Bismuth

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Bismuth,  83Bi
Bismuth crystals and 1cm3 cube.jpg
Bismuth
Pronunciation /ˈbɪzməθ/ (BIZ-məth)
Appearancelustrous brownish silver
Standard atomic weight Ar, std(Bi)208.98040(1) [1]
Bismuth in the periodic table
Hydrogen Helium
Lithium Beryllium Boron Carbon Nitrogen Oxygen Fluorine Neon
Sodium Magnesium Aluminium Silicon Phosphorus Sulfur Chlorine Argon
Potassium Calcium Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper Zinc Gallium Germanium Arsenic Selenium Bromine Krypton
Rubidium Strontium Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium Palladium Silver Cadmium Indium Tin Antimony Tellurium Iodine Xenon
Caesium Barium Lanthanum Cerium Praseodymium Neodymium Promethium Samarium Europium Gadolinium Terbium Dysprosium Holmium Erbium Thulium Ytterbium Lutetium Hafnium Tantalum Tungsten Rhenium Osmium Iridium Platinum Gold Mercury (element) Thallium Lead Bismuth Polonium Astatine Radon
Francium Radium Actinium Thorium Protactinium Uranium Neptunium Plutonium Americium Curium Berkelium Californium Einsteinium Fermium Mendelevium Nobelium Lawrencium Rutherfordium Dubnium Seaborgium Bohrium Hassium Meitnerium Darmstadtium Roentgenium Copernicium Nihonium Flerovium Moscovium Livermorium Tennessine Oganesson
Sb

Bi

Mc
leadbismuthpolonium
Atomic number (Z)83
Group group 15 (pnictogens)
Period period 6
Block p-block
Element category   post-transition metal
Electron configuration [ Xe ] 4f14 5d10 6s2 6p3
Electrons per shell
2, 8, 18, 32, 18, 5
Physical properties
Phase at  STP solid
Melting point 544.7  K (271.5 °C,520.7 °F)
Boiling point 1837 K(1564 °C,2847 °F)
Density (near r.t.)9.78 g/cm3
when liquid (at m.p.)10.05 g/cm3
Heat of fusion 11.30  kJ/mol
Heat of vaporization 179 kJ/mol
Molar heat capacity 25.52 J/(mol·K)
Vapor pressure
P (Pa)1101001 k10 k100 k
at T (K)94110411165132515381835
Atomic properties
Oxidation states −3, −2, −1, +1, +2, +3, +4, +5 (a mildly acidic oxide)
Electronegativity Pauling scale: 2.02
Ionization energies
  • 1st: 703 kJ/mol
  • 2nd: 1610 kJ/mol
  • 3rd: 2466 kJ/mol
  • (more)
Atomic radius empirical:156  pm
Covalent radius 148±4 pm
Van der Waals radius 207 pm
Color lines in a spectral range Bismuth spectrum visible.png
Color lines in a spectral range
Spectral lines of bismuth
Other properties
Natural occurrence primordial
Crystal structure rhombohedral [2]
Rhombohedral.svg
Speed of sound thin rod1790 m/s(at 20 °C)
Thermal expansion 13.4 µm/(m·K)(at 25 °C)
Thermal conductivity 7.97 W/(m·K)
Electrical resistivity 1.29 µΩ·m(at 20 °C)
Magnetic ordering diamagnetic
Magnetic susceptibility 280.1·10−6 cm3/mol [3]
Young's modulus 32 GPa
Shear modulus 12 GPa
Bulk modulus 31 GPa
Poisson ratio 0.33
Mohs hardness 2.25
Brinell hardness 70–95 MPa
CAS Number 7440-69-9
History
Discovery Claude François Geoffroy (1753)
Main isotopes of bismuth
Iso­tope Abun­dance Half-life (t1/2) Decay mode Pro­duct
207Bi syn 31.55 y β+ 207Pb
208Bisyn3.68×105 yβ+ 208Pb
209Bi100%1.9×1019 y α 205Tl
210Bi trace 5.012 d β 210Po
α 206Tl
210mBisyn3.04×106 y IT 210Bi
α 206Tl
| references

Bismuth is a chemical element with the symbol  Bi and atomic number 83. It is a pentavalent post-transition metal and one of the pnictogens with chemical properties resembling its lighter homologs arsenic and antimony. Elemental bismuth may occur naturally, although its sulfide and oxide form important commercial ores. The free element is 86% as dense as lead. It is a brittle metal with a silvery white color when freshly produced, but surface oxidation can give it a pink tinge. Bismuth is the most naturally diamagnetic element, and has one of the lowest values of thermal conductivity among metals.

Chemical element a species of atoms having the same number of protons in the atomic nucleus

A chemical element is a species of atom having the same number of protons in their atomic nuclei. For example, the atomic number of oxygen is 8, so the element oxygen consists of all atoms which have exactly 8 protons.

Symbol (chemistry)

In relation to the chemical elements, a symbol is a code for a chemical element. Symbols for chemical elements normally consist of one or two letters from the Latin alphabet and are written with the first letter capitalised.

Atomic number number of protons found in the nucleus of an atom

The atomic number or proton number of a chemical element is the number of protons found in the nucleus of an atom. It is identical to the charge number of the nucleus. The atomic number uniquely identifies a chemical element. In an uncharged atom, the atomic number is also equal to the number of electrons.

