Cadmium

Cadmium, ₄₈Cd

Cadmium
Pronunciation	/ˈkædmiəm/ ​(KAD-mee-əm)
Appearance	silvery bluish-gray metallic
Standard atomic weight Ar°(Cd)
	112.414±0.004 112.41±0.01 (abridged)
Cadmium in the periodic table
Hydrogen Helium Lithium Beryllium Boron Carbon Nitrogen Oxygen Fluorine Neon Sodium Magnesium Aluminium Silicon Phosphorus Sulfur Chlorine Argon Potassium Calcium Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper Zinc Gallium Germanium Arsenic Selenium Bromine Krypton Rubidium Strontium Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium Palladium Silver Cadmium Indium Tin Antimony Tellurium Iodine Xenon Caesium Barium Lanthanum Cerium Praseodymium Neodymium Promethium Samarium Europium Gadolinium Terbium Dysprosium Holmium Erbium Thulium Ytterbium Lutetium Hafnium Tantalum Tungsten Rhenium Osmium Iridium Platinum Gold Mercury (element) Thallium Lead Bismuth Polonium Astatine Radon Francium Radium Actinium Thorium Protactinium Uranium Neptunium Plutonium Americium Curium Berkelium Californium Einsteinium Fermium Mendelevium Nobelium Lawrencium Rutherfordium Dubnium Seaborgium Bohrium Hassium Meitnerium Darmstadtium Roentgenium Copernicium Nihonium Flerovium Moscovium Livermorium Tennessine Oganesson Zn ↑ Cd ↓ Hg silver ← cadmium → indium
Atomic number (Z)	48
Group	group 12
Period	period 5
Block	d-block
Electron configuration	[Kr] 4d10 5s2
Electrons per shell	2, 8, 18, 18, 2
Physical properties
Phase at STP	solid
Melting point	594.22 K ​(321.07 °C, ​609.93 °F)
Boiling point	1040 K ​(767 °C, ​1413 °F)
Density (at 20° C)	8.649 g/cm3
when liquid (at m.p.)	7.996 g/cm3
Heat of fusion	6.21 kJ/mol
Heat of vaporization	99.87 kJ/mol
Molar heat capacity	26.020 J/(mol·K)
Vapor pressure P (Pa) 1 10 100 1 k 10 k 100 k at T (K) 530 583 654 745 867 1040
Atomic properties
Oxidation states	−2, +1, +2 (a mildly basic oxide)
Electronegativity	Pauling scale: 1.69
Ionization energies	1st: 867.8 kJ/mol 2nd: 1631.4 kJ/mol 3rd: 3616 kJ/mol
Atomic radius	empirical: 151 pm
Covalent radius	144±9 pm
Van der Waals radius	158 pm
Spectral lines of cadmium
Other properties
Natural occurrence	primordial
Crystal structure	​hexagonal close-packed (hcp) (hP2)
Lattice constants	a = 297.89 pm c = 561.66 pm (at 20 °C)
Thermal expansion	30.95×10−6/K (at 20 °C)
Thermal conductivity	96.6 W/(m⋅K)
Electrical resistivity	72.7 nΩ⋅m (at 22 °C)
Magnetic ordering	diamagnetic
Molar magnetic susceptibility	−19.8×10−6 cm3/mol
Young's modulus	50 GPa
Shear modulus	19 GPa
Bulk modulus	42 GPa
Speed of sound thin rod	2310 m/s (at 20 °C)
Poisson ratio	0.30
Mohs hardness	2.0
Brinell hardness	203–220 MPa
CAS Number	7440-43-9
History
Discovery and first isolation	Karl Samuel Leberecht Hermann and Friedrich Stromeyer (1817)
Named by	Friedrich Stromeyer (1817)
Isotopes of cadmium
Main isotopes Decay abun­dance half-life (t1/2) mode pro­duct 106Cd 1.25% stable 107Cd synth 6.5 h ε 107Ag 108Cd 0.89% stable 109Cd synth 462.6 d ε 109Ag 110Cd 12.5% stable 111Cd 12.8% stable 112Cd 24.1% stable 113Cd 12.2% 8.04×1015 y β− 113In 113mCd synth 14.1 y β− 113In IT 113Cd 114Cd 28.8% stable 115Cd synth 53.46 h β− 115In 116Cd 7.51% 2.8×1019 y β−β− 116Sn

Cadmium (Template:PronEng) is a chemical element with the symbol Cd and atomic number 48. A relatively abundant (price 3.55 USD/lb as of 2008-02-15), soft, bluish-white, transition metal, cadmium is known to cause cancer and occurs with zinc ores. Cadmium is used largely in batteries and pigments, for example in plastic products.

Characteristics

Cadmium is a soft, malleable, ductile, toxic, bluish-white bivalent metal. It is similar in many respects to zinc but reacts to form more complex compounds.

