Silver is a chemical element with symbol Ag (from the
derived from the
Proto-Indo-European h₂erǵ: "shiny" or "white") 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 specialised
confectionery. Its compounds are used in photographic and
Dilute solutions of silver nitrate and other silver compounds are used
as disinfectants and microbiocides (oligodynamic effect), added to
bandages and wound-dressings, catheters, and other medical
3.1 Oxides and chalcogenides
3.3 Other inorganic compounds
3.4 Coordination compounds
6 Symbolic role
7 Occurrence and production
8 Monetary use
Jewellery and silverware
9.5 Chemical equipment
11 See also
14 External links
Silver is extremely ductile, and can be drawn into a monoatomic
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 an extremely soft, 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 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 is 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 electrical conductivity of silver is the greatest of all metals,
greater even than copper, but it is not widely used for this property
because of the higher cost. 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.
World War II
World War II in the US, 13540 tons of silver were used in
electromagnets for enriching uranium, mainly because of the wartime
shortage of copper. Pure silver has the highest thermal
conductivity of any metal, although the conductivity of carbon (in the
diamond allotrope) and superfluid helium-4 are even higher. Silver
also has the lowest contact resistance of any metal.
Silver readily forms alloys with copper and gold, as well as 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).
Main article: Isotopes of silver
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) u; 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 characterized, 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.
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
Isotopes of silver range in relative atomic mass from 92.950 u
(93Ag) to 129.950 u (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. The discoverers suggest the
coalescence and differentiation of iron-cored small planets may have
occurred 10 million years after a nucleosynthetic event. 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.
Oxidation states and stereochemistries of silver
AgF, AgCl, AgBr
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 (E0(Ag+/Ag) =
+0.799 V). In group 11, silver has the lowest first ionization
energy (showing the instability of the 5s orbital), but has higher
second and third ionization 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 stabilize. 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 large enough for this factor to have a much
smaller effect, and furthermore the second ionisation energy of silver
is greater than that for copper. Hence, Ag+ is the stable species in
aqueous solution and solids, with Ag2+ being much less stable as it
Despite the above formulations, most silver compounds have significant
covalent character due to the small size and high first ionization
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 as a noble metal along with gold. 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). Unlike copper,
silver will not react with the halogens, with the exception of the
notoriously reactive fluorine gas, with which it forms the difluoride.
While silver is not attacked by non-oxidizing 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 metal is attacked by strong oxidizers such as potassium
4) and potassium dichromate (K
7), 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 +1 state is by far the most
common, followed by the easily reducible +2 state. 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 oxidizing 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 oxidized
by the strong oxidizing agent peroxodisulfate to black AgO, a mixed
silver(I,III) oxide of formula AgIAgIIIO2. Some other mixed oxides
with silver in non-integral oxidation states, namely 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
The three common silver halide precipitates: from left to right,
silver iodide, silver bromide, and silver chloride.
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 synthesize 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
color 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
Crystals of silver nitrate
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
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.
3 (s) → 3 N
2 (g) + 2 Ag (s)
Structure of the diamminesilver(I) complex, [Ag(NH3)2]+
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 stabilized 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 polarized 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]−.
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]+.
Main article: Organosilver chemistry
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
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):
Different colors of silver–copper–gold alloys
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.
The word "silver" appears in Anglo-Saxon in various spellings, such as
seolfor and siolfor. A similar form is seen throughout the Germanic
Old High German
Old High German silabar and silbir). The chemical
symbol Ag is from the
Latin word for "silver", argentum (compare
Ancient Greek ἄργυρος, árgyros), from the Proto-Indo-European
root *h₂erǵ- (formerly reconstructed as *arǵ-), meaning "white" or
"shining": this was the usual
Proto-Indo-European word for the metal,
whose reflexes are missing in Germanic and Balto-Slavic. The
Balto-Slavic words for silver are quite similar to the Germanic ones
(e.g. Russian серебро [serebro], Polish srebro, Lithuanian
sidabras) and they may have a common origin, although this is
uncertain: some scholars have suggested the Akkadian sarpu "refined
silver" as this origin, related to the word sarapu "to refine or
Silver plate from the 4th century
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
Sardinia in early the 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.
Silver mining and processing in Kutná Hora, Bohemia, 1490s
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
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 10000
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. 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
Siberia and the
Russian Far East
Russian Far East as well as in Australia
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
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.
16th-century fresco painting of Judas being paid thirty pieces of
silver for his betrayal of Jesus
Silver plays a certain role in mythology and has found various usage
as a metaphor and in folklore. The Greek poet Hesiod's Works and Days
(lines 109–201) lists different ages of man named after metals like
gold, silver, bronze and iron to account for successive ages of
Metamorphoses contains another retelling of the
story, containing an illustration of silver's metaphorical use of
signifying the second-best in a series, better than bronze but worse
But when good Saturn, banish'd from above,
Was driv'n to Hell, the world was under Jove.
