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https://en.wikipedia.org/wiki/Zinc
Zinc
Zinc,
30Zn
General properties
Name, symbol
zinc, Zn
Appearance
silver-gray
Pronunciation
/zk/
ZINGK
[3]
Zn
copper zinc gallium
Cd
30
Group, block
Period
period 4
Element category
transition metal,
alternatively considered a
post-transition metal
Standard atomic
weight () (Ar)
65.38(2)[1]
Electron
configuration
[Ar] 3d10 4s 2
2, 8, 18, 2
per shell
Physical properties
Phase
solid
Melting point
692.68 K (419.53 C,
787.15 F)
Boiling point
7.14 g/cm3
6.57 g/cm3
Heat of fusion
7.32 kJ/mol
Heat of vaporization
115 kJ/mol
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P (Pa)
10
100
1k
10 k
100 k
at T (K)
610
670
750
852
990
1179
25.470 J/(molK)
vapor pressure
Atomic properties
Oxidation states
Electronegativity
Ionization energies
Atomic radius
empirical: 134 pm
Covalent radius
1224 pm
139 pm
[6]
Contents
1 Characteristics
1.1 Physical properties
1.2 Occurrence
1.3 Isotopes
2 Compounds and chemistry
2.1 Reactivity
2.2 Zinc(I) compounds
2.3 Zinc (II) compounds
3 History
3.1 Ancient use
3.2 Early studies and naming
3.3 Isolation
3.4 Later work
4 Production
4.1 Mining and processing
4.2 Environmental impact
5 Applications
5.1 Anti-corrosion and batteries
5.2 Alloys
5.3 Other industrial uses
5.4 Dietary supplement
5.5 Zinc lozenges and the common
cold
5.6 Topical use
5.7 Organic chemistry
6 Biological role
6.1 Enzymes
6.2 Other proteins
6.3 Dietary intake
6.4 Deficiency
7 Soil remediation
Miscellanea
Crystal structure
hexagonal close-packed
(hcp)
Speed of sound
thin rod
Thermal expansion
Thermal
conductivity
116 W/(mK)
Electrical resistivity
59.0 nm (at 20 C)
Magnetic ordering
diamagnetic
Young's modulus
108 GPa
Shear modulus
43 GPa
Bulk modulus
70 GPa
Poisson ratio
0.25
Mohs hardness
2.5
Brinell hardness
327412 MPa
CAS Number
7440-66-6
History
Discovery
Indian metallurgists
(before 1000 BCE)
First isolation
Andreas Sigismund
Marggraf (1746)
Recognized as a
unique metal by
Rasaratna Samuccaya
(800)
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7.1 Agriculture
8 Precautions
8.1 Toxicity
8.2 Poisoning
9 See also
10 Notes
11 References
12 Bibliography
13 External links
https://en.wikipedia.org/wiki/Zinc
iso
64
Zn
65
Zn
Physical properties
Zinc, also referred to in nonscientific contexts as
spelter,[9] is a bluish-white, lustrous,
diamagnetic metal,[10] though most common
commercial grades of the metal have a dull
[11]
half-life
DM
DE (MeV) DP
64
Ni
1.3519
65
1.1155
Cu
243.8 d
66
67
68
Zn
Zn
Zn
Characteristics
NA
69
syn
56 min
0.906
69
69m
syn
13.76 h
0.906
69
70
70
71
syn
2.4 min
2.82
71
71m
syn
3.97 d
2.82
71
72
syn
46.5 h
0.458
72
Zn
Zn
Zn
Zn
Zn
Zn
Ga
Ga
Ge
Ga
Ga
Ga
finish.
It is somewhat less dense than iron
and has a hexagonal crystal structure, with a
distorted form of hexagonal close packing, in which each atom has six nearest neighbors (at
265.9 pm) in its own plane and six others at a greater distance of 290.6 pm. [12] The metal is hard
and brittle at most temperatures but becomes malleable between 100 and 150 C. [10][11] Above
210 C, the metal becomes brittle again and can be pulverized by beating. [13] Zinc is a fair
conductor of electricity.[10] For a metal, zinc has relatively low melting (419.5 C) and boiling
points (907 C).[14] Its melting point is the lowest of all the transition metals aside from mercury
and cadmium.[14]
Many alloys contain zinc, including brass, an alloy of copper and zinc. Other metals long known
to form binary alloys with zinc are aluminium, antimony, bismuth, gold, iron, lead, mercury, silver,
tin, magnesium, cobalt, nickel, tellurium and sodium.[15] Although neither zinc nor zirconium are
ferromagnetic, their alloy ZrZn2 exhibits ferromagnetism below 35 K.[10]
A bar of zinc generates a characteristic sound when bent, similar to tin cry.
