Lanthanide
Overview
 
The lanthanide or lanthanoid (IUPAC nomenclature
IUPAC nomenclature
A chemical nomenclature is a set of rules to generate systematic names for chemical compounds. The nomenclature used most frequently worldwide is the one created and developed by the International Union of Pure and Applied Chemistry ....

) series comprises the fifteen metal
Metal
A metal , is an element, compound, or alloy that is a good conductor of both electricity and heat. Metals are usually malleable and shiny, that is they reflect most of incident light...

lic chemical element
Chemical element
A chemical element is a pure chemical substance consisting of one type of atom distinguished by its atomic number, which is the number of protons in its nucleus. Familiar examples of elements include carbon, oxygen, aluminum, iron, copper, gold, mercury, and lead.As of November 2011, 118 elements...

s with atomic number
Atomic number
In chemistry and physics, the atomic number is the number of protons found in the nucleus of an atom and therefore identical to the charge number of the nucleus. It is conventionally represented by the symbol Z. The atomic number uniquely identifies a chemical element...

s 57 through 71, from lanthanum
Lanthanum
Lanthanum is a chemical element with the symbol La and atomic number 57.Lanthanum is a silvery white metallic element that belongs to group 3 of the periodic table and is the first element of the lanthanide series. It is found in some rare-earth minerals, usually in combination with cerium and...

 through lutetium. These fifteen elements, along with chemically similar scandium
Scandium
Scandium is a chemical element with symbol Sc and atomic number 21. A silvery-white metallic transition metal, it has historically been sometimes classified as a rare earth element, together with yttrium and the lanthanoids...

 and yttrium
Yttrium
Yttrium is a chemical element with symbol Y and atomic number 39. It is a silvery-metallic transition metal chemically similar to the lanthanides and it has often been classified as a "rare earth element". Yttrium is almost always found combined with the lanthanides in rare earth minerals and is...

, are often collectively known as the rare earth elements.

The informal chemical symbol Ln is used in general discussions of lanthanide chemistry.
Encyclopedia
The lanthanide or lanthanoid (IUPAC nomenclature
IUPAC nomenclature
A chemical nomenclature is a set of rules to generate systematic names for chemical compounds. The nomenclature used most frequently worldwide is the one created and developed by the International Union of Pure and Applied Chemistry ....

) series comprises the fifteen metal
Metal
A metal , is an element, compound, or alloy that is a good conductor of both electricity and heat. Metals are usually malleable and shiny, that is they reflect most of incident light...

lic chemical element
Chemical element
A chemical element is a pure chemical substance consisting of one type of atom distinguished by its atomic number, which is the number of protons in its nucleus. Familiar examples of elements include carbon, oxygen, aluminum, iron, copper, gold, mercury, and lead.As of November 2011, 118 elements...

s with atomic number
Atomic number
In chemistry and physics, the atomic number is the number of protons found in the nucleus of an atom and therefore identical to the charge number of the nucleus. It is conventionally represented by the symbol Z. The atomic number uniquely identifies a chemical element...

s 57 through 71, from lanthanum
Lanthanum
Lanthanum is a chemical element with the symbol La and atomic number 57.Lanthanum is a silvery white metallic element that belongs to group 3 of the periodic table and is the first element of the lanthanide series. It is found in some rare-earth minerals, usually in combination with cerium and...

 through lutetium. These fifteen elements, along with chemically similar scandium
Scandium
Scandium is a chemical element with symbol Sc and atomic number 21. A silvery-white metallic transition metal, it has historically been sometimes classified as a rare earth element, together with yttrium and the lanthanoids...

 and yttrium
Yttrium
Yttrium is a chemical element with symbol Y and atomic number 39. It is a silvery-metallic transition metal chemically similar to the lanthanides and it has often been classified as a "rare earth element". Yttrium is almost always found combined with the lanthanides in rare earth minerals and is...

, are often collectively known as the rare earth elements.

The informal chemical symbol Ln is used in general discussions of lanthanide chemistry. All but one of the lanthanides are f-block
F-block
The f-block of the periodic table of the elements consists of those elements whose atoms or ions have valence electrons in f-orbitals. Actual electronic configurations may be slightly different from what is predicted by the Aufbau principle...

 elements, corresponding to the filling of the 4f electron shell
Electron shell
An electron shell may be thought of as an orbit followed by electrons around an atom's nucleus. The closest shell to the nucleus is called the "1 shell" , followed by the "2 shell" , then the "3 shell" , and so on further and further from the nucleus. The shell letters K,L,M,.....