Succeeding times a silver age behold,
Excelling brass, but more excell'd by gold.
— Ovid, Metamorphoses, Book I, trans. John Dryden
In folklore, silver was commonly thought to have mystic powers: for
example, a bullet cast from silver is often supposed in such folklore
the only weapon that is effective against a werewolf, witch, or other
monsters. From this the idiom of a silver bullet developed
into figuratively referring to any simple solution with very high
effectiveness or almost miraculous results, as in the widely discussed
software engineering paper No
Silver production has also inspired figurative language. Clear
references to cupellation occur throughout the
Old Testament of the
Bible, such as in Jeremiah's rebuke to Judah: "The bellows are burned,
the lead is consumed of the fire; the founder melteth in vain: for the
wicked are not plucked away. Reprobate silver shall men call them,
because the Lord hath rejected them." (
Jeremiah 6:19–20) Jeremiah
was also aware of sheet silver, exemplifying the malleability and
ductility of the metal: "
Silver spread into plates is brought from
Tarshish, and gold from Uphaz, the work of the workman, and of the
hands of the founder: blue and purple is their clothing: they are all
the work of cunning men." (
Silver also has more negative cultural meanings: the idiom thirty
pieces of silver, referring to a reward for betrayal, references the
Judas Iscariot is said in the
New Testament to have taken from
Jewish leaders in
Jerusalem to turn
Jesus of Nazareth over to soldiers
of the high priest Caiaphas. Ethically, silver also symbolizes
greed and degradation of consciousness; this is the negative aspect,
the perverting of its value.
Occurrence and production
Acanthite sample from the Chispas Mine in Sonora, Mexico; scale at
bottom of image as one inch with a rule at one centimetre
The abundance of silver in the Earth's crust is 0.08 parts per
million, almost exactly the same as that of mercury. It mostly occurs
in sulfide ores, especially acanthite and argentite, Ag2S. Argentite
deposits sometimes also contain native silver when they occur in
reducing environments, and when in contact with salt water they are
converted to chlorargyrite (including horn silver), AgCl, which is
Chile and New South Wales. Most other silver minerals
are silver pnictides or chalcogenides; they are generally lustrous
semiconductors. Most true silver deposits, as opposed to argentiferous
deposits of other metals, came from
Tertiary period vulcanism.
The principal sources of silver are the ores of copper, copper-nickel,
lead, and lead-zinc obtained from Peru, Bolivia, Mexico, China,
Poland and Serbia. Peru,
been mining silver since 1546, and are still major world producers.
Top silver-producing mines are Cannington (Australia), Fresnillo
(Mexico), San Cristóbal (Bolivia), Antamina (Peru), Rudna (Poland),
and Penasquito (Mexico). Top near-term mine development projects
through 2015 are Pascua Lama (Chile), Navidad (Argentina), Jaunicipio
(Mexico), Malku Khota (Bolivia), and Hackett River (Canada).
In Central Asia, Tajikistan is known to have some of the largest
silver deposits in the world.
Silver is usually found in nature combined with other metals, or in
minerals that contain silver compounds, generally in the form of
sulfides such as galena (lead sulfide) or cerussite (lead carbonate).
So the primary production of silver requires the smelting and then
cupellation of argentiferous lead ores, a historically important
Lead melts at 327 °C, lead oxide at 888 °C
and silver melts at 960 °C. To separate the silver, the alloy is
melted again at the high temperature of 960 °C to 1000 °C
in an oxidizing environment. The lead oxidises to lead monoxide, then
known as litharge, which captures the oxygen from the other metals
present. The liquid lead oxide is removed or absorbed by capillary
action into the hearth linings.
Ag(s) + 2Pb(s) + O
2(g) → 2PbO(absorbed) + Ag(l)
Today, silver metal is primarily produced instead as a secondary
byproduct of electrolytic refining of copper, lead, and zinc, and by
application of the
Parkes process on lead bullion from ore that also
contains silver. In such processes, silver follows the non-ferrous
metal in question through its concentration and smelting, and is later
purified out. For example, in copper production, purified copper is
electrolytically deposited on the cathode, while the less reactive
precious metals such as silver and gold collect under the anode as the
so-called "anode slime". This is then separated and purified of base
metals by treatment with hot aerated dilute sulfuric acid and heating
with lime or silica flux, before the silver is purified to over 99.9%
purity via electrolysis in nitrate solution.
Commercial-grade fine silver is at least 99.9% pure, and purities
greater than 99.999% are available. In 2014,
Mexico was the top
producer of silver (5,000 tonnes or 18.7% of the world's total of
26,800 t), followed by
China (4,060 t) and
Peru (3,780 t).