Occurrence
Zinc makes up about 75 ppm (0.0075%) of Earth's crust, making it the 24th most abundant
element. Soil contains 5770 ppm of zinc with an average of 64 ppm. Seawater has only 30 ppb
zinc and the atmosphere contains 0.14 g/m3.[16]
The element is normally found in association with other base metals such as copper and lead in
ores.[17] Zinc is a chalcophile, meaning the element has a low affinity for oxides and prefers to
bond with sulfides. Chalcophiles formed as the crust solidified under the reducing conditions of
the early Earth's atmosphere. [18] Sphalerite, which is a form of zinc sulfide, is the most heavily
mined zinc-containing ore because its concentrate contains 6062% zinc. [17]
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Sphalerite (ZnS)
Isotopes
64
abundance).[26] This isotope has such a long half-life, at 4.3 1018 a,[27] that its radioactivity can
70
be ignored.[28] Similarly, Zn (0.6%), with a half-life of 1.3 1016 a is not usually considered to be
66
67
68
radioactive. The other isotopes found in nature are Zn (28%), Zn (4%) and Zn (19%).
Several dozen radioisotopes have been characterized.
is the most long-lived radioisotope, followed by
65
72
nuclear isomers. 69mZn has the longest half-life, 13.76 h. [26] The superscript m indicates a
metastable isotope. The nucleus of a metastable isotope is in an excited state and will return to
61
the ground state by emitting a photon in the form of a gamma ray. Zn has three excited states
and
73
65
Zn,
71
Zn,
77
Zn and
78
The most common decay mode of a radioisotope of zinc with a mass number lower than 66 is
electron capture. The decay product resulting from electron capture is an isotope of copper. [26]
n
30Zn
+ e 29Cu
The most common decay mode of a radioisotope of zinc with mass number higher than 66 is beta
decay (), which produces an isotope of gallium.[26]
n
30Zn
31Ga + e + e
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Zinc burns in air with a bright bluish-green flame, giving off fumes of zinc oxide.[32] Zinc reacts
readily with acids, alkalis and other non-metals.[33] Extremely pure zinc reacts only slowly at room
temperature with acids. [32] Strong acids, such as hydrochloric or sulfuric acid, can remove the
passivating layer and subsequent reaction with water releases hydrogen gas. [32]
The chemistry of zinc is dominated by the +2 oxidation state. When compounds in this oxidation
state are formed the outer shell s electrons are lost, which yields a bare zinc ion with the
electronic configuration [Ar]3d 10.[34] In aqueous solution an octahedral complex, [Zn(H2O)6]
2+
is
the predominant species.[35] The volatilization of zinc in combination with zinc chloride at
temperatures above 285 C indicates the formation of Zn2Cl2, a zinc compound with a +1
oxidation state.[32] No compounds of zinc in oxidation states other than +1 or +2 are known. [36]
Calculations indicate that a zinc compound with the oxidation state of +4 is unlikely to exist.[37]
Zinc chemistry is similar to the chemistry of the late first-row transition metals nickel and copper,
though it has a filled d-shell, so its compounds are diamagnetic and mostly colorless.[38] The
ionic radii of zinc and magnesium happen to be nearly identical. Because of this some of their
salts have the same crystal structure[39] and in circumstances where ionic radius is a determining
factor zinc and magnesium chemistries have much in common. [32] Otherwise there is little
similarity. Zinc tends to form bonds with a greater degree of covalency and it forms much more
stable complexes with N- and S- donors.[38] Complexes of zinc are mostly 4- or 6- coordinate
although 5-coordinate complexes are known. [32]
Zinc(I) compounds
Zinc(I) compounds are rare, and requires bulky ligands to stabilize the low oxidation state. Most
zinc(I) compounds contains formally the [Zn 2]2+ core, which is analogous to the [Hg 2]2+ dimeric
cation present in mercury(I) compounds. The diamagnetic nature of the ion confirms its dimeric
structure. The first zinc(I) compound containing the ZnZn bond, (5-C5Me5)2Zn2, is also the
first dimetallocene. The [Zn 2]2+ ion rapidly disproportionates into zinc metal and zinc(II), and has
only been obtained as a yellow glass formed by cooling a solution of metallic zinc in molten
ZnCl2.[40]
Zinc acetate
[41]
Zinc chloride
[42][43]
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relatively low melting points and are considered to have more covalent character. [45]
In weak basic solutions containing Zn
2+
In stronger alkaline solutions, this hydroxide is dissolved to form zincates ([Zn(OH)4] ).[32] The
nitrate Zn(NO3)2, chlorate Zn(ClO3)2, sulfate ZnSO4, phosphate Zn 3(PO4)2, molybdate ZnMoO4,
cyanide Zn(CN)2, arsenite Zn(AsO2)2, arsenate Zn(AsO4)28H2O and the chromate ZnCrO4 (one
of the few colored zinc compounds) are a few examples of other common inorganic compounds
of zinc.[46][47] One of the simplest examples of an organic compound of zinc is the acetate
(Zn(O2CCH3)2).