Contents

Bismuth was long considered the element with the highest atomic mass that is stable, but in 2003 it was discovered to be extremely weakly radioactive: its only primordial isotope, bismuth-209, decays via alpha decay with a half-life more than a billion times the estimated age of the universe. [4] [5] Because of its tremendously long half-life, bismuth may still be considered stable for almost all purposes. [5]

Bismuth-209 is the isotope of bismuth with the longest known half-life of any radioisotope that undergoes α-decay. It has 83 protons and a magic number of 126 neutrons, and an atomic mass of 208.9803987 amu. Primordial bismuth consists entirely of this isotope.

Alpha decay emission of alpha particles by a decaying radioactive atom

Alpha decay or α-decay is a type of radioactive decay in which an atomic nucleus emits an alpha particle and thereby transforms or 'decays' into a different atomic nucleus, with a mass number that is reduced by four and an atomic number that is reduced by two. An alpha particle is identical to the nucleus of a helium-4 atom, which consists of two protons and two neutrons. It has a charge of +2 e and a mass of 4 u. For example, uranium-238 decays to form thorium-234. Alpha particles have a charge +2 e, but as a nuclear equation describes a nuclear reaction without considering the electrons – a convention that does not imply that the nuclei necessarily occur in neutral atoms – the charge is not usually shown.

Half-life is the time required for a quantity to reduce to half its initial value. The term is commonly used in nuclear physics to describe how quickly unstable atoms undergo, or how long stable atoms survive, radioactive decay. The term is also used more generally to characterize any type of exponential or non-exponential decay. For example, the medical sciences refer to the biological half-life of drugs and other chemicals in the human body. The converse of half-life is doubling time.

Bismuth metal has been known since ancient times, although it was often confused with lead and tin, which share some physical properties. The etymology is uncertain, but possibly comes from Arabic bi ismid, meaning having the properties of antimony [6] or the German words weiße Masse or Wismuth ("white mass"), translated in the mid-sixteenth century to New Latin bisemutum. [7]

New Latin form of the Latin language between c. 1375 and c. 1900

New Latin was a revival in the use of Latin in original, scholarly, and scientific works between c. 1375 and c. 1900. Modern scholarly and technical nomenclature, such as in zoological and botanical taxonomy and international scientific vocabulary, draws extensively from New Latin vocabulary. In such use, New Latin is subject to new word formation. As a language for full expression in prose or poetry, however, it is often distinguished from its successor, Contemporary Latin.

Bismuth compounds account for about half the production of bismuth. They are used in cosmetics, pigments, and a few pharmaceuticals, notably bismuth subsalicylate, used to treat diarrhea. [5] Bismuth's unusual propensity to expand as it solidifies is responsible for some of its uses, such as in casting of printing type. [5] Bismuth has unusually low toxicity for a heavy metal. [5] As the toxicity of lead has become more apparent in recent years, there is an increasing use of bismuth alloys (presently about a third of bismuth production) as a replacement for lead.

Bismuth subsalicylate Antacid medication

Bismuth subsalicylate, sold under the brand name Pepto-Bismol, is an antacid medication used to treat temporary discomforts of the stomach and gastrointestinal tract, such as diarrhea, indigestion, heartburn and nausea. It is also commonly known as pink bismuth.

Toxicity The ability of a chemical to cause damage to life

Toxicity is the degree to which a chemical substance or a particular mixture of substances can damage an organism. Toxicity can refer to the effect on a whole organism, such as an animal, bacterium, or plant, as well as the effect on a substructure of the organism, such as a cell (cytotoxicity) or an organ such as the liver (hepatotoxicity). By extension, the word may be metaphorically used to describe toxic effects on larger and more complex groups, such as the family unit or society at large. Sometimes the word is more or less synonymous with poisoning in everyday usage.

History

The name bismuth dates from around the 1660s, and is of uncertain etymology. It is one of the first 10 metals to have been discovered. Bismuth appears in the 1660s, from obsolete German Bismuth, Wismut, Wissmuth (early 16th century); perhaps related to Old High German hwiz ("white"). [7] The New Latin bisemutum (due to Georgius Agricola, who Latinized many German mining and technical words) is from the German Wismuth, perhaps from weiße Masse, "white mass". [8] The element was confused in early times with tin and lead because of its resemblance to those elements. Bismuth has been known since ancient times, so no one person is credited with its discovery. Agricola, in De Natura Fossilium (c. 1546) states that bismuth is a distinct metal in a family of metals including tin and lead. This was based on observation of the metals and their physical properties. [9] Miners in the age of alchemy also gave bismuth the name tectum argenti, or "silver being made," in the sense of silver still in the process of being formed within the Earth. [10] [11] [12]

German language West Germanic language

German is a West Germanic language that is mainly spoken in Central Europe. It is the most widely spoken and official or co-official language in Germany, Austria, Switzerland, South Tyrol (Italy), the German-speaking Community of Belgium, and Liechtenstein. It is also one of the three official languages of Luxembourg and a co-official language in the Opole Voivodeship in Poland. The languages which are most similar to German are the other members of the West Germanic language branch: Afrikaans, Dutch, English, the Frisian languages, Low German/Low Saxon, Luxembourgish, and Yiddish. There are also strong similarities in vocabulary with Danish, Norwegian and Swedish, although those belong to the North Germanic group. German is the second most widely spoken Germanic language, after English.

Old High German earliest stage of the German language, spoken from 500/750 to 1050 AD

Old High German is the earliest stage of the German language, conventionally covering the period from around 750 to 1050. There is no standardised or supra-regional form of German at this period, and Old High German is an umbrella term for the group of continental West Germanic dialects which underwent the set of consonantal changes called the Second Sound Shift.