1,000 oz silver bar
The earliest known coins of the Western world were minted in the
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
Indian rupee from the time
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
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
As of January 2018, silver is valued at around $554 per kilogram, or
about $17 per ounce.
Silver prices are normally quoted in Troy ounces which equals 31.1034
grams. Prices most commonly shown in US dollars, a London silver
price occurs daily where major international banks conduct and publish
a fixing at noon London time. Unlike the gold A.m. and P.m. fix there
is only one silver fixing per day.
Jewellery and silverware
Silver toilet set of Alexandra Nikolaevna
The major use of silver besides coinage throughout most of history was
in the manufacture of jewellery and other general-use items, and this
continues to be a major use today. Examples include table silver for
cutlery, for which silver is highly suited due to its antibacterial
properties. Western concert flutes are usually plated with or made out
of sterling silver; in fact, most silverware is only silver-plated
rather than made out of pure silver; the silver is normally put in
place by electroplating. Silver-plated glass (as opposed to metal) is
used for mirrors, vacuum flasks, and Christmas tree decorations.
Because pure silver is very soft, most silver used for these purposes
is alloyed with copper, with finenesses of 925/1000, 835/1000, and
800/1000 being common. One drawback is the easy tarnishing of silver
in the presence of hydrogen sulfide and its derivatives. Including
precious metals such as palladium, platinum, and gold gives resistance
to tarnishing but is quite costly; base metals like zinc, cadmium,
silicon, and germanium do not totally prevent corrosion and tend to
affect the lustre and colour of the alloy. Electrolytically refined
pure silver plating is effective at increasing resistance to
tarnishing. The usual solutions for restoring the lustre of tarnished
silver are dipping baths that reduce the silver sulfide surface to
metallic silver, and cleaning off the layer of tarnish with a paste;
the latter approach also has the welcome side effect of polishing the
silver concurrently. A simple chemical approach to removal of the
sulfide tarnish is to bring silver items into contact with aluminium
foil whilst immersed in water containing a conducting salt, such as
sodium chloride.
Main article: Medical uses of silver
In medicine, silver is incorporated into wound dressings and used as
an antibiotic coating in medical devices. Wound dressings containing
silver sulfadiazine or silver nanomaterials are used to treat external
Silver is also used in some medical applications, such as
urinary catheters (where tentative evidence indicates it reduces
catheter-related urinary tract infections) and in endotracheal
breathing tubes (where evidence suggests it reduces
ventilator-associated pneumonia). The silver ion is bioactive
and in sufficient concentration readily kills bacteria in vitro. They
interfere with enzymes in the bacteria that transport nutrients, form
structures, synthesise cell walls, and bond with the bacteria's
genetic material. Microbes cannot develop resistance to silver as they
can to antibiotics, and hence silver and silver nanoparticles are used
as an antimicrobial in a variety of industrial, healthcare, and
domestic application: for example, infusing clothing with nanosilver
particles thus allows them to stay odourless for longer.
Silver compounds are taken up by the body like mercury compounds, but
lack the toxicity of the latter.
Silver and its alloys are used in
cranial surgery to replace bone, and silver–tin–mercury amalgams
are used in dentistry.
Silver diammine fluoride, the fluoride salt
of a coordination complex with the formula [Ag(NH3)2]F, is a topical
medicament (drug) used to treat and prevent dental caries (cavities)
and relieve dentinal hypersensitivity.
Silver is very important in electronics for conductors and electrodes
on account of its high electrical conductivity even when tarnished.
Bulk silver and silver foils were used to make vacuum tubes, and
continue to be used today in the manufacture of semiconductor devices,
circuits, and their components. For example, silver is used in high
quality connectors for RF, VHF, and higher frequencies, particularly
in tuned circuits such as cavity filters where conductors cannot be
scaled by more than 6%. Printed circuits and
RFID antennas are made
with silver paints, Powdered silver and its alloys are used in
paste preparations for conductor layers and electrodes, ceramic
capacitors, and other ceramic components.
Silver-containing brazing alloys are used for brazing metallic
materials, mostly cobalt, nickel, and copper-based alloys, tool
steels, and precious metals. The basic components are silver and
copper, with other elements selected according to the specific
application desired: examples include zinc, tin, cadmium, palladium,
manganese, and phosphorus.
Silver provides increased workability and
corrosion resistance during usage.
Silver is useful in the manufacture of chemical equipment on account
of its low chemical reactivity, high thermal conductivity, and being
Silver crucibles (alloyed with 0.15% nickel to avoid
recrystallisation of the metal at red heat) are used for carrying out
Copper and silver are also used when doing chemistry
with fluorine. Equipment made to work at high temperatures is often
Silver and its alloys with gold are used as wire or
ring seals for oxygen compressors and vacuum equipment.
Silver metal is a good catalyst for oxidation reactions; in fact it is
somewhat too good for most purposes, as finely divided silver tends to
result in complete oxidation of organic substances to carbon dioxide
and water, and hence coarser-grained silver tends to be used instead.
