77 9 Iridium

911
References
78 ! Platinum
Platinum
Appearance
grayish white
General properties
Name, symbol, number platinum, Pt, 78
Pronunciation /:plt.n.Dm/
or /:plt.nDm/
Element category transition metal
Group, period, block 10,6, d
Standard atomic weight
195.084 gmol
>1
Electron configuration
[e] 4f
14
5d
9
6s
1
Electrons per shell 2, 8, 18, 32, 17, 1 (Image)
Physical properties
Phase solid
Density (near r.t.)
21.45 gcm
>3
Liquid density at m.p.
19.77 gcm
>3
Melting point 2041.4K,1768.3C,3214.9F
Boiling point 4098K,3825C,6917F
Heat of fusion
22.17 kJmol
>1
Heat of vaporization
469 kJmol
>1
Specific heat capacity
(25 C) 25.86 Jmol
>1
K
>1
Vapor pressure
P/Pa 1 10 100 1 k 10 k 100 k
at T/K 2330 (2550) 2815 3143 3556 4094
Atomic properties
78 9 Platinum
912
Oxidation states 6, 5, 4, 3 , 2, 1, -1, -2
(mildly basic oxide)
Electronegativity 2.28 (Pauling scale)
Ionization energies
1st: 870 kJmol
>1
2nd: 1791 kJmol
>1
Atomic radius 139 pm
Covalent radius 1365 pm
Van der Waals radius 175 pm
Miscellanea
Crystal structure face-centered cubic
Magnetic ordering paramagnetic
Electrical resistivity (20C) 105 nm
Thermal conductivity
(300 K) 71.6Wm
>1
K
>1
Thermal expansion
(25 C) 8.8 mm
>1
K
>1
Tensile strength 125-240 MPa
Young's modulus 168 GPa
Shear modulus 61 GPa
Bulk modulus 230 GPa
Poisson ratio 0.38
Mohs hardness 494.5
Vickers hardness 549 MPa
Brinell hardness 392 MPa
CAS registry number 7440-06-4
Most stable isotopes
iso NA half-life DM DE (MeV) DP
190
Pt
0.014%
6.510
11
y
3.18 186
Os
192
Pt
0.782% 192
Pt is stable with 114 neutron
193
Pt
syn 50 y ? 193
Ir
194
Pt
32.967% 194
Pt is stable with 116 neutron
195
Pt
33.832% 195
Pt is stable with 117 neutron
196
Pt
25.242% 196
Pt is stable with 118 neutron
198
Pt
7.163% 198
Pt is stable with 120 neutron
Platinum ( /:plt.n.Dm/ or /:plt.nDm/) is a chemical element with the chemical symbol Pt and an atomic
number of 78. Its name is derived from the Spanish term platina del Pinto, which is literally translated into "little
silver of the Pinto River."
[1]
It is a dense, malleable, ductile, precious, gray-white transition metal. Even though it has
six naturally occurring isotopes, platinum is one of the rarest elements in the Earth's crust and has an average
78 9 Platinum
913
abundance of approximately 0.005mg/kg. It occurs in some nickel and copper ores along with some native deposits,
mostly in South Africa, which accounts for 80% of the world production.
As a member of the platinum group of elements, as well as of the group 10 of the periodic table of elements,
platinum is generally unreactive. It exhibits a remarkable resistance to corrosion, even at high temperatures, and as
such is considered a noble metal. As a result, platinum is often found chemically uncombined as native platinum.
Because it occurs naturally in the alluvial sands of various rivers, it was first used by pre-Columbian South American
natives to produce artifacts. It was referenced in European writings as early as 16th century, but it was not until
Antonio de Ulloa published a report on a new metal of Colombian origin in 1748 that it became investigated by
scientists.
Platinum is used in catalytic converters, laboratory equipment, electrical contacts and electrodes, platinum resistance
thermometers, dentistry equipment, and jewelry. Because only a few hundred tonnes are produced annually, it is a
scarce material, and is highly valuable and is a major precious metal commodity. Being a heavy metal, it leads to
health issues upon exposure to its salts, but due to its corrosion resistance it is not toxic as a metal. Some of its
compounds, most notably cisplatin, are applied in chemotherapy against certain types of cancer.
