Tin

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Tin,  50Sn
Sn-Alpha-Beta.jpg
Tin
Allotropes alpha, α (gray); beta, β (white)
Appearancesilvery-white (beta, β) or gray (alpha, α)
Standard atomic weight Ar, std(Sn)118.710(7) [1]
Tin 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
Ge

Sn

Pb
indiumtinantimony
Atomic number (Z)50
Group group 14 (carbon group)
Period period 5
Block p-block
Element category   Post-transition metal
Electron configuration [ Kr ] 4d10 5s2 5p2
Electrons per shell
2, 8, 18, 18, 4
Physical properties
Phase at  STP solid
Melting point 505.08  K (231.93 °C,449.47 °F)
Boiling point 2875 K(2602 °C,4716 °F)
Density (near r.t.)white, β: 7.265 g/cm3
gray, α: 5.769 g/cm3
when liquid (at m.p.)6.99 g/cm3
Heat of fusion white, β: 7.03  kJ/mol
Heat of vaporization white, β: 296.1 kJ/mol
Molar heat capacity white, β: 27.112 J/(mol·K)
Vapor pressure
P (Pa)1101001 k10 k100 k
at T (K)149716571855210724382893
Atomic properties
Oxidation states −4, −3, −2, −1, +1, [2] +2, +3, [3] +4 (an  amphoteric oxide)
Electronegativity Pauling scale: 1.96
Ionization energies
  • 1st: 708.6 kJ/mol
  • 2nd: 1411.8 kJ/mol
  • 3rd: 2943.0 kJ/mol
Atomic radius empirical:140  pm
Covalent radius 139±4 pm
Van der Waals radius 217 pm
Color lines in a spectral range Tin spectrum visible.png
Color lines in a spectral range
Spectral lines of tin
Other properties
Natural occurrence primordial
Crystal structure body-centered tetragonal
Tetragonal-body-centered.svg

white (β)
Crystal structure face-centered diamond-cubic
Diamond cubic crystal structure.svg

gray (α)
Speed of sound thin rod2730 m/s(at r.t.)(rolled)
Thermal expansion 22.0 µm/(m·K)(at 25 °C)
Thermal conductivity 66.8 W/(m·K)
Electrical resistivity 115 nΩ·m(at 0 °C)
Magnetic ordering gray: diamagnetic [4]
white (β): paramagnetic
Magnetic susceptibility (white) +3.1·10−6 cm3/mol(298 K) [5]
Young's modulus 50 GPa
Shear modulus 18 GPa
Bulk modulus 58 GPa
Poisson ratio 0.36
Brinell hardness 50–440 MPa
CAS Number 7440-31-5
History
Discovery around 3500 BC
Main isotopes of tin
Iso­tope Abun­dance Half-life (t1/2) Decay mode Pro­duct
112Sn0.97% stable
114Sn0.66%stable
115Sn0.34%stable
116Sn14.54%stable
117Sn7.68%stable
118Sn24.22%stable
119Sn8.59%stable
120Sn32.58%stable
122Sn4.63%stable
124Sn5.79%stable
126Sn trace 2.3×105 y β 126Sb
| references

Tin is a chemical element with the symbol Sn (from Latin : stannum) and atomic number 50. Tin is a silvery metal that characteristicly has a faint yellow hue. Tin, like indium, is soft enough to be cut without much force. [6] 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, in most tin alloys (such as pewter) the metal solidifies 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 on Earth 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.

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 8 protons.

Symbol (chemistry) an arbitrary or conventional sign used in chemical science to represent a chemical element

In chemistry, a symbol is an abbreviation 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 every atom of that element. The atomic number uniquely identifies a chemical element. It is identical to the charge number of the nucleus. In an uncharged atom, the atomic number is also equal to the number of electrons.

Contents

The first tin alloy used on a large scale was bronze, made of 1/8 tin and 7/8 copper, from as early as 3000 BC. After 600 BC, pure metallic tin was produced. Pewter, which is an alloy of 85–90% tin with the remainder commonly consisting of copper, antimony, and lead, was used for flatware from the Bronze Age until the 20th century. In modern times, tin is used in many alloys, most notably tin/lead soft solders, which are typically 60% or more tin, and in the manufacture of transparent, electrically conducting films of indium tin oxide in optoelectronic applications. Another large application for tin is corrosion-resistant tin plating of steel. Because of the low toxicity of inorganic tin, tin-plated steel is widely used for food packaging as tin cans. However, some organotin compounds can be almost as toxic as cyanide.

Alloy mixture or metallic solid solution composed of two or more elements

An alloy is a combination of metals or a combination of one or more metals with non-metallic elements. For example, combining the metallic elements gold and copper produces red gold, gold and silver becomes white gold, and silver combined with copper produces sterling silver. Elemental iron, combined with non-metallic carbon or silicon, produces alloys called steel or silicon steel. The resulting mixture forms a substance with properties that often differ from those of the pure metals, such as increased strength or hardness. Unlike other substances that may contain metallic bases but do not behave as metals, such as aluminium oxide (sapphire), beryllium aluminium silicate (emerald) or sodium chloride (salt), an alloy will retain all the properties of a metal in the resulting material, such as electrical conductivity, ductility, opaqueness, and luster. Alloys are used in a wide variety of applications, from the steel alloys, used in everything from buildings to automobiles to surgical tools, to exotic titanium-alloys used in the aerospace industry, to beryllium-copper alloys for non-sparking tools. In some cases, a combination of metals may reduce the overall cost of the material while preserving important properties. In other cases, the combination of metals imparts synergistic properties to the constituent metal elements such as corrosion resistance or mechanical strength. Examples of alloys are steel, solder, brass, pewter, duralumin, bronze and amalgams.

