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An amalgam is an
alloy An alloy is a mixture of chemical elements of which in most cases at least one is a metal, metallic element, although it is also sometimes used for mixtures of elements; herein only metallic alloys are described. Metallic alloys often have prop ...
of mercury with another
metal A metal () is a material that, when polished or fractured, shows a lustrous appearance, and conducts electrical resistivity and conductivity, electricity and thermal conductivity, heat relatively well. These properties are all associated wit ...
. It may be a liquid, a soft paste or a solid, depending upon the proportion of mercury. These alloys are formed through
metallic bonding Metallic bonding is a type of chemical bonding that arises from the electrostatic attractive force between conduction electrons (in the form of an electron cloud of delocalized electrons) and positively charged metal ions. It may be desc ...
, with the electrostatic attractive force of the conduction electrons working to bind all the positively charged metal ions together into a crystal lattice structure. Almost all metals can form amalgams with mercury, the notable exceptions being
iron Iron is a chemical element; it has symbol Fe () and atomic number 26. It is a metal that belongs to the first transition series and group 8 of the periodic table. It is, by mass, the most common element on Earth, forming much of Earth's o ...
,
platinum Platinum is a chemical element; it has Symbol (chemistry), symbol Pt and atomic number 78. It is a density, dense, malleable, ductility, ductile, highly unreactive, precious metal, precious, silverish-white transition metal. Its name origina ...
,
tungsten Tungsten (also called wolfram) is a chemical element; it has symbol W and atomic number 74. It is a metal found naturally on Earth almost exclusively in compounds with other elements. It was identified as a distinct element in 1781 and first ...
, and
tantalum Tantalum is a chemical element; it has Symbol (chemistry), symbol Ta and atomic number 73. It is named after Tantalus, a figure in Greek mythology. Tantalum is a very hard, ductility, ductile, lustre (mineralogy), lustrous, blue-gray transition ...
.
Gold Gold is a chemical element; it has chemical symbol Au (from Latin ) and atomic number 79. In its pure form, it is a brightness, bright, slightly orange-yellow, dense, soft, malleable, and ductile metal. Chemically, gold is a transition metal ...
-mercury amalgam is used in the extraction of gold from ore, and dental amalgams are made with metals such as silver, copper, indium, tin and zinc.


Important amalgams


Zinc amalgam

Zinc amalgam finds use in organic synthesis (e.g., for the Clemmensen reduction). It is the reducing agent in the Jones reductor, used in analytical chemistry. Formerly the zinc plates of dry batteries were amalgamated with a small amount of mercury to prevent deterioration in storage. It is a binary solution (liquid-solid) of mercury and zinc.


Potassium amalgam

For the
alkali metals The alkali metals consist of the chemical elements lithium (Li), sodium (Na), potassium (K),The symbols Na and K for sodium and potassium are derived from their Latin names, ''natrium'' and ''kalium''; these are still the origins of the names ...
, amalgamation is exothermic, and distinct chemical forms can be identified, such as KHg and KHg2. KHg is a gold-coloured compound with a melting point of 178 °C, and KHg2 a silver-coloured compound with a melting point of 278 °C. These amalgams are very sensitive to air and water, but can be worked with under dry nitrogen. The Hg-Hg distance is around 300  picometres, Hg-K around 358 pm. Phases K5Hg7 and KHg11 are also known;
rubidium Rubidium is a chemical element; it has Symbol (chemistry), symbol Rb and atomic number 37. It is a very soft, whitish-grey solid in the alkali metal group, similar to potassium and caesium. Rubidium is the first alkali metal in the group to have ...
,
strontium Strontium is a chemical element; it has symbol Sr and atomic number 38. An alkaline earth metal, it is a soft silver-white yellowish metallic element that is highly chemically reactive. The metal forms a dark oxide layer when it is exposed to ...
and
barium Barium is a chemical element; it has symbol Ba and atomic number 56. It is the fifth element in group 2 and is a soft, silvery alkaline earth metal. Because of its high chemical reactivity, barium is never found in nature as a free element. Th ...
undecamercurides are known and isostructural. Sodium amalgam (NaHg2) has a different structure, with the mercury atoms forming hexagonal layers, and the sodium atoms a linear chain which fits into the holes in the hexagonal layers, but the
potassium Potassium is a chemical element; it has Symbol (chemistry), symbol K (from Neo-Latin ) and atomic number19. It is a silvery white metal that is soft enough to easily cut with a knife. Potassium metal reacts rapidly with atmospheric oxygen to ...
atom is too large for this structure to work in KHg2.


