Silver

Overview

Silver is a chemical element; it has symbol Ag (from Latin argentum) and atomic number 47. A soft, white, lustrous transition metal, it exhibits the highest electrical conductivity, thermal conductivity and reflectivity of any metal. Silver is found in the Earth's crust in the pure, free elemental form ("native silver"), as an alloy with gold (electrum) and other metals, and in minerals such as acanthite, argentite and chlorargyrite. Most silver is recovered as a byproduct of lead–zinc, copper and gold mining and refining. Silver has long been valued as a precious metal and coinage metal. It is one of the seven metals of antiquity, and has had an enduring role in monetary systems, jewellery, tableware and decorative arts. Its purity is commonly measured on a per-mille basis; a 94%-pure alloy is described as "0.940 fine". Because pure silver is relatively soft, silver used in jewellery, coinage and household objects is often alloyed with copper or other metals. Beyond currency and investment uses such as coins and bullion, silver is an important industrial material. It is used in photovoltaics, electrical contacts and conductors, printed electronics, brazing alloys, catalysis, specialised mirrors and window coatings, and antimicrobial materials. Silver halides are important in photographic film, photographic paper and photochromic glass, although demand for photographic silver has declined with the spread of digital imaging.

Characteristics

Silver is similar in its physical and chemical properties to its two vertical neighbours in group 11 of the periodic table: copper, and gold. Its 47 electrons are arranged in the configuration [Kr]4d105s1, similarly to copper ([Ar]3d104s1) and gold ([Xe]4f145d106s1); group 11 is one of the few groups in the d-block which has a completely consistent set of electron configurations. This distinctive electron configuration, with a single electron in the highest occupied s subshell over a filled d subshell, accounts for many of the singular properties of metallic silver. Silver is a relatively soft and extremely ductile and malleable transition metal, though it is slightly less malleable than gold. Silver crystallises in a face-centred cubic lattice with bulk coordination number 12, where only the single 5s electron is delocalised, similarly to copper and gold. Unlike metals with incomplete d-shells, metallic bonds in silver are lacking a covalent character and are relatively weak. This observation explains the low hardness and high ductility of single crystals of silver. Silver has a brilliant, white, metallic lustre that can take a high polish, and which is so characteristic that the name of the metal itself has become a colour name. Protected silver has greater optical reflectivity than aluminium at all wavelengths longer than ~450 nm. At wavelengths shorter than 450 nm, silver's reflectivity is inferior to that of aluminium and drops to zero near 310 nm. Very high electrical and thermal conductivity are common to the elements in group 11, because their single s electron is free and does not interact with the filled d subshell, as such interactions (which occur in the preceding transition metals) lower electron mobility. The thermal conductivity of silver is among the highest of all materials, although the thermal conductivity of carbon (in the diamond allotrope) and superfluid helium-4 are higher. The electrical conductivity of silver is the highest of all metals, greater even than copper. Silver also has the lowest contact resistance of any metal. Silver is rarely used for its electrical conductivity, due to its high cost, although an exception is in radio-frequency engineering, particularly at VHF and higher frequencies where silver plating improves electrical conductivity because those currents tend to flow on the surface of conductors rather than through the interior. During World War II in the US, 13540 tons of silver were used for the electromagnets in calutrons for enriching uranium, mainly because of the wartime shortage of copper. Silver readily forms alloys with copper, gold, and zinc. Zinc-silver alloys with low zinc concentration may be considered as face-centred cubic solid solutions of zinc in silver, as the structure of the silver is largely unchanged while the electron concentration rises as more zinc is added. Increasing the electron concentration further leads to body-centred cubic (electron concentration 1.5), complex cubic (1.615), and hexagonal close-packed phases (1.75).

