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 4 elements. The elements in question are

gallium Gallium is a chemical element; it has Chemical symbol, symbol Ga and atomic number 31. Discovered by the French chemist Paul-Émile Lecoq de Boisbaudran in 1875, elemental gallium is a soft, silvery metal at standard temperature and pressure. ...

germanium Germanium is a chemical element; it has Symbol (chemistry), symbol Ge and atomic number 32. It is lustrous, hard-brittle, grayish-white and similar in appearance to silicon. It is a metalloid or a nonmetal in the carbon group that is chemically ...

arsenic Arsenic is a chemical element; it has Symbol (chemistry), symbol As and atomic number 33. It is a metalloid and one of the pnictogens, and therefore shares many properties with its group 15 neighbors phosphorus and antimony. Arsenic is not ...

selenium Selenium is a chemical element; it has symbol (chemistry), symbol Se and atomic number 34. It has various physical appearances, including a brick-red powder, a vitreous black solid, and a grey metallic-looking form. It seldom occurs in this elem ...

bromine Bromine is a chemical element; it has chemical symbol, symbol Br and atomic number 35. It is a volatile red-brown liquid at room temperature that evaporates readily to form a similarly coloured vapour. Its properties are intermediate between th ...

, and

krypton Krypton (from 'the hidden one') is a chemical element; it has symbol (chemistry), symbol Kr and atomic number 36. It is a colorless, odorless noble gas that occurs in trace element, trace amounts in the Earth's atmosphere, 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 In physics and chemistry, ionization energy (IE) is the minimum energy required to remove the most loosely bound electron of an isolated gaseous atom, positive ion, or molecule. The first ionization energy is quantitatively expressed as :X(g) ...

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 the inert gases, sometimes referred to as aerogens) are the members of Group (periodic table), group 18 of the periodic table: helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), radon (Rn) and, in some ...

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; it has Symbol (chemistry), symbol In and atomic number 49. It is a silvery-white post-transition metal and one of the softest elements. Chemically, indium is similar to gallium and thallium, and its properties are la ...

and

thallium Thallium is a chemical element; it has Symbol (chemistry), symbol Tl and atomic number 81. It is a silvery-white post-transition metal that is not found free in nature. When isolated, thallium resembles tin, but discolors when exposed to air. Che ...

, since other effects, e.g. the inert-pair effect, 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 and ionic radii of the elements in the lanthanide series, from left to right. It is caused by the poor shielding effect of nuclear charge by the 4f electrons alo ...

, 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