Georgius Agricola German mineralogist

Georgius Agricola was a universally educated German Humanist scholar and one of the leading experts on mineralogy and metallurgy of his time, born in the small town of Glauchau, in the Electorate of Saxony of the Holy Roman Empire. He is well known for his pioneering work De re metallica libri XII, that was published in 1556, one year after his death. This 12-volume work is a comprehensive and systematic study, classification and methodical guide on all available factual and practical aspects, that are of concern for mining, the mining sciences and metallurgy, investigated and researched in its natural environment by means of direct observation. Unrivalled in its complexity and accuracy, it served as the standard reference work for two centuries. Agricola stated in the preface, that he will exclude all those things which I have not myself seen, or have not read or heard of.[...].That which I have neither seen, nor carefully considered after reading or hearing of, I have not written about. He thereby refuses to rely on abstruse methods through philosophical considerations and instead submits his work to the strict principles of the modern scientific method, centuries before its time. As a scholar of the Renaissance he was committed to a universal approach towards learning and research and published over 40 complete scholarly works during his professional life on a wide range of subjects and disciplines, such as pedagogy, medicine, metrology, mercantilism, pharmacy, philosophy, geology, history and many more. His innovative and comprehensive scholarly work, based on new and precise methods of production and control is remarkable and has earned him international admiration to this day.

Beginning with Johann Heinrich Pott in 1738, [13] Carl Wilhelm Scheele and Torbern Olof Bergman, the distinctness of lead and bismuth became clear, and Claude François Geoffroy demonstrated in 1753 that this metal is distinct from lead and tin. [11] [14] [15] Bismuth was also known to the Incas and used (along with the usual copper and tin) in a special bronze alloy for knives. [16]

Carl Wilhelm Scheele Swedish chemist

Carl Wilhelm Scheele was a Swedish Pomeranian and German pharmaceutical chemist. Isaac Asimov called him "hard-luck Scheele" because he made a number of chemical discoveries before others who are generally given the credit. For example, Scheele discovered oxygen, and identified molybdenum, tungsten, barium, hydrogen, and chlorine before Humphry Davy, among others. Scheele discovered organic acids tartaric, oxalic, uric, lactic, and citric, as well as hydrofluoric, hydrocyanic, and arsenic acids. He preferred speaking German to Swedish his whole life, as German was commonly spoken among Swedish pharmacists.

Claude François Geoffroy was a French chemist. In 1753 he proved the chemical element bismuth to be distinct from lead, becoming the official discoverer of the element. Before this time, bismuth-containing minerals were frequently misidentified as either lead, tin, or antimony ores. His observations on the matter were published in the Mémoires de l’académie française in 1753.

Bismuth bronze or bismuth brass is a copper alloy which typically contains 1-3% bismuth by weight, although some alloys contain over 6% Bi. This bronze alloy is very corrosion-resistant, a property which makes it suitable for use in environments such as the ocean. Bismuth bronzes and brasses are more malleable, thermally conductive, and polish better than regular brasses. The most common industrial application of these metals are as bearings, however the material has been in use since the late nineteenth century as kitchenware and mirrors. Bismuth bronze was also found in ceremonial Inca knives at Machu Picchu. Recently, pressure for the substitution of hazardous metals has increased and with it bismuth bronze is being marketed as a green alternative to leaded bronze bearings and bushings.

Characteristics

Left: synthetic bismuth crystal exhibiting the stairstep crystal structure and iridescence colors, which are produced by interference of light within the oxide film on its surface. Right: a 1 cm cube of unoxidised bismuth metal Wismut Kristall und 1cm3 Wuerfel.jpg
Left: synthetic bismuth crystal exhibiting the stairstep crystal structure and iridescence colors, which are produced by interference of light within the oxide film on its surface. Right: a 1 cm cube of unoxidised bismuth metal

Physical characteristics

Pressure-temperature phase diagram of bismuth. TC refers to the superconducting transition temperature Bi phase diagram.png
Pressure-temperature phase diagram of bismuth. TC refers to the superconducting transition temperature

Bismuth is a brittle metal with a white, silver-pink hue, often with an iridescent oxide tarnish showing many colors from yellow to blue. The spiral, stair-stepped structure of bismuth crystals is the result of a higher growth rate around the outside edges than on the inside edges. The variations in the thickness of the oxide layer that forms on the surface of the crystal cause different wavelengths of light to interfere upon reflection, thus displaying a rainbow of colors. When burned in oxygen, bismuth burns with a blue flame and its oxide forms yellow fumes. [14] Its toxicity is much lower than that of its neighbors in the periodic table, such as lead, antimony, and polonium.

No other metal is verified to be more naturally diamagnetic than bismuth. [14] [17] (Superdiamagnetism is a different physical phenomenon.) Of any metal, it has one of the lowest values of thermal conductivity (after manganese, and maybe neptunium and plutonium) and the highest Hall coefficient. [18] It has a high electrical resistivity. [14] When deposited in sufficiently thin layers on a substrate, bismuth is a semiconductor, despite being a post-transition metal. [19] Elemental bismuth is denser in the liquid phase than the solid, a characteristic it shares with germanium, silicon, gallium and water. [20] Bismuth expands 3.32% on solidification; therefore, it was long a component of low-melting typesetting alloys, where it compensated for the contraction of the other alloying components [14] [21] [22] [23] to form almost isostatic bismuth-lead eutectic alloys.