Organozinc compounds are those that contain zinccarbon covalent bonds. Diethylzinc
((C2H5)2Zn) is a reagent in synthetic chemistry. It was first reported in 1848 from the reaction of
zinc and ethyl iodide, and was the first compound known to contain a metalcarbon sigma
bond.[48]
History
Ancient use
Various isolated examples of the use of impure zinc in ancient times
have been discovered. Zinc ores were used to make the zinccopper
alloy brass many centuries prior to the discovery of zinc as a
separate element. Judean brass from the 14th to 10th centuries BC
contains 23% zinc.[2]
Knowledge of how to produce brass spread to Ancient Greece by the
7th century BC, but few varieties were made. [3] Ornaments made of
alloys containing 8090% zinc, with lead, iron, antimony, and other
metals making up the remainder, have been found that are 2,500
years old.[17] A possibly prehistoric statuette containing 87.5% zinc
was found in a Dacian archaeological site.[49]
The oldest known pills were made of the zinc carbonates
hydrozincite and smithsonite. The pills were used for sore eyes and
were found aboard the Roman ship Relitto del Pozzino, which
wrecked in 140 BC.[50][51]
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remnants in smelting ovens was usually discarded as it was thought to be worthless. [56]
The Berne zinc tablet is a votive plaque dating to Roman Gaul made of an alloy that is mostly
zinc.[57]
The Charaka Samhita, thought to have been written between 300 and 500 AD, [58] mentions a
metal which, when oxidized, produces pushpanjan, thought to be zinc oxide. [59] Zinc mines at
Zawar, near Udaipur in India, have been active since the Mauryan period. The smelting of metallic
zinc here, however, appears to have begun around the 12th century AD. [60][61] One estimate is
that this location produced an estimated million tonnes of metallic zinc and zinc oxide from the
12th to 16th centuries.[19] Another estimate gives a total production of 60,000 tonnes of metallic
zinc over this period.[60] The Rasaratna Samuccaya, written in approximately the 13th century AD,
mentions two types of zinc-containing ores: one used for metal extraction and another used for
medicinal purposes.[61]
the metal as "zincum" or "zinken" in his book Liber Mineralium II, in the 16th century. [63][65] The
word is probably derived from the German zinke, and supposedly meant "tooth-like, pointed or
jagged" (metallic zinc crystals have a needle-like appearance). [66] Zink could also imply "tin-like"
because of its relation to German zinn meaning tin.[67] Yet another possibility is that the word is
derived from the Persian word seng meaning stone.[68] The metal was also called Indian tin,
tutanego, calamine, and spinter. [17]
German metallurgist Andreas Libavius received a quantity of what he called "calay" of Malabar
from a cargo ship captured from the Portuguese in 1596. [69] Libavius described the properties of
the sample, which may have been zinc. Zinc was regularly imported to Europe from the Orient in
the 17th and early 18th centuries,[63] but was at times very expensive.[note 1]
Isolation
The isolation of metallic zinc was achieved in India by 1300 AD, [70][71][72] much earlier than in the
West. Before it was made in Europe, it was imported from India around 1600 CE. [73] Postlewayt's
Universal Dictionary, a contemporary source giving technological information in Europe, did not
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mention zinc before 1751 but the element was studied before
then.[61][74]
Flemish metallurgist and alchemist P. M. de Respour reported that
he had extracted metallic zinc from zinc oxide in 1668. [19] By the start
of the 18th century, tienne Franois Geoffroy described how zinc
oxide condenses as yellow crystals on bars of iron placed above zinc
ore being smelted.[19] In Britain, John Lane is said to have carried out
experiments to smelt zinc, probably at Landore, prior to his
bankruptcy in 1726.[75]
In 1738 in Great Britain, William Champion patented a process to
extract zinc from calamine in a vertical retort style smelter.[76] His
technology was somewhat similar to that used at Zawar zinc mines in
Rajasthan, but there is no evidence that he visited the Orient. [73]
Andreas Sigismund
Marggraf is given credit
for first isolating pure zinc
Later work
William Champion's brother, John, patented a process in 1758 for
calcining zinc sulfide into an oxide usable in the retort process. [17]
Prior to this, only calamine could be used to produce zinc. In 1798,
Johann Christian Ruberg improved on the smelting process by
building the first horizontal retort smelter. [78] Jean-Jacques Daniel
Dony built a different kind of horizontal zinc smelter in Belgium,
which processed even more zinc.[63] Italian doctor Luigi Galvani
discovered in 1780 that connecting the spinal cord of a freshly
dissected frog to an iron rail attached by a brass hook caused the
frog's leg to twitch.[79] He incorrectly thought he had discovered an
ability of nerves and muscles to create electricity and called the effect
Galvanization was named
after Luigi Galvani.
Galvani's friend, Alessandro Volta, continued researching this effect and invented the Voltaic pile
in 1800.[79] The basic unit of Volta's pile was a simplified galvanic cell, which is made of a plate of
copper and a plate of zinc connected to each other externally and separated by an electrolyte.
These were stacked in series to make the Voltaic cell, which in turn produced electricity by
directing electrons from the zinc to the copper and allowing the zinc to corrode. [79]
The non-magnetic character of zinc and its lack of color in solution delayed discovery of its
importance to biochemistry and nutrition. [81] This changed in 1940 when carbonic anhydrase, an
enzyme that scrubs carbon dioxide from blood, was shown to have zinc in its active site.[81] The
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Production
Mining and processing
Zinc is the fourth most common metal in use, trailing only
iron, aluminium, and copper with an annual production of
about 13 million tonnes.[20] The world's largest zinc
producer is Nyrstar, a merger of the Australian OZ Minerals
and the Belgian Umicore.[83] About 70% of the world's zinc
originates from mining, whereas the remaining 30% comes
Tonnes
China
5,000,000
Australia
1,500,000
Peru
1,300,000
India
820,000
United States
700,000
Mexico
700,000
Country
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condenser.[86] The below set of equations demonstrate this process: [86] This allows it to be
separated from the other metallic impurities which are involatile.
