A lanthanide () is any of the 15 metallic chemical elements with atomic numbers 57–71, from lanthanum through lutetium. In the periodic table, the first fourteen (up to ytterbium) fill the 4f orbitals. Lutetium (element 71) is also often considered a lanthanide, despite being a d-block element and a transition metal. The IUPAC lists the 15 elements La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, under the collective name lanthanoid (), which it recommends as chemically more correct for this series. The informal chemical symbol Ln is used in general discussions of lanthanide chemistry to refer to any lanthanide. All but one of the lanthanides are f-block elements, corresponding to the filling of the 4f electron shell. Lutetium is a d-block element (thus also a transition metal), and on this basis its inclusion has been questioned; however, like its congeners scandium and yttrium in group 3, it behaves similarly to the other 14. The term rare-earth element or rare-earth metal is often used to include the stable group 3 elements Sc, Y, and Lu in addition to the 4f elements. All lanthanide elements form trivalent cations, Ln3+, whose chemistry is largely determined by the ionic radius, which decreases steadily from lanthanum (La) to lutetium (Lu). Several lanthanides can also form +2 and even +4 oxidation states.
In presentations of the periodic table, the f-block elements are customarily shown as two additional rows below the main body of the table. This convention is entirely a matter of aesthetics and formatting practicality; a rarely used wide-formatted periodic table inserts the 4f and 5f series in their proper places, as parts of the table's sixth and seventh rows (periods), respectively.
Etymology The term "lanthanide" was introduced by Victor Goldschmidt in 1925. Despite their abundance, the technical term "lanthanides" is interpreted to reflect a sense of elusiveness on the part of these elements, as it comes from the Greek λανθανειν (lanthanein), "to lie hidden". The word reflects their property of "hiding" behind each other in minerals. The term derives from lanthanum, first discovered in 1838, at that time a so-called new rare-earth element "lying hidden" or "escaping notice" in a cerium mineral, and it is an irony that lanthanum was later identified as the first in an entire series of chemically similar elements and gave its name to the whole series. These elements are called lanthanides because the elements in the series are chemically similar to lanthanum. Because "lanthanide" means "like lanthanum", it has been argued that lanthanum cannot logically be a lanthanide, but the International Union of Pure and Applied Chemistry (IUPAC) acknowledges its inclusion based on common usage. The current IUPAC recommendation is that the name lanthanoid be used rather than lanthanide, as the suffix "-ide" is preferred for negative ions, whereas the suffix "-oid" indicates similarity to one of the members of the containing family of elements. However, lanthanide is still commonly used.
Physical properties of the elements The properties of the lanthanides arise from the order in which the electron shells of these elements are filled—the outermost (6s) has the same configuration for all of them, and a deeper (4f) shell is progressively filled with electrons as the atomic number increases from 57 towards 71. For many years, mixtures of more than one rare earth were considered to be single elements, such as neodymium and praseodymium being thought to be the single element didymium. Very small differences in solubility are used in solvent and ion-exchange purification methods for these elements, which require repeated application to obtain a purified metal. The diverse applications of refined metals and their compounds can be attributed to the subtle and pronounced variations in their electronic, electrical, optical, and magnetic properties.
* Between initial Xe and final 6s2 electronic shells ** Sm has a close packed structure like most of the lanthanides but has an unusual 9 layer repeat Gschneider and Daane (1988) attribute the trend in melting point which increases across the series, (lanthanum (920 °C) – lutetium (1622 °C)) to the extent of hybridization of the 6s, 5d, and 4f orbitals. The hybridization is believed to be at its greatest for cerium, which has the lowest melting point of all, 795 °C. The lanthanide metals are soft; their hardness increases across the series. Europium stands out, as it has the lowest density in the series at 5.24 g/cm3 and the largest metallic radius in the series at 208.4 pm. It can be compared to barium, which has a metallic radius of 222 pm. It is believed that the metal contains the larger Eu2+ ion and that there are only two electrons in the conduction band. Ytterbium also has a large metallic radius, and a similar explanation is suggested. The resistivities of the lanthanide metals are relatively high, ranging from 29 to 134 μΩ·cm. These values can be compared to a good conductor such as aluminium, which has a resistivity of 2.655 μΩ·cm. With the exceptions of La, Yb, and Lu (which have no unpaired f electrons), the lanthanides are strongly paramagnetic, and this is reflected in their magnetic susceptibilities. Gadolinium becomes ferromagnetic at below 16 °C (Curie point). The other heavier lanthanides – terbium, dysprosium, holmium, erbium, thulium, and ytterbium – become ferromagnetic at much lower temperatures.
* Not including initial [Xe] core f → f transitions are symmetry forbidden (or Laporte-forbidden), which is also true of transition metals. However, transition metals are able to use vibronic coupling to break this rule. The valence orbitals in lanthanides are almost entirely non-bonding and as such little effective vibronic coupling takes, hence the spectra from f → f transitions are much weaker and narrower than those from d → d transitions. In general this makes the colors of lanthanide complexes far fainter than those of transition metal complexes.
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