; lutetium, a d-block
D-block
The d-block is the portion of the periodic table that contains the element groups 3-12. These groups correspond to the filling of the atomic d-orbital subshell, with electron configurations ranging from s2d1 to s2d10...

 element, is also generally considered to be a lanthanide due to its chemical similarities with the other fourteen. All of the lanthanide elements form trivalent cations, Ln3+, whose chemistry is largely determined by the ionic radius, which decreases steadily from lanthanum to lutetium.
Atomic Number
Atomic number
In chemistry and physics, the atomic number is the number of protons found in the nucleus of an atom and therefore identical to the charge number of the nucleus. It is conventionally represented by the symbol Z. The atomic number uniquely identifies a chemical element...

57 58 59 60 61 62 63 64 65 66 67 68 69 70 71
Symbol (Names linked)
Chemical element
A chemical element is a pure chemical substance consisting of one type of atom distinguished by its atomic number, which is the number of protons in its nucleus. Familiar examples of elements include carbon, oxygen, aluminum, iron, copper, gold, mercury, and lead.As of November 2011, 118 elements...

La
Lanthanum
Lanthanum is a chemical element with the symbol La and atomic number 57.Lanthanum is a silvery white metallic element that belongs to group 3 of the periodic table and is the first element of the lanthanide series. It is found in some rare-earth minerals, usually in combination with cerium and...

Ce
Cerium
Cerium is a chemical element with the symbol Ce and atomic number 58. It is a soft, silvery, ductile metal which easily oxidizes in air. Cerium was named after the dwarf planet . Cerium is the most abundant of the rare earth elements, making up about 0.0046% of the Earth's crust by weight...

Pr
Praseodymium
Praseodymium is a chemical element that has the symbol Pr and atomic number 59. Praseodymium is a soft, silvery, malleable and ductile metal in the lanthanide group. It is too reactive to be found in native form, and when artificially prepared, it slowly develops a green oxide coating.The element...

Nd
Neodymium
Neodymium is a chemical element with the symbol Nd and atomic number 60. It is a soft silvery metal that tarnishes in air. Neodymium was discovered in 1885 by the Austrian chemist Carl Auer von Welsbach. It is present in significant quantities in the ore minerals monazite and bastnäsite...

Pm
Promethium
Promethium is a chemical element with the symbol Pm and atomic number 61. It is notable for being the only exclusively radioactive element besides technetium that is followed by chemical elements with stable isotopes.- Prediction :...

Sm
Samarium
Samarium is a chemical element with the symbol Sm, atomic number 62 and atomic weight 150.36. It is a moderately hard silvery metal which readily oxidizes in air. Being a typical member of the lanthanide series, samarium usually assumes the oxidation state +3...

Eu
Europium
Europium is a chemical element with the symbol Eu and atomic number 63. It is named after the continent of Europe. It is a moderately hard silvery metal which readily oxidizes in air and water...

Gd
Gadolinium
Gadolinium is a chemical element with the symbol Gd and atomic number 64. It is a silvery-white, malleable and ductile rare-earth metal. It is found in nature only in combined form. Gadolinium was first detected spectroscopically in 1880 by de Marignac who separated its oxide and is credited with...

Tb
Terbium
Terbium is a chemical element with the symbol Tb and atomic number 65. It is a silvery-white rare earth metal that is malleable, ductile and soft enough to be cut with a knife...

Dy
Dysprosium
Dysprosium is a chemical element with the symbol Dy and atomic number 66. It is a rare earth element with a metallic silver luster. Dysprosium is never found in nature as a free element, though it is found in various minerals, such as xenotime...

Ho
Holmium
Holmium is a chemical element with the symbol Ho and atomic number 67. Part of the lanthanide series, holmium is a rare earth element. Its oxide was first isolated from rare earth ores in 1878 and the element was named after the city of Stockholm....

Er
Erbium
Erbium is a chemical element in the lanthanide series, with the symbol Er and atomic number 68. A silvery-white solid metal when artificially isolated, natural erbium is always found in chemical combination with other elements on Earth...

Tm
Thulium
Thulium is a chemical element that has the symbol Tm and atomic number 69. Thulium is the second least abundant of the lanthanides . It is an easily workable metal with a bright silvery-gray luster...

Yb
Ytterbium
Ytterbium is a chemical element with the symbol Yb and atomic number 70. A soft silvery metallic element, ytterbium is a rare earth element of the lanthanide series and is found in the minerals gadolinite, monazite, and xenotime. The element is sometimes associated with yttrium or other related...

Lu
M3+ f-electrons 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
M3+ radius (assuming 6-coordination) - 101 99 98.3 97 95.8 94.7 93.8 92.3 91.2 90.1 89.0 88.0 86.8 86.1

The lanthanide elements are the group of elements with atomic number
Atomic number
In chemistry and physics, the atomic number is the number of protons found in the nucleus of an atom and therefore identical to the charge number of the nucleus. It is conventionally represented by the symbol Z. The atomic number uniquely identifies a chemical element...

 increasing from 57 (lanthanum) to 71 (lutetium). They are termed lanthanide because the lighter elements in the series are chemically similar to lanthanum
Lanthanum
Lanthanum is a chemical element with the symbol La and atomic number 57.Lanthanum is a silvery white metallic element that belongs to group 3 of the periodic table and is the first element of the lanthanide series. It is found in some rare-earth minerals, usually in combination with cerium and...