2 ZnO + C 2 Zn + CO2
ZnO + CO Zn + CO2
In electrowinning, zinc is leached from the ore concentrate by sulfuric acid:[90]
ZnO + H2SO4 ZnSO4 + H2O
Finally, the zinc is reduced by electrolysis.[86]
2 ZnSO4 + 2 H2O 2 Zn + 2 H2SO4 + O2
The sulfuric acid regenerated is recycled to the leaching step.
Zinc present in electric arc furnace dusts due to use of galvanised feedstock is recovered by a
number of processes, predominately the Waelz process (90% as of 2014).[91]
Environmental impact
The production for sulfidic zinc ores produces large amounts of sulfur dioxide and cadmium
vapor. Smelter slag and other residues of process also contain significant amounts of heavy
metals. About 1.1 million tonnes of metallic zinc and 130 thousand tonnes of lead were mined
and smelted in the Belgian towns of La Calamine and Plombires between 1806 and 1882.[92]
The dumps of the past mining operations leach significant amounts of zinc and cadmium, and, as
a result, the sediments of the Geul River contain significant amounts of heavy metals. [92] About
two thousand years ago emissions of zinc from mining and smelting totaled 10 thousand tonnes
a year. After increasing 10-fold from 1850, zinc emissions peaked at 3.4 million tonnes per year in
the 1980s and declined to 2.7 million tonnes in the 1990s, although a 2005 study of the Arctic
troposphere found that the concentrations there did not reflect the decline. Anthropogenic and
natural emissions occur at a ratio of 20 to 1. [93]
Levels of zinc in rivers flowing through industrial or mining areas can be as high as 20 ppm.[94]
Effective sewage treatment greatly reduces this; treatment along the Rhine, for example, has
decreased zinc levels to 50 ppb. [94] Concentrations of zinc as low as 2 ppm adversely affects the
amount of oxygen that fish can carry in their blood. [95]
Historically responsible for high heavy metal levels in the Derwent River,[96] the zinc works at Lutana is the
largest exporter in Tasmania, generating 2.5% of the state's GDP, and producing over 250 thousand tonnes
of zinc per year.[97]
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Soils contaminated with zinc through the mining of zinc-containing ores, refining, or where
zinc-containing sludge is used as fertilizer, can contain several grams of zinc per kilogram of dry
soil. Levels of zinc in excess of 500 ppm in soil interfere with the ability of plants to absorb other
essential metals, such as iron and manganese. Zinc levels of 2000 ppm to 180,000 ppm (18%)
have been recorded in some soil samples. [94]
Applications
Major applications of zinc include (numbers are given for the US) [98]
1.
2.
3.
4.
Galvanizing (55%)
Alloys (21%)
Brass and bronze (16%)
Miscellaneous (8%)
degrades through time as the zinc corrodes away. [101] The zinc is applied electrochemically or as
molten zinc by hot-dip galvanizing or spraying. Galvanization is used on chain-link fencing, guard
rails, suspension bridges, lightposts, metal roofs, heat exchangers, and car bodies. [16]
The relative reactivity of zinc and its ability to attract oxidation to itself makes it an efficient
sacrificial anode in cathodic protection (CP). For example, cathodic protection of a buried pipeline
can be achieved by connecting anodes made from zinc to the pipe. [101] Zinc acts as the anode
(negative terminus) by slowly corroding away as it passes electric current to the steel pipeline.
[101][note 2]
corrosion.
Zinc is also used to cathodically protect metals that are exposed to sea water from
[102]
A zinc disc attached to a ship's iron rudder will slowly corrode, whereas the rudder
stays unattacked.[100] Other similar uses include a plug of zinc attached to a propeller or the
metal protective guard for the keel of the ship.
