D-block contraction
Encyclopedia
d-block 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 the Ga
, Ge
, As
, Se
and Br
. Their electronic configurations include completely filled d orbitals (d10). 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
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
, La
. Sc
, Y
, La
are group 3 elements and have three valence electrons above a noble gas
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 and thallium, 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
which is caused by inadequate shielding of nuclear charge by electrons occupying f orbitals.
Period 4 element
A period 4 element is one of the chemical elements in the fourth row of the periodic table of the elements. The periodic table is laid out in rows to illustrate recurring trends in the chemical behaviour of the elements as their atomic number increases: a new row is begun when chemical behaviour...
4 elements. The elements in question are the Ga
Gallium
Gallium is a chemical element that has the symbol Ga and atomic number 31. Elemental gallium does not occur in nature, but as the gallium salt in trace amounts in bauxite and zinc ores. A soft silvery metallic poor metal, elemental gallium is a brittle solid at low temperatures. As it liquefies...
, Ge
Germanium
Germanium is a chemical element with the symbol Ge and atomic number 32. It is a lustrous, hard, grayish-white metalloid in the carbon group, chemically similar to its group neighbors tin and silicon. The isolated element is a semiconductor, with an appearance most similar to elemental silicon....
, As
Arsenic
Arsenic is a chemical element with the symbol As, atomic number 33 and relative atomic mass 74.92. Arsenic occurs in many minerals, usually in conjunction with sulfur and metals, and also as a pure elemental crystal. It was first documented by Albertus Magnus in 1250.Arsenic is a metalloid...
, Se
Selenium
Selenium is a chemical element with atomic number 34, chemical symbol Se, and an atomic mass of 78.96. It is a nonmetal, whose properties are intermediate between those of adjacent chalcogen elements sulfur and tellurium...
and Br
Bromine
Bromine ") is a chemical element with the symbol Br, an atomic number of 35, and an atomic mass of 79.904. It is in the halogen element group. The element was isolated independently by two chemists, Carl Jacob Löwig and Antoine Jerome Balard, in 1825–1826...
. Their electronic configurations include completely filled d orbitals (d10). d-block contraction is best illustrated by comparing some properties of the group 13 elements to highlight the effect on gallium.
| Element | Atomic electron config. | Sum 1st - 3d I.P Ionization potential The ionization energy of a chemical species, i.e. an atom or molecule, is the energy required to remove an electron from the species to a practically infinite distance. Large atoms or molecules have a low ionization energy, while small molecules tend to have higher ionization energies.The property... s kJ Joule The joule ; symbol J) is a derived unit of energy or work in the International System of Units. It is equal to the energy expended in applying a force of one newton through a distance of one metre , or in passing an electric current of one ampere through a resistance of one ohm for one second... /mol Mole (unit) The mole is a unit of measurement used in chemistry to express amounts of a chemical substance, defined as an amount of a substance that contains as many elementary entities as there are atoms in 12 grams of pure carbon-12 , the isotope of carbon with atomic weight 12. This corresponds to a value... | M3+ electron config. | M3+ radius (pm) |
|---|---|---|---|---|
| Boron Boron Boron is the chemical element with atomic number 5 and the chemical symbol B. Boron is a metalloid. Because boron is not produced by stellar nucleosynthesis, it is a low-abundance element in both the solar system and the Earth's crust. However, boron is concentrated on Earth by the... , B |
{He Helium Helium is the chemical element with atomic number 2 and an atomic weight of 4.002602, which is represented by the symbol He. It is a colorless, odorless, tasteless, non-toxic, inert, monatomic gas that heads the noble gas group in the periodic table... }2s22p1 |
6887.4 | {He Helium Helium is the chemical element with atomic number 2 and an atomic weight of 4.002602, which is represented by the symbol He. It is a colorless, odorless, tasteless, non-toxic, inert, monatomic gas that heads the noble gas group in the periodic table... } |
|
| Aluminium Aluminium Aluminium or aluminum is a silvery white member of the boron group of chemical elements. It has the symbol Al, and its atomic number is 13. It is not soluble in water under normal circumstances.... , Al |
{Ne Neon Neon is the chemical element that has the symbol Ne and an atomic number of 10. Although a very common element in the universe, it is rare on Earth. A colorless, inert noble gas under standard conditions, neon gives a distinct reddish-orange glow when used in either low-voltage neon glow lamps or... }3s23p1 |
5139 | {Ne Neon Neon is the chemical element that has the symbol Ne and an atomic number of 10. Although a very common element in the universe, it is rare on Earth. A colorless, inert noble gas under standard conditions, neon gives a distinct reddish-orange glow when used in either low-voltage neon glow lamps or... } |
53.5 |
