Diagonal relationship

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Pictorial representation of examples of diagonal relationship. DiagonalRelation.png
Pictorial representation of examples of diagonal relationship.

In chemistry, a diagonal relationship is said to exist between certain pairs of diagonally adjacent elements in the second and third periods (first 20 elements) of the periodic table. These pairs (lithium (Li) and magnesium (Mg), beryllium (Be) and aluminium (Al), boron (B) and silicon (Si), etc.) exhibit similar properties; for example, boron and silicon are both semiconductors, forming halides that are hydrolysed in water and have acidic oxides.

Further diagonal similarities have also been suggested for carbon-phosphorus and nitrogen-sulfur, along with extending the Li-Mg and Be-Al relationships down into the transition elements (such as scandium). [1]

The organization of elements on the periodic table into horizontal rows and vertical columns makes certain relationships more apparent (periodic law). Moving rightward and descending the periodic table have opposite effects on atomic radii of isolated atoms. Moving rightward across the period decreases the atomic radii of atoms, while moving down the group will increase the atomic radii. [2]

Similarly, on moving rightward a period, the elements become progressively more covalent [ clarification needed ], less basic and more electronegative, whereas on moving down a group the elements become more ionic, more basic and less electronegative. Thus, on both descending a period and crossing a group by one element, the changes "cancel" each other out, and elements with similar properties which have similar chemistry are often found – the atomic radius, electronegativity, properties of compounds (and so forth) of the diagonal members are similar.

The reasons for the existence of diagonal relationships are not fully understood, but charge density is a factor. For example, Li+ is a small cation with a +1 charge and Mg2+ is somewhat larger with a +2 charge, so the ionic potential of each of the two ions is roughly the same. It was revealed by an examination that the charge density of lithium is much closer to that of magnesium than to those of the other alkali metals. [3] Using the Li–Mg pair (under room temperature and pressure):

  1. When combined with oxygen under standard conditions, Li and Mg form only normal oxides whereas Na forms peroxide and metals below Na, in addition, form superoxides.
  2. Li is the only group 1 element which forms a stable nitride, Li3N. [4] Mg, as well as other group 2 elements, also form nitrides. [4]
  3. Lithium carbonate, phosphate and fluoride are sparingly soluble in water. The corresponding group 2 salts are insoluble. (Think lattice and solvation energies).
  4. Both Li and Mg form covalent organometallic compounds. LiMe and MgMe2 (cf. Grignard reagents) are both valuable synthetic reagents. The other group 1 and group 2 analogues are ionic and extremely reactive (and hence difficult to manipulate). [5]
  5. Chlorides of both Li and Mg are deliquescent (absorb moisture from surroundings) and soluble in alcohol and pyridine. Lithium chloride, like magnesium chloride (MgCl2·6H2O) separates out from hydrated crystal LiCl·2H2O.
  6. Lithium carbonate and magnesium carbonate are both unstable and can produce corresponding oxides and carbon dioxide when they are heated.

Related Research Articles

<span class="mw-page-title-main">Alkali metal</span> Group of highly reactive chemical elements

The alkali metals consist of the chemical elements lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), and francium (Fr). Together with hydrogen they constitute group 1, which lies in the s-block of the periodic table. All alkali metals have their outermost electron in an s-orbital: this shared electron configuration results in their having very similar characteristic properties. Indeed, the alkali metals provide the best example of group trends in properties in the periodic table, with elements exhibiting well-characterised homologous behaviour. This family of elements is also known as the lithium family after its leading element.

Electronegativity, symbolized as χ, is the tendency for an atom of a given chemical element to attract shared electrons when forming a chemical bond. An atom's electronegativity is affected by both its atomic number and the distance at which its valence electrons reside from the charged nucleus. The higher the associated electronegativity, the more an atom or a substituent group attracts electrons. Electronegativity serves as a simple way to quantitatively estimate the bond energy, and the sign and magnitude of a bond's chemical polarity, which characterizes a bond along the continuous scale from covalent to ionic bonding. The loosely defined term electropositivity is the opposite of electronegativity: it characterizes an element's tendency to donate valence electrons.

<span class="mw-page-title-main">Ionic bonding</span> Chemical bonding involving attraction between ions

Ionic bonding is a type of chemical bonding that involves the electrostatic attraction between oppositely charged ions, or between two atoms with sharply different electronegativities, and is the primary interaction occurring in ionic compounds. It is one of the main types of bonding, along with covalent bonding and metallic bonding. Ions are atoms with an electrostatic charge. Atoms that gain electrons make negatively charged ions. Atoms that lose electrons make positively charged ions. This transfer of electrons is known as electrovalence in contrast to covalence. In the simplest case, the cation is a metal atom and the anion is a nonmetal atom, but these ions can be more complex, e.g. molecular ions like NH+
4
or SO2−
4
. In simpler words, an ionic bond results from the transfer of electrons from a metal to a non-metal to obtain a full valence shell for both atoms.

Carbon compounds are defined as chemical substances containing carbon. More compounds of carbon exist than any other chemical element except for hydrogen. Organic carbon compounds are far more numerous than inorganic carbon compounds. In general bonds of carbon with other elements are covalent bonds. Carbon is tetravalent but carbon free radicals and carbenes occur as short-lived intermediates. Ions of carbon are carbocations and carbanions are also short-lived. An important carbon property is catenation as the ability to form long carbon chains and rings.

<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, is an ordered arrangement of 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 states 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.

<span class="mw-page-title-main">Alkaline earth metal</span> Group of chemical elements

The alkaline earth metals are six chemical elements in group 2 of the periodic table. They are beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), and radium (Ra). The elements have very similar properties: they are all shiny, silvery-white, somewhat reactive metals at standard temperature and pressure.