With a standard electrode potential (SEP) of 0.76 volts, zinc is used as an anode material for
batteries. (More reactive lithium (SEP 3.04 V) is used for anodes in lithium batteries ). Powdered
zinc is used in this way in alkaline batteries and sheets of zinc metal form the cases for and act
as anodes in zinccarbon batteries.[103][104] Zinc is used as the anode or fuel of the zinc-air
battery/fuel cell.[105][106][107] The zinc-cerium redox flow battery also relies on a zinc-based
negative half-cell.[108]
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Alloys
A widely used alloy that contains zinc is brass, in which copper is alloyed with anywhere from 3%
to 45% zinc, depending upon the type of brass. [101] Brass is generally more ductile and stronger
than copper and has superior corrosion resistance.[101] These properties make it useful in
communication equipment, hardware, musical instruments, and water valves. [101]
Other widely used alloys that contain zinc include nickel silver,
typewriter metal, soft and aluminium solder, and commercial
bronze.[10] Zinc is also used in contemporary pipe organs as a
substitute for the traditional lead/tin alloy in pipes. [109] Alloys
of 8588% zinc, 410% copper, and 28% aluminium find
limited use in certain types of machine bearings. Zinc is the
primary metal used in making American one cent coins since
Alloys of primarily zinc with small amounts of copper, aluminium, and magnesium are useful in
die casting as well as spin casting, especially in the automotive, electrical, and hardware
industries.[10] These alloys are marketed under the name Zamak.[112] An example of this is zinc
aluminium. The low melting point together with the low viscosity of the alloy makes the production
of small and intricate shapes possible. The low working temperature leads to rapid cooling of the
cast products and therefore fast assembly is possible. [10][113] Another alloy, marketed under the
brand name Prestal, contains 78% zinc and 22% aluminium and is reported to be nearly as
strong as steel but as malleable as plastic. [10][114] This superplasticity of the alloy allows it to be
molded using die casts made of ceramics and cement. [10]
Similar alloys with the addition of a small amount of lead can be cold-rolled into sheets. An alloy
of 96% zinc and 4% aluminium is used to make stamping dies for low production run applications
for which ferrous metal dies would be too expensive. [115] In building facades, roofs or other
applications in which zinc is used as sheet metal and for methods such as deep drawing, roll
forming or bending, zinc alloys with titanium and copper are used.[116] Unalloyed zinc is too brittle
for these kinds of manufacturing processes. [116]
As a dense, inexpensive, easily worked material, zinc is used as a lead replacement. In the wake
of lead concerns, zinc appears in weights for various applications ranging from fishing [117] to tire
balances and flywheels.[118]
Cadmium zinc telluride (CZT) is a semiconductive alloy that can be divided into an array of small
sensing devices.[119] These devices are similar to an integrated circuit and can detect the energy
of incoming gamma ray photons.[119] When placed behind an absorbing mask, the CZT sensor
array can also be used to determine the direction of the rays. [119]
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Zn, the most abundant isotope of zinc, is very susceptible to neutron activation, being
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transmuted into the highly radioactive Zn, which has a half-life of 244 days and produces
intense gamma radiation. Because of this, Zinc Oxide used in nuclear reactors as an
64
anti-corrosion agent is depleted of Zn before use, this is called depleted zinc oxide. For the
same reason, zinc has been proposed as a salting material for nuclear weapons (cobalt is
64
fallout.[130] Such a weapon is not known to have ever been built, tested, or used. [130] Zn is also
used as a tracer to study how alloys that contain zinc wear out, or the path and the role of zinc in
organisms.[131]
Zinc dithiocarbamate complexes are used as agricultural fungicides; these include Zineb,
Metiram, Propineb and Ziram.[132] Zinc naphthenate is used as wood preservative. [133] Zinc, in
the form of ZDDP, is also used as an anti-wear additive for metal parts in engine oil. [134]
Dietary supplement
Zinc is included in most single tablet over-the-counter daily vitamin and mineral supplements.[135]
Preparations include zinc oxide, zinc acetate, and zinc gluconate.[135] It is believed to possess
antioxidant properties, which may protect against accelerated aging of the skin and muscles of
the body; studies differ as to its effectiveness. [136] Zinc also helps speed up the healing process
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degeneration.[140] Zinc
supplementation is an effective treatment for acrodermatitis
enteropathica, a genetic disorder affecting zinc absorption that
was previously fatal to babies born with it. [52]
Gastroenteritis is strongly attenuated by ingestion of zinc, and this effect could be due to direct
antimicrobial action of the zinc ions in the gastrointestinal tract, or to the absorption of the zinc
and re-release from immune cells (all granulocytes secrete zinc), or both. [141][142] In 2011,
researchers at John Jay College of Criminal Justice reported that dietary zinc supplements can
mask the presence of drugs in urine. Similar claims have been made in web forums on that
topic.[143]
Although not yet tested as a therapy in humans, a growing body of evidence indicates that zinc
may preferentially kill prostate cancer cells. Because zinc naturally homes to the prostate and
because the prostate is accessible with relatively non-invasive procedures, its potential as a
chemotherapeutic agent in this type of cancer has shown promise. [144] However, other studies
have demonstrated that chronic use of zinc supplements in excess of the recommended dosage
may actually increase the chance of developing prostate cancer, also likely due to the natural
buildup of this heavy metal in the prostate. [145]
Topical use
Topical administration of zinc preparations include ones used on the skin, often in the form of zinc
oxide. Zinc preparations can protect against sunburn in the summer and windburn in the
winter.[52] Applied thinly to a baby's diaper area (perineum) with each diaper change, it can
protect against diaper rash.[52]
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Chelated zinc is used in toothpastes and mouthwashes to prevent bad breath.[148] Zinc pyrithione
is widely applied in shampoos because of its anti-dandruff function. [149] Zinc ions are effective
antimicrobial agents even at low concentrations. [150]
Organic chemistry
There are many important organozinc
compounds. Organozinc chemistry is the
science of organozinc compounds
describing their physical properties,
synthesis and reactions.[151][152][153][154]
Among important applications is the
Frankland-Duppa Reaction in which an
oxalate ester(ROCOCOOR) reacts with an
alkyl halide R'X, zinc and hydrochloric acid
to the -hydroxycarboxylic esters
RR'COHCOOR,[155] the Reformatskii
reaction which converts -halo-esters and
aldehydes to -hydroxy-esters, the
Addition of diphenylzinc to an aldehyde
SimmonsSmith reaction in which the
carbenoid (iodomethyl)zinc iodide reacts
with alkene(or alkyne) and converts them to cyclopropane, the Addition reaction of organozinc
compounds to carbonyl compounds. The Barbier reaction (1899) is the zinc equivalent of the
magnesium Grignard reaction and is better of the two. In presence of just about any water the
formation of the organomagnesium halide will fail, whereas the Barbier reaction can even take
place in water. On the downside organozincs are much less nucleophilic than Grignards, are
expensive and difficult to handle. Commercially available diorganozinc compounds are
dimethylzinc, diethylzinc and diphenylzinc. In one study[156][157] the active organozinc compound
is obtained from much cheaper organobromine precursors:
The Negishi coupling is also an important reaction for the formation of new carbon carbon bonds
between unsaturated carbon atoms in alkenes, arenes and alkynes. The catalysts are nickel and
palladium. A key step in the catalytic cycle is a transmetalation in which a zinc halide exchanges
its organic substituent for another halogen with the palladium (nickel) metal center. The
Fukuyama coupling is another coupling reaction but this one with a thioester as reactant forming
a ketone.