For instance, 15% silver supported on α-Al2O3 or silicates is a
catalyst for the oxidation of ethylene to ethylene oxide at
230–270 °C. Dehydrogenation of methanol to formaldehyde is
conducted at 600–720 °C over silver gauze or crystals as the
catalyst, as is dehydrogenation of isopropanol to acetone. In the gas
phase, glycol yields glyoxal and ethanol yields acetaldehyde, while
organic amines are dehydrated to nitriles.
The photosensitivity of the silver halides allowed for their use in
traditional photography, although digital photography, which does not
use silver, is now dominant. The photosensitive emulsion used in
black-and-white photography is a suspension of silver halide crystals
in gelatin, possibly mixed in with some noble metal compounds for
improved photosensitivity, developing, and tuning. Colour photography
requires the addition of special dye components and sensitisers, so
that the initial black-and-white silver image couples with a different
dye component. The original silver images are bleached off and the
silver is then recovered and recycled.
Silver nitrate is the starting
material in all cases.
The use of silver nitrate and silver halides in photography has
rapidly declined with the advent of digital technology. From the peak
global demand for photographic silver in 1999 (267,000,000 troy ounces
or 8304.6 metric tonnes) the market contracted almost 70% by
Nanosilver particles, between 10 and 100 nanometres in size, are
used in many applications. They are used in conductive inks for
printed electronics, and have a much lower melting point than larger
silver particles of micrometre size. They are also used medicinally in
antibacterials and antifungals in much the same way as larger silver
A tray of South Asian sweets, with some pieces covered with shiny
Pure silver metal is used as a food colouring. It has the E174
designation and is approved in the European Union. Traditional
Pakistani and Indian dishes sometimes include decorative silver foil
known as vark, and in various other cultures, silver dragée are
used to decorate cakes, cookies, and other dessert items.
Photochromic lenses include silver halides, so that ultraviolet light
in natural daylight liberates metallic silver, darkening the lenses.
The silver halides are reformed in lower light intensities. Colourless
silver chloride films are used in radiation detectors.
incorporating Ag+ ions are used to desalinate seawater during rescues,
using silver ions to precipitate chloride as silver chloride. Silver
is also used for its antibacterial properties for water sanitisation,
but the application of this is limited by limits on silver
Colloidal silver is similarly used to disinfect closed
swimming pools; while it has the advantage of not giving off a smell
like hypochlorite treatments do, colloidal silver is not effective
enough for more contaminated open swimming pools. Small silver iodide
crystals are used in cloud seeding to cause rain.
Silver compounds have low toxicity compared to those of most other
heavy metals, as they are poorly absorbed by the human body when
digested, and that which does get absorbed is rapidly converted to
insoluble silver compounds or complexed by metallothionein. However,
silver fluoride and silver nitrate are caustic and can cause tissue
damage, resulting in gastroenteritis, diarrhoea, falling blood
pressure, cramps, paralysis, and respiratory arrest. Animals
repeatedly dosed with silver salts have been observed to experience
anaemia, slowed growth, necrosis of the liver, and fatty degeneration
of the liver and kidneys; rats implanted with silver foil or injected
with colloidal silver have been observed to develop localised tumours.
Parenterally admistered colloidal silver causes acute silver
poisoning. Some waterborne species are particularly sensitive to
silver salts and those of the other precious metals; in most
situations, however, silver does not pose serious environmental
In large doses, silver and compounds containing it can be absorbed
into the circulatory system and become deposited in various body
tissues, leading to argyria, which results in a blue-grayish
pigmentation of the skin, eyes, and mucous membranes.
Argyria is rare,
and so far as is known, does not otherwise harm a person's health,
though it is disfiguring and usually permanent. Mild forms of argyria
are sometimes mistaken for cyanosis.
Metallic silver, like copper, is an antibacterial agent, which was
known to the ancients and first scientifically investigated and named
the oligodynamic effect by Carl Nägeli.
Silver ions damage the
metabolism of bacteria even at such low concentrations as
0.01–0.1 milligrams per litre; metallic silver has a similar
effect due to the formation of silver oxide. This effect is lost in
the presence of sulfur due to the extreme insolubility of silver
Some silver compounds are very explosive, such as the nitrogen
compounds silver azide, silver amide, and silver fulminate, as well as
silver acetylide, silver oxalate, and silver(II) oxide. They can
explode on heating, force, drying, illumination, or sometimes
spontaneously. To avoid the formation of such compounds, ammonia and
acetylene should be kept away from silver equipment. Salts of silver
with strongly oxidising acids such as silver chlorate and silver
nitrate can explode on contact with materials that can be readily
oxidised, such as organic compounds, sulfur and soot.
List of countries by silver production
List of silver compounds
Silver as an investment
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