Isotopes

Naturally occurring silver is composed of two stable isotopes, 107Ag and 109Ag, with 107Ag being slightly more abundant (51.839% natural abundance). This almost equal abundance is rare in the periodic table. The atomic weight is 107.8682(2) Da; this value is very important because of the importance of silver compounds, particularly halides, in gravimetric analysis. Both isotopes of silver are produced in stars via the s-process (slow neutron capture), as well as in supernovas via the r-process (rapid neutron capture). Twenty-eight radioisotopes have been characterised, the most stable being 105Ag with a half-life of 41.29 days, 111Ag with a half-life of 7.45 days, and 112Ag with a half-life of 3.13 hours. Silver has numerous nuclear isomers, the most stable being 108mAg (t1/2 = 418 years), 110mAg (t1/2 = 249.79 days) and 106mAg (t1/2 = 8.28 days). All of the remaining radioactive isotopes have half-lives of less than an hour, and the majority of these have half-lives of less than three minutes. Isotopes of silver range in atomic mass from 92.950 Da (93Ag) to 129.950 Da (130Ag); the primary decay mode before the most abundant stable isotope, 107Ag, is electron capture and the primary mode after is beta decay. The primary decay products before 107Ag are palladium (element 46) isotopes, and the primary products after are cadmium (element 48) isotopes. The palladium isotope 107Pd decays by beta emission to 107Ag with a half-life of 6.5 million years. Iron meteorites are the only objects with a high-enough palladium-to-silver ratio to yield measurable variations in 107Ag abundance. Radiogenic 107Ag was first discovered in the Santa Clara meteorite in 1978. 107Pd–107Ag correlations observed in bodies that have clearly been melted since the accretion of the Solar System must reflect the presence of unstable nuclides in the early Solar System.

Chemistry

Silver is a rather unreactive metal. This is because its filled 4d shell is not very effective in shielding the electrostatic forces of attraction from the nucleus to the outermost 5s electron, and hence silver is near the bottom of the electrochemical series (Eo(Ag+/Ag) = +0.799 V). In group 11, silver has the lowest first ionisation energy (showing the instability of the 5s orbital), but has higher second and third ionisation energies than copper and gold (showing the stability of the 4d orbitals), so that the chemistry of silver is predominantly that of the +1 oxidation state, reflecting the increasingly limited range of oxidation states along the transition series as the d-orbitals fill and stabilise. Unlike copper, for which the larger hydration energy of Cu2+ as compared to Cu+ is the reason why the former is the more stable in aqueous solution and solids despite lacking the stable filled d-subshell of the latter, with silver this effect is swamped by its larger second ionisation energy. Hence, Ag+ is the stable species in aqueous solution and solids, with Ag2+ being much less stable as it oxidises water. Most silver compounds have significant covalent character due to the small size and high first ionisation energy (730.8 kJ/mol) of silver. Furthermore, silver's Pauling electronegativity of 1.93 is higher than that of lead (1.87), and its electron affinity of 125.6 kJ/mol is much higher than that of hydrogen (72.8 kJ/mol) and not much less than that of oxygen (141.0 kJ/mol). Due to its full d-subshell, silver in its main +1 oxidation state exhibits relatively few properties of the transition metals proper from groups 4 to 10, forming rather unstable organometallic compounds, forming linear complexes showing very low coordination numbers like 2, and forming an amphoteric oxide as well as Zintl phases like the post-transition metals. Unlike the preceding transition metals, the +1 oxidation state of silver is stable even in the absence of π-acceptor ligands. Silver does not react with air, even at red heat, and thus was considered by alchemists to be a noble metal. Its reactivity is intermediate between that of copper (which forms copper(I) oxide when heated in air to red heat) and gold. Like copper, silver reacts with sulfur and its compounds; in their presence, silver tarnishes in air to form the black silver sulfide (copper forms the green sulfate instead, while gold does not react). While silver is not attacked by non-oxidising acids, the metal dissolves readily in hot concentrated sulfuric acid, as well as dilute or concentrated nitric acid. In the presence of air, and especially in the presence of hydrogen peroxide, silver dissolves readily in aqueous solutions of cyanide. The three main forms of deterioration in historical silver artifacts are tarnishing, formation of silver chloride due to long-term immersion in salt water, as well as reaction with nitrate ions or oxygen. Fresh silver chloride is pale yellow, becoming purplish on exposure to light; it projects slightly from the surface of the artifact or coin. The precipitation of copper in ancient silver can be used to date artifacts, as copper is nearly always a constituent of silver alloys. Silver metal is attacked by strong oxidant such as potassium permanganate (KMnO4) and potassium dichromate (K2Cr2O7), and in the presence of potassium bromide (KBr). These compounds are used in photography to bleach silver images, converting them to silver bromide that can either be fixed with thiosulfate or redeveloped to intensify the original image. Silver forms cyanide complexes (silver cyanide) that are soluble in water in the presence of an excess of cyanide ions. Silver cyanide solutions are used in electroplating of silver. The common oxidation states of silver are (in order of commonness): +1 (the most stable state; for example, silver nitrate, AgNO3); +2 (highly oxidising; for example, silver(II) fluoride, AgF2); and even very rarely +3 (extreme oxidising; for example, potassium tetrafluoroargentate(III), KAgF4). The +3 state requires very strong oxidising agents to attain, such as fluorine or peroxodisulfate, and some silver(III) compounds react with atmospheric moisture and attack glass. Indeed, silver(III) fluoride is usually obtained by reacting silver or silver monofluoride with the strongest known oxidising agent, krypton difluoride.