Characteristics
Physical
As a pure metal, platinum is silvery-white, lustrous, ductile, and malleable.
[2]
It does not oxidize at any temperature,
although it is corroded by halogens, cyanides, sulfur, and caustic alkalis. Platinum is insoluble in hydrochloric and
nitric acid, but dissolves in aqua regia to form chloroplatinic acid, H
2
PtCl
6
.
[3]
Platinum's resistance to wear and
tarnish is well suited for making fine jewelry. The metal has an excellent resistance to corrosion and high
temperature and has stable electrical properties. All of these characteristics have been exploited for industrial
applications.
[4]
Chemical
Platinum dissolves in hot aqua regia
The most common oxidation states of platinum are +2 and +4. The +1
and +3 oxidation states are less common, and are often stabilized by
metal bonding in bimetallic (or polymetallic) species. As is expected,
tetracoordinate platinum(II) compounds tend to adopt 16-electron
square planar geometries. While elemental platinum is generally
unreactive, it dissolves in aqua regia to give soluble hexachloroplatinic
acid ("H
2
PtCl
6
", formally (H
3
O)
2
PtCl
6
nH
2
O ):
[5]
Pt + 4 HNO
3
+ 6 HCl ? H
2
PtCl
6
+ 4 NO
2
+ 4 H
2
O
As a soft acid, platinum has a great affinity for sulfur, such as on
dimethyl sulfoxide (DMSO); numerous DMSO complexes have been
reported and care should be taken in the choice of reaction solvent.
[6]
Isotopes
Platinum has six naturally occurring isotopes:
190
Pt,
192
Pt,
194
Pt,
195
Pt,
196
Pt, and
198
Pt. The most abundant of these
is
195
Pt, comprising 33.83% of all platinum. It is the only stable isotope with a non-zero spin; with a spin of
1
/
2
,
195
Pt
satellite peaks are often observed in
1
H and
31
P NMR spectroscopy (i.e. Pt-phosphine and Pt-alkyl complexes).
190
Pt
is the least abundant at only 0.01%. Of the naturally occurring isotopes, only
190
Pt is unstable, though it decays with
a half-life of 6.510
11
years.
198
Pt undergoes alpha decay, but because its half-life is estimated at longer than
3.210
14
years, it is considered stable. Platinum also has 31 synthetic isotopes ranging in atomic mass from 166 to
78 9 Platinum
914
202, making the total number of known isotopes 37. The least stable of these is
166
Pt with a half-life of 300s, while
the most stable is
193
Pt with a half-life of 50years. Most platinum isotopes decay by some combination of beta
decay and alpha decay.
188
Pt,
191
Pt, and
193
Pt decay primarily by electron capture.
190
Pt and
198
Pt have double beta
decay paths.
[7]
Occurrence
A native platinum nugget, Kondyor mine,
Khabarovsk Krai
Platinum output in 2005
Platinum is an extremely rare metal,
[8]
occurring at a concentration of
only 0.005 ppm in the Earth's crust.
[9]

[10]
It is sometimes mistaken for
silver (Ag). Platinum is often found chemically uncombined as native
platinum and alloyed with iridium as platiniridium. Most often the
native platinum is found in secondary deposits; platinum is combined
with the other platinum group metals in alluvial deposits. The alluvial
deposits used by pre-Columbian people in the Choc Department,
Colombia are still a source for platinum group metals. Another large
alluvial deposit is in the Ural Mountains, Russia, and it is still mined.
[3]
In nickel and copper deposits, platinum group metals occur as sulfides
(e.g., (Pt,Pd)S), tellurides (e.g., PtBiTe), antimonides (PdSb), and
arsenides (e.g., PtAs
2
), and as end alloys with nickel or copper.
Platinum arsenide, sperrylite (PtAs
2
), is a major source of platinum
associated with nickel ores in the Sudbury Basin deposit in Ontario,
Canada. At Platinum, Alaska, about 545,000 troy ounces had been
mined between 1927 and 1975. The mine ceased operations in
1990.
