D-block contraction

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Atomic radius of elements of the groups 2, 13 and 14, showing the "d-block contraction", especially for Ga and Ge D-block contraction--EN.png
Atomic radius of elements of the groups 2, 13 and 14, showing the "d-block contraction", especially for Ga and Ge

The d-block contraction (sometimes called scandide contraction [1] ) 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, germanium, arsenic, selenium, bromine, and krypton [ citation needed ]. 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.

ElementAtomic electron config.Sum 1st – 3rd I.Ps kJ/mol M3+ electron config.M3+ radius (pm)
Boron, B[ He ] 2s2 2p16887.4[ He ]
Aluminium, Al[ Ne ] 3s2 3p15139[ Ne ]53.5
Gallium, Ga[ Ar ] 3d10 4s2 4p15521.1[ Ar ] 3d1062
Indium, In[ Kr ] 4d10 5s2 5p15083[ Kr ] 4d1080
Thallium, Tl[ Xe ] 4f14 5d10 6s2 6p15438.4[ Xe ] 4f14 5d1088.5

Gallium can be seen to be anomalous. The most obvious effect is that the sum of the first three ionization potentials 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 electron core. In contrast to the group 13 elements, this sequence shows a smooth reduction.

ElementAtomic electron config.Sum 1st – 3rd I.Ps kJ/mol M3+ electron config.M3+ radius (pm)
Boron, B[ He ] 2s2 2p16887.4[ He ]
Aluminium, Al[ Ne ] 3s2 3p15139[ Ne ]53.5
Scandium, Sc[ Ar ] 3d1 4s24256.7[ Ar ]74.5
Yttrium, Y[ Kr ] 4d1 5s23760[ Kr ]90
Lanthanum, La[ Xe ] 5d1 6s23455.4[ Xe ]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, 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, which is caused by inadequate shielding of the nuclear charge by electrons occupying f orbitals.

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<span class="mw-page-title-main">Lawrencium</span> Chemical element, symbol Lr and atomic number 103

Lawrencium is a synthetic chemical element; it has symbol Lr and atomic number 103. It is named in honor of Ernest Lawrence, inventor of the cyclotron, a device that was used to discover many artificial radioactive elements. A radioactive metal, lawrencium is the eleventh transuranic element and the last member of the actinide series. Like all elements with atomic number over 100, lawrencium can only be produced in particle accelerators by bombarding lighter elements with charged particles. Fourteen isotopes of lawrencium are currently known; the most stable is 266Lr with half-life 11 hours, but the shorter-lived 260Lr is most commonly used in chemistry because it can be produced on a larger scale.

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<span class="mw-page-title-main">Periodic table</span> Tabular arrangement of the chemical elements ordered by atomic number

The periodic table, also known as the periodic table of the elements, arranges the chemical elements into rows ("periods") and columns ("groups"). It is an icon of chemistry and is widely used in physics and other sciences. It is a depiction of the periodic law, which says that when the elements are arranged in order of their atomic numbers an approximate recurrence of their properties is evident. The table is divided into four roughly rectangular areas called blocks. Elements in the same group tend to show similar chemical characteristics.

In chemistry, a transition metal is a chemical element in the d-block of the periodic table, though the elements of group 12 are sometimes excluded. The lanthanide and actinide elements are called inner transition metals and are sometimes considered to be transition metals as well.

<span class="mw-page-title-main">Atomic radius</span> Measure of the size of an atom

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 are various non-equivalent definitions of atomic radius. Four widely used definitions of atomic radius are: Van der Waals radius, ionic radius, metallic radius and covalent radius. Typically, because of the difficulty to isolate atoms in order to measure their radii separately, atomic radius is measured in a chemically bonded state; however theoretical calculations are simpler when considering atoms in isolation. The dependencies on environment, probe, and state lead to a multiplicity of definitions.

<span class="mw-page-title-main">Ionization energy</span> Energy needed to remove an electron

In physics and chemistry, ionization energy (IE) (American English spelling), ionisation energy (British English spelling) 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

<span class="mw-page-title-main">Electron configuration</span> Mode of arrangement of electrons in different shells of an atom

In atomic physics and quantum chemistry, the electron configuration is the distribution of electrons of an atom or molecule in atomic or molecular orbitals. For example, the electron configuration of the neon atom is 1s2 2s2 2p6, meaning that the 1s, 2s and 2p subshells are occupied by 2, 2 and 6 electrons respectively.