Oxides and chalcogenides

Silver and gold have rather low chemical affinities for oxygen, lower than copper, and it is therefore expected that silver oxides are thermally quite unstable. Soluble silver(I) salts precipitate dark-brown silver(I) oxide, Ag2O, upon the addition of alkali. (The hydroxide AgOH exists only in solution; otherwise it spontaneously decomposes to the oxide.) Silver(I) oxide is very easily reduced to metallic silver, and decomposes to silver and oxygen above 160 °C. This and other silver(I) compounds may be oxidised by the strong oxidising agent peroxodisulfate to black AgO, a mixed silver(I,III) oxide of formula AgIAgIIIO2. Some other silver oxides, such as Ag2O3 and Ag3O4, are also known, as is Ag3O, which behaves as a metallic conductor. Silver(I) sulfide, Ag2S, is very readily formed from its constituent elements and is the cause of the black tarnish on some old silver objects. It may also be formed from the reaction of hydrogen sulfide with silver metal or aqueous Ag+ ions. Many non-stoichiometric selenides and tellurides are known; in particular, AgTe~3 is a low-temperature superconductor.

Halides

The only known dihalide of silver is the difluoride, AgF2, which can be obtained from the elements under heat. A strong yet thermally stable and therefore safe fluorinating agent, silver(II) fluoride is often used to synthesise hydrofluorocarbons. In stark contrast to this, all four silver(I) halides are known. The fluoride, chloride, and bromide have the sodium chloride structure, but the iodide has three known stable forms at different temperatures; that at room temperature is the cubic zinc blende structure. They can all be obtained by the direct reaction of their respective elements. As the halogen group is descended, the silver halide gains more and more covalent character, solubility decreases, and the colour changes from the white chloride to the yellow iodide as the energy required for ligand-metal charge transfer (X−Ag+ → XAg) decreases. The fluoride is anomalous, as the fluoride ion is so small that it has a considerable solvation energy and hence is highly water-soluble and forms di- and tetrahydrates. The other three silver halides are highly insoluble in aqueous solutions and are very commonly used in gravimetric analytical methods. All four are photosensitive (though the monofluoride is so only to ultraviolet light), especially the bromide and iodide which photodecompose to silver metal, and thus were used in traditional photography. The reaction involved is:

X− + hν → X + e− (excitation of the halide ion, which gives up its extra electron into the conduction band) Ag+ + e− → Ag (liberation of a silver ion, which gains an electron to become a silver atom) The process is not reversible because the silver atom liberated is typically found at a crystal defect or an impurity site, so that the electron's energy is lowered enough that it is "trapped".