| Gallium Gallium Gallium is a chemical element that has the symbol Ga and atomic number 31. Elemental gallium does not occur in nature, but as the gallium salt in trace amounts in bauxite and zinc ores. A soft silvery metallic poor metal, elemental gallium is a brittle solid at low temperatures. As it liquefies... , Ga |
{Ar Argon Argon is a chemical element represented by the symbol Ar. Argon has atomic number 18 and is the third element in group 18 of the periodic table . Argon is the third most common gas in the Earth's atmosphere, at 0.93%, making it more common than carbon dioxide... }3d104s24p1 |
5521.1 | {Ar Argon Argon is a chemical element represented by the symbol Ar. Argon has atomic number 18 and is the third element in group 18 of the periodic table . Argon is the third most common gas in the Earth's atmosphere, at 0.93%, making it more common than carbon dioxide... }3d10 |
62 |
| Indium Indium Indium is a chemical element with the symbol In and atomic number 49. This rare, very soft, malleable and easily fusible post-transition metal is chemically similar to gallium and thallium, and shows the intermediate properties between these two... , In |
{Kr Krypton Krypton is a chemical element with the symbol Kr and atomic number 36. It is a member of Group 18 and Period 4 elements. A colorless, odorless, tasteless noble gas, krypton occurs in trace amounts in the atmosphere, is isolated by fractionally distilling liquified air, and is often used with other... }4d105s25p1 |
5083 | {Kr Krypton Krypton is a chemical element with the symbol Kr and atomic number 36. It is a member of Group 18 and Period 4 elements. A colorless, odorless, tasteless noble gas, krypton occurs in trace amounts in the atmosphere, is isolated by fractionally distilling liquified air, and is often used with other... } 4d10 |
80 |
| Thallium Thallium Thallium is a chemical element with the symbol Tl and atomic number 81. This soft gray poor metal resembles tin but discolors when exposed to air. The two chemists William Crookes and Claude-Auguste Lamy discovered thallium independently in 1861 by the newly developed method of flame spectroscopy... , Tl |
{Xe Xenon Xenon is a chemical element with the symbol Xe and atomic number 54. The element name is pronounced or . A colorless, heavy, odorless noble gas, xenon occurs in the Earth's atmosphere in trace amounts... }4f145d106s26p1 |
5438.4 | {Xe Xenon Xenon is a chemical element with the symbol Xe and atomic number 54. The element name is pronounced or . A colorless, heavy, odorless noble gas, xenon occurs in the Earth's atmosphere in trace amounts... }5d10 |
88.5 |
Gallium can be seen to be anomalous. The most obvious effect is that the sum of the first three ionization potential
Ionization potential
The ionization energy of a chemical species, i.e. an atom or molecule, is the energy required to remove an electron from the species to a practically infinite distance. Large atoms or molecules have a low ionization energy, while small molecules tend to have higher ionization energies.The property...
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
Boron
Boron is the chemical element with atomic number 5 and the chemical symbol B. Boron is a metalloid. Because boron is not produced by stellar nucleosynthesis, it is a low-abundance element in both the solar system and the Earth's crust. However, boron is concentrated on Earth by the...
, Al
Aluminium
Aluminium or aluminum is a silvery white member of the boron group of chemical elements. It has the symbol Al, and its atomic number is 13. It is not soluble in water under normal circumstances....
, Sc
Scandium
Scandium is a chemical element with symbol Sc and atomic number 21. A silvery-white metallic transition metal, it has historically been sometimes classified as a rare earth element, together with yttrium and the lanthanoids...
, Y
Yttrium
Yttrium is a chemical element with symbol Y and atomic number 39. It is a silvery-metallic transition metal chemically similar to the lanthanides and it has often been classified as a "rare earth element". Yttrium is almost always found combined with the lanthanides in rare earth minerals and is...
, La
Lanthanum
Lanthanum is a chemical element with the symbol La and atomic number 57.Lanthanum is a silvery white metallic element that belongs to group 3 of the periodic table and is the first element of the lanthanide series. It is found in some rare-earth minerals, usually in combination with cerium and...
. Sc
Scandium
Scandium is a chemical element with symbol Sc and atomic number 21. A silvery-white metallic transition metal, it has historically been sometimes classified as a rare earth element, together with yttrium and the lanthanoids...
, Y
Yttrium
Yttrium is a chemical element with symbol Y and atomic number 39. It is a silvery-metallic transition metal chemically similar to the lanthanides and it has often been classified as a "rare earth element". Yttrium is almost always found combined with the lanthanides in rare earth minerals and is...
, La
Lanthanum
Lanthanum is a chemical element with the symbol La and atomic number 57.Lanthanum is a silvery white metallic element that belongs to group 3 of the periodic table and is the first element of the lanthanide series. It is found in some rare-earth minerals, usually in combination with cerium and...
are group 3 elements and have three valence electrons above a noble gas
Noble gas
The noble gases are a group of chemical elements with very similar properties: under standard conditions, they are all odorless, colorless, monatomic gases, with very low chemical reactivity...
electron core. In contrast to the group 13 elements this sequence shows a smooth reduction.