Though virtually unseen in nature, high-purity bismuth can form distinctive, colorful hopper crystals. It is relatively nontoxic and has a low melting point just above 271 °C, so crystals may be grown using a household stove, although the resulting crystals will tend to be lower quality than lab-grown crystals. [24]

At ambient conditions bismuth shares the same layered structure as the metallic forms of arsenic and antimony, [25] crystallizing in the rhombohedral lattice [26] (Pearson symbol hR6, space group R3m No. 166), which is often classed into trigonal or hexagonal crystal systems. [2] When compressed at room temperature, this Bi-I structure changes first to the monoclinic Bi-II at 2.55 GPa, then to the tetragonal Bi-III at 2.7 GPa, and finally to the body-centered cubic Bi-IV at 7.7 GPa. The corresponding transitions can be monitored via changes in electrical conductivity; they are rather reproducible and abrupt, and are therefore used for calibration of high-pressure equipment. [27] [28]

Chemical characteristics

Bismuth is stable to both dry and moist air at ordinary temperatures. When red-hot, it reacts with water to make bismuth(III) oxide. [29]

2 Bi + 3 H2O → Bi2O3 + 3 H2

It reacts with fluorine to make bismuth(V) fluoride at 500 °C or bismuth(III) fluoride at lower temperatures (typically from Bi melts); with other halogens it yields only bismuth(III) halides. [30] [31] [32] The trihalides are corrosive and easily react with moisture, forming oxyhalides with the formula BiOX. [33]

2 Bi + 3 X2 → 2 BiX3 (X = F, Cl, Br, I)

Bismuth dissolves in concentrated sulfuric acid to make bismuth(III) sulfate and sulfur dioxide. [29]

6 H2SO4 + 2 Bi → 6 H2O + Bi2(SO4)3 + 3 SO2

It reacts with nitric acid to make bismuth(III) nitrate.

Bi + 6 HNO3 → 3 H2O + 3 NO2 + Bi(NO3)3

It also dissolves in hydrochloric acid, but only with oxygen present. [29]

4 Bi + 3 O2 + 12 HCl → 4 BiCl3 + 6 H2O

It is used as a transmetalating agent in the synthesis of alkaline-earth metal complexes:

3 Ba + 2 BiPh3 → 3 BaPh2 + 2 Bi

Isotopes

The only primordial isotope of bismuth, bismuth-209, was traditionally regarded as the heaviest stable isotope, but it had long been suspected [34] to be unstable on theoretical grounds. This was finally demonstrated in 2003, when researchers at the Institut d'Astrophysique Spatiale in Orsay, France, measured the alpha emission half-life of 209
Bi
to be 1.9×1019 years, [35] over a billion times longer than the current estimated age of the universe. [5] Owing to its extraordinarily long half-life, for all presently known medical and industrial applications, bismuth can be treated as if it is stable and nonradioactive. The radioactivity is of academic interest because bismuth is one of a few elements whose radioactivity was suspected and theoretically predicted before being detected in the laboratory. [5] Bismuth has the longest known alpha decay half-life, although tellurium-128 has a double beta decay half-life of over 2.2×1024 years. [36] Bismuth's extremely long half life means that less than one billionth of the bismuth present at the formation of the planet Earth would have decayed into thallium since then.

Several isotopes of bismuth with short half-lives occur within the radioactive disintegration chains of actinium, radium, and thorium, and more have been synthesized experimentally. Bismuth-213 is also found on the decay chain of uranium-233. [37]

Commercially, the radioactive isotope bismuth-213 can be produced by bombarding radium with bremsstrahlung photons from a linear particle accelerator. In 1997, an antibody conjugate with bismuth-213, which has a 45-minute half-life and decays with the emission of an alpha particle, was used to treat patients with leukemia. This isotope has also been tried in cancer treatment, for example, in the targeted alpha therapy (TAT) program. [38] [39]

Chemical compounds

Bismuth forms trivalent and pentavalent compounds, the trivalent ones being more common. Many of its chemical properties are similar to those of arsenic and antimony, 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, Bi
2
O
3
. [20] [40] When molten, at temperatures above 710 °C, this oxide corrodes any metal oxide, and even platinum. [32] On reaction with base, it forms two series of oxyanions: BiO
2
, which is polymeric and forms linear chains, and BiO3−
3
. The anion in Li
3
BiO
3
is actually a cubic octameric anion, Bi
8
O24−
24
, whereas the anion in Na
3
BiO
3
is tetrameric. [41]

The dark red bismuth(V) oxide, Bi
2
O
5
, is unstable, liberating O
2
gas upon heating. [42] The compound NaBiO3 is a strong oxidising agent. [43]

Bismuth sulfide, Bi
2
S
3
, occurs naturally in bismuth ores. [44] It is also produced by the combination of molten bismuth and sulfur. [31]

Bismuth oxychloride (BiOCl) structure (mineral bismoclite). Bismuth atoms shown as grey, oxygen red, chlorine green. MatlockiteStructure.png
Bismuth oxychloride (BiOCl) structure (mineral bismoclite). Bismuth atoms shown as grey, oxygen red, chlorine green.