Other inorganic compounds

White silver nitrate, AgNO3, is a versatile precursor to many other silver compounds, especially the halides, and is much less sensitive to light. It was once called lunar caustic because silver was called luna by the ancient alchemists, who believed that silver was associated with the Moon. It is often used for gravimetric analysis, exploiting the insolubility of the heavier silver halides which it is a common precursor to. Silver nitrate is used in many ways in organic synthesis, e.g. for deprotection and oxidations. Ag+ binds alkenes reversibly, and silver nitrate has been used to separate mixtures of alkenes by selective absorption. The resulting adduct can be decomposed with ammonia to release the free alkene. Yellow silver carbonate, Ag2CO3 can be easily prepared by reacting aqueous solutions of sodium carbonate with a deficiency of silver nitrate. Its principal use is for the production of silver powder for use in microelectronics. It is reduced with formaldehyde, producing silver free of alkali metals:

Ag2CO3 + CH2O → 2 Ag + 2 CO2 + H2 Silver carbonate is also used as a reagent in organic synthesis such as the Koenigs–Knorr reaction. In the Fétizon oxidation, silver carbonate on celite acts as an oxidising agent to form lactones from diols. It is also employed to convert alkyl bromides into alcohols. Silver fulminate, AgCNO, a powerful, touch-sensitive explosive used in percussion caps, is made by reaction of silver metal with nitric acid in the presence of ethanol. Other dangerously explosive silver compounds are silver azide, AgN3, formed by reaction of silver nitrate with sodium azide, and silver acetylide, Ag2C2, formed when silver reacts with acetylene gas in ammonia solution. In its most characteristic reaction, silver azide decomposes explosively, releasing nitrogen gas: given the photosensitivity of silver salts, this behaviour may be induced by shining a light on its crystals.

2 AgN3(s) → 3 N2(g) + 2 Ag(s)

Coordination compounds

Silver complexes tend to be similar to those of its lighter homologue copper. Silver(III) complexes tend to be rare and very easily reduced to the more stable lower oxidation states, though they are slightly more stable than those of copper(III). For instance, the square planar periodate [Ag(IO5OH)2](−5 and tellurate [Ag{TeO4(OH)2}2]5− complexes may be prepared by oxidising silver(I) with alkaline peroxodisulfate. The yellow diamagnetic AgF4− is much less stable, fuming in moist air and reacting with glass. Silver(II) complexes are more common. Like the valence isoelectronic copper(II) complexes, they are usually square planar and paramagnetic, which is increased by the greater field splitting for 4d electrons than for 3d electrons. Aqueous Ag2+, produced by oxidation of Ag+ by ozone, is a very strong oxidising agent, even in acidic solutions: it is stabilised in phosphoric acid due to complex formation. Peroxodisulfate oxidation is generally necessary to give the more stable complexes with heterocyclic amines, such as [Ag(py)4]2+ and [Ag(bipy)2]2+: these are stable provided the counterion cannot reduce the silver back to the +1 oxidation state. [AgF4]2− is also known in its violet barium salt, as are some silver(II) complexes with N- or O-donor ligands such as pyridine carboxylates. By far the most important oxidation state for silver in complexes is +1. The Ag+ cation is diamagnetic, like its homologues Cu+ and Au+, as all three have closed-shell electron configurations with no unpaired electrons: its complexes are colourless provided the ligands are not too easily polarised such as I−. Ag+ forms salts with most anions, but it is reluctant to coordinate to oxygen and thus most of these salts are insoluble in water: the exceptions are the nitrate, perchlorate, and fluoride. The tetracoordinate tetrahedral aqueous ion [Ag(H2O)4]+ is known, but the characteristic geometry for the Ag+ cation is 2-coordinate linear. For example, silver chloride dissolves readily in excess aqueous ammonia to form [Ag(NH3)2]+; silver salts are dissolved in photography due to the formation of the thiosulfate complex [Ag(S2O3)2]3−; and cyanide extraction for silver (and gold) works by the formation of the complex [Ag(CN)2]−. Silver cyanide forms the linear polymer {Ag–C≡N→Ag–C≡N→}; silver thiocyanate has a similar structure, but forms a zigzag instead because of the sp3-hybridized sulfur atom. Chelating ligands are unable to form linear complexes and thus silver(I) complexes with them tend to form polymers; a few exceptions exist, such as the near-tetrahedral diphosphine and diarsine complexes [Ag(L−L)2]+.