Chemical

The most common oxidation state of cadmium is +2, though rare examples of +1 can be found. Cadmium burns in air and forms a brown amorph cadmium oxide (CdO), the crystalline modification is dark red and changes color when heated, similar to zinc oxide. Hydrochloric acid, sulfuric acid and nitric acid dissolve cadmium by forming cadmium chloride (CdCl₂) cadmium sulfate (CdSO₄) or cadmium nitrate (Cd(NO₃)₂). The oxidation state +1 can be reached by dissolving cadmium in a mixture of cadmium chloride and aluminium chloride, forming the Cd₂²⁺ which is similar to the Hg₂²⁺ in mercury(I) chloride.

Cd + CdCl₂ + 2AlCl₃ → 2Cd[AlCl₄]

Isotopes

Main article: isotopes of cadmium

Naturally occurring cadmium is composed of 8 isotopes. For two of them, natural radioactivity was observed, and three others are predicted to be radioactive but their decays were never observed, due to extremely long half-life times. The two natural radioactive isotopes are ¹¹³Cd (beta decay, half-life is 7.7 × 10¹⁵ years) and ¹¹⁶Cd (two-neutrino double beta decay, half-life is 2.9 × 10¹⁹ years). The other three are ¹⁰⁶Cd, ¹⁰⁸Cd (double electron capture), and ¹¹⁴Cd (double beta decay); only lower limits on their half-life times have been set. At least three isotopes - ¹¹⁰Cd, ¹¹¹Cd, and ¹¹²Cd - are absolutely stable. Among the isotopes absent in the natural cadmium, the most long-lived are ¹⁰⁹Cd with a half-life of 462.6 days, and ¹¹⁵Cd with a half-life of 53.46 hours. All of the remaining radioactive isotopes have half-lives that are less than 2.5 hours, and the majority of these have half-lives that are less than 5 minutes. This element also has 8 known meta states, with the most stable being ^113mCd (t_½ 14.1 years), ^115mCd (t_½ 44.6 days), and ^117mCd (t_½ 3.36 hours).

The cadmium-113 total cross section clearly showing the cadmium cutoff.

The known isotopes of cadmium range in atomic mass from 94.950 u (⁹⁵Cd) to 131.946 u (¹³²Cd). The primary decay mode before the second-most-abundant stable isotope, ¹¹²Cd, is electron capture, and the primary modes after are beta emission and electron capture. The primary decay product before ¹¹²Cd is element 47 (silver), and the primary product after is element 49 (indium).

One particular isotope of cadmium, ¹¹³Cd, absorbs neutrons with very high probability if they have an energy below the cadmium cutoff and transmits them readily otherwise. The cadmium cutoff is about 0.5 eV. Neutrons with energy below the cutoff are deemed slow neutrons, distinguishing them from intermediate and fast neutrons.

Applications

Batteries

Ni-Cd batteries

About three-quarters of cadmium is used in batteries, predominantly in rechargeable nickel-cadmium batteries. Nickel-cadmium cells have a nominal cell potential of 1.2 V. The cell consists of a positive nickel hydroxide electrode plate and a negative cadmium electrode plate separated by an alkaline electrolyte (potassium hydroxide). The next generation of Nickel-metal hydride batteries reduced the use of Ni-Cd batteries. The European Union banned the use of Cadmium in electronics in 2004 with several exceptions but reduced the allowed content of cadmium in electronics to 0.002 %.

Other uses

Most of the remaining quarter is used mainly for pigments, coatings and plating, and as stabilizers for plastics. Other uses include:

Train painted with Cadmium yellow

• In some of the lowest-melting alloys
• In bearing alloys, due to a low coefficient of friction and very good fatigue resistance
• In electroplating (6% cadmium)
• In many kinds of solder
• As a barrier to control nuclear fission
• In black and white television phosphors and in the blue and green phosphors for color television picture tubes
• As a photoconductive surface coating for photocopier drums. (Cadmium Sulphide)
• In paint pigments: Cadmium forms various Salts, with cadmium sulfide being the most common. This sulfide is used as a yellow pigment. Cadmium selenide can be used as red pigment, commonly called cadmium red. To painters that work with the pigment, cadmium yellows, oranges, and reds are the most potent colours to use. In fact, during production, these colours are significantly toned down before they are ground with oils and binders, or blended into watercolours, gouaches, acrylics, and other paint and pigment formulations. These pigments are toxic, and it is recommended to use a barrier cream on the hands to prevent absorption through the skin when working with them. Cadmium blue, green, and violet do not exist.
• In some semiconductors such as cadmium sulfide, cadmium selenide, and cadmium telluride, which can be used for light detection or solar cells. HgCdTe is sensitive to infrared.
• In PVC as stabilizers.
• In molecular biology, used to block voltage-dependent calcium channels from fluxing calcium ions.

See also Category:Cadmium compounds.

History

Cadmium (Latin cadmia, Greek καδμεία meaning "calamine", a cadmium-bearing mixture of minerals, which was named after the Greek mythological character, Κάδμος Cadmus) was discovered in Germany in 1817 by Friedrich Strohmeyer. Strohmeyer found the new element within an impurity in zinc carbonate (calamine), and, for 100 years, Germany remained the only important producer of the metal. The metal was named after the Latin word for calamine, since the metal was found in this zinc compound. Strohmeyer noted that some impure samples of calamine changed color when heated but pure calamine did not.

