Lanthanum is a
chemical element with the
symbol La and
atomic number 57. It is a
soft,
ductile, silvery-white
metal
A metal (from ancient Greek, Greek μέταλλον ''métallon'', "mine, quarry, metal") is a material that, when freshly prepared, polished, or fractured, shows a lustrous appearance, and conducts electrical resistivity and conductivity, e ...
that tarnishes slowly when exposed to air. It is the eponym of the
lanthanide series, a group of 15 similar elements between lanthanum and
lutetium in the
periodic table, of which lanthanum is the first and the prototype. Lanthanum is traditionally counted among the
rare earth elements. Like most other rare earth elements, the usual
oxidation state is +3. Lanthanum has no biological role in humans but is essential to some bacteria. It is not particularly toxic to humans but does show some antimicrobial activity.
Lanthanum usually occurs together with
cerium
Cerium is a chemical element with the symbol Ce and atomic number 58. Cerium is a soft, ductile, and silvery-white metal that tarnishes when exposed to air. Cerium is the second element in the lanthanide series, and while it often shows the +3 ...
and the other rare earth elements. Lanthanum was first found by the Swedish chemist
Carl Gustaf Mosander in 1839 as an impurity in
cerium nitrate – hence the name ''lanthanum'', from the
Ancient Greek (), meaning 'to lie hidden'. Although it is classified as a rare earth element, lanthanum is the 28th most abundant element in the Earth's crust, almost three times as abundant as
lead. In minerals such as
monazite and
bastnäsite, lanthanum composes about a quarter of the lanthanide content. It is extracted from those minerals by a process of such complexity that pure lanthanum metal was not isolated until 1923.
Lanthanum compounds have numerous applications as
catalysts, additives in glass, carbon arc lamps for studio lights and projectors, ignition elements in
lighters and torches,
electron cathodes,
scintillators,
gas tungsten arc welding electrodes, and other things.
Lanthanum carbonate is used as a
phosphate binder in cases of
high levels of phosphate in the blood seen with
kidney failure.
Characteristics
Physical
Lanthanum is the first element and prototype of the lanthanide series. In the periodic table, it appears to the right of the
alkaline earth metal barium and to the left of the lanthanide cerium. Its placement has been disputed, but most who study the matter along with a 2021 IUPAC provisional report consider lanthanum to be best placed as the first of the f-block elements.
[
] The 57 electrons of a lanthanum atom are arranged in the
configuration ed
16s
2, with three valence electrons outside the noble gas core. In chemical reactions, lanthanum almost always gives up these three valence electrons from the 5d and 6s
subshells to form the +3 oxidation state, achieving the stable configuration of the preceding noble gas
xenon.
[Greenwood and Earnshaw, p. 1106] Some lanthanum(II) compounds are also known, but they are much less stable.
Among the lanthanides, lanthanum is exceptional as it has no 4f electrons as a single gas-phase atom. Thus it is only very weakly
paramagnetic, unlike the strongly paramagnetic later lanthanides (with the exceptions of the last two,
ytterbium and
lutetium, where the 4f shell is completely full). However, the 4f shell of lanthanum can become partially occupied in chemical environments and participate in chemical bonding.
For example, the melting points of the trivalent lanthanides (all but
europium and ytterbium) are related to the extent of hybridisation of the 6s, 5d, and 4f electrons (lowering with increasing 4f involvement), and lanthanum has the second-lowest melting point among them: 920 °C. (Europium and ytterbium have lower melting points because they delocalise about two electrons per atom rather than three.) This chemical availability of f orbitals justifies lanthanum's placement in the f-block despite its anomalous ground-state configuration
(which is merely the result of strong interelectronic repulsion making it less profitable to occupy the 4f shell, as it is small and close to the core electrons).
The lanthanides become harder as the series is traversed: as expected, lanthanum is a soft metal. Lanthanum has a relatively high
resistivity of 615 nΩm at room temperature; in comparison, the value for the good conductor aluminium is only 26.50 nΩm.
[Greenwood and Earnshaw, p. 1429] Lanthanum is the least volatile of the lanthanides.
Like most of the lanthanides, lanthanum has a
hexagonal crystal structure at room temperature. At 310 °C, lanthanum changes to a
face-centered cubic structure, and at 865 °C, it changes to a
body-centered cubic structure.