Bismuth oxychloride (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). [45]

Bismuthine and bismuthides

Unlike the lighter pnictogens nitrogen, phosphorus, and arsenic, but similar to antimony, bismuth does not form a stable hydride. Bismuth hydride, bismuthine (BiH
3
), is an endothermic compound that spontaneously decomposes at room temperature. It is stable only below −60 °C. [41] Bismuthides are intermetallic 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 fermions in bulk. It is a natural, three-dimensional counterpart to graphene with similar electron mobility and velocity. Graphene and topological insulators (such as those in 3DTDS) are both crystalline materials that are electrically insulating inside but conducting on the surface, allowing them to function as transistors and other electronic devices. While sodium bismuthide (Na
3
Bi
) 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 and spintronics applications. [46] [47]

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 Bi5+
9
cations and BiCl2−
5
and Bi
2
Cl2−
8
anions. [41] [48] The Bi5+
9
cation has a distorted tricapped trigonal prismatic molecular geometry, and is also found in Bi
10
Hf
3
Cl
18
, which is prepared by reducing a mixture of hafnium(IV) chloride and bismuth chloride with elemental bismuth, having the structure [Bi+
] [Bi5+
9
] [HfCl2−
6
]
3
. [41] :50 Other polyatomic bismuth cations are also known, such as Bi2+
8
, found in Bi
8
(AlCl
4
)
2
. [48] Bismuth also forms a low-valence bromide with the same structure as "BiCl". There is a true monoiodide, BiI, which contains chains of Bi
4
I
4
units. BiI decomposes upon heating to the triiodide, BiI
3
, and elemental bismuth. A monobromide of the same structure also exists. [41] In oxidation state +3, bismuth forms trihalides with all of the halogens: BiF
3
, BiCl
3
, BiBr
3
, and BiI
3
. All of these except BiF
3
are hydrolyzed by water. [41]

Bismuth(III) chloride reacts with hydrogen chloride in ether solution to produce the acid HBiCl
4
. [29]

The oxidation state +5 is less frequently encountered. One such compound is BiF
5
, a powerful oxidizing and fluorinating agent. It is also a strong fluoride acceptor, reacting with xenon tetrafluoride to form the XeF+
3
cation: [29]

BiF
5
+ XeF
4
XeF+
3
BiF
6

Aqueous species

In aqueous solution, the Bi3+
ion is solvated to form the aqua ion Bi(H
2
O)3+
8
in strongly acidic conditions. [49] At pH > 0 polynuclear species exist, the most important of which is believed to be the octahedral complex [Bi
6
O
4
(OH)
4
]6+
. [50]

Occurrence and production

Bismite mineral Bismite.jpg
Bismite mineral

In the Earth's crust, bismuth is about twice as abundant as gold. The most important ores of bismuth are bismuthinite and bismite. [14] Native bismuth is known from Australia, Bolivia, and China. [51] [52]

According to the United States Geological Survey, the world mining production of bismuth in 2016 was 10,200 tonnes, with the major contributions from China (7,400 tonnes), Vietnam (2,000 tonnes) and Mexico (700 tonnes). [53] The refinery production in 2016 was 17,100 tonnes, of which China produced 11,000, Mexico 539 and Japan 428 tonnes. [54] The difference reflects bismuth's status as a byproduct of extraction of other metals such as lead, copper, tin, molybdenum and tungsten. [55] World bismuth production from refineries is a more complete and reliable statistic. [56] [57] [58]

Bismuth travels in crude lead bullion (which can contain up to 10% bismuth) through several stages of refining, until it is removed by the Kroll-Betterton process which separates the impurities as slag, or the electrolytic Betts process. Bismuth will behave similarly with another of its major metals, copper. [56] The raw bismuth metal from both processes contains still considerable amounts of other metals, foremost lead. By reacting the molten mixture with chlorine gas the metals are converted to their chlorides while bismuth remains unchanged. Impurities can also be removed by various other methods for example with fluxes and treatments yielding high-purity bismuth metal (over 99% Bi).

Price

World mine production and annual averages of bismuth price (New York, not adjusted for inflation). BiPrice.png
World mine production and annual averages of bismuth price (New York, not adjusted for inflation).

The price for pure bismuth metal has been relatively stable through most of the 20th century, except for a spike in the 1970s. Bismuth has always been produced mainly as a byproduct of lead refining, and thus the price usually reflected the cost of recovery and the balance between production and demand. [59]

Demand for bismuth was small prior to World War II and was pharmaceutical – bismuth compounds were used to treat such conditions as digestive disorders, sexually transmitted diseases and burns. Minor amounts of bismuth metal were consumed in fusible alloys for fire sprinkler systems and fuse wire. During World War II bismuth was considered a strategic material, used for solders, fusible alloys, medications and atomic research. To stabilize the market, the producers set the price at $1.25 per pound (2.75 $/kg) during the war and at $2.25 per pound (4.96 $/kg) from 1950 until 1964. [59]

In the early 1970s, the price rose rapidly as a result of increasing demand for bismuth as a metallurgical additive to aluminium, iron and steel. This was followed by a decline owing to increased world production, stabilized consumption, and the recessions of 1980 and 1981–82. In 1984, the price began to climb as consumption increased worldwide, especially in the United States and Japan. In the early 1990s, research began on the evaluation of bismuth as a nontoxic replacement for lead in ceramic glazes, fishing sinkers, food-processing equipment, free-machining brasses for plumbing applications, lubricating greases, and shot for waterfowl hunting. [60] Growth in these areas remained slow during the middle 1990s, in spite of the backing of lead replacement by the US Government, but intensified around 2005. This resulted in a rapid and continuing increase in price. [59]

Recycling

Most bismuth is produced as a byproduct of other metal-extraction processes including the smelting of lead, and also of tungsten and copper. Its sustainability is dependent on increased recycling, which is problematic.