. Strictly speaking, both lanthanum and lutetium have been labeled as group 3 element
Group 3 element
The group 3 elements are a group of chemical elements in the periodic table. This group, like other d-block groups, should contain four elements, but it is not agreed what elements belong in the group...

s, because they both have a single valence electron in the d shell. However, both elements are often included in any general discussion of the chemistry of the lanthanide elements.

In presentations of the periodic table
Periodic table
The periodic table of the chemical elements is a tabular display of the 118 known chemical elements organized by selected properties of their atomic structures. Elements are presented by increasing atomic number, the number of protons in an atom's atomic nucleus...

, the lanthanides and the actinides are customarily shown as two additional rows below the main body of the table, with placeholders or else a selected single element of each series (either lanthanum
Lanthanum
Lanthanum is a chemical element with the symbol La and atomic number 57.Lanthanum is a silvery white metallic element that belongs to group 3 of the periodic table and is the first element of the lanthanide series. It is found in some rare-earth minerals, usually in combination with cerium and...

 or lutetium, and either actinium
Actinium
Actinium is a radioactive chemical element with the symbol Ac and atomic number 89, which was discovered in 1899. It was the first non-primordial radioactive element to be isolated. Polonium, radium and radon were observed before actinium, but they were not isolated until 1902...

 or lawrencium
Lawrencium
Lawrencium is a radioactive synthetic chemical element with the symbol Lr and atomic number 103. In the periodic table of the elements, it is a period 7 d-block element and the last element of actinide series...

, respectively) shown in a single cell of the main table, between barium
Barium
Barium is a chemical element with the symbol Ba and atomic number 56. It is the fifth element in Group 2, a soft silvery metallic alkaline earth metal. Barium is never found in nature in its pure form due to its reactivity with air. Its oxide is historically known as baryta but it reacts with...

 and hafnium
Hafnium
Hafnium is a chemical element with the symbol Hf and atomic number 72. A lustrous, silvery gray, tetravalent transition metal, hafnium chemically resembles zirconium and is found in zirconium minerals. Its existence was predicted by Dmitri Mendeleev in 1869. Hafnium was the penultimate stable...

, and radium
Radium
Radium is a chemical element with atomic number 88, represented by the symbol Ra. Radium is an almost pure-white alkaline earth metal, but it readily oxidizes on exposure to air, becoming black in color. All isotopes of radium are highly radioactive, with the most stable isotope being radium-226,...

 and rutherfordium
Rutherfordium
Rutherfordium is a chemical element with symbol Rf and atomic number 104, named in honor of New Zealand physicist Ernest Rutherford. It is a synthetic element and radioactive; the most stable known isotope, 267Rf, has a half-life of approximately 1.3 hours.In the periodic table of the elements,...

, respectively. This convention is entirely a matter of aesthetics
Aesthetics
Aesthetics is a branch of philosophy dealing with the nature of beauty, art, and taste, and with the creation and appreciation of beauty. It is more scientifically defined as the study of sensory or sensori-emotional values, sometimes called judgments of sentiment and taste...

 and formatting practicality; a rarely used wide-formatted periodic table
Periodic table (wide)
This is a version of the periodic table of the elements that places all elements of one period in the same row. For more information on its contents and history, see the article Periodic table.----- See also :*Periodic table*Periodic table...

 inserts the lanthanide and actinide series in their proper places, as parts of the table's sixth and seventh rows (periods).

Etymology

Together with scandium
Scandium
Scandium is a chemical element with symbol Sc and atomic number 21. A silvery-white metallic transition metal, it has historically been sometimes classified as a rare earth element, together with yttrium and the lanthanoids...

 and yttrium
Yttrium
Yttrium is a chemical element with symbol Y and atomic number 39. It is a silvery-metallic transition metal chemically similar to the lanthanides and it has often been classified as a "rare earth element". Yttrium is almost always found combined with the lanthanides in rare earth minerals and is...

, the trivial name
Trivial name
In chemistry, a trivial name is a common name or vernacular name; it is a non-systematic name or non-scientific name. That is, the name is not recognised according to the rules of any formal system of nomenclature...

