The lanthanide contraction is the greater-than-expected decrease in

atomic radii 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 ...

ionic radii Ionic radius, ''r''ion, is the radius of a monatomic ion in an ionic crystal structure. Although neither atoms nor ions have sharp boundaries, they are treated as if they were hard spheres with radii such that the sum of ionic radii of the cation ...

of the elements in the

lanthanide The lanthanide () or lanthanoid () series of chemical elements comprises the 15 metallic chemical elements with atomic numbers 57–71, from lanthanum through lutetium. These elements, along with the chemically similar elements scandium and yt ...

series from

atomic number The atomic number or nuclear charge number (symbol ''Z'') of a chemical element is the charge number of an atomic nucleus. For ordinary nuclei, this is equal to the proton number (''n''p) or the number of protons found in the nucleus of ever ...

57,

lanthanum Lanthanum is a chemical element with the symbol La and atomic number 57. It is a soft, ductile, silvery-white metal that tarnishes slowly when exposed to air. It is the eponym of the lanthanide series, a group of 15 similar elements between l ...

, to 71, lutetium, which results in smaller than otherwise expected

/ionic radii for the subsequent elements starting with 72,

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 many zirconium minerals. Its existence was predicted by Dmitri M ...

. Jolly, William L. ''Modern Inorganic Chemistry'', McGraw-Hill 1984, p. 22 The term was coined by the Norwegian geochemist

Victor Goldschmidt Victor Moritz Goldschmidt (27 January 1888 in Zürich – 20 March 1947 in Oslo) was a Norwegian mineralogist considered (together with Vladimir Vernadsky) to be the founder of modern geochemistry and crystal chemistry, developer of the Golds ...

in his series "Geochemische Verteilungsgesetze der Elemente" (Geochemical distribution laws of the elements). Goldschmidt, Victor M. "Geochemische Verteilungsgesetze der Elemente", Part V "Isomorphie und Polymorphie der Sesquioxyde. Die Lanthaniden-Kontraktion und ihre Konsequenzen", Oslo, 1925

Cause

The effect results from poor shielding of nuclear charge (nuclear attractive force on electrons) by 4f electrons; the 6s electrons are drawn towards the nucleus, thus resulting in a smaller atomic radius. In single-electron atoms, the average separation of an electron from the nucleus is determined by the subshell it belongs to, and decreases with increasing charge on the nucleus; this, in turn, leads to a decrease in

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 ...

. In multi-electron atoms, the decrease in radius brought about by an increase in nuclear charge is partially offset by increasing electrostatic repulsion among electrons. In particular, a " shielding effect" operates: i.e., as electrons are added in outer shells, electrons already present shield the outer electrons from nuclear charge, making them experience a lower effective charge on the nucleus. The shielding effect exerted by the inner electrons decreases in the order ''s'' > ''p'' > ''d'' > ''f''. Usually, as a particular subshell is filled in a period, the atomic radius decreases. This effect is particularly pronounced in the case of lanthanides, as the 4''f'' subshell which is filled across these elements is not very effective at shielding the outer shell (n=5 and n=6) electrons. Thus the shielding effect is less able to counter the decrease in radius caused by increasing nuclear charge. This leads to "lanthanide contraction". The ionic radius drops from 103 pm for lanthanum(III) to 86.1 pm for lutetium(III). About 10% of the lanthanide contraction has been attributed to relativistic effects.

Effects

The results of the increased attraction of the outer shell electrons across the lanthanide period may be divided into effects on the lanthanide series itself including the decrease in ionic radii, and influences on the following or post-lanthanide elements.

Properties of the lanthanides

The

of the lanthanides decrease from 103 pm ( La³⁺) to 86 pm ( Lu³⁺) in the lanthanide series, as electrons are added to the 4f shell. This first f shell is inside the full 5s and 5p shells (as well as the 6s shell in the neutral atom); the 4f shell is well-localized near the atomic nucleus and has little effect on chemical bonding. The decrease in atomic and ionic radii does affect their chemistry, however. Without the lanthanide contraction, a chemical separation of lanthanides would be extremely difficult. However, this contraction makes the chemical separation of period 5 and period 6 transition metals of the same group rather difficult. There is a general trend of increasing

Vickers hardness The Vickers hardness test was developed in 1921 by Robert L. Smith and George E. Sandland at Vickers Ltd as an alternative to the Brinell method to measure the hardness of materials. The Vickers test is often easier to use than other hardness ...

, Brinell hardness,

density Density (volumetric mass density or specific mass) is the substance's mass per unit of volume. The symbol most often used for density is ''ρ'' (the lower case Greek letter rho), although the Latin letter ''D'' can also be used. Mathematicall ...

and

melting point The melting point (or, rarely, liquefaction point) of a substance is the temperature at which it changes state from solid to liquid. At the melting point the solid and liquid phase exist in equilibrium. The melting point of a substance depen ...

from

to lutetium (with

europium Europium is a chemical element with the symbol Eu and atomic number 63. Europium is the most reactive lanthanide by far, having to be stored under an inert fluid to protect it from atmospheric oxygen or moisture. Europium is also the softest lan ...

and ytterbium being the most notable exceptions; in the metallic state, they are divalent rather than trivalent). Lutetium is the hardest and densest lanthanide and has the highest melting point.

Influence on the post-lanthanides

The elements following the lanthanides in the periodic table are influenced by the lanthanide contraction. The radii of the period-6 transition metals are smaller than would be expected if there were no lanthanides, and are in fact very similar to the radii of the period-5 transition metals since the effect of the additional electron shell is almost entirely offset by the lanthanide contraction. For example, the atomic radius of the metal

zirconium Zirconium is a chemical element with the symbol Zr and atomic number 40. The name ''zirconium'' is taken from the name of the mineral zircon, the most important source of zirconium. The word is related to Persian '' zargun'' (zircon; ''zar-gun'' ...

, Zr (a period-5 transition element), is 155 pm ( empirical value) and that of

, Hf (the corresponding period-6 element), is 159 pm. The ionic radius of Zr⁴⁺ is 84 pm and that of Hf⁴⁺ is 83 pm. The radii are very similar even though the number of electrons increases from 40 to 72 and the

atomic mass The atomic mass (''m''a or ''m'') is the mass of an atom. Although the SI unit of mass is the kilogram (symbol: kg), atomic mass is often expressed in the non-SI unit dalton (symbol: Da) – equivalently, unified atomic mass unit (u). 1&n ...

increases from 91.22 to 178.49 g/mol. The increase in mass and the unchanged radii lead to a steep increase in

from 6.51 to 13.35 g/cm³. Zirconium and hafnium, therefore, have very similar chemical behavior, having closely similar radii and electron configurations. Radius-dependent properties such as lattice energies, solvation energies, and stability constants of complexes are also similar. Because of this similarity, hafnium is found only in association with zirconium, which is much more abundant. This also meant that hafnium was discovered as a separate element in 1923, 134 years after zirconium was discovered in 1789.

Titanium Titanium is a chemical element with the symbol Ti and atomic number 22. Found in nature only as an oxide, it can be reduced to produce a lustrous transition metal with a silver color, low density, and high strength, resistant to corrosion i ...

, on the other hand, is in the same group, but differs enough from those two metals that it is seldom found with them.

References

External links