Bismuth is a chemical element with symbol Bi and atomic number 83. Bismuth, a pentavalent post-transition metal, chemically resembles 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 is often seen in air with a pink tinge owing to surface oxidation. Bismuth is the most naturally diamagnetic element and has one of the lowest values of thermal conductivity among metals.
Bismuth metal has been known from ancient times, although until the 18th century 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 or German words weisse masse or wismuth (“white mass”), translated in the mid-sixteenth century to New Latin bisemutum.
Bismuth has long been considered as the element with the highest atomic mass that is stable. However, in 2003 it was discovered to be slightly radioactive: its only primordial isotope, bismuth-209, decays with a half life more than a billion times the estimated age of the universe.
Bismuth compounds account for about half the production of bismuth. They are used in cosmetics, pigments, and a few pharmaceuticals, notably Pepto-Bismol. Bismuth’s unusual propensity to expand upon freezing is responsible for some of its uses, such as in casting of printing type. Bismuth has unusually low toxicity for a heavy metal. 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.
History
The name bismuth is from ca. 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”). 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.” 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 (ca. 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. 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.
Beginning with Johann Heinrich Pott in 1738, 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. Bismuth was also known to the Incas and used (along with the usual copper and tin) in a special bronze alloy for knives.
Physical characteristics
Bismuth is a brittle metal with a white, silver-pink hue, often occurring in its native form, 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 causes 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. 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. (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. It has a high electrical resistance. When deposited in sufficiently thin layers on a substrate, bismuth is a semiconductor, rather than an other metal.
Elemental bismuth is denser in the liquid phase than the solid, a characteristic it shares with antimony, germanium, silicon and gallium. 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, 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.
At ambient conditions shares the same layered structure as the metallic forms of arsenic and antimony,[22] crystallizing in the rhombohedral lattice (Pearson symbol hR6, space group R3m No. 166), which is often classed into trigonal or hexagonal crystal systems. 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.
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.
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.[27][28][29] The trihalides are corrosive and easily react with moisture, forming oxyhalides with the formula BiOX.
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.
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.
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 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 209Bi to be 1.9×1019 years, over a billion times longer than the current estimated age of the universe. 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 few elements whose radioactivity was suspected and theoretically predicted, before being detected in the laboratory. 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.
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.
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.
Occurrence and production
In the Earth’s crust, bismuth is about twice as abundant as gold. The most important ores of bismuth are bismuthinite and bismite. Native bismuth is known from Australia, Bolivia, and China.
According to the United States Geological Survey, the world mining production of bismuth in 2010 was 8,900 tonnes, with the major contributions from China (6,500 tonnes), Peru (1,100 tonnes) and Mexico (850 tonnes). The refinery production was 16,000 tonnes, of which China produced 13,000, Mexico 850 and Belgium 800 tonnes. The difference reflects bismuth’s status as a byproduct of extraction of other metals such as lead, copper, tin, molybdenum and tungsten.
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. 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). World bismuth production from refineries is a more complete and reliable statistic.
Price
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.
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.
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. 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.
Recycling
Whereas bismuth is most available today as a byproduct, its sustainability is more dependent on recycling. Bismuth is mostly a byproduct of lead smelting, along with silver, zinc, antimony, and other metals, and also of tungsten production, along with molybdenum and tin, and also of copper production. Recycling bismuth is difficult in many of its end uses, primarily because of scattering.
Probably the easiest to recycle would be bismuth-containing fusible alloys in the form of larger objects, then larger soldered objects. Half of the world’s solder consumption is in electronics (i.e., circuit boards). As the soldered objects get smaller or contain little solder or little bismuth, the recovery gets progressively more difficult and less economic, although solder with a higher silver content will be more worthwhile recovering. Next in recycling feasibility would be sizeable catalysts with a fair bismuth content, perhaps as bismuth phosphomolybdate, and then bismuth used in galvanizing and as a free-machining metallurgical additive.
Bismuth in uses where it is dispersed most widely include stomach medicines (bismuth subsalicylate), paints (bismuth vanadate) on a dry surface, pearlescent cosmetics (bismuth oxychloride), and bismuth-containing bullets that have been fired. The bismuth scattered in these uses is unrecoverable with present technology.
The most important sustainability fact about bismuth is its byproduct status, which can either improve sustainability (i.e., vanadium or manganese nodules) or, for bismuth from lead ore, constrain it; bismuth is constrained. The extent that the constraint on bismuth can be ameliorated or not is going to be tested by the future of the lead storage battery, since 90% of the world market for lead is in storage batteries for gasoline or diesel-powered motor vehicles.
The life-cycle assessment of bismuth will focus on solders, one of the major uses of bismuth, and the one with the most complete information. The average primary energy use for solders is around 200 MJ per kg, with the high-bismuth solder (58% Bi) only 20% of that value, and three low-bismuth solders (2% to 5% Bi) running very close to the average. The global warming potential averaged 10 to 14 kg carbon dioxide, with the high-bismuth solder about two-thirds of that and the low-bismuth solders about average. The acidification potential for the solders is around 0.9 to 1.1 kg sulfur dioxide equivalent, with the high-bismuth solder and one low-bismuth solder only one-tenth of the average and the other low-bismuth solders about average. There is very little life-cycle information on other bismuth alloys or compounds.
Applications
Bismuth has few commercial applications, none of which is particularly large. Taking the US as an example, 884 tonnes of bismuth were consumed in 2010, of which 63% went into chemicals (including pharmaceuticals, pigments, and cosmetics), 26% into metallurgical additives for casting and galvanizing, 7% into bismuth alloys, solders and ammunition, and the balance into research and other uses.
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. (starts 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.
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