Bronze metal alloy

Bronze is an alloy consisting primarily of copper, commonly with about 12–12.5% tin and often with the addition of other metals and sometimes non-metals or metalloids such as arsenic, phosphorus or silicon. These additions produce a range of alloys that may be harder than copper alone, or have other useful properties, such as stiffness, ductility, or machinability.

Copper Chemical element with atomic number 29

Copper is a chemical element with the symbol Cu and atomic number 29. It is a soft, malleable, and ductile metal with very high thermal and electrical conductivity. A freshly exposed surface of pure copper has a pinkish-orange color. Copper is used as a conductor of heat and electricity, as a building material, and as a constituent of various metal alloys, such as sterling silver used in jewelry, cupronickel used to make marine hardware and coins, and constantan used in strain gauges and thermocouples for temperature measurement.

Characteristics

Physical

Droplet of solidified molten tin Tin-2.jpg
Droplet of solidified molten tin

Tin is a soft, malleable, ductile and highly crystalline silvery-white metal. When a bar of tin is bent, a crackling sound known as the "tin cry" can be heard from the twinning of the crystals. [7] Tin melts at low temperatures of about 232 °C (450 °F), the lowest in group 14. The melting point is further lowered to 177.3 °C (351.1 °F) for 11 nm particles. [8] [9]

Crystal solid material whose constituent atoms, molecules, or ions are arranged in an ordered pattern extending in all three spatial dimensions

A crystal or crystalline solid is a solid material whose constituents are arranged in a highly ordered microscopic structure, forming a crystal lattice that extends in all directions. In addition, macroscopic single crystals are usually identifiable by their geometrical shape, consisting of flat faces with specific, characteristic orientations. The scientific study of crystals and crystal formation is known as crystallography. The process of crystal formation via mechanisms of crystal growth is called crystallization or solidification.

Metal element, compound, or alloy that is a good conductor of both electricity and heat

A metal is a material that, when freshly prepared, polished, or fractured, shows a lustrous appearance, and conducts electricity and heat relatively well. Metals are typically malleable or ductile. A metal may be a chemical element such as iron; an alloy such as stainless steel; or a molecular compound such as polymeric sulfur nitride.

A tin cry is the characteristic sound heard when a bar of tin is bent. Variously described as a "screaming" or "crackling" sound, the effect is caused by the crystal twinning in the metal. The sound is not particularly loud, despite terms like "crying" and "screaming". It is very noticeable when a hot-dip tin coated sheet metal is bent at high speed over rollers during processing.

External video
Nuvola apps kaboodle.svg β–α transition of tin at −40 °C (time lapse; one second of the video is one hour in real time

β-tin (the metallic form, or white tin, BCT structure), which is stable at and above room temperature, is malleable. In contrast, α-tin (nonmetallic form, or gray tin), which is stable below 13.2 °C (55.8 °F), is brittle. α-tin has a diamond cubic crystal structure, similar to diamond, silicon or germanium. α-tin has no metallic properties at all because its atoms form a covalent structure in which electrons cannot move freely. It is a dull-gray powdery material with no common uses other than a few specialized semiconductor applications. [7] These two allotropes, α-tin and β-tin, are more commonly known as gray tin and white tin, respectively. Two more allotropes, γ and σ, exist at temperatures above 161 °C (322 °F)  and pressures above several GPa. [10] In cold conditions, β-tin tends to transform spontaneously into α-tin, a phenomenon known as "tin pest" or "tin disease". (Tin pest was a particular problem in northern Europe in the 18th century as organ pipes made of tin alloy would sometimes be affected during long cold winters. There are anecdotal claims that tin pest destroyed some of Captain Scott's stores in the ill-fated expedition (see tin pest). Some unverifiable sources also say that, during Napoleon's Russian campaign of 1812, the temperatures became so cold that the tin buttons on the soldiers' uniforms disintegrated over time, contributing to the defeat of the Grande Armée, [11] a persistent legend that probably has no background in real events. [12] ) Although the α-β transformation temperature is nominally 13.2 °C (55.8 °F), impurities (e.g. Al, Zn, etc.) lower the transition temperature well below 0 °C (32 °F) and, on the addition of antimony or bismuth, the transformation might not occur at all, increasing the durability of the tin. [13]

Diamond cubic three-dimensional repeating pattern formed by the atoms of a diamond crystal

The diamond cubic crystal structure is a repeating pattern of 8 atoms that certain materials may adopt as they solidify. While the first known example was diamond, other elements in group 14 also adopt this structure, including α-tin, the semiconductors silicon and germanium, and silicon/germanium alloys in any proportion.

Crystal structure Ordered arrangement of atoms, ions, or molecules in a crystalline material

In crystallography, crystal structure is a description of the ordered arrangement of atoms, ions or molecules in a crystalline material. Ordered structures occur from the intrinsic nature of the constituent particles to form symmetric patterns that repeat along the principal directions of three-dimensional space in matter.

Silicon Chemical element with atomic number 14

Silicon is a chemical element with the symbol Si and atomic number 14. It is a hard and brittle crystalline solid with a blue-grey metallic lustre; and it is a tetravalent metalloid and semiconductor. It is a member of group 14 in the periodic table: carbon is above it; and germanium, tin, and lead are below it. It is relatively unreactive. Because of its high chemical affinity for oxygen, it was not until 1823 that Jöns Jakob Berzelius was first able to prepare it and characterize it in pure form. Its melting and boiling points of 1414 °C and 3265 °C respectively are the second-highest among all the metalloids and nonmetals, being only surpassed by boron. Silicon is the eighth most common element in the universe by mass, but very rarely occurs as the pure element in the Earth's crust. It is most widely distributed in dusts, sands, planetoids, and planets as various forms of silicon dioxide (silica) or silicates. More than 90% of the Earth's crust is composed of silicate minerals, making silicon the second most abundant element in the Earth's crust after oxygen.