 "rare earths" is sometimes used to describe all the lanthanides. This name arises from the minerals from which they were isolated, which were uncommon oxide-type minerals. However, the use of the name is deprecated by IUPAC, as the elements are neither rare in abundance nor "earths" (an obsolete term for water-insoluble strongly basic oxide
Oxide
An oxide is a chemical compound that contains at least one oxygen atom in its chemical formula. Metal oxides typically contain an anion of oxygen in the oxidation state of −2....

s of electropositive metals incapable of being smelted into metal using late 18th century technology) . Cerium
Cerium
Cerium is a chemical element with the symbol Ce and atomic number 58. It is a soft, silvery, ductile metal which easily oxidizes in air. Cerium was named after the dwarf planet . Cerium is the most abundant of the rare earth elements, making up about 0.0046% of the Earth's crust by weight...

 is the 26th most abundant element in the Earth's crust, neodymium
Neodymium
Neodymium is a chemical element with the symbol Nd and atomic number 60. It is a soft silvery metal that tarnishes in air. Neodymium was discovered in 1885 by the Austrian chemist Carl Auer von Welsbach. It is present in significant quantities in the ore minerals monazite and bastnäsite...

 is more abundant than gold
Gold
Gold is a chemical element with the symbol Au and an atomic number of 79. Gold is a dense, soft, shiny, malleable and ductile metal. Pure gold has a bright yellow color and luster traditionally considered attractive, which it maintains without oxidizing in air or water. Chemically, gold is a...

 and even thulium
Thulium
Thulium is a chemical element that has the symbol Tm and atomic number 69. Thulium is the second least abundant of the lanthanides . It is an easily workable metal with a bright silvery-gray luster...

 (the least common naturally occurring lanthanide) is more abundant than iodine
Iodine
Iodine is a chemical element with the symbol I and atomic number 53. The name is pronounced , , or . The name is from the , meaning violet or purple, due to the color of elemental iodine vapor....

. Despite their abundance, even the technical term "lanthanides" could be interpreted to reflect a sense of elusiveness on the part of these elements, as it comes from the Greek λανθανειν (lanthanein), "to lie hidden". However, if not referring to their natural abundance, but rather to their property of "hiding" behind each other in minerals, this interpretation is in fact appropriate. The etymology of the term must be sought in the first discovery of lanthanum
Lanthanum
Lanthanum is a chemical element with the symbol La and atomic number 57.Lanthanum is a silvery white metallic element that belongs to group 3 of the periodic table and is the first element of the lanthanide series. It is found in some rare-earth minerals, usually in combination with cerium and...

, at that time a so-called new rare earth element "lying hidden" in a cerium
Cerium
Cerium is a chemical element with the symbol Ce and atomic number 58. It is a soft, silvery, ductile metal which easily oxidizes in air. Cerium was named after the dwarf planet . Cerium is the most abundant of the rare earth elements, making up about 0.0046% of the Earth's crust by weight...

 mineral, and it is an irony that lanthanum was later identified as the first in an entire series of chemically similar elements and could give name to the whole series. The term lanthanide was probably introduced by Victor Goldschmidt
Victor Goldschmidt
Victor Moritz Goldschmidt was a mineralogist considered to be the founder of modern geochemistry and crystal chemistry, developer of the Goldschmidt Classification of elements.-Early life & career:Goldschmidt was born in Zürich...

 in 1925.

Chemical compounds

The electronic structure of the lanthanide elements, with minor exceptions is [Xe]6s24fn. In their compounds, the 6s electrons are lost and the ions have the configuration [Xe]4fm. The chemistry of the lanthanides differs from main group element
Main group element
In chemistry and atomic physics, main group elements are elements in groups whose lightest members are represented by helium, lithium,...

s and transition metal
Transition metal
The term transition metal has two possible meanings:*The IUPAC definition states that a transition metal is "an element whose atom has an incomplete d sub-shell, or which can give rise to cations with an incomplete d sub-shell." Group 12 elements are not transition metals in this definition.*Some...

s because of the nature of the 4f orbitals. These orbitals are "buried" inside the atom and are shielded from the atom's environment by the 4d and 5p electrons. As a consequence of this, the chemistry of the elements is largely determined by their size, which decreases gradually from 102 pm (La3+) with increasing atomic number to 86 pm (Lu3+), the so-called lanthanide contraction
Lanthanide contraction
Lanthanide contraction is a term used in chemistry to describe the decrease in ionic radii of the elements in the lanthanide series from atomic number 58, Cerium to 71, Lutetium, which results in smaller than otherwise expected ionic radii for the subsequent elements starting with 72, Hafnium...

. All the lanthanide elements exhibit the oxidation state
Oxidation state
In chemistry, the oxidation state is an indicator of the degree of oxidation of an atom in a chemical compound. The formal oxidation state is the hypothetical charge that an atom would have if all bonds to atoms of different elements were 100% ionic. Oxidation states are typically represented by...