Sodium amalgam

Sodium Sodium is a chemical element; it has Symbol (chemistry), symbol Na (from Neo-Latin ) and atomic number 11. It is a soft, silvery-white, highly reactive metal. Sodium is an alkali metal, being in group 1 element, group 1 of the peri ...
amalgam is produced as a byproduct of the
chloralkali process The chloralkali process (also chlor-alkali and chlor alkali) is an industrial process for the electrolysis of sodium chloride (NaCl) solutions. It is the technology used to produce chlorine and sodium hydroxide (caustic soda), which are commodi ...
and used as an important reducing agent in organic and inorganic chemistry. With water, it decomposes into concentrated
sodium hydroxide Sodium hydroxide, also known as lye and caustic soda, is an inorganic compound with the formula . It is a white solid ionic compound consisting of sodium cations and hydroxide anions . Sodium hydroxide is a highly corrosive base (chemistry), ...
solution, hydrogen and mercury, which can then return to the chloralkali process anew. If absolutely water-free alcohol is used instead of water, an
alkoxide In chemistry, an alkoxide is the conjugate base of an alcohol and therefore consists of an organic group bonded to a negatively charged oxygen atom. They are written as , where R is the organyl substituent. Alkoxides are strong bases and, whe ...
of sodium is produced instead of the alkali solution.


Aluminium amalgam

Aluminium Aluminium (or aluminum in North American English) is a chemical element; it has chemical symbol, symbol Al and atomic number 13. It has a density lower than that of other common metals, about one-third that of steel. Aluminium has ...
can form an amalgam through a reaction with mercury. Aluminium amalgam may be prepared by either grinding aluminium pellets or wire in mercury, or by allowing aluminium wire or foil to react with a solution of
mercuric chloride Mercury(II) chloride (mercury bichloride, mercury dichloride, mercuric chloride), historically also sulema or corrosive sublimate, is the inorganic chemical compound of mercury and chlorine with the formula HgCl2, used as a laboratory reagent. ...
. This amalgam is used as a reagent to reduce compounds, such as the reduction of
imine In organic chemistry, an imine ( or ) is a functional group or organic compound containing a carbon–nitrogen double bond (). The nitrogen atom can be attached to a hydrogen or an organic group (R). The carbon atom has two additional single bon ...
s to
amine In chemistry, amines (, ) are organic compounds that contain carbon-nitrogen bonds. Amines are formed when one or more hydrogen atoms in ammonia are replaced by alkyl or aryl groups. The nitrogen atom in an amine possesses a lone pair of elec ...
s. The aluminium is the ultimate electron donor, and the mercury serves to mediate the electron transfer. The reaction itself and the waste from it contain mercury, so special safety precautions and disposal methods are needed. As an environmentally friendlier alternative, hydrides or other reducing agents can often be used to accomplish the same synthetic result. Another environmentally friendly alternative is an alloy of aluminium and gallium which similarly renders the aluminium more reactive by preventing it from forming an oxide layer.


Tin amalgam

Tin amalgam was used in the middle of the 19th century as a reflective mirror coating.


Other amalgams

A variety of amalgams are known that are of interest mainly in the research context. *
Ammonium Ammonium is a modified form of ammonia that has an extra hydrogen atom. It is a positively charged (cationic) polyatomic ion, molecular ion with the chemical formula or . It is formed by the protonation, addition of a proton (a hydrogen nucleu ...
amalgam is a grey, soft, spongy mass discovered in 1808 by
Humphry Davy Sir Humphry Davy, 1st Baronet (17 December 177829 May 1829) was a British chemist and inventor who invented the Davy lamp and a very early form of arc lamp. He is also remembered for isolating, by using electricity, several Chemical element, e ...
and
Jöns Jakob Berzelius Jöns is a Swedish given name and a surname. Notable people with the given name include: * Jöns Jacob Berzelius (1779–1848), Swedish chemist * Jöns Budde (1435–1495), Franciscan friar from the Brigittine monastery in NaantaliVallis Grati ...
. It decomposes readily at room temperature or in contact with water or alcohol: *: \mathrm *
Thallium Thallium is a chemical element; it has Symbol (chemistry), symbol Tl and atomic number 81. It is a silvery-white post-transition metal that is not found free in nature. When isolated, thallium resembles tin, but discolors when exposed to air. Che ...
amalgam has a freezing point of −58 °C, which is lower than that of pure mercury (−38.8 °C) so it has found a use in low temperature thermometers. *
Gold Gold is a chemical element; it has chemical symbol Au (from Latin ) and atomic number 79. In its pure form, it is a brightness, bright, slightly orange-yellow, dense, soft, malleable, and ductile metal. Chemically, gold is a transition metal ...
amalgam: Refined gold, when finely ground and brought into contact with mercury where the surfaces of both metals are clean, amalgamates readily and quickly forms alloys ranging from AuHg2 to Au8Hg. *
Lead Lead () is a chemical element; it has Chemical symbol, symbol Pb (from Latin ) and atomic number 82. It is a Heavy metal (elements), heavy metal that is density, denser than most common materials. Lead is Mohs scale, soft and Ductility, malleabl ...
forms an amalgam when filings are mixed with mercury and is also listed as a naturally occurring alloy called leadamalgam in the Nickel–Strunz classification.