<span class="mw-page-title-main">Period (periodic table)</span> Method of visualizing the relationship between elements

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<span class="mw-page-title-main">Group 3 element</span> Group of chemical elements

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In chemistry, the shielding effect sometimes referred to as atomic shielding or electron shielding describes the attraction between an electron and the nucleus in any atom with more than one electron. The shielding effect can be defined as a reduction in the effective nuclear charge on the electron cloud, due to a difference in the attraction forces on the electrons in the atom. It is a special case of electric-field screening. This effect also has some significance in many projects in material sciences.

In atomic physics, the effective nuclear charge is the actual amount of positive (nuclear) charge experienced by an electron in a multi-electron atom. The term "effective" is used because the shielding effect of negatively charged electrons prevent higher energy electrons from experiencing the full nuclear charge of the nucleus due to the repelling effect of inner layer. The effective nuclear charge experienced by an electron is also called the core charge. It is possible to determine the strength of the nuclear charge by the oxidation number of the atom. Most of the physical and chemical properties of the elements can be explained on the basis of electronic configuration. Consider the behavior of ionization energies in the periodic table. It is known that the magnitude of ionization potential depends upon the following factors:

  1. Size of atom;
  2. The nuclear charge;
  3. The screening effect of the inner shells, and
  4. The extent to which the outermost electron penetrates into the charge cloud set up by the inner lying electron.
<span class="mw-page-title-main">Valence electron</span> An electron in the outer shell of an atoms energy levels

In chemistry and physics, valence electrons are electrons in the outermost shell of an atom, and that can participate in the formation of a chemical bond if the outermost shell is not closed. In a single covalent bond, a shared pair forms with both atoms in the bond each contributing one valence electron.

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 oxidation states that are two less than the group valency for the heavier elements of groups 13, 14, 15 and 16. The term "inert pair" was first proposed by Nevil Sidgwick in 1927. The name suggests that the outermost s electron pairs are more tightly bound to the nucleus in these atoms, and therefore more difficult to ionize or share.

<span class="mw-page-title-main">Aufbau principle</span> Principle of atomic physics

The Aufbau principle, also called the Aufbau rule, states that in the ground state of an atom or ion, electrons fill subshells of the lowest available energy, then they fill subshells of higher energy. For example, the 1s subshell is filled before the 2s subshell is occupied. In this way, the electrons of an atom or ion form the most stable electron configuration possible. An example is the configuration 1s2 2s2 2p6 3s2 3p3 for the phosphorus atom, meaning that the 1s subshell has 2 electrons, and so on.

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 along with the expected periodic trend of increasing electronegativity and nuclear charge on moving from left to right. About 10% of the lanthanide contraction has been attributed to relativistic effects.

Core electrons are the electrons in an atom that are not valence electrons and do not participate in chemical bonding. The nucleus and the core electrons of an atom form the atomic core. Core electrons are tightly bound to the nucleus. Therefore, unlike valence electrons, core electrons play a secondary role in chemical bonding and reactions by screening the positive charge of the atomic nucleus from the valence electrons.

<span class="mw-page-title-main">Periodic trends</span> Specific recurring patterns that are present in the modern periodic table

In chemistry, periodic trends are specific patterns that are present in the periodic table that illustrate different aspects of certain elements when grouped by period and/or group. They were discovered by the Russian chemist Dmitri Mendeleev in the year 1863. Major periodic trends include atomic radius, ionization energy, electron affinity, electronegativity, valency and metallic character. These trends exist because of the similar electron configurations of the elements within their respective groups or periods; they reflect the periodic nature of the elements. These trends give a qualitative assessment of the properties of each element.

A block of the periodic table is a set of elements unified by the atomic orbitals their valence electrons or vacancies lie in. The term seems to have been first used by Charles Janet. Each block is named after its characteristic orbital: s-block, p-block, d-block, f-block and g-block.

<span class="mw-page-title-main">Kainosymmetry</span>

Kainosymmetry describes the first atomic orbital of each azimuthal quantum number (ℓ). Such orbitals include 1s, 2p, 3d, 4f, 5g, and so on. The term kainosymmetric was coined by Sergey Shchukarev. Pekka Pyykkö referred to such orbitals as primogenic instead. Such orbitals are much smaller than all other orbitals with the same ℓ and have no radial nodes, giving the elements that fill them special properties. They are usually less metallic than their heavier homologues, prefer lower oxidation states, and have smaller atomic and ionic radii.

References

  1. "Lanthanide Contraction- D Block Contraction (Scandide Contraction)". chem.libretexts.org. Chemistry Libretexts. August 22, 2020. Retrieved December 6, 2020. The d block contraction, also known as the Scandide Contraction, describes the atomic radius trend that the d block elements (Transition metals) experience.