Chemical
As expected from
periodic trends, lanthanum has the largest
atomic radius
The atomic radius of a chemical element is a measure of the size of its atom, usually the mean or typical distance from the center of the nucleus to the outermost isolated electron. Since the boundary is not a well-defined physical entity, there ...
of the lanthanides. Hence, it is the most reactive among them, tarnishing quite rapidly in air, turning completely dark after several hours and can readily burn to form
lanthanum(III) oxide, La
2O
3, which is almost as
basic as
calcium oxide.
[Greenwood and Earnshaw, p. 1105–7] A centimeter-sized sample of lanthanum will corrode completely in a year as its oxide
spalls off like iron
rust, instead of forming a protective oxide coating like
aluminium, scandium, yttrium, and lutetium. Lanthanum reacts with the
halogens at room temperature to form the trihalides, and upon warming will form
binary compounds with the nonmetals nitrogen, carbon, sulfur, phosphorus, boron, selenium, silicon and arsenic.
Lanthanum reacts slowly with water to form
lanthanum(III) hydroxide, La(OH)
3.
In dilute
sulfuric acid, lanthanum readily forms the aquated tripositive ion : this is colorless in aqueous solution since La
3+ has no d or f electrons.
Lanthanum is the strongest and
hardest base among the
rare earth elements, which is again expected from its being the largest of them.
[Greenwood and Earnshaw, p. 1434]
Some lanthanum(II) compounds are also known, but they are much less stable.
Therefore, in officially naming compounds of lanthanum its oxidation number always is to be mentioned.
Isotopes
Naturally occurring lanthanum is made up of two isotopes, the stable
139La and the
primordial long-lived radioisotope 138La.
139La is by far the most abundant, making up 99.910% of natural lanthanum: it is produced in the
s-process (slow
neutron capture, which occurs in low- to medium-mass stars) and the
r-process (rapid neutron capture, which occurs in core-collapse
supernovae). It is the only stable isotope of lanthanum.
The very rare isotope
138La is one of the few primordial
odd–odd nuclei, with a long half-life of 1.05×10
11 years. It is one of the proton-rich
p-nuclei which cannot be produced in the
s- or
r-processes.
138La, along with the even rarer
180mTa, is produced in the ν-process, where
neutrinos interact with stable nuclei.
All other lanthanum isotopes are
synthetic Synthetic things are composed of multiple parts, often with the implication that they are artificial. In particular, 'synthetic' may refer to:
Science
* Synthetic chemical or compound, produced by the process of chemical synthesis
* Synthetic ...
: with the exception of
137La with a half-life of about 60,000 years, all of them have half-lives less than a day, and most have half-lives less than a minute. The isotopes
139La and
140La occur as
fission products of uranium.
Compounds
Lanthanum oxide is a white solid that can be prepared by direct reaction of its constituent elements. Due to the large size of the La
3+ ion, La
2O
3 adopts a hexagonal 7-coordinate structure that changes to the 6-coordinate structure of
scandium oxide (Sc
2O
3) and
yttrium oxide (Y
2O
3) at high temperature. When it reacts with water,
lanthanum hydroxide is formed:
a lot of heat is evolved in the reaction and a hissing sound is heard. Lanthanum hydroxide will react with atmospheric
carbon dioxide to form the basic carbonate.
[Greenwood and Earnshaw, p. 1107–8]
Lanthanum fluoride
Lanthanum trifluoride is a refractory ionic compound of lanthanum and fluorine.
The LaF3 structure
Bonding is ionic with lanthanum highly coordinated. The cation sits at the center of a trigonal prism. Nine fluorine atoms are close: three at ...
is insoluble in water and can be used as a
qualitative test for the presence of La
3+. The heavier halides are all very soluble
deliquescent compounds. The anhydrous halides are produced by direct reaction of their elements, as heating the hydrates causes hydrolysis: for example, heating hydrated LaCl
3 produces LaOCl.
Lanthanum reacts exothermically with hydrogen to produce the dihydride LaH
2, a black,
pyrophoric, brittle, conducting compound with the
calcium fluoride structure.
This is a non-stoichiometric compound, and further absorption of hydrogen is possible, with a concomitant loss of electrical conductivity, until the more salt-like LaH
3 is reached.