Commercial grades of tin (99.8%) resist transformation because of the inhibiting effect of the small amounts of bismuth, antimony, lead, and silver present as impurities. Alloying elements such as copper, antimony, bismuth, cadmium, and silver increase its hardness. Tin tends rather easily to form hard, brittle intermetallic phases, which are often undesirable. It does not form wide solid solution ranges in other metals in general, and few elements have appreciable solid solubility in tin. Simple eutectic systems, however, occur with bismuth, gallium, lead, thallium and zinc. [13]

Bismuth Chemical element with atomic number 83

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.

Gallium Chemical element with atomic number 31

Gallium is a chemical element with the symbol Ga and atomic number 31. Elemental gallium is a soft, silvery blue metal at standard temperature and pressure; however in its liquid state it becomes silvery white. If too much force is applied, the gallium may fracture conchoidally. It is in group 13 of the periodic table, and thus has similarities to the other metals of the group, aluminium, indium, and thallium. Gallium does not occur as a free element in nature, but as gallium(III) compounds in trace amounts in zinc ores and in bauxite. Elemental gallium is a liquid at temperatures greater than 29.76 °C (85.57 °F), above room temperature, but below the normal human body temperature of 37 °C (99 °F). Hence, the metal will melt in a person's hands.

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.

Tin becomes a superconductor below 3.72  K [14] and was one of the first superconductors to be studied; the Meissner effect, one of the characteristic features of superconductors, was first discovered in superconducting tin crystals. [15]

The kelvin is the base unit of temperature in the International System of Units (SI), having the unit symbol K. It is named after the Belfast-born, Glasgow University engineer and physicist William Thomson, 1st Baron Kelvin (1824–1907).

Meissner effect Expulsion of a magnetic field from a superconductor during its transition to the superconducting state

The Meissner effect is the expulsion of a magnetic field from a superconductor during its transition to the superconducting state. The German physicists Walther Meissner and Robert Ochsenfeld discovered this phenomenon in 1933 by measuring the magnetic field distribution outside superconducting tin and lead samples. The samples, in the presence of an applied magnetic field, were cooled below their superconducting transition temperature, whereupon the samples cancelled nearly all interior magnetic fields. They detected this effect only indirectly because the magnetic flux is conserved by a superconductor: when the interior field decreases, the exterior field increases. The experiment demonstrated for the first time that superconductors were more than just perfect conductors and provided a uniquely defining property of the superconductor state. The ability for the expulsion effect is determined by the nature of equilibrium formed by the neutralization within the unit cell of a superconductor.

Chemical

Tin resists corrosion from water, but can be attacked by acids and alkalis. Tin can be highly polished and is used as a protective coat for other metals. [7] A protective oxide (passivation) layer prevents further oxidation, the same that forms on pewter and other tin alloys. [16] Tin acts as a catalyst when oxygen is in solution and helps to accelerate the chemical reaction.[ clarification needed ] [7]

Isotopes

Tin has ten stable isotopes, with atomic masses of 112, 114 through 120, 122 and 124, the greatest number of any element. Of these, the most abundant are 120Sn (almost a third of all tin), 118Sn, and 116Sn, while the least abundant is 115Sn. The isotopes with even mass numbers have no nuclear spin, while those with odd have a spin of +1/2. Tin, with its three common isotopes 116Sn, 118Sn and 120Sn, is among the easiest elements to detect and analyze by NMR spectroscopy, and its chemical shifts are referenced against SnMe
4
. [note 1] [17]

This large number of stable isotopes is thought to be a direct result of the atomic number 50, a "magic number" in nuclear physics. Tin also occurs in 29 unstable isotopes, encompassing all the remaining atomic masses from 99 to 137. Apart from 126Sn, with a half-life of 230,000 years, all the radioisotopes have a half-life of less than a year. The radioactive 100Sn, discovered in 1994, and 132Sn are two of the few nuclides with a "doubly magic" nucleus: despite being unstable, having very lopsided proton–neutron ratios, they represent endpoints beyond which stability drops off rapidly. [18] Another 30 metastable isomers have been characterized for isotopes between 111 and 131, the most stable being 121mSn with a half-life of 43.9 years. [19]

The relative differences in the abundances of tin's stable isotopes can be explained by their different modes of formation in stellar nucleosynthesis. 116Sn through 120Sn inclusive are formed in the s-process (slow neutron capture) in most stars and hence they are the most common isotopes, while 122Sn and 124Sn are only formed in the r-process (rapid neutron capture) in supernovae and are less common. (The isotopes 117Sn through 120Sn also receive contributions from the r-process.) Finally, the rarest proton-rich isotopes, 112Sn, 114Sn, and 115Sn, cannot be made in significant amounts in the s- or r-processes and are considered among the p-nuclei, whose origins are not well understood yet. Some speculated mechanisms for their formation include proton capture as well as photodisintegration, although 115Sn might also be partially produced in the s-process, both directly, and as the daughter of long-lived 115In. [20]

Etymology

The word tin is shared among Germanic languages and can be traced back to reconstructed Proto-Germanic *tin-om; cognates include German Zinn, Swedish tenn and Dutch tin. It is not found in other branches of Indo-European, except by borrowing from Germanic (e.g., Irish tinne from English). [21] [22]

The Latin name stannum originally meant an alloy of silver and lead, and came to mean 'tin' in the 4th century [23] —the earlier Latin word for it was plumbum candidum, or "white lead". Stannum apparently came from an earlier stāgnum (meaning the same substance), [21] the origin of the Romance and Celtic terms for tin. [21] [24] The origin of stannum/stāgnum is unknown; it may be pre-Indo-European. [25]

The Meyers Konversations-Lexikon speculates on the contrary that stannum is derived from (the ancestor of) Cornish stean, and is proof that Cornwall in the first centuries AD was the main source of tin.