| Element | Atomic electron config. | Sum 1st - 3d I.P Ionization potential The ionization energy of a chemical species, i.e. an atom or molecule, is the energy required to remove an electron from the species to a practically infinite distance. Large atoms or molecules have a low ionization energy, while small molecules tend to have higher ionization energies.The property... s kJ Joule The joule ; symbol J) is a derived unit of energy or work in the International System of Units. It is equal to the energy expended in applying a force of one newton through a distance of one metre , or in passing an electric current of one ampere through a resistance of one ohm for one second... /mol Mole (unit) The mole is a unit of measurement used in chemistry to express amounts of a chemical substance, defined as an amount of a substance that contains as many elementary entities as there are atoms in 12 grams of pure carbon-12 , the isotope of carbon with atomic weight 12. This corresponds to a value... | M3+ electron config. | M3+ radius (pm) |
|---|---|---|---|---|
| Boron Boron Boron is the chemical element with atomic number 5 and the chemical symbol B. Boron is a metalloid. Because boron is not produced by stellar nucleosynthesis, it is a low-abundance element in both the solar system and the Earth's crust. However, boron is concentrated on Earth by the... , B |
{He Helium Helium is the chemical element with atomic number 2 and an atomic weight of 4.002602, which is represented by the symbol He. It is a colorless, odorless, tasteless, non-toxic, inert, monatomic gas that heads the noble gas group in the periodic table... }2s22p1 |
6887.4 | {He Helium Helium is the chemical element with atomic number 2 and an atomic weight of 4.002602, which is represented by the symbol He. It is a colorless, odorless, tasteless, non-toxic, inert, monatomic gas that heads the noble gas group in the periodic table... } |
|
| Aluminium Aluminium Aluminium or aluminum is a silvery white member of the boron group of chemical elements. It has the symbol Al, and its atomic number is 13. It is not soluble in water under normal circumstances.... , Al |
{Ne Neon Neon is the chemical element that has the symbol Ne and an atomic number of 10. Although a very common element in the universe, it is rare on Earth. A colorless, inert noble gas under standard conditions, neon gives a distinct reddish-orange glow when used in either low-voltage neon glow lamps or... }3s23p1 |
5139 | {Ne Neon Neon is the chemical element that has the symbol Ne and an atomic number of 10. Although a very common element in the universe, it is rare on Earth. A colorless, inert noble gas under standard conditions, neon gives a distinct reddish-orange glow when used in either low-voltage neon glow lamps or... } |
53.5 |
| Scandium Scandium Scandium is a chemical element with symbol Sc and atomic number 21. A silvery-white metallic transition metal, it has historically been sometimes classified as a rare earth element, together with yttrium and the lanthanoids... , Sc |
{Ar Argon Argon is a chemical element represented by the symbol Ar. Argon has atomic number 18 and is the third element in group 18 of the periodic table . Argon is the third most common gas in the Earth's atmosphere, at 0.93%, making it more common than carbon dioxide... }3d14s2 |
4256.7 | {Ar Argon Argon is a chemical element represented by the symbol Ar. Argon has atomic number 18 and is the third element in group 18 of the periodic table . Argon is the third most common gas in the Earth's atmosphere, at 0.93%, making it more common than carbon dioxide... } |
74.5 |
| Yttrium Yttrium Yttrium is a chemical element with symbol Y and atomic number 39. It is a silvery-metallic transition metal chemically similar to the lanthanides and it has often been classified as a "rare earth element". Yttrium is almost always found combined with the lanthanides in rare earth minerals and is... , Y |
{Kr Krypton Krypton is a chemical element with the symbol Kr and atomic number 36. It is a member of Group 18 and Period 4 elements. A colorless, odorless, tasteless noble gas, krypton occurs in trace amounts in the atmosphere, is isolated by fractionally distilling liquified air, and is often used with other... }4d15s2 |
3760 | {Kr Krypton Krypton is a chemical element with the symbol Kr and atomic number 36. It is a member of Group 18 and Period 4 elements. A colorless, odorless, tasteless noble gas, krypton occurs in trace amounts in the atmosphere, is isolated by fractionally distilling liquified air, and is often used with other... } |
90 |
| Lanthanum Lanthanum Lanthanum is a chemical element with the symbol La and atomic number 57.Lanthanum is a silvery white metallic element that belongs to group 3 of the periodic table and is the first element of the lanthanide series. It is found in some rare-earth minerals, usually in combination with cerium and... , La |
{Xe Xenon Xenon is a chemical element with the symbol Xe and atomic number 54. The element name is pronounced or . A colorless, heavy, odorless noble gas, xenon occurs in the Earth's atmosphere in trace amounts... }5d16s2 |
3455.4 | {Xe Xenon Xenon is a chemical element with the symbol Xe and atomic number 54. The element name is pronounced or . A colorless, heavy, odorless noble gas, xenon occurs in the Earth's atmosphere in trace amounts... } |
103.2 |
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 and thallium, other effects e.g. the inert pair effect
Inert pair effect
The inert pair effect is the tendency of the outermost s electrons to remain nonionized or unshared in compounds of post-transition metals. The term inert pair effect is often used in relation to the increasing stability of oxidation states that are 2 less than the group valency for the heavier...
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
Lanthanide contraction
Lanthanide contraction is a term used in chemistry to describe the decrease in ionic radii of the elements in the lanthanide series from atomic number 58, Cerium to 71, Lutetium, which results in smaller than otherwise expected ionic radii for the subsequent elements starting with 72, Hafnium...
which is caused by inadequate shielding of nuclear charge by electrons occupying f orbitals.