Like LaI
2 and LaI, LaH
2 is probably an
electride compound.
Due to the large ionic radius and great electropositivity of La
3+, there is not much covalent contribution to its bonding and hence it has a limited
coordination chemistry, like yttrium and the other lanthanides.
[Greenwood and Earnshaw, pp. 1108–9] Lanthanum oxalate does not dissolve very much in alkali-metal oxalate solutions, and
3(H2O)2">a(acac)3(H2O)2decomposes around 500 °C. Oxygen is the most common
donor atom
A coordination complex consists of a central atom or ion, which is usually metallic and is called the ''coordination centre'', and a surrounding array of bound molecules or ions, that are in turn known as '' ligands'' or complexing agents. Man ...
in lanthanum complexes, which are mostly ionic and often have high coordination numbers over 6: 8 is the most characteristic, forming
square antiprismatic and
dodecadeltahedral structures. These high-coordinate species, reaching up to coordination number 12 with the use of
chelating ligands such as in La
2(SO
4)
3·9H
2O, often have a low degree of symmetry because of stereo-chemical factors.
Lanthanum chemistry tends not to involve π bonding due to the electron configuration of the element: thus its organometallic chemistry is quite limited. The best characterized organolanthanum compounds are the
cyclopentadienyl complex
A cyclopentadienyl complex is a coordination complex of a metal and cyclopentadienyl groups (, abbreviated as Cp−). Cyclopentadienyl ligands almost invariably bind to metals as a pentahapto (''η''5-) bonding mode. The metal–cyclopentadien ...
La(C
5H
5)
3, which is produced by reacting anhydrous LaCl
3 with NaC
5H
5 in
tetrahydrofuran, and its methyl-substituted derivatives.
[Greenwood and Earnshaw, p. 1110]
History
In 1751, the Swedish mineralogist
Axel Fredrik Cronstedt discovered a heavy mineral from the mine at
Bastnäs
Bastnäs ( sv, Bastnäs or ) is an ore field near Riddarhyttan, Västmanland, Sweden. The mines in Bastnäs were earliest mentioned in 1692. Iron, copper and rare-earth elements were extracted from the mines and 4,500 tons of cerium was produced b ...
, later named
cerite. Thirty years later, the fifteen-year-old
Wilhelm Hisinger, from the family owning the mine, sent a sample of it to
Carl Scheele
Carl Wilhelm Scheele (, ; 9 December 1742 – 21 May 1786) was a Swedish German pharmaceutical chemist.
Scheele discovered oxygen (although Joseph Priestley published his findings first), and identified molybdenum, tungsten, barium, hyd ...
, who did not find any new elements within. In 1803, after Hisinger had become an ironmaster, he returned to the mineral with
Jöns Jacob Berzelius and isolated a new oxide which they named ''ceria'' after the
dwarf planet Ceres, which had been discovered two years earlier. Ceria was simultaneously independently isolated in Germany by
Martin Heinrich Klaproth.
[Greenwood and Earnshaw, p. 1424] Between 1839 and 1843, ceria was shown to be a mixture of oxides by the Swedish surgeon and chemist
Carl Gustaf Mosander, who lived in the same house as Berzelius and studied under him: he separated out two other oxides which he named ''lanthana'' and ''
didymia''.
He partially decomposed a sample of
cerium nitrate by roasting it in air and then treating the resulting oxide with dilute
nitric acid. That same year,
Axel Erdmann, a student also at the Karolinska Institute, discovered lanthanum in a new mineral from Låven island located in a Norwegian fjord.
Finally, Mosander explained his delay, saying that he had extracted a second element from cerium, and this he called didymium. Although he didn't realise it, didymium too was a mixture, and in 1885 it was separated into praseodymium and neodymium.
Since lanthanum's properties differed only slightly from those of cerium, and occurred along with it in its salts, he named it from the
Ancient Greek ''λανθάνειν''
anthanein(lit. ''to lie hidden'').
Relatively pure lanthanum metal was first isolated in 1923.