History

Ceremonial giant bronze dirk of the Plougrescant-Ommerschans type, Plougrescant, France, 1500-1300 BC. Sword bronze age (2nd version).jpg
Ceremonial giant bronze dirk of the Plougrescant-Ommerschans type, Plougrescant, France, 1500–1300 BC.

Tin extraction and use can be dated to the beginnings of the Bronze Age around 3000 BC, when it was observed that copper objects formed of polymetallic ores with different metal contents had different physical properties. [26] The earliest bronze objects had a tin or arsenic content of less than 2% and are therefore believed to be the result of unintentional alloying due to trace metal content in the copper ore. [27] The addition of a second metal to copper increases its hardness, lowers the melting temperature, and improves the casting process by producing a more fluid melt that cools to a denser, less spongy metal. [27] This was an important innovation that allowed for the much more complex shapes cast in closed molds of the Bronze Age. Arsenical bronze objects appear first in the Near East where arsenic is commonly found in association with copper ore, but the health risks were quickly realized and the quest for sources of the much less hazardous tin ores began early in the Bronze Age. [28] This created the demand for rare tin metal and formed a trade network that linked the distant sources of tin to the markets of Bronze Age cultures.[ citation needed ]

Cassiterite (SnO2), the tin oxide form of tin, was most likely the original source of tin in ancient times. Other forms of tin ores are less abundant sulfides such as stannite that require a more involved smelting process. Cassiterite often accumulates in alluvial channels as placer deposits because it is harder, heavier, and more chemically resistant than the accompanying granite. [29] Cassiterite is usually black or generally dark in color, and these deposits can be easily seen in river banks. Alluvial (placer) deposits could be easily collected and separated by methods similar to gold panning.[ citation needed ]

Compounds and chemistry

In the great majority of its compounds, tin has the oxidation state II or IV.

Inorganic compounds

Halide compounds are known for both oxidation states. For Sn(IV), all four halides are well known: SnF4, SnCl4, SnBr4, and SnI4. The three heavier members are volatile molecular compounds, whereas the tetrafluoride is polymeric. All four halides are known for Sn(II) also: SnF2, SnCl2, SnBr2, and SnI2. All are polymeric solids. Of these eight compounds, only the iodides are colored. [30]

Tin(II) chloride (also known as stannous chloride) is the most important tin halide in a commercial sense. Illustrating the routes to such compounds, chlorine reacts with tin metal to give SnCl4 whereas the reaction of hydrochloric acid and tin produces SnCl2 and hydrogen gas. Alternatively SnCl4 and Sn combine to stannous chloride by a process called comproportionation: [31]

SnCl4 + Sn → 2 SnCl2

Tin can form many oxides, sulfides, and other chalcogenide derivatives. The dioxide SnO2 (cassiterite) forms when tin is heated in the presence of air. [30] SnO2 is amphoteric, which means that it dissolves in both acidic and basic solutions. [32] Stannates with the structure [Sn(OH)6]2−, like K2[Sn(OH)6], are also known, though the free stannic acid H2[Sn(OH)6] is unknown.

Sulfides of tin exist in both the +2 and +4 oxidation states: tin(II) sulfide and tin(IV) sulfide (mosaic gold).

Ball-and-stick models of the structure of solid stannous chloride (SnCl2). Tin(II)-chloride-xtal-1996-3D-balls-front.png
Ball-and-stick models of the structure of solid stannous chloride (SnCl2).

Hydrides

Stannane (SnH4), with tin in the +4 oxidation state, is unstable. Organotin hydrides are however well known, e.g. tributyltin hydride (Sn(C4H9)3H). [7] These compound release transient tributyl tin radicals, which are rare examples of compounds of tin(III). [34]

Organotin compounds

Organotin compounds, sometimes called stannanes, are chemical compounds with tin–carbon bonds. [35] Of the compounds of tin, the organic derivatives are the most useful commercially. [36] Some organotin compounds are highly toxic and have been used as biocides. The first organotin compound to be reported was diethyltin diiodide ((C2H5)2SnI2), reported by Edward Frankland in 1849. [37]

Most organotin compounds are colorless liquids or solids that are stable to air and water. They adopt tetrahedral geometry. Tetraalkyl- and tetraaryltin compounds can be prepared using Grignard reagents: [36]

SnCl
4
+ 4 RMgBr → R
4
Sn
+ 4 MgBrCl

The mixed halide-alkyls, which are more common and more important commercially than the tetraorgano derivatives, are prepared by redistribution reactions:

SnCl
4
+ R
4
Sn
→ 2 SnCl2R2

Divalent organotin compounds are uncommon, although more common than related divalent organogermanium and organosilicon compounds. The greater stabilization enjoyed by Sn(II) is attributed to the "inert pair effect". Organotin(II) compounds include both stannylenes (formula: R2Sn, as seen for singlet carbenes) and distannylenes (R4Sn2), which are roughly equivalent to alkenes. Both classes exhibit unusual reactions. [38]