 +3. In addition Ce3+ can lose its single f electron to form Ce4+ with the stable electronic configuration of xenon. Also, Eu3+ can gain an electron to form Eu2+ with the f7 configuration which has the extra stability of a half-filled shell. Promethium
Promethium
Promethium is a chemical element with the symbol Pm and atomic number 61. It is notable for being the only exclusively radioactive element besides technetium that is followed by chemical elements with stable isotopes.- Prediction :...

 is effectively a man-made element
Synthetic element
In chemistry, a synthetic element is a chemical element that is too unstable to occur naturally on Earth, and therefore has to be created artificially. So far 30 synthetic elements have been discovered—that is, synthesized...

 as all its isotopes are radioactive with half-lives of less than 20 y.

In terms of reduction potentials, the Ln0/3+ couples are nearly the same for all lanthanides, ranging from -1.99 (for Eu) to -2.35 V (for Pr). Thus, these metals are highly reducing, with reducing power similar to alkaline earth metals such as Mg (-2.36 V).

Separation of lanthanides

The similarity in ionic radius between adjacent lanthanide elements makes it difficult to separate them from each other in naturally occurring ores and other mixtures. Historically, the very laborious processes of cascading
Cascade (chemical engineering)
In chemical engineering, a cascade is a plant consisting of several similar stages with each processing the output from the previous stage. Cascades are most commonly used in isotope separation, distillation and other separation or purification processes....

 and fractional crystallization
Fractional crystallization (chemistry)
In chemistry, fractional crystallization is a method of refining substances based on differences in solubility. If a mixture of two or more substances in solution is allowed to crystallize, for example by allowing the temperature of the solution to decrease, the precipitate will contain more of...

 was used. Because the lanthanide ions have slightly different radii, the lattice energy
Lattice energy
The lattice energy of an ionic solid is a measure of the strength of bonds in that ionic compound. It is usually defined as the enthalpy of formation of the ionic compound from gaseous ions and as such is invariably exothermic. Lattice energy may also be defined as the energy required to completely...

 of their salts and hydration energies of the ions will be slightly different, leading to a small difference in solubility
Solubility
Solubility is the property of a solid, liquid, or gaseous chemical substance called solute to dissolve in a solid, liquid, or gaseous solvent to form a homogeneous solution of the solute in the solvent. The solubility of a substance fundamentally depends on the used solvent as well as on...

. Salts of the formula Ln(NO3)3.2NH4NO3.4H2O can be used. Industrially, the elements are separated from each other by solvent extraction. Typically an aqueous solution of nitrates is extracted into kerosene containing tri-n-butylphosphate, (BunO)3PO. The strength of the complexes
Stability constants of complexes
A stability constant is an equilibrium constant for the formation of a complex in solution. It is a measure of the strength of the interaction between the reagents that come together to form the complex...

 formed increases as the ionic radius decreases, so solubility in the organic phase increases. Complete separation can be achieved continuously by use of countercurrent exchange
Countercurrent exchange
Countercurrent exchange is a mechanism occurring in nature and mimicked in industry and engineering, in which there is a crossover of some property, usually heat or some component, between two flowing bodies flowing in opposite directions to each other. The flowing bodies can be liquids, gases, or...

 methods. The elements can also be separated by ion-exchange chromatography, making use of the fact that the stability constant
Stability constants of complexes
A stability constant is an equilibrium constant for the formation of a complex in solution. It is a measure of the strength of the interaction between the reagents that come together to form the complex...

 for formation of EDTA
EDTA
Ethylenediaminetetraacetic acid, widely abbreviated as EDTA , is a polyamino carboxylic acid and a colourless, water-soluble solid. Its conjugate base is named ethylenediaminetetraacetate. It is widely used to dissolve limescale. Its usefulness arises because of its role as a hexadentate ligand...

 complexes increases for log K ≈ 15.5 for [La(EDTA)]- to log K ≈ 19.8 for [Lu(EDTA)]-.

Ln(III) compounds

The trivalent lanthanides mostly form ionic salts. The trivalent ions are hard
HSAB theory
The HSAB concept is an acronym for 'hard and soft acids and bases. Also known as the Pearson acid base concept, HSAB is widely used in chemistry for explaining stability of compounds, reaction mechanisms and pathways....

 acceptors and form more stable complexes with oxygen-donor ligands than with nitrogen-donor ligands. The larger ions are 9-coordinate in aqueous solution, [Ln(H2O)9]3+ but the smaller ions are 8-coordinate, [Ln(H2O)8]3+. There is some evidence that the later lanthanides have more water molecules in the second coordination sphere. Complexation with monodentate ligands is generally weak because it is difficult to displace water molecules from the first coordination sphere. Stronger complexes are formed with chelating ligands because of the chelate effect, such as the tetra-anion derived from 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA).