Occurrence and production
Lanthanum is the third-most abundant of all the lanthanides, making up 39 mg/kg of the Earth's crust, behind
neodymium
Neodymium is a chemical element with the symbol Nd and atomic number 60. It is the fourth member of the lanthanide series and is considered to be one of the rare-earth metals. It is a hard, slightly malleable, silvery metal that quickly tarn ...
at 41.5 mg/kg and cerium at 66.5 mg/kg. It is almost three times as abundant as
lead in the Earth's crust. Despite being among the so-called "rare earth metals", lanthanum is thus not rare at all, but it is historically so named because it is rarer than "common earths" such as lime and magnesia, and historically only a few deposits were known. Lanthanum is considered a rare earth metal because the process to mine it is difficult, time-consuming, and expensive.
Lanthanum is rarely the dominant lanthanide found in the rare earth minerals, and in their chemical formulae it is usually preceded by cerium. Rare examples of La-dominant minerals are monazite-(La) and lanthanite-(La).
The La
3+ ion is similarly sized to the early lanthanides of the cerium group (those up to
samarium and
europium) that immediately follow in the periodic table, and hence it tends to occur along with them in
phosphate,
silicate and
carbonate minerals, such as
monazite (M
IIIPO
4) and
bastnäsite (M
IIICO
3F), where M refers to all the rare earth metals except scandium and the radioactive
promethium (mostly Ce, La, and Y).
[Greenwood and Earnshaw, p. 1103] Bastnäsite is usually lacking in
thorium and the heavy lanthanides, and the purification of the light lanthanides from it is less involved. The ore, after being crushed and ground, is first treated with hot concentrated sulfuric acid, evolving carbon dioxide,
hydrogen fluoride, and
silicon tetrafluoride: the product is then dried and leached with water, leaving the early lanthanide ions, including lanthanum, in solution.
[Greenwood and Earnshaw, p. 1426–9]
The procedure for monazite, which usually contains all the rare earths as well as thorium, is more involved. Monazite, because of its magnetic properties, can be separated by repeated electromagnetic separation. After separation, it is treated with hot concentrated sulfuric acid to produce water-soluble sulfates of rare earths. The acidic filtrates are partially neutralized with
sodium hydroxide to pH 3–4. Thorium precipitates out of solution as hydroxide and is removed. After that, the solution is treated with
ammonium oxalate
The ammonium cation is a positively-charged polyatomic ion with the chemical formula or . It is formed by the protonation of ammonia (). Ammonium is also a general name for positively charged or protonated substituted amines and quaternary amm ...
to convert rare earths to their insoluble
oxalates. The oxalates are converted to oxides by annealing. The oxides are dissolved in nitric acid that excludes one of the main components,
cerium
Cerium is a chemical element with the symbol Ce and atomic number 58. Cerium is a soft, ductile, and silvery-white metal that tarnishes when exposed to air. Cerium is the second element in the lanthanide series, and while it often shows the +3 ...
, whose oxide is insoluble in HNO
3. Lanthanum is separated as a double salt with ammonium nitrate by crystallization. This salt is relatively less soluble than other rare earth double salts and therefore stays in the residue.
Care must be taken when handling some of the residues as they contain
228Ra, the daughter of
232Th, which is a strong gamma emitter.
Lanthanum is relatively easy to extract as it has only one neighbouring lanthanide, cerium, which can be removed by making use of its ability to be oxidised to the +4 state; thereafter, lanthanum may be separated out by the historical method of
fractional crystallization of La(NO
3)
3·2NH
4NO
3·4H
2O, or by
ion-exchange techniques when higher purity is desired.
Lanthanum metal is obtained from its oxide by heating it with
ammonium chloride or fluoride and hydrofluoric acid at 300-400 °C to produce the chloride or fluoride:
:La
2O
3 + 6 NH
4Cl → 2 LaCl
3 + 6 NH
3 + 3 H
2O
This is followed by reduction with alkali or alkaline earth metals in vacuum or argon atmosphere:
:LaCl
3 + 3 Li → La + 3 LiCl
Also, pure lanthanum can be produced by electrolysis of molten mixture of anhydrous LaCl
3 and NaCl or KCl at elevated temperatures.
Applications
The first historical application of lanthanum was in gas lantern
mantles.
Carl Auer von Welsbach used a mixture of
lanthanum oxide and
zirconium oxide, which he called ''Actinophor'' and patented in 1886. The original mantles gave a green-tinted light and were not very successful, and his first company, which established a factory in
Atzgersdorf in 1887, failed in 1889.