Occurrence

Sample of cassiterite, the main ore of tin. Cassiterite09.jpg
Sample of cassiterite, the main ore of tin.
Granular pieces of cassiterite, collected by placer mining TinOreUSGOV.jpg
Granular pieces of cassiterite, collected by placer mining

Tin is generated via the long s-process in low-to-medium mass stars (with masses of 0.6 to 10 times that of Sun), and finally by beta decay of the heavy isotopes of indium. [39]

Tin is the 49th most abundant element in Earth's crust, representing 2  ppm compared with 75 ppm for zinc, 50 ppm for copper, and 14 ppm for lead. [40]

Tin does not occur as the native element but must be extracted from various ores. Cassiterite (SnO2) is the only commercially important source of tin, although small quantities of tin are recovered from complex sulfides such as stannite, cylindrite, franckeite, canfieldite, and teallite. Minerals with tin are almost always associated with granite rock, usually at a level of 1% tin oxide content. [41]

Because of the higher specific gravity of tin dioxide, about 80% of mined tin is from secondary deposits found downstream from the primary lodes. Tin is often recovered from granules washed downstream in the past and deposited in valleys or the sea. The most economical ways of mining tin are by dredging, hydraulicking, or open pits. Most of the world's tin is produced from placer deposits, which can contain as little as 0.015% tin. [42]

World tin mine reserves (tonnes, 2011) [43]
CountryReserves
Flag of the People's Republic of China.svg  China 1,500,000
Flag of Malaysia.svg  Malaysia 250,000
Flag of Peru.svg  Peru 310,000
Flag of Indonesia.svg  Indonesia 800,000
Flag of Brazil.svg  Brazil 590,000
Flag of Bolivia.svg  Bolivia 400,000
Flag of Russia.svg  Russia 350,000
Flag of Australia (converted).svg  Australia 180,000
Flag of Thailand.svg  Thailand 170,000
  Other180,000
  Total4,800,000

About 253,000 tonnes of tin have been mined in 2011, mostly in China (110,000 t), Indonesia (51,000 t), Peru (34,600 t), Bolivia (20,700 t) and Brazil (12,000 t). [43] Estimates of tin production have historically varied with the dynamics of economic feasibility and the development of mining technologies, but it is estimated that, at current consumption rates and technologies, the Earth will run out of mine-able tin in 40 years. [44] Lester Brown has suggested tin could run out within 20 years based on an extremely conservative extrapolation of 2% growth per year. [45]

Economically recoverable tin reserves [41]
YearMillion tonnes
19654,265
19703,930
19759,060
19809,100
19853,060
19907,100
20007,100 [43]
20105,200 [43]

Secondary, or scrap, tin is also an important source of the metal. Recovery of tin through secondary production, or recycling of scrap tin, is increasing rapidly. Whereas the United States has neither mined since 1993 nor smelted tin since 1989, it was the largest secondary producer, recycling nearly 14,000 tonnes in 2006. [43]

New deposits are reported in southern Mongolia, [46] and in 2009, new deposits of tin were discovered in Colombia by the Seminole Group Colombia CI, SAS. [47]

Production

Tin is produced by carbothermic reduction of the oxide ore with carbon or coke. Both reverberatory furnace and electric furnace can be used. [48] [49] [50]

Mining and smelting

Industry

Candlestick made of tin Candlestick made of Tin by Royal Selangor.JPG
Candlestick made of tin

The ten largest companies produced most of the world's tin in 2007.

Most of the world's tin is traded on the London Metal Exchange (LME), from 8 countries, under 17 brands. [51]

Largest tin producing companies (tonnes) [52]
CompanyPolity200620072017 [53] 2006-2017
%Change
Yunnan Tin China52,33961,12974,50042.3
PT TimahIndonesia44,68958,32530,200-32.4
Malaysia Smelting CorpMalaysia22,85025,47127,20019.0
Yunnan ChengfengChina21,76518,00026,80023.1
Minsur Peru40,97735,94018,000-56.1
EM VintoBolivia11,8049,44812,6006.7
Guangxi China TinChina//11,500/
ThaisarcoThailand27,82819,82610,600-61.9
Metallo-Chimique Belgium8,0498,3729,70020.5
Gejiu Zi LiChina//8,700/

An International Tin Council was established in 1947 to control the price of tin, until it collapsed in 1985. In 1984, an Association of Tin Producing Countries was created, with Australia, Bolivia, Indonesia, Malaysia, Nigeria, Thailand, and Zaire as members. [54]

Price and exchanges

World production and price (US exchange) of tin. SnPrice.png
World production and price (US exchange) of tin.

Tin is unique among other mineral commodities because of the complex agreements between producer countries and consumer countries dating back to 1921. The earlier agreements tended to be somewhat informal and sporadic and led to the "First International Tin Agreement" in 1956, the first of a continuously numbered series that effectively collapsed in 1985. Through this series of agreements, the International Tin Council (ITC) had a considerable effect on tin prices. The ITC supported the price of tin during periods of low prices by buying tin for its buffer stockpile and was able to restrain the price during periods of high prices by selling tin from the stockpile. This was an anti-free-market approach, designed to assure a sufficient flow of tin to consumer countries and a profit for producer countries. However, the buffer stockpile was not sufficiently large, and during most of those 29 years tin prices rose, sometimes sharply, especially from 1973 through 1980 when rampant inflation plagued many world economies. [55]