It was once believed that bismuth could be practically recycled from the soldered joints in electronic equipment. Recent efficiencies in solder application in electronics mean there is substantially less solder deposited, and thus less to recycle. While recovering the silver from silver-bearing solder may remain economic, recovering bismuth is substantially less so. [61]

Next in recycling feasibility would be sizeable catalysts with a fair bismuth content, such as bismuth phosphomolybdate.[ citation needed ], bismuth used in galvanizing, and as a free-machining metallurgical additive.[ citation needed ]

Bismuth in uses where it is dispersed most widely include certain stomach medicines (bismuth subsalicylate), paints (bismuth vanadate), pearlescent cosmetics (bismuth oxychloride), and bismuth-containing bullets. Recycling bismuth from these uses is impractical.

Applications

18th-century engraving of bismuth processing. During this era, bismuth was used to treat some digestive complaints. Processing of bismuth. Etching. Wellcome V0023568.jpg
18th-century engraving of bismuth processing. During this era, bismuth was used to treat some digestive complaints.

Bismuth has few commercial applications, and those applications that use it generally require small quantities relative to other raw materials. In the United States, for example, 733 tonnes of bismuth were consumed in 2016, of which 70% went into chemicals (including pharmaceuticals, pigments, and cosmetics) and 11% into bismuth alloys. [62]

Some manufacturers use bismuth as a substitute in equipment for potable water systems such as valves to meet "lead-free" mandates in the U.S. (began in 2014). This is a fairly large application since it covers all residential and commercial building construction.

In the early 1990s, researchers began to evaluate bismuth as a nontoxic replacement for lead in various applications.

Medicines

Bismuth is an ingredient in some pharmaceuticals, [5] although the use of some of these substances is declining. [45]

Cosmetics and pigments

Bismuth oxychloride (BiOCl) is sometimes used in cosmetics, as a pigment in paint for eye shadows, hair sprays and nail polishes. [5] [45] [66] [67] This compound is found as the mineral bismoclite and in crystal form contains layers of atoms (see figure above) that refract light chromatically, resulting in an iridescent appearance similar to nacre of pearl. It was used as a cosmetic in ancient Egypt and in many places since. Bismuth white (also "Spanish white") can refer to either bismuth oxychloride or bismuth oxynitrate (BiONO3), when used as a white pigment. Bismuth vanadate is used as a light-stable non-reactive paint pigment (particularly for artists' paints), often as a replacement for the more toxic cadmium sulfide yellow and orange-yellow pigments. The most common variety in artists' paints is a lemon yellow, visually indistinguishable from its cadmium-containing alternative.

Metal and alloys

Bismuth is used in metal alloys with other metals such as iron, to create alloys to go into automatic sprinkler systems for fires. It was also used to make bismuth bronze which was used in the Bronze Age.

Lead replacement

The density difference between lead (11.32 g/cm3) and bismuth (9.78 g/cm3) is small enough that for many ballistics and weighting applications, bismuth can substitute for lead. For example, it can replace lead as a dense material in fishing sinkers. It has been used as a replacement for lead in shot, bullets and less-lethal riot gun ammunition. The Netherlands, Denmark, England, Wales, the US, and many other countries now prohibit the use of lead shot for the hunting of wetland birds, as many birds are prone to lead poisoning owing to mistaken ingestion of lead (instead of small stones and grit) to aid digestion, or even prohibit the use of lead for all hunting, such as in the Netherlands. Bismuth-tin alloy shot is one alternative that provides similar ballistic performance to lead. (Another less expensive but also more poorly performing alternative is "steel" shot, which is actually soft iron.) Bismuth's lack of malleability does, however, make it unsuitable for use in expanding hunting bullets.[ citation needed ]

Bismuth, as a dense element of high atomic weight, is used in bismuth-impregnated latex shields to shield from X-ray in medical examinations, such as CTs, mostly as it is considered non-toxic. [68]

The European Union's Restriction of Hazardous Substances Directive (RoHS) for reduction of lead has broadened bismuth's use in electronics as a component of low-melting point solders, as a replacement for traditional tin-lead solders. [62] Its low toxicity will be especially important for solders to be used in food processing equipment and copper water pipes, although it can also be used in other applications including those in the automobile industry, in the EU for example. [69]

Bismuth has been evaluated as a replacement for lead in free-machining brasses for plumbing applications, [70] although it does not equal the performance of leaded steels. [69]

Other metal uses and specialty alloys

Many bismuth alloys have low melting points and are found in specialty applications such as solders. Many automatic sprinklers, electric fuses, and safety devices in fire detection and suppression systems contain the eutectic In19.1-Cd5.3-Pb22.6-Sn8.3-Bi44.7 alloy that melts at 47 °C (117 °F) [14] This is a convenient temperature since it is unlikely to be exceeded in normal living conditions. Low-melting alloys, such as Bi-Cd-Pb-Sn alloy which melts at 70 °C, are also used in automotive and aviation industries. Before deforming a thin-walled metal part, it is filled with a melt or covered with a thin layer of the alloy to reduce the chance of breaking. Then the alloy is removed by submerging the part in boiling water. [71]

Bismuth is used to make free-machining steels and free-machining aluminium alloys for precision machining properties. It has similar effect to lead and improves the chip breaking during machining. The shrinking on solidification in lead and the expansion of bismuth compensate each other and therefore lead and bismuth are often used in similar quantities. [72] [73] Similarly, alloys containing comparable parts of bismuth and lead exhibit a very small change (on the order 0.01%) upon melting, solidification or aging. Such alloys are used in high-precision casting, e.g. in dentistry, to create models and molds. [71] Bismuth is also used as an alloying agent in production of malleable irons [62] and as a thermocouple material. [14]

Bismuth is also used in aluminium-silicon cast alloys in order to refine silicon morphology. However, it indicated a poisoning effect on modification of strontium (Sr). [74] [75] Some bismuth alloys, such as Bi35-Pb37-Sn25, are combined with non-sticking materials such as mica, glass and enamels because they easily wet them allowing to make joints to other parts. Addition of bismuth to caesium enhances the quantum yield of caesium cathodes. [45] Sintering of bismuth and manganese powders at 300 °C produces a permanent magnet and magnetostrictive material, which is used in ultrasonic generators and receivers working in the 10–100 kHz range and in magnetic memory devices. [76]

Other uses as compounds

Bismuth vanadate, a yellow pigment Bismuthvanadat.jpg
Bismuth vanadate, a yellow pigment

Toxicology and ecotoxicology

See also bismuthia, a rare dermatological condition that results from the prolonged use of bismuth.