[11]
The rare sulfide mineral cooperite, (Pt,Pd,Ni)S, contains
platinum along with palladium and nickel. Cooperite occurs in the
Merensky Reef within the Bushveld complex, Gauteng, South Africa.
[12]
In 1865, chromites were identified in the Bushveld region of South Africa, followed by the discovery of platinum in
1906.
[13]
The largest known primary reserves are in the Bushveld complex in South Africa.
[14]
The large
copper9nickel deposits near Norilsk in Russia, and the Sudbury Basin, Canada, are the two other large deposits. In
the Sudbury Basin, the huge quantities of nickel ore processed make up for the fact platinum is present as only 0.5
ppm in the ore. Smaller reserves can be found in the United States,
[14]
for example in the Absaroka Range in
Montana.
[15]
In 2009, South Africa was the top producer of platinum, with an almost 80% share, followed by Russia
at 11%.
[16]
Platinum exists in higher abundances on the Moon and in meteorites. Correspondingly, platinum is found in slightly
higher abundances at sites of bolide impact on the Earth that are associated with resulting post-impact volcanism,
and can be mined economically; the Sudbury Basin is one such example.
[17]
78 9 Platinum
915
Compounds
Halides
Hexachloroplatinic acid mentioned above is probably the most important platinum compound, as it serves as the
precursor for many other platinum compounds. By itself, it has various applications in photography, zinc etchings,
indelible ink, plating, mirrors, porcelain coloring, and as a catalyst.
[18]
Treatment of hexachloroplatinic acid with an ammonium salt, such as ammonium chloride, gives ammonium
hexachloroplatinate,
[5]
which is relatively insoluble in ammonium solutions. Heating this ammonium salt in the
presence of hydrogen reduces it to elemental platinum. Potassium hexachloroplatinate is similarly insoluble, and
hexachloroplatinic acid has been used in the determination of potassium ions by gravimetry.
[19]
When hexachloroplatinic acid is heated, it decomposes through platinum(IV) chloride and platinum(II) chloride to
elemental platinum, although the reactions do not occur stepwise:
[20]
(H
3
O)
2
PtCl
6
nH
2
O PtCl
4
+ 2 HCl + (n + 2) H
2
O
PtCl
4
PtCl
2
+ Cl
2
PtCl
2
Pt + Cl
2
All three reactions are reversible. Platinum(II) and platinum(IV) bromides are known as well. Platinum hexafluoride
is a strong oxidizer capable of oxidizing oxygen.
Oxides
Platinum(IV) oxide, PtO
2
, also known as Adams' catalyst, is a black powder which is soluble in KOH solutions and
concentrated acids.
[21]
PtO
2
and the less common PtO both decompose upon heating.
[2]
Platinum(II,IV) oxide,
Pt
3
O
4
, is formed in the following reaction:
2 Pt
2+
+ Pt
4+
+ 4 O
2>
? Pt
3
O
4
Platinum also forms a trioxide, where it is present in the +4 oxidation state.
Other compounds
Unlike palladium acetate, platinum(II) acetate is not commercially available. Where a base is desired, the halides
have been used in conjunction with sodium acetate.
[6]
The use of platinum(II) acetylacetonate has also been
reported.
[22]
Several barium platinides have been synthesized in which platinum exhibits negative oxidation states ranging from
>1 to >2. These include BaPt, Ba
3
Pt
2
, and Ba
2
Pt.
[23]
Caesium platinide, Cs
2
Pt, has been shown to contain Pt
2>
anions.
[24]
Platinum also exhibits negative oxidation states at surfaces reduced electrochemically.
[25]
The negative
oxidation states exhibited by platinum are unusual for metallic elements, and they are attributed to the relativistic
stabilization of the 6s orbitals.
[24]
Zeise's salt, containing an ethylene ligand, was one of the first organometallic compounds discovered.
Dichloro(cycloocta-1,5-diene)platinum(II) is a commercially available olefin complex, which contains easily
displaceable cod ligands ("cod" being an abbreviation of 1,5-cyclooctadiene). The cod complex and the halides are
convenient starting points to platinum chemistry.
