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Silver

Silver

Chemical element with atomic number 47

Silver is a chemical element with the symbol Ag and atomic number 47. A soft, white, lustrous transition metal, it exhibits the highest electrical conductivity, thermal conductivity, and reflectivity of any metal. The metal is found in the Earth's crust in the pure, free elemental form ("native silver"), as an alloy with gold and other metals, and in minerals such as argentite and chlorargyrite. Most silver is produced as a byproduct of copper, gold, lead, and zinc refining.

Silver has long been valued as a precious metal. Silver metal is used in many bullion coins, sometimes alongside gold: while it is more abundant than gold, it is much less abundant as a native metal. Its purity is typically measured on a per-mille basis; a 94%-pure alloy is described as "0.940 fine". As one of the seven metals of antiquity, silver has had an enduring role in most human cultures.

Other than in currency and as an investment medium (coins and bullion), silver is used in solar panels, water filtration, jewellery, ornaments, high-value tableware and utensils (hence the term "silverware"), in electrical contacts and conductors, in specialized mirrors, window coatings, in catalysis of chemical reactions, as a colorant in stained glass, and in specialized confectionery. Its compounds are used in photographic and X-ray film. Dilute solutions of silver nitrate and other silver compounds are used as disinfectants and microbiocides (oligodynamic effect), added to bandages, wound-dressings, catheters, and other medical instruments.

Characteristics

Silver is extremely ductile, and can be drawn into a wire one atom wide.

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 crystallizes in a face-centered cubic lattice with bulk coordination number 12, where only the single 5s electron is delocalized, 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 is extremely ductile, and can be drawn into a wire one atom wide.

Silver has a brilliant, white, metallic luster that can take a high polish, and which is so characteristic that the name of the metal itself has become a colour name. Unlike copper and gold, the energy required to excite an electron from the filled d band to the s-p conduction band in silver is large enough (around 385 kJ/mol) that it no longer corresponds to absorption in the visible region of the spectrum, but rather in the ultraviolet; hence silver is not a coloured metal. 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).

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 dimerizes 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 stabilized 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.

Different colors of silver–copper–gold alloys

History

Silver was one of the seven metals of antiquity that were known to prehistoric humans and whose discovery is thus lost to history. In particular, 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. However, unlike copper, silver did not lead to the growth of metallurgy on account of its low structural strength, and 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 civilizations, 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, Erzgebirge, Alsace, the Lahn region, Siegerland, Silesia, Hungary, Norway, Steiermark, Salzburg, 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, before which the world production of silver was around a meagre 50 tonnes per year. In the Americas, high temperature silver-lead cupellation technology was developed by pre-Inca civilizations 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 center." 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.

Silver vase, circa 2400 BC

Silver mining and processing in Kutná Hora, Bohemia, 1490s

Monetary use

A 2004 American Silver Eagle bullion coin, minted in .999 fine silver.

The earliest known coins were minted in the kingdom of Lydia in Asia Minor around 600 BC. The coins of Lydia were made of electrum, which is a naturally occurring alloy of gold and silver, that was available within the territory of Lydia. Since that time, silver standards, in which the standard economic unit of account is a fixed weight of silver, have been widespread throughout the world until the 20th century. Notable silver coins through the centuries include the Greek drachma, the Roman denarius, the Islamic dirham, the karshapana from ancient India and rupee from the time of the Mughal Empire (grouped with copper and gold coins to create a trimetallic standard), and the Spanish dollar.

The ratio between the amount of silver used for coinage and that used for other purposes has fluctuated greatly over time; for example, in wartime, more silver tends to have been used for coinage to finance the war.

Today, silver bullion has the ISO 4217 currency code XAG, one of only four precious metals to have one (the others being palladium, platinum, and gold). Silver coins are produced from cast rods or ingots, rolled to the correct thickness, heat-treated, and then used to cut blanks from. These blanks are then milled and minted in a coining press; modern coining presses can produce 8000 silver coins per hour.

Price

Silver prices are normally quoted in troy ounces. One troy ounce is equal to 31.1034768 grams. The London silver fix is published every working day at noon London time. This price is determined by several major international banks and is used by London bullion market members for trading that day. Prices are most commonly shown as the United States dollar (USD), the Pound sterling (GBP), and the Euro (EUR).

In medicine

Main article: Colloidal silver

Until the middle of the 20th century, silver nitrate was used as an external antiseptic called lapis . In the light, it decomposes into free silver, nitrogen dioxide and molecular oxygen. However, at present, many much more effective antiseptics are used in all areas.

Since 1990, alternative medicine has seen a resurgence in the use of colloidal silver as a treatment for numerous ailments. There are mixed results in laboratory studies: some studies show that the antimicrobial effect of silver is very small, while others show that a solution of 5-30 ppm is effective against staphylococcus aureus and E. coli. This contradiction is associated with the size of colloidal silver nanoparticles - the smaller their size, the more pronounced the antimicrobial effect . It should be noted that similar properties of nanoparticles are characteristic of most transition metals.and are associated with the destruction of the bacterial cell membrane during the sorption of the nanoparticle. This, however, appears only in very pure solutions.

Timeline

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