Ln(II) and Ln(IV) compounds

The most common divalent derivatives of the lanthanides are for Eu(II), which achieves a favorable f7 configuration. Divalent halide derivatives are known for all of the lanthanides. They are either conventional salts or are Ln(III) "electride
Electride
An electride is an ionic compound in which an electron is the anion. The first electrides to be studied in depth were solutions of alkali metals in ammonia. When sodium metal dissolves in ammonia, the result is a blue solution consisting of [Na6]+ and solvated electrons. Such solutions are powerful...

"-like salts. The simple salts include YbI2, EuI2, and SmI2. The electride-like salts, described as Ln2+, 2I-, e-, include NdI2, DyI2 and TmI2. Many of the iodides form soluble complexes with ethers, e.g. TmI2(dimethoxyethane)3. Samarium(II) iodide
Samarium(II) iodide
Samarium iodide is a green solid composed of samarium and iodine, with a melting point of 520 °C where the samarium atom has a coordination number of seven in a capped octahedral configuration...

 is a useful reducing agent.

Ce(IV) in ceric ammonium nitrate is a useful oxidising agent. Otherwise tetravalent lanthanides are rare. The Ce(IV) is the exception owing to the tendency to form an unfilled f shell.

Organometallic compounds

Lanthanide-carbon σ bonds are well known but they exhibit carbanion-like behavior, unlike transition metal organometallic compounds. Because of their large size, lanthanides tend to form more stable organometallic derivatives with bulky ligands to give compounds such as Ln[CH(SiMe3)3]. Similarly complexes of cyclopentadienyl anion
Cyclopentadiene
Cyclopentadiene is an organic compound with the formula C5H6. This colorless liquid has a strong and unpleasant odor. At room temperature, this cyclic diene dimerizes over the course of hours to give dicyclopentadiene via a Diels–Alder reaction...

, e.g. [Ln(C5H5)3], are far less common than the corresponding pentamethylcyclopentadienyl
Pentamethylcyclopentadiene
1,2,3,4,5-Pentamethylcyclopentadiene is a cyclic diolefin with the formula C5Me5H . 1,2,3,4,5-Pentamethylcyclopentadiene is the precursor to the ligand 1,2,3,4,5-pentamethylcyclopentadienyl, which is often denoted as Cp*...

, e.g. [Ln(C5Me5)3Cl]. Analogues of uranocene
Uranocene
Uranocene U2 is the most notable cyclooctatetraenide of the f elements and one of the first organouranium compounds to be synthesized. Uranocene is a member of the actinocenes, a group of metallocenes incorporating elements from the actinide series...

 are derived from dilithiocyclooctatetraene, Li2C8H8. Organic lanthanide(II) compounds are also known, such as Cp*2Eu.

Magnetic and spectroscopic properties

All the trivalent lanthanide ions, except lutetium, have unpaired f electrons. However the magnetic moments deviate considerably from the spin-only values
Magnetochemistry
Magnetochemistry is concerned with the magnetic properties of chemical compounds. Magnetic properties arise from the spin and orbital angular momentum of the electrons contained in a compound. Compounds are diamagnetic when they contain no unpaired electrons. Molecular compounds that contain one or...

 because of strong spin-orbit coupling. The maximum number of unpaired electrons is 7, in Gd3+, with a magnetic moment of 7.94 B.M., but the largest magnetic moments, at 10.4-10.7 B.M., are exhibited by Dy3+ and Ho3+. However, in Gd3+ all the electrons have parallel spin and this property is important for the use of gadolinium complexes as contrast reagent
MRI contrast agent
MRI contrast agents are a group of contrast media used to improve the visibility of internal body structures in magnetic resonance imaging . The most commonly used compounds for contrast enhancement are gadolinium-based. MRI contrast agents alter the relaxation times of tissues and body cavities...

 in MRI scans.

Crystal field splitting is rather small for the lanthanide ions and is less important than spin-orbit coupling in regard to energy levels. Transitions of electrons between f orbitals are forbidden by the Laporte rule
Laporte rule
The Laporte rule is a spectroscopic selection rule. It states that electronic transitions that conserve either symmetry or asymmetry with respect to an inversion center — i.e., g → g, or u → u respectively—are forbidden...

. Furthermore, because of the "buried" nature of the f orbitals, coupling with molecular vibrations is weak. Consequently the spectra of lanthanide ions are rather weak and the absorption bands are similarly narrow. Glass containing holmium oxide
Holmium(III) oxide
Holmium oxide, or holmium oxide is a chemical compound of a rare-earth element holmium and oxygen with the formula Ho2O3. Together with dysprosium oxide holmium oxide is one of the most powerfully paramagnetic substances known. The oxide, also called holmia, occurs as a component of the related...

 and holmium oxide solutions (usually in perchloric acid
Perchloric acid
Perchloric acid is the inorganic compound with the formula HClO4. Usually encountered as an aqueous solution, this colourless compound is a strong acid comparable in strength to sulfuric and nitric acids. It is a powerful oxidizer, but its aqueous solutions up to appr. 70% are remarkably inert,...