[6]
Cisplatin, or cis-diamminedichloroplatinum(II) is the first of a series of square planar platinum(II)-containing
chemotherapy drugs, including carboplatin and oxaliplatin. These compounds are capable of crosslinking DNA, and
kill cells by similar pathways to alkylating chemotherapeutic agents.
[26]
78 9 Platinum
916
The hexachloroplatinate ion Dichloro(cycloocta-1,5-diene)platinum(II) Cisplatin
History
Platinum occurs naturally in the alluvial sands of various rivers, though there is little evidence of its use by ancient
people. However, the metal was used by pre-Columbian Americans near modern-day Esmeraldas, Ecuador to
produce artifacts of a white gold-platinum alloy. The first European reference to platinum appears in 1557 in the
writings of the Italian humanist Julius Caesar Scaliger as a description of an unknown noble metal found between
Darin and Mexico, "which no fire nor any Spanish artifice has yet been able to liquefy."
[27]
This alchemical
symbol for platinum
was made by joining
the symbols of silver
and gold.
Antonio de Ulloa is credited with the discovery of
platinum.
In 1741, Charles Wood, a British metallurgist, found various samples
of Colombian platinum in Jamaica, which he sent to William
Brownrigg for further investigation. Antonio de Ulloa, also credited
with the discovery of platinum, returned to Spain from the French
Geodesic Mission in 1746 after having been there for eight years. His
historical account of the expedition included a description of platinum
as being neither separable nor calcinable. Ulloa also anticipated the
discovery of platinum mines. After publishing the report in 1748, Ulloa
did not continue to investigate the new metal. In 1758, he was sent to
superintend mercury mining operations in Huancavelica.
[27]
In 1750, after studying the platinum sent to him by Wood, Brownrigg
presented a detailed account of the metal to the Royal Society,
mentioning that he had seen no mention of it in any previous accounts
of known minerals. Brownrigg also made note of platinum's extremely
high melting point and refractoriness toward borax. Other chemists
across Europe soon began studying platinum, including Torbern
Bergman, Jns Jakob Berzelius, William Lewis, and Pierre Macquer.
In 1752, Henrik Scheffer published a detailed scientific description of
the metal, which he referred to as "white gold", including an account of
how he succeeded in fusing platinum ore with the aid of arsenic.
Scheffer described platinum as being less pliable than gold, but with
similar resistance to corrosion.
[27]
Carl von Sickingen researched platinum extensively in 1772. He
succeeded in making malleable platinum by alloying it with gold,
dissolving the alloy in aqua regia, precipitating the platinum with
ammonium chloride, igniting the ammonium chloroplatinate, and hammering the resulting finely divided platinum to
make it cohere. Franz Karl Achard made the first platinum crucible in 1784. He worked with the platinum by fusing
it with arsenic, then later volatilizing the arsenic.
[27]
In 1786, Charles III of Spain provided a library and laboratory to Pierre-Franois Chabaneau to aid in his research of
platinum. Chabaneau succeeded in removing various impurities from the ore, including gold, mercury, lead, copper,
78 9 Platinum
917
and iron. This led him to believe he was working with a single metal, but in truth the ore still contained the
yet-undiscovered platinum group metals. This led to inconsistent results in his experiments. At times, the platinum
seemed malleable, but when it was alloyed with iridium, it would be much more brittle. Sometimes the metal was
entirely incombustible, but when alloyed with osmium, it would volatilize. After several months, Chabaneau
succeeded in producing 23kilograms of pure, malleable platinum by hammering and compressing the sponge form
while white-hot. Chabeneau realized the infusibility of platinum would lend value to objects made of it, and so
started a business with Joaqun Cabezas producing platinum ingots and utensils. This started what is known as the
"platinum age" in Spain.
[27]
In 2007, Gerhard Ertl won the Nobel Prize in Chemistry for determining the detailed molecular mechanisms of the
catalytic oxidation of carbon monoxide over platinum (catalytic converter).