Zinc has found many applications as catalyst in organic synthesis including asymmetric
synthesis, being cheap and easily available alternative to precious metal complexes. The results
(yield and ee) obtained by using chiral zinc catalysts are comparable to those achieved by
palladium, ruthenium, iridium and others and therefore more and more zinc becomes metal of
choice for this purpose.[158]
Biological role
Zinc is an essential trace element for humans[159] and other animals,[160] for plants[93] and for
microorganisms.[161] Zinc is found in nearly 100 specific enzymes[162] (other sources[163] say
300), serves as structural ions in transcription factors and is stored and transferred in
metallothioneins.[164] It is "typically the second most abundant transition metal in organisms" after
iron and it is the only metal which appears in all enzyme classes.[93]
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In proteins, Zn ions are often coordinated to the amino acid side chains of aspartic acid, glutamic
acid, cysteine and histidine. The theoretical and computational description of this zinc binding in
proteins (as well as that of other transition metals) is difficult. [165]
There are 24 grams of zinc[166] distributed throughout the human body. Most zinc is in the brain,
muscle, bones, kidney, and liver, with the highest concentrations in the prostate and parts of the
eye.[167] Semen is particularly rich in zinc, which is a key factor in prostate gland function and
reproductive organ growth.[168]
In humans, zinc plays "ubiquitous biological roles". [6] It interacts with "a wide range of organic
ligands",[6] and has roles in the metabolism of RNA and DNA, signal transduction, and gene
expression. It also regulates apoptosis. A 2006 study estimated that about 10% of human
proteins (2800) potentially bind zinc, in addition to hundreds which transport and traffic zinc; a
similar in silico study in the plant Arabidopsis thaliana found 2367 zinc-related proteins. [93]
In the brain, zinc is stored in specific synaptic vesicles by glutamatergic neurons[169] and can
"modulate brain excitability".[6] It plays a key role in synaptic plasticity and so in learning.[170]
However, it has been called "the brain's dark horse" [169] because it also can be a neurotoxin,
suggesting zinc homeostasis plays a critical role in normal functioning of the brain and central
nervous system.[169]
Enzymes
Zinc is an efficient Lewis
acid, making it a useful
catalytic agent in
hydroxylation and other
enzymatic reactions.[162]
The metal also has a
flexible coordination
geometry, which allows
proteins using it to rapidly
shift conformations to
perform biological
reactions.[171] Two
examples of zinc-containing enzymes are carbonic anhydrase
and carboxypeptidase, which are vital to the processes of
In vertebrate blood, carbonic anhydrase converts CO2 into bicarbonate and the same enzyme
transforms the bicarbonate back into CO2 for exhalation through the lungs. [173] Without this
enzyme, this conversion would occur about one million times slower[174] at the normal blood pH
of 7 or would require a pH of 10 or more. [175] The non-related -carbonic anhydrase is required in
plants for leaf formation, the synthesis of indole acetic acid (auxin) and alcoholic
fermentation.[176]
Carboxypeptidase cleaves peptide linkages during digestion of proteins. A coordinate covalent
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bond is formed between the terminal peptide and a C=O group attached to zinc, which gives the
carbon a positive charge. This helps to create a hydrophobic pocket on the enzyme near the zinc,
which attracts the non-polar part of the protein being digested. [172]
Other proteins
Zinc serves a purely structural role in zinc fingers, twists and clusters.[177] Zinc fingers form parts
of some transcription factors, which are proteins that recognize DNA base sequences during the
2+
replication and transcription of DNA. Each of the nine or ten Zn ions in a zinc finger helps
maintain the finger's structure by coordinately binding to four amino acids in the transcription
factor.[174] The transcription factor wraps around the DNA helix and uses its fingers to accurately
bind to the DNA sequence.
