The d-block contraction (sometimes called scandide contraction) is a term used in chemistry to describe the effect of having full d orbitals on the

period Period may refer to: Common uses * Era, a length or span of time * Full stop (or period), a punctuation mark Arts, entertainment, and media * Period (music), a concept in musical composition * Periodic sentence (or rhetorical period), a concept ...

4 elements. The elements in question are

gallium Gallium is a chemical element with the Symbol (chemistry), symbol Ga and atomic number 31. Discovered by France, French chemist Paul-Émile Lecoq de Boisbaudran in 1875, Gallium is in boron group, group 13 of the periodic table and is similar to ...

germanium Germanium is a chemical element with the symbol Ge and atomic number 32. It is lustrous, hard-brittle, grayish-white and similar in appearance to silicon. It is a metalloid in the carbon group that is chemically similar to its group neighbors ...

arsenic Arsenic is a chemical element with the symbol As and atomic number 33. Arsenic occurs in many minerals, usually in combination with sulfur and metals, but also as a pure elemental crystal. Arsenic is a metalloid. It has various allotropes, b ...

selenium Selenium is a chemical element with the symbol Se and atomic number 34. It is a nonmetal (more rarely considered a metalloid) with properties that are intermediate between the elements above and below in the periodic table, sulfur and tellurium, ...

bromine Bromine is a chemical element with the symbol Br and atomic number 35. It is the third-lightest element in group 17 of the periodic table ( halogens) and is a volatile red-brown liquid at room temperature that evaporates readily to form a simi ...

, and

krypton Krypton (from grc, κρυπτός, translit=kryptos 'the hidden one') is a chemical element with the symbol Kr and atomic number 36. It is a colorless, odorless, tasteless noble gas that occurs in trace amounts in the atmosphere and is of ...

. Their electronic configurations include completely filled d orbitals (d¹⁰). The d-block contraction is best illustrated by comparing some properties of the group 13 elements to highlight the effect on gallium. Gallium can be seen to be anomalous. The most obvious effect is that the sum of the first three

ionization potential Ionization, or Ionisation is the process by which an atom or a molecule acquires a negative or positive charge by gaining or losing electrons, often in conjunction with other chemical changes. The resulting electrically charged atom or molecule ...

s of gallium is higher than that of aluminium, whereas the trend in the group would be for it to be lower. The second table below shows the trend in the sum of the first three ionization potentials for the elements B, Al, Sc, Y, and La. Sc, Y, and La have three valence electrons above a

noble gas The noble gases (historically also the inert gases; sometimes referred to as aerogens) make up a class of chemical elements with similar properties; under standard conditions, they are all odorless, colorless, monatomic gases with very low ch ...

electron core. In contrast to the group 13 elements, this sequence shows a smooth reduction. Other effects of the d-block contraction are that the Ga³⁺ ion is smaller than expected, being closer in size to Al³⁺. Care must be taken in interpreting the ionization potentials for

indium Indium is a chemical element with the symbol In and atomic number 49. Indium is the softest metal that is not an alkali metal. It is a silvery-white metal that resembles tin in appearance. It is a post-transition metal that makes up 0.21 parts ...

and

thallium Thallium is a chemical element with the symbol Tl and atomic number 81. It is a gray post-transition metal that is not found free in nature. When isolated, thallium resembles tin, but discolors when exposed to air. Chemists William Crookes an ...

, since other effects, e.g. the

inert pair effect The inert-pair effect is the tendency of the two electrons in the outermost atomic ''s''-orbital to remain unshared in compounds of post-transition metals. The term ''inert-pair effect'' is often used in relation to the increasing stability of ox ...

, become increasingly important for the heavier members of the group.
The cause of the d-block contraction is the poor shielding of the nuclear charge by the electrons in the d orbitals. The outer valence electrons are more strongly attracted by the nucleus causing the observed increase in ionization potentials. The d-block contraction can be compared to the

lanthanide contraction The lanthanide contraction is the greater-than-expected decrease in atomic radii/ionic radii of the elements in the lanthanide series from atomic number 57, lanthanum, to 71, lutetium, which results in smaller than otherwise expected atomic radii ...

, which is caused by inadequate shielding of the nuclear charge by electrons occupying f orbitals.

References

*{{Greenwood&Earnshaw Chemical bonding Atomic radius

See also

References