During the late 1970s and early 1980s, the U.S. Government tin stockpile was in an aggressive selling mode, partly to take advantage of the historically high tin prices. The sharp recession of 1981–82 proved to be quite harsh on the tin industry. Tin consumption declined dramatically. The ITC was able to avoid truly steep declines through accelerated buying for its buffer stockpile; this activity required the ITC to borrow extensively from banks and metal trading firms to augment its resources. The ITC continued to borrow until late 1985 when it reached its credit limit. Immediately, a major "tin crisis" followed — tin was delisted from trading on the London Metal Exchange for about three years, the ITC dissolved soon afterward, and the price of tin, now in a free-market environment, plummeted sharply to $4 per pound and remained at that level through the 1990s. [55] The price increased again by 2010 with a rebound in consumption following the 2008–09 world economic crisis, accompanying restocking and continued growth in consumption by the world's developing economies. [43]

London Metal Exchange (LME) is the principal trading site for tin. [43] Other tin contract markets are Kuala Lumpur Tin Market (KLTM) and Indonesia Tin Exchange (INATIN). [56]

The price per kg over years:

Tin (US$ per kg) [57]
20082009201020112012
Price18.5113.5720.4126.0521.13

Applications

World consumption of refined tin by end use, 2006 TinConsChart.jpg
World consumption of refined tin by end use, 2006

In 2006, about half of all tin produced was used in solder. The rest was divided between tin plating, tin chemicals, brass and bronze alloys, and niche uses. [58]

Solder

A coil of lead-free solder wire Ex Lead freesolder.jpg
A coil of lead-free solder wire

Tin has long been used in alloys with lead as solder, in amounts 5 to 70% w/w. Tin with lead forms a eutectic mixture at the weight proportion of 61.9% tin and 38.1% lead (the atomic proportion: 73.9% tin and 26.1% lead), with melting temperature of 183 °C (361.4 °F) . Such solders are primarily used for joining pipes or electric circuits. Since the European Union Waste Electrical and Electronic Equipment Directive (WEEE Directive) and Restriction of Hazardous Substances Directive came into effect on 1 July 2006, the lead content in such alloys has decreased. Replacing lead has many problems, including a higher melting point, and the formation of tin whiskers causing electrical problems. Tin pest can occur in lead-free solders, leading to loss of the soldered joint. Replacement alloys are rapidly being found, although problems of joint integrity remain. [59]

Tin plating

Tin bonds readily to iron and is used for coating lead, zinc and steel to prevent corrosion. Tin-plated steel containers are widely used for food preservation, and this forms a large part of the market for metallic tin. A tinplate canister for preserving food was first manufactured in London in 1812. [60] Speakers of British English call them "tins", while speakers of American English call them "cans" or "tin cans". One derivation of such use is the slang term "tinnie" or "tinny", meaning "can of beer" in Australia. The tin whistle is so called because it was first mass-produced in tin-plated steel. [61] [62] Copper cooking vessels such as saucepans and frying pans are frequently lined with a thin plating of tin, since the combination of acid foods with copper can be toxic.

Specialized alloys

Pewter plate Pewterplate exb.jpg
Pewter plate

Tin in combination with other elements forms a wide variety of useful alloys. Tin is most commonly alloyed with copper. Pewter is 85–99% tin; [63] bearing metal has a high percentage of tin as well. [64] [65] Bronze is mostly copper (12% tin), while addition of phosphorus gives phosphor bronze. Bell metal is also a copper–tin alloy, containing 22% tin. Tin has sometimes been used in coinage; for example, it once formed a single-digit percentage (usually five percent or less) of American [66] and Canadian [67] pennies. Because copper is often the major metal in such coins, sometimes including zinc, these could be called bronze and/or brass alloys.

Tin plated metal from a can. Inside of a tin platted can.jpg
Tin plated metal from a can.
Artisan Alfonso Santiago Leyva and his son working with tin sheets. Alfonso Santiago Leyva and his son Toma|us working.jpg
Artisan Alfonso Santiago Leyva and his son working with tin sheets.

The niobium–tin compound Nb3Sn is commercially used in coils of superconducting magnets for its high critical temperature (18 K) and critical magnetic field (25  T). A superconducting magnet weighing as little as two kilograms is capable of the magnetic field of a conventional electromagnet weighing tons. [68]

A small percentage of tin is added to zirconium alloys for the cladding of nuclear fuel. [69]

Most metal pipes in a pipe organ are of a tin/lead alloy, with 50/50 being the most common composition. The proportion of tin in the pipe defines the pipe's tone, since tin has a desirable tonal resonance. When a tin/lead alloy cools, the lead phase solidifies first, then when the eutectic temperature is reached the remaining liquid forms the layered tin/lead eutectic structure, which is shiny and the contrast with the lead phase produces a mottled or spotted effect. This metal alloy is referred to as spotted metal. Major advantages of using tin for pipes include its appearance, its workability, and resistance to corrosion. [70] [71]

Optoelectronics

The oxides of indium and tin are electrically conductive and transparent, and are used to make transparent electrically conducting films with applications in Optoelectronics devices such as liquid crystal displays. [72]

Other applications

A 21st-century reproduction barn lantern made of punched tin. Punched tin barn lantern.jpeg
A 21st-century reproduction barn lantern made of punched tin.

Punched tin-plated steel, also called pierced tin, is an artisan technique originating in central Europe for creating housewares that are both functional and decorative. Decorative piercing designs exist in a wide variety, based on local tradition and the artisan's personal creations. Punched tin lanterns are the most common application of this artisan technique. The light of a candle shining through the pierced design creates a decorative light pattern in the room where it sits. Lanterns and other punched tin articles were created in the New World from the earliest European settlement. A well-known example is the Revere lantern, named after Paul Revere. [73]

Before the modern era, in some areas of the Alps, a goat or sheep's horn would be sharpened and a tin panel would be punched out using the alphabet and numbers from one to nine. This learning tool was known appropriately as "the horn". Modern reproductions are decorated with such motifs as hearts and tulips.