Modern uses of lanthanum include:
* One material used for anodic material of
nickel-metal hydride batteries is . Due to high cost to extract the other lanthanides, a
mischmetal with more than 50% of lanthanum is used instead of pure lanthanum. The compound is an
intermetallic component of the type.
NiMH batteries can be found in many models of the
Toyota Prius sold in the US. These larger nickel-metal hydride batteries require massive quantities of lanthanum for the production. The 2008
Toyota Prius NiMH battery requires of lanthanum. As engineers push the technology to increase fuel efficiency, twice that amount of lanthanum could be required per vehicle.
* Hydrogen sponge alloys can contain lanthanum. These alloys are capable of storing up to 400 times their own volume of hydrogen gas in a reversible adsorption process. Heat energy is released every time they do so; therefore these alloys have possibilities in energy conservation systems.
*
Mischmetal, a
pyrophoric alloy used in lighter flints, contains 25% to 45% lanthanum.
*
Lanthanum oxide and the
boride are used in electronic
vacuum tubes as
hot cathode materials with strong emissivity of
electrons. Crystals of are used in high-brightness, extended-life, thermionic electron emission sources for
electron microscopes and
Hall-effect thrusters.
*
Lanthanum trifluoride () is an essential component of a heavy fluoride glass named
ZBLAN. This glass has superior transmittance in the infrared range and is therefore used for fiber-optical communication systems.
* Cerium-doped
lanthanum bromide and
lanthanum chloride are the recent inorganic
scintillators, which have a combination of high light yield, best energy resolution, and fast response. Their high yield converts into superior energy resolution; moreover, the light output is very stable and quite high over a very wide range of temperatures, making it particularly attractive for high-temperature applications. These scintillators are already widely used commercially in detectors of
neutrons or
gamma rays.
*
Carbon arc lamp
An arc lamp or arc light is a lamp that produces light by an electric arc (also called a voltaic arc).
The carbon arc light, which consists of an arc between carbon electrodes in air, invented by Humphry Davy in the first decade of the 1800s ...
s use a mixture of rare earth elements to improve the light quality. This application, especially by the
motion picture industry for studio lighting and projection, consumed about 25% of the rare-earth compounds produced until the phase out of carbon arc lamps.
*
Lanthanum(III) oxide () improves the alkali resistance of
glass and is used in making special optical glasses, such as infrared-absorbing glass, as well as
camera and
telescope lenses, because of the high
refractive index and low dispersion of rare-earth glasses.
Lanthanum oxide is also used as a grain-growth additive during the liquid-phase
sintering of
silicon nitride and
zirconium diboride.
* Small amounts of lanthanum added to
steel improves its
malleability, resistance to impact, and
ductility, whereas addition of lanthanum to
molybdenum decreases its hardness and sensitivity to temperature variations.
* Small amounts of lanthanum are present in many pool products to remove the phosphates that feed algae.
* Lanthanum oxide additive to tungsten is used in
gas tungsten arc welding electrodes, as a substitute for
radioactive thorium.
* Various compounds of lanthanum and other rare-earth elements (oxides, chlorides, etc.) are components of various catalysis, such as
petroleum cracking catalysts.
* Lanthanum-barium
radiometric dating is used to estimate age of rocks and ores, though the technique has limited popularity.
*
Lanthanum carbonate was approved as a medication (Fosrenol,
Shire Pharmaceuticals) to absorb excess
phosphate in cases of
hyperphosphatemia seen in
end-stage kidney disease.
* Lanthanum fluoride is used in phosphor lamp coatings. Mixed with europium fluoride, it is also applied in the crystal membrane of
fluoride ion-selective electrodes.
* Like
horseradish peroxidase, lanthanum is used as an electron-dense tracer in
molecular biology.
* Lanthanum-modified bentonite (or
phoslock Phoslock is the commercial name for a bentonite clay in which the sodium and/or calcium ions are exchanged for lanthanum. The lanthanum contained within Phoslock reacts with phosphate to form an inert mineral known as rhabdophane (LaPO4.\mathitH2O). ...
) is used to remove phosphates from water in lake treatments.
