An oxide () is a chemical compound that contains at least one oxygen atom and one other element in its chemical formula. "Oxide" itself is the dianion of oxygen, an O2– (molecular) ion. with oxygen in the oxidation state of −2. Most of the E ...
, subcarbonate or subnitrate. *As catalyst for the fluorination of arylboronic pinacol esters through a Bi(III)/Bi(V) catalytic cycle, mimicking transition metals in electrophilic fluorination.


See also

*
Lead compounds Compounds of lead exist with lead in two main oxidation states: +2 and +4. The former is more common. Inorganic lead(IV) Compound (chemistry), compounds are typically strong oxidants or exist only in highly acidic solutions. Chemistry Various ...


References

{{Bismuth compounds Bismuth Bismuth compounds Chemical compounds by element