) have sharp optical absorption peaks in the spectral range 200–900 nm and can be used as a wavelength
Wavelength
In physics, the wavelength of a sinusoidal wave is the spatial period of the wave—the distance over which the wave's shape repeats.It is usually determined by considering the distance between consecutive corresponding points of the same phase, such as crests, troughs, or zero crossings, and is a...

 calibration standard for optical spectrophotometers
Monochromator
A monochromator is an optical device that transmits a mechanically selectable narrow band of wavelengths of light or other radiation chosen from a wider range of wavelengths available at the input...

, and are available commercially.

As f-f transitions are Laporte-forbidden, once an electron has been excited, decay to the ground state will be slow. This makes them suitable for use in laser
Laser
A laser is a device that emits light through a process of optical amplification based on the stimulated emission of photons. The term "laser" originated as an acronym for Light Amplification by Stimulated Emission of Radiation...

s as it makes the population inversion
Population inversion
In physics, specifically statistical mechanics, a population inversion occurs when a system exists in state with more members in an excited state than in lower energy states...

 easy to achieve. The Nd:YAG laser
Nd:YAG laser
Nd:YAG is a crystal that is used as a lasing medium for solid-state lasers. The dopant, triply ionized neodymium, typically replaces yttrium in the crystal structure of the yttrium aluminium garnet , since they are of similar size...

 is one that is widely used. Europium-doped yttrium vanadate was the first red phosphor  to enable the development of colour television screens. Lanthanide ions have notable luminescent properties due to their unique 4f orbitals. Laporte forbidden f-f transitions can be activated by excitation of a bound "antenna" ligand. This leads to sharp emission bands throughout the visible, NIR, and IR and relatively long luminescence lifetimes.

Geochemistry

The lanthanide contraction
Lanthanide contraction
Lanthanide contraction is a term used in chemistry to describe the decrease in ionic radii of the elements in the lanthanide series from atomic number 58, Cerium to 71, Lutetium, which results in smaller than otherwise expected ionic radii for the subsequent elements starting with 72, Hafnium...

 is responsible for the great geochemical divide that splits the lanthanides into light and heavy-lanthanide enriched minerals, the latter being almost inevitably associated with and dominated by yttrium. This divide is reflected in the first two "rare earths" that were discovered: yttria
Yttrium(III) oxide
Yttrium oxide is Y2O3. It is an air-stable, white solid substance. Yttrium oxide is used as a common starting material for both materials science as well as inorganic compounds.-Materials science:...

 (1794) and ceria
Cerium(IV) oxide
Cerium oxide, also known as ceric oxide, ceria, cerium oxide or cerium dioxide, is an oxide of the rare earth metal cerium...

 (1803). The geochemical divide has put more of the light lanthanides in the Earth's crust, but more of the heavy members in the Earth's mantle. The result is that although large rich ore-bodies are found that are enriched in the light lanthanides, correspondingly large ore-bodies for the heavy members are few. The principal ores are monazite
Monazite
Monazite is a reddish-brown phosphate mineral containing rare earth metals. It occurs usually in small isolated crystals. There are actually at least four different kinds of monazite, depending on relative elemental composition of the mineral:...

 and bastnaesite. Monazite sands usually contain all the lanthanide elements, but the heavier elements are lacking in bastnaesite. The lanthanides obey the Oddo-Harkins rule
Oddo-Harkins rule
The Oddo-Harkins rule holds that elements with an even atomic number are more common than elements with an odd atomic number .-Definition:...

 - odd-numbered elements are less abundant than their even-numbered neighbours.

Three of the lanthanide elements have radioactive isotopes with long half-lives (138La, 147Sm and 176Lu) that can be used to date minerals and rocks from Earth, the Moon and meteorites.

Biological effects

Compared to most other nondietary element
Dietary mineral
Dietary minerals are the chemical elements required by living organisms, other than the four elements carbon, hydrogen, nitrogen, and oxygen present in common organic molecules. Examples of mineral elements include calcium, magnesium, potassium, sodium, zinc, and iodine...

s, non-radioactive lanthanides are classified as having low toxicity.

Technological applications

Lanthanide elements and their compounds have many uses but the quantities consumed are relatively small in comparison to other elements. About 15000 ton/year of the lanthanides are consumed as catalysts and in the production of glasses. This 15000 tons corresponds to about 85% of the lanthanide production. From the perspective of value, however, applications in phosphors and magnets are more important.