In blood plasma, zinc is bound to and transported by albumin (60%, low-affinity) and transferrin
(10%).[166] Because transferrin also transports iron, excessive iron reduces zinc absorption, and
vice versa. A similar antagonism exists with copper. [178] The concentration of zinc in blood plasma
stays relatively constant regardless of zinc intake. [179] Cells in the salivary gland, prostate,
immune system and intestine use zinc signaling as one way to communicate with other cells. [180]
Zinc may be held in metallothionein reserves within microorganisms or in the intestines or liver of
animals.[181] Metallothionein in intestinal cells is capable of adjusting absorption of zinc by
1540%.[182] However, inadequate or excessive zinc intake can be harmful; excess zinc
particularly impairs copper absorption because metallothionein absorbs both metals. [183]
Dietary intake
In the U.S., the Recommended Dietary Allowance (RDA) is 8 mg/day
for women and 11 mg/day for men.[184] Median intake in the U.S.
around 2000 was 9 mg/day for women and 14 mg/day in men. [185]
Oysters, lobster[186] and red meats, especially beef, lamb and liver
have some of the highest concentrations of zinc in food. [168]
Zinc supplements should only be ingested when there is zinc
deficiency or increased zinc necessity (e.g. after surgeries, traumata
or burns).[187][188] Persistent intake of high doses of zinc can cause
copper deficiency.[187]
The concentration of zinc in plants varies based on levels of the
element in soil. When there is adequate zinc in the soil, the food
plants that contain the most zinc are wheat (germ and bran) and
[189]
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were consumed compared with those seen after consumption of zinc acetate and sulfate
salts.[191] However, harmful excessive supplementation is a problem among the relatively affluent,
and should probably not exceed 20 mg/day in healthy people, [192] although the U.S. National
Research Council set a Tolerable Upper Intake of 40 mg/day. [193]
For fortification, however, a 2003 review recommended zinc oxide in cereals as cheap, stable, and
as easily absorbed as more expensive forms.[194] A 2005 study found that various compounds of
zinc, including oxide and sulfate, did not show statistically significant differences in absorption
when added as fortificants to maize tortillas. [195] A 1987 study found that zinc picolinate was
better absorbed than zinc gluconate or zinc citrate. [196] However, a study published in 2008
determined that zinc glycinate is the best absorbed of the four dietary supplement types
available.[197]
Deficiency
Zinc deficiency is usually due to insufficient dietary intake, but can be associated with
malabsorption, acrodermatitis enteropathica, chronic liver disease, chronic renal disease, sickle
cell disease, diabetes, malignancy, and other chronic illnesses. [7] Groups at risk for zinc
deficiency include the elderly, children in developing countries, and those with renal insufficiency.
Symptoms of mild zinc deficiency are diverse.[185] Clinical outcomes include depressed growth,
diarrhea, impotence and delayed sexual maturation, alopecia, eye and skin lesions, impaired
appetite, altered cognition, impaired host defense properties, defects in carbohydrate utilization,
and reproductive teratogenesis.[179] Mild zinc deficiency depresses immunity, [198] although
excessive zinc does also.[166] Animals with a diet deficient in zinc require twice as much food in
order to attain the same weight gain as animals given sufficient zinc. [125]
Despite some concerns,[199] western vegetarians and vegans have not been found to suffer from
overt zinc deficiencies any more than meat-eaters. [200] Major plant sources of zinc include cooked
dried beans, sea vegetables, fortified cereals, soyfoods, nuts, peas, and seeds. [199] However,
phytates in many whole-grains and fiber in many foods may interfere with zinc absorption and
marginal zinc intake has poorly understood effects. The zinc chelator phytate, found in seeds and
cereal bran, can contribute to zinc malabsorption. [7] There is some evidence to suggest that more
than the US RDA (15 mg) of zinc daily may be needed in those whose diet is high in phytates,
such as some vegetarians. [199] These considerations must be balanced against the fact that there
is a paucity of adequate zinc biomarkers, and the most widely used indicator, plasma zinc, has
poor sensitivity and specificity.[201] Diagnosing zinc deficiency is a persistent challenge. [6]
Nearly two billion people in the developing world are deficient in zinc. [7] In children it causes an
increase in infection and diarrhea, contributing to the death of about 800,000 children worldwide
per year.[6] The World Health Organization advocates zinc supplementation for severe
malnutrition and diarrhea.[202] Zinc supplements help prevent disease and reduce mortality,
especially among children with low birth weight or stunted growth. [202] However, zinc
supplements should not be administered alone, because many in the developing world have
several deficiencies, and zinc interacts with other micronutrients. [203]
Soil remediation
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The Ericoid Mycorrhizal Fungi Calluna, Erica and Vaccinium can grow in zinc metalliferous
soils.[204]
Agriculture
Zinc deficiency is crop plants' most common micronutrient deficiency; it is particularly common in
high-pH soils.[205] Zinc-deficient soil is cultivated in the cropland of about half of Turkey and
India, a third of China, and most of Western Australia, and substantial responses to zinc
fertilization have been reported in these areas. [93] Plants that grow in soils that are zinc-deficient
are more susceptible to disease. Zinc is primarily added to the soil through the weathering of
rocks, but humans have added zinc through fossil fuel combustion, mine waste, phosphate
fertilizers, pesticide (zinc phosphide), limestone, manure, sewage sludge, and particles from
galvanized surfaces. Excess zinc is toxic to plants, although zinc toxicity is far less
widespread.[93]
Precautions
Toxicity
Although zinc is an essential requirement for good health, excess zinc can be harmful. Excessive
absorption of zinc suppresses copper and iron absorption. [183] The free zinc ion in solution is
highly toxic to plants, invertebrates, and even vertebrate fish. [206] The Free Ion Activity Model is
well-established in the literature, and shows that just micromolar amounts of the free ion kills
some organisms. A recent example showed 6 micromolar killing 93% of all Daphnia in water.[207]
The free zinc ion is a powerful Lewis acid up to the point of being corrosive. Stomach acid
contains hydrochloric acid, in which metallic zinc dissolves readily to give corrosive zinc chloride.