[28]
Production
1,000 cubic centimeters of 99.9% pure platinum,
worth about US910,000 at 30 October 2009
prices
Platinum, along with the rest of the platinum metals is, obtained
commercially as a by-product from nickel and copper mining and
processing. During electrorefining of copper, noble metals, such as
silver, gold and the platinum group metals, as well as selenium and
tellurium, settle to the bottom of the cell as "anode mud", which forms
the starting point for the extraction of the platinum group metals.
[29]
[30]
If pure platinum is found in placer deposits or other ores, it is isolated
from them by various methods of subtracting impurities. Because
platinum is significantly denser than many of its impurities, the lighter
impurities can be removed by simply floating them away in a liquid.
Platinum is also nonmagnetic, while nickel and iron are both magnetic.
These two impurities are thus removed by running an electromagnet over the mixture. Because platinum has a higher
melting point than most other substances, many impurities can be burned or melted away without melting the
platinum. Finally, platinum is resistant to hydrochloric and sulfuric acids, while other substances are readily attacked
by them. Metal impurities can be removed by stirring the mixture in either of the two acids and recovering the
remaining platinum.
[31]
One suitable method for purification for the raw platinum, which contains platinum, gold, and the other platinum
group metals, is to process it with aqua regia, in which palladium, gold and platinum are dissolved, while osmium,
iridium, ruthenium and rhodium stay unreacted. The gold is precipitated by the addition of iron(III) chloride and
after filtering off the gold, the platinum is precipitated as ammonium chloroplatinate by the addition of ammonium
chloride. Ammonium chloroplatinate can be converted to the metal by heating.
[32]
Applications
Cross section of a metal-core catalytic converter
Of the 239tonnes of platinum sold in 2006, 130tonnes were used for
vehicle emissions control devices, 49tonnes for jewelry, 13.3tonnes in
electronics, and 11.2tonnes in the chemical industry as a catalyst. The
remaining 35.5tonnes went to various other minor applications, such
as electrodes, anticancer drugs, oxygen sensors, spark plugs and
turbine engines.
[33]
78 9 Platinum
918
Catalysis
The most common use of platinum is as a catalyst in chemical reactions, many times as platinum black. It has been
employed in this application since the early 19th century, when platinum powder was used to catalyze the ignition of
hydrogen. Its most important application is in automobiles as a catalytic converter, which allows the complete
combustion of low concentrations of unburned hydrocarbons from the exhaust into carbon dioxide and water vapor.
Platinum is also used in the petroleum industry as a catalyst in a number of separate processes, but especially in
catalytic reforming of straight run naphthas into higher-octane gasoline which becomes rich in aromatic compounds.
PtO
2
, also known as Adams' catalyst, is used as a hydrogenation catalyst, specifically for vegetable oils.
[18]
Platinum
metal also strongly catalyzes the decomposition of hydrogen peroxide into water and oxygen gas.
[34]
Standard
International Prototype Meter bar
From 1889 to 1960, the meter was defined as the length of a
platinum-iridium (90:10) alloy bar, known as the International
Prototype Meter bar. The previous bar was made of platinum in 1799.
The International Prototype Kilogram remains defined by a cylinder of
the same platinum-iridium alloy made in 1879.
[35]
The standard hydrogen electrode also uses a platinized platinum
electrode due to its corrosion resistance, and other attributes.
[36]
Precious metal
Platinum Eagle
Platinum is a precious metal commodity; its bullion has the ISO currency code of PT.
Coins, bars, and ingots are traded or collected. Platinum finds use in jewelry, usually as a
90995% alloy, due to its inertness and shine. Jewelry trade publications advise jewelers
to present minute surface scratches (which they term patina) as a desirable feature.
[37]
[38]
In watchmaking, Vacheron Constantin, Patek Philippe, Rolex, Breitling, and other
companies use platinum for producing their limited edition watch series. Watchmakers
appreciate the unique properties of platinum, as it neither tarnishes nor wears out
(relative to gold).
[39]
Average price of platinum from 1991 to 2007 in
US per troy ounce (~20/g)
[40]
The price of platinum, like other industrial commodities, is more
volatile than that of gold. In 2008, the price of platinum ranged from
774 to 2,252 per oz.