Organometallic

Under standard conditions, silver does not form simple carbonyls, due to the weakness of the Ag–C bond. A few are known at very low temperatures around 6–15 K, such as the green, planar paramagnetic Ag(CO)3, which dimerises at 25–30 K, probably by forming Ag–Ag bonds. Additionally, the silver carbonyl [Ag(CO)][B(OTeF5)4] is known. Polymeric AgLX complexes with alkenes and alkynes are known, but their bonds are thermodynamically weaker than even those of the platinum complexes (though they are formed more readily than those of the analogous gold complexes): they are also quite unsymmetrical, showing the weak π bonding in group 11. Ag–C σ bonds may also be formed by silver(I), like copper(I) and gold(I), but the simple alkyls and aryls of silver(I) are even less stable than those of copper(I) (which tend to explode under ambient conditions). For example, poor thermal stability is reflected in the relative decomposition temperatures of AgMe (−50 °C) and CuMe (−15 °C) as well as those of PhAg (74 °C) and PhCu (100 °C). The C–Ag bond is stabilised by perfluoroalkyl ligands, for example in AgCF(CF3)2. Alkenylsilver compounds are also more stable than their alkylsilver counterparts. Silver-NHC complexes are easily prepared, and are commonly used to prepare other NHC complexes by displacing labile ligands. For example, the reaction of the bis(NHC)silver(I) complex with bis(acetonitrile)palladium dichloride or chlorido(dimethyl sulfide)gold(I):

Intermetallic

Silver forms alloys with most other elements on the periodic table. The elements from groups 1–3, except for hydrogen, lithium, and beryllium, are very miscible with silver in the condensed phase and form intermetallic compounds; those from groups 4–9 are only poorly miscible; the elements in groups 10–14 (except boron and carbon) have very complex Ag–M phase diagrams and form the most commercially important alloys; and the remaining elements on the periodic table have no consistency in their Ag–M phase diagrams. By far the most important such alloys are those with copper: most silver used for coinage and jewellery is in reality a silver–copper alloy, and the eutectic mixture is used in vacuum brazing. The two metals are completely miscible as liquids but not as solids; their importance in industry comes from the fact that their properties tend to be suitable over a wide range of variation in silver and copper concentration, although most useful alloys tend to be richer in silver than the eutectic mixture (71.9% silver and 28.1% copper by weight, and 60.1% silver and 28.1% copper by atom). Most other binary alloys are of little use: for example, silver–gold alloys are too soft and silver–cadmium alloys too toxic. Ternary alloys have much greater importance: dental amalgams are usually silver–tin–mercury alloys, silver–copper–gold alloys are very important in jewellery (usually on the gold-rich side) and have a vast range of hardnesses and colours, silver–copper–zinc alloys are useful as low-melting brazing alloys, and silver–cadmium–indium (involving three adjacent elements on the periodic table) is useful in nuclear reactors because of its high thermal neutron capture cross-section, good conduction of heat, mechanical stability, and resistance to corrosion in hot water.

Etymology

The word silver appears in Old English with various spellings, such as seolfor and siolfor. Its cognates include Old High German silabar, Gothic silubr and Old Norse silfr, all ultimately derived from Proto-Germanic *silubrą. The Balto-Slavic words for silver resemble those of the Germanic branch (e.g. Russian серебро́ serebró, Polish srebro and Lithuanian sidãbras), and so does the Celtiberian term silabur 'money'. They could have a common Indo-European origin, although their morphology rather suggests a non-Indo-European Wanderwort. Some scholars have thus proposed a Paleo-Hispanic origin, pointing to Basque zilar as evidence, though this remains speculative. The chemical symbol Ag is from the Latin word for silver, argentum, from the Proto-Indo-European root *h₂erǵ-, meaning 'white' or 'shining'. This was the usual PIE term for the metal, whose reflexes are missing in Germanic and Balto-Slavic.