Even though cadmium and its compounds are highly toxic, the British Pharmaceutical Codex from 1907 states that cadmium iodide was used as a medicine to treat "enlarged joints, scrofulous glands, and chilblains".

In 1927, the International Conference on Weights and Measures redefined the meter in terms of a red cadmium spectral line (1m = 1,553,164.13 wavelengths). This definition has since been changed (see krypton).

Occurrence

Cadmium metal

Cadmium output in 2005

World production trend

In 2001, China was the top producer of cadmium with almost one-sixth world share closely followed by South Korea and Japan, reports the British Geological Survey.

Cadmium-containing ores are rare and are found to occur in small quantities. However, traces do naturally occur in phosphate, and have been shown to transmit in food through fertilizer application. Greenockite (CdS), the only cadmium mineral of importance, is nearly always associated with sphalerite (ZnS). As a consequence, cadmium is produced mainly as a byproduct from mining, smelting, and refining sulfide ores of zinc, and, to a lesser degree, lead and copper. Small amounts of cadmium, about 10% of consumption, are produced from secondary sources, mainly from dust generated by recycling iron and steel scrap. Production in the United States began in 1907, but it was not until after World War I that cadmium came into wide use.

See also Category:Cadmium minerals.

Extraction

Cadmium is a common impurity in zinc, and it is most often isolated during the production of zinc. Zinc sulfide ores are roasted in the presence of oxygen, converting the zinc sulfide to the oxide. Zinc metal is produced either by smelting the oxide with carbon or by electrolysis in sulfuric acid. Cadmium is isolated from the zinc metal by vacuum distillation if the zinc is smelted, or cadmium sulfate is precipitated out of the electrolysis solution.

Biological role

A role of cadmium in biology has been recently discovered. A cadmium-dependent carbonic anhydrase has been found in marine diatoms. Cadmium does the same job as zinc in other anhydrases, but the diatoms live in environments with very low zinc concentrations, thus biology has taken cadmium rather than zinc, and made it work. The discovery was made using X-ray absorption fluorescence spectroscopy (XAFS), and cadmium was characterised by noting the energy of the X-rays that were absorbed.

Image of the violet light from a helium cadmium metal vapor laser. The highly monochromatic color arises from the 441.563 nm transition line of cadmium.

Toxicity

Main article: Cadmium poisoning

Cadmium poisoning is an occupational hazard associated with industrial processes such as metal plating and the production of nickel-cadmium batteries, pigments, plastics, and other synthetics. The primary route of exposure in industrial settings is inhalation. Inhalation of cadmium-containing fumes can result initially in metal fume fever but may progress to chemical pneumonitis, pulmonary edema, and death.

Cadmium is also a potential environmental hazard. Human exposures to environmental cadmium are primarily the result of the burning of fossil fuels and municipal wastes. However, there have been notable instances of toxicity as the result of long-term exposure to cadmium in contaminated food and water. In the decades following World War II, Japanese mining operations contaminated the Jinzu River with cadmium and traces of other toxic metals. As a consequence, cadmium accumulated in the rice crops growing along the riverbanks downstream of the mines. The local agricultural communities consuming the contaminated rice developed Itai-itai disease and renal abnormalities, including proteinuria and glucosuria. Cadmium is one of six substances banned by the European Union's Restriction on Hazardous Substances (RoHS) directive, which bans certain hazardous substances in electronics.

Cadmium and several cadmium-containing compounds are known carcinogens and can induce many types of cancer.

Current research has found that cadmium toxicity may be carried into the body by zinc binding proteins; in particular, proteins that contain zinc finger protein structures. Zinc and cadmium are in the same group on the periodic table, contain the same common oxidation state (+2), and when ionized are almost the same size. Due to these similarities, cadmium can replace zinc in many biological systems, in particular, systems that contain softer ligands such as sulfur. Cadmium can bind up to ten times more strongly than zinc in certain biological systems, and is notoriously difficult to remove. In addition, cadmium can replace magnesium and calcium in certain biological systems, although these replacements are rare.

Tobacco smoking is the most important single source of cadmium exposure in the general population. It has been estimated that about 10% of the cadmium content of a cigarette is inhaled through smoking. The absorption of cadmium from the lungs is much more effective than that from the gut, and as much as 50% of the cadmium inhaled via cigarette smoke may be absorbed.

On average, smokers have 4-5 times higher blood cadmium concentrations and 2-3 times higher kidney cadmium concentrations than non-smokers. Despite the high cadmium content in cigarette smoke, there seems to be little exposure to cadmium from passive smoking. No significant effect on blood cadmium concentrations could be detected in children exposed to environmental tobacco smoke.

See also

• List of breast carcinogenic substances

External links

• ATSDR Case Studies in Environmental Medicine: Cadmium Toxicity U.S. Department of Health and Human Services
• IARC Monograph "Cadmium and Cadmium Compounds"
• National Pollutant Inventory - Cadmium and compounds
• WebElements.com – Cadmium
• Los Alamos National Laboratory – Cadmium
• [3] Warning Moose and Deer Liver
• National Institute for Occupational Safety and Health - Cadmium Page
• USGS Comodity Report cadmium