* Lanthanum telluride (La
3Te
4) is considered to be applied in the field of radioisotope power system (nuclear power plant) due to its significant conversion capabilities. The transmuted elements and isotopes in the segment will not react with the material itself, thus presenting no harm to the safety of the power plant. Though iodine, which can be generated during transmutation, is suspected to react with La
3Te
4 segment, the quantity of iodine is small enough to possess threat to the power system.
Biological role
Lanthanum has no known biological role in humans. The element is very poorly absorbed after oral administration and when injected its elimination is very slow.
Lanthanum carbonate (Fosrenol) was approved as a
phosphate binder to absorb excess phosphate in cases of
end stage renal disease.
While lanthanum has pharmacological effects on several receptors and ion channels, its specificity for the
GABA receptor is unique among trivalent cations. Lanthanum acts at the same modulatory site on the
GABA receptor
The GABA receptors are a class of receptors that respond to the neurotransmitter gamma-aminobutyric acid (GABA), the chief inhibitory compound in the mature vertebrate central nervous system. There are two classes of GABA receptors: GABAA and ...
as
zinc, a known negative
allosteric modulator. The lanthanum cation La
3+ is a positive allosteric modulator at native and recombinant GABA receptors, increasing open channel time and decreasing desensitization in a subunit configuration dependent manner.
Lanthanum is an essential cofactor for the methanol dehydrogenase of the
methanotrophic bacterium ''
Methylacidiphilum fumariolicum
''Methylacidiphilum fumariolicum '' is an autotrophic bacterium first described in 2007 growing on volcanic pools near Naples, Italy. It grows in mud at temperatures between 50 °C and 60 °C and an acidic pH of 2–5. It is able to ox ...
'' SolV, although the great chemical similarity of the lanthanides means that it may be substituted with cerium, praseodymium, or neodymium without ill effects, and with the smaller samarium, europium, or gadolinium giving no side effects other than slower growth.
Precautions
Lanthanum has a low to moderate level of toxicity and should be handled with care. The injection of lanthanum solutions produces
hyperglycemia, low blood pressure, degeneration of the
spleen and
hepatic alterations. The application in carbon arc light led to the exposure of people to rare earth element oxides and fluorides, which sometimes led to
pneumoconiosis. As the La
3+ ion is similar in size to the Ca
2+ ion, it is sometimes used as an easily traced substitute for the latter in medical studies.
Lanthanum, like the other lanthanides, is known to affect human metabolism, lowering cholesterol levels, blood pressure, appetite, and risk of blood coagulation. When injected into the brain, it acts as a painkiller, similarly to
morphine and other opiates, though the mechanism behind this is still unknown.
Prices
The price for a (metric) ton
000 kgof ''Lanthanum oxide 99% (FOB China in USD/Mt)'' is given by the Institute of Rare Earths Elements and Strategic Metals as below $2,000 for most of the period from early 2001 to September 2010 (at $10,000 in the short term in 2008); it rose steeply to $140,000 in mid-2011 and fell back just as rapidly to $38,000 by early 2012. The average price for the last six months (April to September 2022) is given by the Institute as follows: ''Lanthanum Oxide - 99.9%min FOB China - 1308 EUR/mt'' and for ''Lanthanum Metal - 99%min FOB China - 3706 EUR/mt''.
[Information and notation: .access-date=27 October 2022.]
See also
, CASNo_Ref =
, CASNo = 7439-91-0
, UNII_Ref =
, UNII = 6I3K30563S
References
Bibliography
*
Further reading
* ''The Industrial Chemistry of the Lanthanons, Yttrium, Thorium and Uranium'', by R. J. Callow, Pergamon Press, 1967
* ''Extractive Metallurgy of Rare Earths'', by C. K. Gupta and N. Krishnamurthy, CRC Press, 2005
* ''Nouveau Traite de Chimie Minerale, Vol. VII. Scandium, Yttrium, Elements des Terres Rares, Actinium'', P. Pascal, Editor, Masson & Cie, 1959
* ''Chemistry of the Lanthanons'', by R. C. Vickery, Butterworths 1953
{{Good article
Chemical elements
Chemical elements with double hexagonal close-packed structure
Lanthanides
Reducing agents
GABAA receptor positive allosteric modulators