[41]
During periods of sustained economic stability and growth, the price of
platinum tends to be as much as twice the price of gold, whereas
during periods of economic uncertainty,
[42]
the price of platinum tends
to decrease due to reduced industrial demand, falling below the price
of gold. Gold prices are more stable in slow economic times, as gold is
considered a safe haven and gold demand is not driven by industrial
uses. In the 18th century, platinum's rarity made King Louis V of France declare it the only metal fit for a king.
[43]
78 9 Platinum
919
Other uses
In the laboratory, platinum wire is used for electrodes; platinum pans and supports are used in thermogravimetric
analysis because of the stringent requirements of chemical inertness upon heating to high temperatures (~1000C).
Platinum is used as an alloying agent for various metal products, including fine wires, noncorrosive laboratory
containers, medical instruments, dental prostheses, electrical contacts, and thermocouples. Platinum-cobalt, an alloy
of roughly three parts platinum and one part cobalt, is used to make relatively strong permanent magnets.
[18]
Platinum-based anodes are used in ships, pipelines, and steel piers.
[3]
Symbol of prestige
An assortment of native platinum nuggets
Platinum's rarity as a metal has caused advertisers to associate it with
exclusivity and wealth. "Platinum" debit cards have greater privileges
than do "gold" ones.
[44]
"Platinum awards" are the second highest
possible, ranking above "gold", "silver" and "bronze", but below
diamond. For example, in the United States, a musical album that has
sold more than 1million copies, will be credited as "platinum",
whereas an album that sold more than 10million copies will be
certified as "diamond".
[45]
Some products, such as blenders and
vehicles, with a silvery-white color are identified as "platinum".
Platinum is considered a precious metal, although its use is not as common as the use of gold or silver. The frame of
the Crown of Queen Elizabeth the Queen Mother, manufactured for her coronation as Consort of King George VI, is
made of platinum. It was the first British crown to be made of this particular metal.
[46]
Health issues
According to the Centers for Disease Control and Prevention, short-term exposure to platinum salts may cause
irritation of the eyes, nose, and throat, and long-term exposure may cause both respiratory and skin allergies. The
current OSHA standard is 2micrograms per cubic meter of air averaged over an 8-hour work shift.
[47]
Certain platinum complexes are used in chemotherapy, and show good activity against some tumors. Cisplatin is
particularly effective against testicular cancer; the cure rate was improved from 10% to 85%.
[48]
However, the side
effects are severe. Cisplatin causes cumulative, irreversible kidney damage and deafness.
[49]
As with other ototoxic
agents, deafness may be secondary to interactions with melanin in the stria vascularis.
As platinum is a catalyst in the manufacture of the silicone rubber and gel components of several types of medical
implants (breast implants, joint replacement prosthetics, artificial lumbar discs, vascular access ports, etc.), the
possibility platinum could enter the body and cause adverse effects has merited study. The Food and Drug
Administration and other institutions have reviewed the issue and found no evidence to suggest toxicity in vivo.
[50]
[51]
78 9 Platinum
920
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[3] CRC contributors (200792008). "Platinum". In Lide, David R.. CRC Handbook of Chemistry and Physics. 4. New York: CRC Press. p.26.
ISBN978-0-8493-0488-0.
[4] Craig, Bruce D; Anderson, David S; International, A.S.M. (1995-01). "Platinum" (http:/ / books. google. com/ books?id=KwgAZJBWb0C&
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ExploreNorth. . Retrieved April 12, 2011. "Platinum is located on the Bering Sea coast, below Red Mountain on the south spit of Goodnews
Bay."
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[18] Krebs, Robert E. (1998). "Platinum". The History and Use of our Earths Chemical Elements. Greenwood Press. pp.1249127.
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[19] Smith, G. F.; Gring, J. L. (1933). "The Separation and Determination of the Alkali Metals Using Perchloric Acid. V. Perchloric Acid and
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External links
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General Electric Company, 1989.
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"Platinum-Group Metals Statistics and Information" (http:/ / minerals. usgs. gov/ minerals/ pubs/ commodity/
platinum/ ). United States Geological Survey.