The 14th International Conference on

Miniaturized Systems for Chemistry and Life Sciences

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Lanthanide





 

Lanthanide

The lanthanide series of chemical elements comprises the 15 metallic chemical elements with atomic numbers 57 through 71, from lanthanum through lutetium. These elements, along with the chemically similar elements scandium and yttrium, are often collectively known as the rare earth elements.

They are called lanthanides because the elements in the series are chemically similar to lanthanum. Both lanthanum and lutetium have been labeled as group 3 elements, because they have a single valence electron in the 5d shell. However, both elements are often included in discussions of the chemistry of lanthanide elements. Lanthanum is the more often omitted of the two, because its placement as a group 3 element is somewhat more common in texts and for semantic reasons: since "lanthanide" means "like lanthanum", it has been argued that lanthanum cannot logically be a lanthanide, but IUPAC acknowledges its inclusion based on common usage.

Samarskite (a mineral which is the source of the name of the element samarium) and other similar minerals in particular also have these elements in association with the nearby metals tantalum, niobium, hafnium, zirconium, vanadium, and titanium, from group 4 and group 5 often in similar oxidation states. Monazite is a phosphate of numerous group 3 + lanthanide + actinide metals and mined especially for the thorium content and specific rare earths especially lanthanum, yttrium and cerium. Cerium and lanthanum as well as other members of the rare earth series are often produced as a metal called mischmetal containing a variable mixture of these elements with cerium and lanthanum predominating; it has direct uses such as lighter flints and other spark sources which do not require extensive purification of one of these metals. There are also rare earth-bearing minerals based on group 2 elements such as yttrocalcite, yttrocerite, yttrofluorite which vary in content of yttrium, cerium, and lanthanum in a particular as well as varying amounts of the others. Other lanthanide/rare earth minerals include bastnasite, florencite, chernovite, perovskite, xenotime, cerite, gadolinite, lanthanite, fergusonite, polycrase, blomstrandine, haleniusite, miserite, loparite, lepersonnite, euxenite, all of which have a range of relative element concentration and may have the symbol of a predominating one such as monazite-ce; group 3 elements do not occur as native element minerals in the fashion of gold, silver, tantalum and many others on earth but may in lunar regolith. Very rare cerium, lanthanum, and presumably other lanthanide/group 3 halides, feldspars and garnets are also known to exist.

The low probability of the 4f electrons existing at the outer region of the atom or ion permits little effective overlap between the orbitals of a lanthanide ion and any binding ligand. Thus lanthanide complexes typically have little or no covalent character and are not influenced by orbital geometries. The lack of orbital interaction also means that varying the metal typically has little effect on the complex (other than size), especially when compared to transition metals. Complexes are held together by weaker electrostatic forces which are omni-directional and thus the ligands alone dictate the symmetry and coordination of complexes. Steric factors therefore dominate, with coordinative saturation of the metal being balanced against inter-ligand repulsion. This results in a diverse range of coordination geometries, many of which are irregular, and also manifests itself in the highly fluxional nature of the complexes. As there is no energetic reason to be locked into a single geometry, rapid intramolecular and intermolecular ligand exchange will take place. This typically results in complexes that rapidly fluctuate between all possible configurations.

Despite this, the use of lanthanide coordination complexes as homogeneous catalysts is largely restricted to the laboratory and there are currently few examples them being used on an industrial scale. It should be noted however, that lanthanides exist in many forms other that coordination complexes and many of these are industrially useful. In particular lanthanide metal oxides are used as heterogeneous catalysts in various industrial processes.

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. 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 and holmium oxide solutions (usually in perchloric acid) have sharp optical absorption peaks in the spectral range 200–900 nm and can be used as a wavelength calibration standard for optical spectrophotometers, and are available commercially.

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.

As mentioned in the industrial applications section above, lanthanide metals are particularly useful in technologies that take advantage of their reactivity to specific wavelengths of light. Certain life science applications take advantage of the unique luminescence properties of lanthanide ion complexes (Ln(III) chelates or cryptates). These are well-suited for this application due to their large Stokes shifts and extremely long emission lifetimes (from microseconds to milliseconds) compared to more traditional fluorophores (e.g., fluorescein, allophycocyanin, phycoerythrin, and rhodamine). The biological fluids or serum commonly used in these research applications contain many compounds and proteins which are naturally fluorescent. Therefore, the use of conventional, steady-state fluorescence measurement presents serious limitations in assay sensitivity. Long-lived fluorophores, such as lanthanides, combined with time-resolved detection (a delay between excitation and emission detection) minimizes prompt fluorescence interference.

Due to their sparse distribution in the earth's crust and low aqueous solubility, the lanthanides have a low availability in the biosphere, and for a long time were not known to naturally form part of any biological molecules. In 2007 a novel methanol dehydrogenase that strictly uses lanthanides as enzymatic cofactors was discovered in a bacterium from the phylum Verrucomicrobia, Methylacidiphilum fumariolicum. This bacterium was found to survive only if there are lanthanides present in the environment. Compared to most other nondietary elements, non-radioactive lanthanides are classified as having low toxicity.







 

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