History

Silver was known in prehistoric times: the three metals of group 11, copper, silver, and gold, occur in the elemental form in nature and were probably used as the first primitive forms of money as opposed to simple bartering. Unlike copper, silver did not lead to the growth of metallurgy, on account of its low structural strength; it was more often used ornamentally or as money. Since silver is more reactive than gold, supplies of native silver were much more limited than those of gold. For example, silver was more expensive than gold in Egypt until around the fifteenth century BC: the Egyptians are thought to have separated gold from silver by heating the metals with salt, and then reducing the silver chloride produced to the metal. The situation changed with the discovery of cupellation, a technique that allowed silver metal to be extracted from its ores. While slag heaps found in Asia Minor and on the islands of the Aegean Sea indicate that silver was being separated from lead as early as the 4th millennium BC, and one of the earliest silver extraction centres in Europe was Sardinia in the early Chalcolithic period, these techniques did not spread widely until later, when it spread throughout the region and beyond. The origins of silver production in India, China, and Japan were almost certainly equally ancient, but are not well-documented due to their great age.

When the Phoenicians first came to what is now Spain, they obtained so much silver that they could not fit it all on their ships, and as a result used silver to weight their anchors instead of lead. By the time of the Greek and Roman civilisations, silver coins were a staple of the economy: the Greeks were already extracting silver from galena by the 7th century BC, and the rise of Athens was partly made possible by the nearby silver mines at Laurium, from which they extracted about 30 tonnes a year from 600 to 300 BC. The stability of the Roman currency relied to a high degree on the supply of silver bullion, mostly from Spain, which Roman miners produced on a scale unparalleled before the discovery of the New World. Reaching a peak production of 200 tonnes per year, an estimated silver stock of 10,000 tonnes circulated in the Roman economy in the middle of the second century AD, five to ten times larger than the combined amount of silver available to medieval Europe and the Abbasid Caliphate around AD 800. The Romans also recorded the extraction of silver in central and northern Europe in the same time period. This production came to a nearly complete halt with the fall of the Roman Empire, not to resume until the time of Charlemagne: by then, tens of thousands of tonnes of silver had already been extracted. Central Europe became the centre of silver production during the Middle Ages, as the Mediterranean deposits exploited by the ancient civilisations had been exhausted. Silver mines were opened in Bohemia, Saxony, Alsace, the Lahn region, Siegerland, Silesia, Hungary, Norway, Steiermark, Schwaz, and the southern Black Forest. Most of these ores were quite rich in silver and could simply be separated by hand from the remaining rock and then smelted; some deposits of native silver were also encountered. Many of these mines were soon exhausted, but a few of them remained active until the Industrial Revolution. In the Americas, high temperature silver-lead cupellation technology was developed by pre-Inca civilisations as early as AD 60–120; silver deposits in India, China, Japan, and pre-Columbian America continued to be mined during this time. With the discovery of America and the plundering of silver by the Spanish conquistadors, Central and South America became the dominant producers of silver until around the beginning of the 18th century, particularly Peru, Bolivia, Chile, and Argentina: the last of these countries later took its name from that of the metal that composed so much of its mineral wealth. The silver trade gave way to a global network of exchange. As one historian put it, silver "went round the world and made the world go round." Much of this silver ended up in the hands of the Chinese. A Portuguese merchant in 1621 noted that silver "wanders throughout all the world... before flocking to China, where it remains as if at its natural centre". Still, much of it went to Spain, allowing Spanish rulers to pursue military and political ambitions in both Europe and the Americas. "New World mines", concluded several historians, "supported the Spanish empire." In the 19th century, primary production of silver moved to North America, particularly Canada, Mexico, and Nevada in the United States: some secondary production from lead and zinc ores also took place in Europe, and deposits in Siberia and the Russian Far East as well as in Australia were mined. Poland emerged as an important producer during the 1970s after the discovery of copper deposits that were rich in silver, before the centre of production returned to the Americas the following decade. Today, Peru and Mexico are still among the primary silver producers, but the distribution of silver production around the world is quite balanced and about one-fifth of the silver supply comes from recycling instead of new production.