Scientific literature indicates that some of the compounds of bismuth are less toxic to humans via ingestion compared to other heavy metals (lead, arsenic, antimony, etc.) [5] presumably due to the comparatively low solubility of bismuth salts. [85] Its biological half-life for whole-body retention is reported to be 5 days but it can remain in the kidney for years in people treated with bismuth compounds. [86]

Bismuth poisoning can occur and has according to some reports been common in relatively recent times. [85] [87] As with lead, bismuth poisoning can result in the formation of a black deposit on the gingiva, known as a bismuth line. [88] [89] [90] Poisoning may be treated with dimercaprol; however, evidence for benefit is unclear. [91] [92]

Bismuth's environmental impacts are not well known; it may be less likely to bioaccumulate than some other heavy metals, and this is an area of active research. [93] [94]

Bioremediation

The fungus Marasmius oreades can be used for the biological remediation of bismuth in polluted soils. [95]

See also

Related Research Articles

Antimony Chemical element with atomic number 51

Antimony is a chemical element with the symbol Sb (from Latin: 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 times and were powdered for use as medicine and cosmetics, often known by the Arabic name, kohl. Metallic antimony was also known, but it was erroneously identified as lead upon its discovery. The earliest known description of the metal in the West was written in 1540 by Vannoccio Biringuccio.

Barium Chemical element with atomic number 56

Barium is a chemical element with the symbol Ba and atomic number 56. It is the fifth element in group 2 and is a soft, silvery alkaline earth metal. Because of its high chemical reactivity, barium is never found in nature as a free element. Its hydroxide, known in pre-modern times as baryta, does not occur as a mineral, but can be prepared by heating barium carbonate.

Cadmium Chemical element with atomic number 48

Cadmium is a chemical element with the symbol Cd and atomic number 48. This soft, silvery-white metal is chemically similar to the two other stable metals in group 12, zinc and mercury. Like zinc, it demonstrates oxidation state +2 in most of its compounds, and like mercury, it has a lower melting point than the transition metals in groups 3 through 11. Cadmium and its congeners in group 12 are often not considered transition metals, in that they do not have partly filled d or f electron shells in the elemental or common oxidation states. The average concentration of cadmium in Earth's crust is between 0.1 and 0.5 parts per million (ppm). It was discovered in 1817 simultaneously by Stromeyer and Hermann, both in Germany, as an impurity in zinc carbonate.

Germanium Chemical element with atomic number 32

Germanium is a chemical element with the symbol Ge and atomic number 32. It is a lustrous, hard-brittle, grayish-white metalloid in the carbon group, chemically similar to its group neighbours silicon and tin. Pure germanium is a semiconductor with an appearance similar to elemental silicon. Like silicon, germanium naturally reacts and forms complexes with oxygen in nature.

Lead Chemical element with atomic number 82

Lead is a chemical element with the symbol Pb 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, lead is silvery with a hint of blue; it tarnishes to a dull gray color when exposed to air. Lead has the highest atomic number of any stable element and three of its isotopes are endpoints of major nuclear decay chains of heavier elements.

Solder metal alloy used to join together metal pieces with higher melting points

Solder is a fusible metal alloy used to create a permanent bond between metal workpieces. The word solder comes from the Middle English word soudur, via Old French solduree and soulder, from the Latin solidare, meaning "to make solid". In fact, solder must first be melted in order to adhere to and connect the pieces together after cooling, which requires that an alloy suitable for use as solder have a lower melting point than the pieces being joined. The solder should also be resistant to oxidative and corrosive effects that would degrade the joint over time. Solder used in making electrical connections also needs to have favorable electrical characteristics.

Tin Chemical element with atomic number 50

Tin is a chemical element with the symbol Sn (from Latin: stannum) and atomic number 50. Tin is a silvery white metal that characteristicly has a faint yellow hue due to slight oxidation. Tin, like indium, is soft enough to be cut without much force. When a bar of tin is bent the so-called "tin cry" can be heard as a result of sliding tin crystals reforming; this trait is shared by indium, cadmium and frozen mercury. Pure tin after solidifying keeps a mirror-like appearance similar to most metals, however most Tin alloys such as in Pewter, the metal soldifies with a dull gray color. Tin is a post-transition metal in group 14 of the periodic table of elements. It is obtained chiefly from the mineral cassiterite, which contains stannic oxide, SnO2. Tin shows a chemical similarity to both of its neighbors in group 14, germanium and lead, and has two main oxidation states, +2 and the slightly more stable +4. Tin is the 49th most abundant element and has, with 10 stable isotopes, the largest number of stable isotopes in the periodic table, thanks to its magic number of protons. It has two main allotropes: at room temperature, the stable allotrope is β-tin, a silvery-white, malleable metal, but at low temperatures, it transforms into the less dense grey α-tin, which has the diamond cubic structure. Metallic tin does not easily oxidize in air.