In America, pie safes and food safes were in use in the days before refrigeration. These were wooden cupboards of various styles and sizes – either floor standing or hanging cupboards meant to discourage vermin and insects and to keep dust from perishable foodstuffs. These cabinets had tinplate inserts in the doors and sometimes in the sides, punched out by the homeowner, cabinetmaker or a tinsmith in varying designs to allow for air circulation while excluding flies. Modern reproductions of these articles remain popular in North America. [74]

Window glass is most often made by floating molten glass on molten tin (float glass), resulting in a flat and flawless surface. This is also called the "Pilkington process". [75]

Tin is also used as a negative electrode in advanced Li-ion batteries. Its application is somewhat limited by the fact that some tin surfaces[ which? ] catalyze decomposition of carbonate-based electrolytes used in Li-ion batteries. [76]

Tin(II) fluoride is added to some dental care products [77] as stannous fluoride (SnF2). Tin(II) fluoride can be mixed with calcium abrasives while the more common sodium fluoride gradually becomes biologically inactive in the presence of calcium compounds. [78] It has also been shown to be more effective than sodium fluoride in controlling gingivitis. [79]

Organotin compounds

Of all the chemical compounds of tin, the organotin compounds are most heavily used. Worldwide industrial production probably exceeds 50,000 tonnes. [80]

PVC stabilizers

The major commercial application of organotin compounds is in the stabilization of PVC plastics. In the absence of such stabilizers, PVC would otherwise rapidly degrade under heat, light, and atmospheric oxygen, resulting in discolored, brittle products. Tin scavenges labile chloride ions (Cl), which would otherwise initiate loss of HCl from the plastic material. [81] Typical tin compounds are carboxylic acid derivatives of dibutyltin dichloride, such as the dilaurate. [82]

Biocides

Some organotin compounds are relatively toxic, with both advantages and problems. They are used for biocidal properties as fungicides, pesticides, algaecides, wood preservatives, and antifouling agents. [81] Tributyltin oxide is used as a wood preservative. [83] Tributyltin was used as additive for ship paint to prevent growth of marine organisms on ships, with use declining after organotin compounds were recognized as persistent organic pollutants with an extremely high toxicity for some marine organisms (the dog whelk, for example). [84] The EU banned the use of organotin compounds in 2003, [85] while concerns over the toxicity of these compounds to marine life and damage to the reproduction and growth of some marine species [81] (some reports describe biological effects to marine life at a concentration of 1 nanogram per liter) have led to a worldwide ban by the International Maritime Organization. [86] Many nations now restrict the use of organotin compounds to vessels greater than 25 m (82 ft) long. [81]

Organic chemistry

Some tin reagents are useful in organic chemistry. In the largest application, stannous chloride is a common reducing agent for the conversion of nitro and oxime groups to amines. The Stille reaction couples organotin compounds with organic halides or pseudohalides. [87]

Li-ion batteries

Tin forms several inter-metallic phases with lithium metal, making it a potentially attractive material for battery applications. Large volumetric expansion of tin upon alloying with lithium and instability of the tin-organic electrolyte interface at low electrochemical potentials are the greatest challenges to employment in commercial cells. The problem was partially solved by Sony. Tin inter-metallic compound with cobalt and carbon has been implemented by Sony in its Nexelion cells released in the late 2000s. The composition of the active material is approximately Sn0.3Co0.4C0.3. Recent research showed that only some crystalline facets of tetragonal (beta) Sn are responsible for undesirable electrochemical activity. [88]

Precautions

Cases of poisoning from tin metal, its oxides, and its salts are almost unknown. On the other hand, certain organotin compounds are almost as toxic as cyanide. [36]

Exposure to tin in the workplace can occur by inhalation, skin contact, and eye contact. The Occupational Safety and Health Administration (OSHA) has set the legal limit (permissible exposure limit) for tin exposure in the workplace as 2 mg/m3 over an 8-hour workday. The National Institute for Occupational Safety and Health (NIOSH) has determined a recommended exposure limit (REL) of 2 mg/m3 over an 8-hour workday. At levels of 100 mg/m3, tin is immediately dangerous to life and health. [89]

See also

Notes

  1. Only H, F, P, Tl and Xe have a higher receptivity for NMR analysis for samples containing isotopes at their natural abundance.

Related Research Articles

Indium Chemical element with atomic number 49

Indium is a chemical element with the symbol In and atomic number 49. Indium is the softest metal that is not an alkali metal. It is a silvery-white metal that resembles tin in appearance. It is a post-transition metal that makes up 0.21 parts per million of the Earth's crust. Indium has a melting point higher than sodium and gallium, but lower than lithium and tin. Chemically, indium is similar to gallium and thallium, and it is largely intermediate between the two in terms of its properties. Indium was discovered in 1863 by Ferdinand Reich and Hieronymous Theodor Richter by spectroscopic methods. They named it for the indigo blue line in its spectrum. Indium was isolated the next year.

Iridium Chemical element with atomic number 77

Iridium is a chemical element with the symbol Ir and atomic number 77. A very hard, brittle, silvery-white transition metal of the platinum group, iridium is the second-densest metal with a density of 22.56 g/cm3 as defined by experimental X-ray crystallography. At room temperature and standard atmospheric pressure, iridium has a calculated density 0.04 g/cm3 higher than osmium measured the same way. It is the most corrosion-resistant metal, even at temperatures as high as 2000 °C. Although only certain molten salts and halogens are corrosive to solid iridium, finely divided iridium dust is much more reactive and can be flammable.