Of the many technological devices, including superconductors, samarium-cobalt and neodymium-iron-boron high-flux rare-earth magnet
Rare-earth magnet
Rare-earth magnets are strong permanent magnets made from alloys of rare earth elements. Developed in the 1970s and 80s, rare-earth magnets are the strongest type of permanent magnets made and have significant performance advantages over ferrite or alnico magnets...

s, magnesium alloys, electronic polishers, refining catalysts and hybrid car components (primarily batteries and magnets). Lanthanide ions are used as the active ions in luminescent materials used in optoelectronics
Optoelectronics
Optoelectronics is the study and application of electronic devices that source, detect and control light, usually considered a sub-field of photonics. In this context, light often includes invisible forms of radiation such as gamma rays, X-rays, ultraviolet and infrared, in addition to visible light...

 applications, most notably the Nd:YAG laser. Erbium-doped fiber amplifiers are significant devices in optical-fiber communication systems. Phosphors with lanthanide dopants are also widely used in cathode ray tube
Cathode ray tube
The cathode ray tube is a vacuum tube containing an electron gun and a fluorescent screen used to view images. It has a means to accelerate and deflect the electron beam onto the fluorescent screen to create the images. The image may represent electrical waveforms , pictures , radar targets and...

 technology such as television
Television
Television is a telecommunication medium for transmitting and receiving moving images that can be monochrome or colored, with accompanying sound...

 sets. The earliest color television CRTs had a poor-quality red; europium as a phosphor dopant made good red phosphors possible. Yttrium iron garnet
Yttrium iron garnet
Yttrium iron garnet is a kind of synthetic garnet, with chemical composition 323, or Y3Fe5O12. It is a ferrimagnetic material with a Curie temperature of 550 K....

 (YIG) spheres have been useful as tunable microwave resonators. Lanthanide oxides are mixed with tungsten
Tungsten
Tungsten , also known as wolfram , is a chemical element with the chemical symbol W and atomic number 74.A hard, rare metal under standard conditions when uncombined, tungsten is found naturally on Earth only in chemical compounds. It was identified as a new element in 1781, and first isolated as...

 to improve their high temperature properties for welding, replacing thorium
Thorium
Thorium is a natural radioactive chemical element with the symbol Th and atomic number 90. It was discovered in 1828 and named after Thor, the Norse god of thunder....

, which was mildly hazardous to work with. Many defense-related products also use lanthanide elements such as night vision goggles, rangefinders, the SPY-1 radar
AN/SPY-1
The AN/SPY-1 is a US naval radar system manufactured by Lockheed Martin. The array is a passive electronically scanned system and is a key component of the Aegis Combat System. The system is computer controlled, using four complementary antennas to provide 360 degree coverage...

 used in some Aegis
Aegis combat system
The Aegis Combat System is an integrated naval weapons system developed by the Missile and Surface Radar Division of RCA, and now produced by Lockheed Martin...

 equipped warships, and the propulsion system of Arleigh Burke-class destroyer
Arleigh Burke class destroyer
The Arleigh Burke class of guided missile destroyers is the United States Navy's first class of destroyer built around the Aegis combat system and the SPY-1D multi-function phased array radar. The class is named for Admiral Arleigh "31-Knot" Burke, the most famous American destroyer officer of...

s all use rare earth elements in critical capacities.

Most lanthanides are widely used in laser
Laser
A laser is a device that emits light through a process of optical amplification based on the stimulated emission of photons. The term "laser" originated as an acronym for Light Amplification by Stimulated Emission of Radiation...

s, and as (co-)dopants in doped-fiber optical amplifiers (e.g. Er-doped fiber amplfiers (EDFAs) which are used as repeaters in the terrestrial and submarine fiber-optic transmission links that carry internet traffic) . These elements deflect ultraviolet
Ultraviolet
Ultraviolet light is electromagnetic radiation with a wavelength shorter than that of visible light, but longer than X-rays, in the range 10 nm to 400 nm, and energies from 3 eV to 124 eV...

 and infrared
Infrared
Infrared light is electromagnetic radiation with a wavelength longer than that of visible light, measured from the nominal edge of visible red light at 0.74 micrometres , and extending conventionally to 300 µm...

 radiation and are commonly used in the production of sunglass lenses. Other applications are summarized in the following table:

The complex [Gd(DOTA)]- is used in magnetic resonance imaging
Magnetic resonance imaging
Magnetic resonance imaging , nuclear magnetic resonance imaging , or magnetic resonance tomography is a medical imaging technique used in radiology to visualize detailed internal structures...

.

External links


Gallery

Period  6
Period 6 element
A period 6 element is one of the chemical elements in the sixth row of the periodic table of the elements, including the lanthanides...

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