Tellurium Chemical element with atomic number 52

Tellurium is a chemical element with the symbol Te and atomic number 52. It is a brittle, mildly toxic, rare, silver-white metalloid. Tellurium is chemically related to selenium and sulfur, all three of which are chalcogens. It is occasionally found in native form as elemental crystals. Tellurium is far more common in the Universe as a whole than on Earth. Its extreme rarity in the Earth's crust, comparable to that of platinum, is due partly its formation of a volatile hydride that caused tellurium to be lost to space as a gas during the hot nebular formation of Earth, and partly to tellurium’s low affinity for oxygen that causes it to bind preferentially to other chalcophiles in dense minerals that sink into the core.

A period 5 element is one of the chemical elements in the fifth row of the periodic table of the elements. The periodic table is laid out in rows to illustrate recurring (periodic) trends in the chemical behaviour of the elements as their atomic number increases: a new row is begun when chemical behaviour begins to repeat, meaning that elements with similar behaviour fall into the same vertical columns. The fifth period contains 18 elements, beginning with rubidium and ending with xenon. As a rule, period 5 elements fill their 5s shells first, then their 4d, and 5p shells, in that order; however, there are exceptions, such as rhodium.

A period 6 element is one of the chemical elements in the sixth row (or period) of the periodic table of the elements, including the lanthanides. The periodic table is laid out in rows to illustrate recurring (periodic) trends in the chemical behaviour of the elements as their atomic number increases: a new row is begun when chemical behaviour begins to repeat, meaning that elements with similar behaviour fall into the same vertical columns. The sixth period contains 32 elements, tied for the most with period 7, beginning with caesium and ending with radon. Lead is currently the last stable element; all subsequent elements are radioactive. For bismuth, however, its only primordial isotope, 209Bi, has a half-life of more than 1019 years, over a billion times longer than the current age of the universe. As a rule, period 6 elements fill their 6s shells first, then their 4f, 5d, and 6p shells, in that order; however, there are exceptions, such as gold.

Pnictogen Group 15 elements of the periodic table with valency 5

A pnictogen is one of the chemical elements in group 15 of the periodic table. This group is also known as the nitrogen family. It consists of the elements nitrogen (N), phosphorus (P), arsenic (As), antimony (Sb), bismuth (Bi), and perhaps the chemically uncharacterized synthetic element moscovium (Mc).

Lead(II) chloride chemical compound

Lead(II) chloride (PbCl2) is an inorganic compound which is a white solid under ambient conditions. It is poorly soluble in water. Lead(II) chloride is one of the most important lead-based reagents. It also occurs naturally in the form of the mineral cotunnite.

Antimony trioxide chemical compound

Antimony(III) oxide is the inorganic compound with the formula Sb2O3. It is the most important commercial compound of antimony. It is found in nature as the minerals valentinite and senarmontite. Like most polymeric oxides, Sb2O3 dissolves in aqueous solutions with hydrolysis.

Oligodynamic effect The toxic effect of metal ions on living cells

The oligodynamic effect is a biocidal effect of metals, especially heavy metals, that occurs even in low concentrations. The health effect was known in India for more than 2700 years as their ancient texts prescribe brass utensils for purity of water and good health.

Bismuth(III) oxide chemical compound

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, but it is usually obtained as a by-product of the smelting of copper and lead ores. Bismuth trioxide is commonly used to produce the "Dragon's eggs" effect in fireworks, as a replacement of red lead.

Bismuth chloride chemical compound

Bismuth chloride (or butter of bismuth) is an inorganic compound with the chemical formula BiCl3. It is a common source of the Bi3+ ion. In the gas phase and in the crystal, the species adopts a pyramidal structure, in accord with VSEPR theory.

Organobismuth chemistry is the chemistry of organometallic compounds containing a carbon to bismuth chemical bond. According to one reviewer, applications are rare even though bismuth and bismuth compounds are the least toxic among the heavy metals and are relatively cheap. The main bismuth oxidation states are Bi(III) and Bi(V) as in all higher group 15 elements. The energy of a bond to carbon in this group decreases in the order P > As > Sb > Bi. The first reported use of bismuth in organic chemistry was in oxidation of alcohols by Challenger in 1934 (using Ph3Bi(OH)2). Knowledge about methylated species of bismuth in environmental and biological media is very limited. Organobismuth heterocycles are bismole and bismabenzene.

Cerium Chemical element with atomic number 58

Cerium is a chemical element with the symbol Ce and atomic number 58. Cerium is a soft, ductile and silvery-white metal that tarnishes when exposed to air, and it is soft enough to be cut with a knife. Cerium is the second element in the lanthanide series, and while it often shows the +3 oxidation state characteristic of the series, it also exceptionally has a stable +4 state that does not oxidize water. It is also considered one of the rare-earth elements. Cerium has no biological role and is not very toxic.

Bismuth oxychloride chemical compound

Bismuth oxychloride is an inorganic compound of bismuth with the formula BiOCl. 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 reflectivity similar to nacre.

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 subnitrate and bismuthyl nitrate. In older texts bismuth oxynitrate is often simply described as BiONO3. Bismuth oxynitrate was once called magisterium bismuti or bismutum subnitricum, and was used as a white pigment, in beauty care, and as a gentle disinfectant for internal and external use.

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Bibliography

PD-icon.svg This article incorporates text from a publication now in the public domain : Brown, R. D., Jr. "Annual Average Bismuth Price", USGS (1998)