Swallowing a post-1982 American one cent piece (97.5% zinc) can cause damage to the stomach
lining due to the high solubility of the zinc ion in the acidic stomach. [208]
There is evidence of induced copper deficiency in those taking 100300 mg of zinc daily. A 2007
trial observed that elderly men taking 80 mg daily were hospitalized for urinary complications
more often than those taking a placebo. [209] The USDA RDA is 11 and 8 mg Zn/day for men and
women, respectively.[184] Levels of 100300 mg may interfere with the utilization of copper and
iron or adversely affect cholesterol. [183] Levels of zinc in excess of 500 ppm in soil interfere with
the ability of plants to absorb other essential metals, such as iron and manganese. [94] There is
also a condition called the zinc shakes or "zinc chills" that can be induced by the inhalation of
freshly formed zinc oxide formed during the welding of galvanized materials.[125] Zinc is a
common ingredient of denture cream which may contain between 17 and 38 mg of zinc per gram.
There have been claims of disability, and even death, due to excessive use of these products.[210]
The U.S. Food and Drug Administration (FDA) has stated that zinc damages nerve receptors in
the nose, which can cause anosmia. Reports of anosmia were also observed in the 1930s when
zinc preparations were used in a failed attempt to prevent polio infections.[211] On June 16, 2009,
the FDA said that consumers should stop using zinc-based intranasal cold products and ordered
their removal from store shelves. The FDA said the loss of smell can be life-threatening because
people with impaired smell cannot detect leaking gas or smoke and cannot tell if food has spoiled
before they eat it.[212] Recent research suggests that the topical antimicrobial zinc pyrithione is a
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potent heat shock response inducer that may impair genomic integrity with induction of
PARP-dependent energy crisis in cultured human keratinocytes and melanocytes.[213]
Poisoning
In 1982, the US Mint began minting pennies coated in copper but made primarily of zinc. With the
new zinc pennies, there is the potential for zinc toxicosis, which can be fatal. One reported case
of chronic ingestion of 425 pennies (over 1 kg of zinc) resulted in death due to gastrointestinal
bacterial and fungal sepsis, whereas another patient, who ingested 12 grams of zinc, only
showed lethargy and ataxia (gross lack of coordination of muscle movements). [214] Several other
cases have been reported of humans suffering zinc intoxication by the ingestion of zinc coins.
[215][216]
Pennies and other small coins are sometimes ingested by dogs, resulting in the need for medical
treatment to remove the foreign body. The zinc content of some coins can cause zinc toxicity,
which is commonly fatal in dogs, where it causes a severe hemolytic anemia, and also liver or
kidney damage; vomiting and diarrhea are possible symptoms. [217] Zinc is highly toxic in parrots
and poisoning can often be fatal. [218] The consumption of fruit juices stored in galvanized cans
has resulted in mass parrot poisonings with zinc. [52]
See also
Zinc alloy electroplating
Wet storage stain
List of countries by zinc production
Notes
1. An East India Company ship carrying a cargo of nearly pure zinc metal from the Orient sank off the
coast Sweden in 1745.(Emsley 2001, p. 502)
2. Electric current will naturally flow between zinc and steel but in some circumstances inert anodes are
used with an external DC source.
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n-butyllithium, then transmetalation with zinc chloride forms diphenylzinc that continues to react in an
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reaction formation of diphenylzinc is accompanied by that of lithium chloride, which if unchecked,
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External links
Zinc Fact Sheet (http://ods.od.nih.gov/factsheets/zinc/)
Wikimedia Commons has
from the U.S. National Institutes of Health
media related to Zinc.
History & Etymology of Zinc
(http://elements.vanderkrogt.net/element.php?sym=Zn)
Look up zinc in
Statistics and Information from the U.S. Geological
Wiktionary, the free
Survey (http://minerals.usgs.gov/minerals
dictionary.
/pubs/commodity/zinc/index.html)
Reducing Agents > Zinc (http://www.organic-chemistry.org/chemicals/reductions/zinc-
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https://en.wikipedia.org/wiki/Zinc
zn.shtm)
American Zinc Association (http://www.zinc.org) Information about the uses and properties
of zinc.
Outline safety data for zinc (http://ptcl.chem.ox.ac.uk/MSDS/ZI/zinc.html)
ISZB (http://www.iszb.org) International Society for Zinc Biology, founded in 2008. An
international, nonprofit organization bringing together scientists working on the biological
actions of zinc.
Zinc-UK (http://zinc-uk.org) Founded in 2010 to bring together scientists in the United
Kingdom working on zinc.
Zinc (http://www.periodicvideos.com/videos/030.htm) at The Periodic Table of Videos
(University of Nottingham)
Retrieved from "https://en.wikipedia.org/w/index.php?title=Zinc&oldid=691985558"
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