<span class="mw-page-title-main">Nonmetal</span> Category of chemical elements

In the context of the periodic table a nonmetal is a chemical element that mostly lacks distinctive metallic properties. They range from colorless gases like hydrogen to shiny crystals like iodine. Physically, they are usually lighter than elements that form metals and are often poor conductors of heat and electricity. Chemically, nonmetals have relatively high electronegativity or usually attract electrons in a chemical bond with another element, and their oxides tend to be acidic.

<span class="mw-page-title-main">Hydride</span> Molecule with a hydrogen bound to a more electropositive element or group

In chemistry, a hydride is formally the anion of hydrogen (H), a hydrogen atom with two electrons. The term is applied loosely. At one extreme, all compounds containing covalently bound H atoms are also called hydrides: water (H2O) is a hydride of oxygen, ammonia is a hydride of nitrogen, etc. For inorganic chemists, hydrides refer to compounds and ions in which hydrogen is covalently attached to a less electronegative element. In such cases, the H centre has nucleophilic character, which contrasts with the protic character of acids. The hydride anion is very rarely observed.

A period 2 element is one of the chemical elements in the second row of the periodic table of the chemical elements. The periodic table is laid out in rows to illustrate recurring (periodic) trends in the chemical behavior of the elements as their atomic number increases; a new row is started when chemical behavior begins to repeat, creating columns of elements with similar properties.

Chemistry is the physical science concerned with the composition, structure, and properties of matter, as well as the changes it undergoes during chemical reactions.

In chemistry, a reactivity series (or reactivity series of elements) is an empirical, calculated, and structurally analytical progression of a series of metals, arranged by their "reactivity" from highest to lowest. It is used to summarize information about the reactions of metals with acids and water, single displacement reactions and the extraction of metals from their ores.

In chemistry, a nitride is a chemical compound of nitrogen. Nitrides can be inorganic or organic, ionic or covalent. The nitride anion, N3- ion, is very elusive but compounds of nitride are numerous, although rarely naturally occurring. Some nitrides have a found applications, such as wear-resistant coatings (e.g., titanium nitride, TiN), hard ceramic materials (e.g., silicon nitride, Si3N4), and semiconductors (e.g., gallium nitride, GaN). The development of GaN-based light emitting diodes was recognized by the 2014 Nobel Prize in Physics. Metal nitrido complexes are also common.

Ionic radius, rion, 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 and anion gives the distance between the ions in a crystal lattice. Ionic radii are typically given in units of either picometers (pm) or angstroms (Å), with 1 Å = 100 pm. Typical values range from 31 pm (0.3 Å) to over 200 pm (2 Å).

<span class="mw-page-title-main">Magnesium nitride</span> Chemical compound

Magnesium nitride, which possesses the chemical formula Mg3N2, is an inorganic compound of magnesium and nitrogen. At room temperature and pressure it is a greenish yellow powder.

Basic oxides are oxides that show basic properties, in opposition to acidic oxides. A basic oxide can either react with water to form a base, or with an acid to form a salt and water in a neutralization reaction.

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

Boron compounds are compounds containing the element boron. In the most familiar compounds, boron has the formal oxidation state +3. These include oxides, sulfides, nitrides, and halides.

The chemical state of a chemical element is due to its electronic, chemical and physical properties as it exists in combination with itself or a group of one or more other elements. A chemical state is often defined as an "oxidation state" when referring to metal cations. When referring to organic materials, a chemical state is usually defined as a chemical group, which is a group of several elements bonded together. Material scientists, solid state physicists, analytical chemists, surface scientists and spectroscopists describe or characterize the chemical, physical and/or electronic nature of the surface or the bulk regions of a material as having or existing as one or more chemical states.

<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.

<i>N</i>-Heterocyclic carbene boryl anion Isoelectronic structure

An N-heterocyclic carbene boryl anion is an isoelectronic structure of an N-heterocyclic carbene (NHC), where the carbene carbon is replaced with a boron atom that has a -1 charge. NHC boryl anions have a planar geometry, and the boron atom is considered to be sp2-hybridized. They serve as extremely strong bases, as they are very nucleophilic. They also have a very strong trans influence, due to the σ-donation coming from the boron atom. NHC boryl anions have stronger electron-releasing character when compared to normal NHCs. These characteristics make NHC boryl anions key ligands in many applications, such as polycyclic aromatic hydrocarbons, and more commonly low oxidation state main group element bonding.

References

  1. Rayner-Canham, Geoff (2011-07-01). "Isodiagonality in the periodic table". Foundations of Chemistry. 13 (2): 121–129. doi:10.1007/s10698-011-9108-y. ISSN   1572-8463. S2CID   97285573.
  2. Ebbing, Darrell and Gammon, Steven D. (2009). "Atomic Radius". General Chemistry (PDF) (9th ed.). Houghton Mifflin. pp. 312–314. ISBN   978-0-618-93469-0. Archived from the original (PDF) on 2019-02-10. Retrieved 2019-02-10.{{cite book}}: CS1 maint: multiple names: authors list (link)
  3. Rayner-Canham, Geoffrey (22 December 2013). Descriptive inorganic chemistry. Overton, Tina (Sixth ed.). New York, NY. ISBN   978-1-4641-2557-7. OCLC   882867766.{{cite book}}: CS1 maint: location missing publisher (link)
  4. 1 2 Clark, Jim (2005). "Reactions of the Group 2 Elements with Air or Oxygen". chemguide. Retrieved January 30, 2012.
  5. Shriver, Duward (2006). Inorganic Chemistry (4th ed.). Oxford University Press. ISBN   978-0199264636. Li/Mg p. 259; Be/Al p. 274; B/Si p. 288.