Platinum Chemical element with atomic number 78

Platinum is a chemical element with the symbol Pt and atomic number 78. It is a dense, malleable, ductile, highly unreactive, precious, silverish-white transition metal. Its name is derived from the Spanish term platino, meaning "little silver".

Rhenium Chemical element with atomic number 75

Rhenium is a chemical element with the symbol Re and atomic number 75. It is a silvery-gray, heavy, third-row transition metal in group 7 of the periodic table. With an estimated average concentration of 1 part per billion (ppb), rhenium is one of the rarest elements in the Earth's crust. Rhenium has the third-highest melting point and highest boiling point of any stable element at 5903 K. Rhenium resembles manganese and technetium chemically and is mainly obtained as a by-product of the extraction and refinement of molybdenum and copper ores. Rhenium shows in its compounds a wide variety of oxidation states ranging from −1 to +7.

Scandium Chemical element with atomic number 21

Scandium is a chemical element with the symbol Sc and atomic number 21. A silvery-white metallic d-block element, it has historically been classified as a rare-earth element, together with yttrium and the lanthanides. It was discovered in 1879 by spectral analysis of the minerals euxenite and gadolinite from Scandinavia.

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.

Titanium Chemical element with atomic number 22

Titanium is a chemical element with the symbol Ti and atomic number 22. It is a lustrous transition metal with a silver color, low density, and high strength. Titanium is resistant to corrosion in sea water, aqua regia, and chlorine.

Tungsten Chemical element with atomic number 74

Tungsten, or wolfram, is a chemical element with the symbol W and atomic number 74. The name tungsten comes from the former Swedish name for the tungstate mineral scheelite, tung sten or "heavy stone". Tungsten is a rare metal found naturally on Earth almost exclusively combined with other elements in chemical compounds rather than alone. It was identified as a new element in 1781 and first isolated as a metal in 1783. Its important ores include wolframite and scheelite.

Zinc Chemical element with atomic number 30

Zinc is a chemical element with the symbol Zn and atomic number 30. Zinc is a slightly brittle metal at room temperature and has a blue-silvery appearance when oxidation is removed. It is the first element in group 12 of the periodic table. In some respects zinc is chemically similar to magnesium: both elements exhibit only one normal oxidation state (+2), and the Zn2+ and Mg2+ ions are of similar size. Zinc is the 24th most abundant element in Earth's crust and has five stable isotopes. The most common zinc ore is sphalerite (zinc blende), a zinc sulfide mineral. The largest workable lodes are in Australia, Asia, and the United States. Zinc is refined by froth flotation of the ore, roasting, and final extraction using electricity (electrowinning).

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.

Flux (metallurgy) type of chemicals used in metallurgy

In metallurgy, a flux is a chemical cleaning agent, flowing agent, or purifying agent. Fluxes may have more than one function at a time. They are used in both extractive metallurgy and metal joining.

Tin(IV) chloride, also known as tin tetrachloride or stannic chloride, is an inorganic compound with the formula SnCl4. It is a colourless hygroscopic liquid, which fumes on contact with air. It is used as a precursor to other tin compounds. It was first discovered by Andreas Libavius (1550–1616) and was known as spiritus fumans libavii.

Stannane chemical compound

Stannane or tin hydride is an inorganic compound with the chemical formula SnH
4
. It is a colourless gas and the tin analogue of methane. Stannane can be prepared by the reaction of SnCl4 and LiAlH4. Stannane decomposes slowly at room temperature to give metallic tin and hydrogen and ignites on contact with air.

Organotin chemistry branch of organic chemistry

Organotin compounds or stannanes are chemical compounds based on tin with hydrocarbon substituents. Organotin chemistry is part of the wider field of organometallic chemistry. The first organotin compound was diethyltin diiodide ((C2H5)2SnI2), discovered by Edward Frankland in 1849. The area grew rapidly in the 1900s, especially after the discovery of the Grignard reagents, which are useful for producing Sn-C bonds. The area remains rich with many applications in industry and continuing activity in the research laboratory.

Tin(IV) oxide chemical compound

Tin(IV) oxide, also known as stannic oxide, is the inorganic compound with the formula SnO2. The mineral form of SnO2 is called cassiterite, and this is the main ore of tin. With many other names, this oxide of tin is an important material in tin chemistry. It is a colourless, diamagnetic, amphoteric solid.

Trimethyltin chloride chemical compound

Trimethyltin chloride is an organotin compound with the formula (CH3)3SnCl. It is a white solid that is highly toxic and malodorous. It is susceptible to hydrolysis.

Triphenyltin chloride chemical compound

Triphenyltin chloride is an organotin compound with formula Sn(C6H5)3Cl. It is a colourless solid that dissolves in organic solvents. It slowly reacts with water. The main use for this compound is as a fungicide and antifoulant. Triphenyl tin chloride is used as a chemosterilant. Triphenyl tins used as a antifeedants against potato cutworm

Tetramethyltin chemical compound

Tetramethyltin is an organometallic compound with the formula (CH3)4Sn. This liquid, one of the simplest organotin compounds, is useful for transition-metal mediated conversion of acid chlorides to methyl ketones and aryl halides to aryl methyl ketones. It is volatile and toxic, so care should be taken when using it in the laboratory.

In chemistry, redistribution usually refers to the exchange of anionic ligands bonded to metal and metalloid centers. The conversion does not involve redox, in contrast to disproportionation reactions. Some useful redistribution reactions are conducted at higher temperatures; upon cooling the mixture, the product mixture is kinetically frozen and the individual products can be separated. In cases where redistribution is rapid at mild temperatures, the reaction is less useful synthetically but still important mechanistically.

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