Dental amalgam

Dentistry has used alloys of mercury with metals such as silver,
copper Copper is a chemical element; it has symbol Cu (from Latin ) 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-orang ...
,
indium Indium is a chemical element; it has Symbol (chemistry), symbol In and atomic number 49. It is a silvery-white post-transition metal and one of the softest elements. Chemically, indium is similar to gallium and thallium, and its properties are la ...
, tin and
zinc Zinc is a chemical element; it has symbol Zn and atomic number 30. It is a slightly brittle metal at room temperature and has a shiny-greyish appearance when oxidation is removed. It is the first element in group 12 (IIB) of the periodic tabl ...
. Amalgam is an "excellent and versatile restorative material" and is used in dentistry because it is inexpensive and relatively easy to use and manipulate during placement. It remains soft for a short time so it can be packed to fill any irregular volume, and then forms a hard compound. Amalgam possesses greater
longevity Longevity may refer to especially long-lived members of a population, whereas ''life expectancy'' is defined Statistics, statistically as the average number of years remaining at a given age. For example, a population's life expectancy at birth ...
when compared to other direct restorative materials, such as composite. However, this difference has decreased with continual development of composite resins. Amalgam is typically compared to resin-based composites because many applications are similar and many physical properties and costs are comparable. Dental amalgam has been studied and is generally considered to be safe for humans, though the validity of some studies and their conclusions have been questioned. In July 2018 the EU, in consideration of the persistent pollution and environmental toxicity of amalgam's mercury, prohibited amalgam for dental treatment of children under 15 years and of pregnant or breastfeeding women.


Use in mining

Mercury has been used in gold and silver mining because of the convenience and the ease with which mercury and the precious metals will amalgamate. In gold placer mining, in which minute specks of gold are washed from sand or gravel deposits, mercury was often used to separate the gold from other heavy minerals. After all of the practical metal had been taken out from the ore, the mercury was dispensed down a long copper trough, which formed a thin coating of mercury on the exterior. The waste ore was then transferred down the trough, and gold in the waste amalgamated with the mercury. This coating would then be scraped off and refined by evaporation to get rid of the mercury, leaving behind somewhat high-purity gold. Mercury amalgamation was first used on silver ores with the development of the patio process in Mexico in 1557. There were also additional amalgamation processes that were created for processing silver ores, including
pan amalgamation The pan amalgamation process is a method to extract silver from ore, using salt and copper(II) sulfate in addition to mercury. The process was widely used from 1609 through the 19th century; it is no longer used. The patio process had been used ...
and the Washoe process.


Gold amalgam


Gold extraction (mining)

Gold amalgam has proved effective where gold fines ("flour gold") would not be extractable from ore using hydro-mechanical methods. Large amounts of mercury were used in placer mining, where deposits composed largely of decomposed granite slurry were separated in long runs of "riffle boxes", with mercury dumped in at the head of the run. The amalgam formed is a heavy dull gray solid mass. The use of mercury in 19th century placer mining in California, now prohibited, has caused extensive pollution problems in riverine and estuarine environments, ongoing to this day. Sometimes substantial slugs of amalgam are found in downstream river and creek bottoms by amateur wet-suited miners seeking gold nuggets with the aid of an engine-powered water vacuum/dredge mounted on a float.


Gold extraction (ore processing)

Where
stamp mill A stamp mill (or stamp battery or stamping mill) is a type of Mill (grinding), mill machine that crushes material by pounding rather than Mill (grinding), grinding, either for further processing or for extraction of metallic ores. Breaking materia ...
s were used to crush gold-bearing ore to fines, a part of the extraction process involved the use of mercury-wetted copper plates, over which the crushed fines were washed. A periodic scraping and re-mercurizing of the plate resulted in amalgam for further processing.


Gold extraction (retorting)

Amalgam obtained by either process was then heated in a distillation retort, recovering the mercury for reuse and leaving behind the gold. As this released mercury vapors to the atmosphere, the process could induce adverse health effects and long term pollution. Today, mercury amalgamation has been replaced by other methods to recuperate gold and silver from ore in developed nations. Hazards of mercurial toxic waste have played a major role in the phasing out of the mercury amalgamation processes. Mercury amalgamation is still regularly used by small-scale gold placer miners (often illegally), particularly in developing countries.


Amalgam probe

Mercury salts are, compared to mercury metal and amalgams, highly toxic due to their solubility in water. The presence of these salts in water can be detected with a probe that uses the readiness of mercury ions to form an amalgam with copper. A
nitric acid Nitric acid is an inorganic compound with the formula . It is a highly corrosive mineral acid. The compound is colorless, but samples tend to acquire a yellow cast over time due to decomposition into nitrogen oxide, oxides of nitrogen. Most com ...
solution of salts under investigation is applied to a piece of copper foil, and any mercury ions present will leave spots of silvery-coloured amalgam. Silver ions leave similar spots but are easily washed away, making this a means of distinguishing silver from mercury. The
redox reaction Redox ( , , reduction–oxidation or oxidation–reduction) is a type of chemical reaction in which the oxidation states of the reactants change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is ...
involved where mercury oxidizes the copper is: :Hg2+ + Cu → Hg + Cu2+.


See also

*


References


Further reading

* Prandtl, W.: ''Humphry Davy, Jöns Jacob Berzelius, zwei führende Chemiker aus der ersten Hälfte des 19. Jahrhunderts''. Wissenschaftliche Verlagsgesellschaft, Stuttgart, 1948 * Hofmann, H., Jander, G.: ''Qualitative Analyse'', 1972, Walter de Gruyter,


External links

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