Periodic table

The periodic table, also known as the periodic table of the (chemical) elements, is a rows and columns arrangement of the chemical elements. It is widely used in chemistry, physics, and other sciences, and is generally seen as an icon of chemistry. It is a graphic formulation of the periodic law, which states that the properties of the chemical elements exhibit an approximate periodic dependence on their atomic numbers. The table is divided into four roughly rectangular areas called blocks. The rows of the table are called periods, and the columns are called groups. Elements from the same group of the periodic table show similar chemical characteristics. Trends run through the periodic table, with nonmetallic character (keeping their own electrons) increasing from left to right across a period, and from down to up across a group, and metallic character (surrendering electrons to other atoms) increasing in the opposite direction. The underlying reason for these trends is electron configurations of atoms. The periodic table exclusively lists electrically neutral atoms that have an equal number of positively charged protons and negatively charged electrons and puts isotopes (atoms with the same number of protons but different numbers of neutrons) at the same place. Other atoms, like nuclides and isotopes, are graphically collected in other tables like the tables of nuclides (often called Segrè charts).

The first periodic table to become generally accepted was that of the Russian chemist Dmitri Mendeleev in 1869: he formulated the periodic law as a dependence of chemical properties on atomic mass. Because not all elements were then known, there were gaps in his periodic table, and Mendeleev successfully used the periodic law to predict properties of some of the missing elements. The periodic law was recognized as a fundamental discovery in the late 19th century, and it was explained with the discovery of the atomic number and pioneering work in quantum mechanics of the early 20th century that illuminated the internal structure of the atom. With Glenn T. Seaborg‘s 1945 discovery that the actinides were in fact f-block rather than d-block elements, a recognisably modern form of the table was reached. The periodic table and law are now a central and indispensable part of modern chemistry.

The periodic table continues to evolve with the progress of science. In nature, only elements up to atomic number 94 exist; to go further, it was necessary to synthesise new elements in the laboratory. Today, all the first 118 elements are known, completing the first seven rows of the table, but chemical characterisation is still needed for the heaviest elements to confirm that their properties match their positions. It is not yet known how far the table will stretch beyond these seven rows and whether the patterns of the known part of the table will continue into this unknown region. Some scientific discussion also continues regarding whether some elements are correctly positioned in today’s table. Many alternative representations of the periodic law exist, and there is some discussion as to whether there is an optimal form of the periodic table.

Overview

The periodic table is a 2-dimensional structured table. The elements are placed in table cells, in reading order of ascending atomic number. The table is divided into four blocks, reflecting the filling of electrons into types of subshell. The table columns are called groups, and the rows are called periods. New periods begin when a new electron shell starts to fill: elements in the same group have the same number of electrons that can be used for chemistry (except for helium in the noble gas group), so that similar physical and chemical properties recur at regular intervals.

Atomic structure

The smallest constituents of all normal matter are known as atoms. Atoms are extremely small, being about one ten-billionth of a meter across; thus their internal structure is governed by quantum mechanics. Atoms consist of a small positively charged nucleus, made of positively charged protons and uncharged neutrons, surrounded by a cloud of negatively charged electrons; the charges cancel out, so atoms are neutral. Electrons participate in chemical reactions, but the nucleus does not. When atoms participate in chemical reactions, they either gain or lose electrons to form positively- or negatively-charged ions; or share electrons with each other.

Atoms can be subdivided into different types based on the number of protons (and thus also electrons) they have. This is called the atomic number, often symbolised Z (for “Zahl” — German for “number”). Each distinct atomic number therefore corresponds to a class of atom: these classes are called the chemical elements. The chemical elements are what the periodic table classifies and organises. Hydrogen is the element with atomic number 1; helium, atomic number 2; lithium, atomic number 3; and so on. Each of these names can be further abbreviated by a one- or two-letter chemical symbol; those for hydrogen, helium, and lithium are respectively H, He, and Li. Neutrons do not affect the atom’s chemical identity, but do affect its weight. Atoms with the same number of protons but different numbers of neutrons are called isotopes of the same chemical element. Naturally occurring elements usually occur as mixes of different isotopes; since each isotope usually occurs with a characteristic abundance, naturally occurring elements have well-defined atomic weights, defined as the average mass of a naturally occurring atom of that element.

Today, 118 elements are known, the first 94 of which are known to occur naturally on Earth at present. Of the 94 natural elements, eighty have a stable isotope and one more (bismuth) has an almost-stable isotope (with a half-life over a billion times the age of the universe). Two more, thorium and uranium, have isotopes undergoing radioactive decay with a half-life comparable to the age of the Earth. The stable elements plus bismuth, thorium, and uranium make up the 83 primordial elements that survived from the Earth’s formation. The remaining eleven natural elements decay quickly enough that their continued trace occurrence rests primarily on being constantly regenerated as intermediate products of the decay of thorium and uranium. All 24 known artificial elements are radioactive.

Electron configuration

The periodic table is a graphic description of the periodic law, which states that the properties and atomic structures of the chemical elements are a periodic function of their atomic number. Elements are placed in the periodic table by their electron configurations, which exhibit periodic recurrences that explain the trends of properties across the periodic table.

An electron can be thought of as inhabiting an atomic orbital, which characterises the probability it can be found in any particular region of the atom. Their energies are quantised, which is to say that they can only take discrete values. Furthermore, electrons obey the Pauli exclusion principle: different electrons must always be in different states. This allows classification of the possible states an electron can take in various energy levels known as shells, divided into individual subshells, which each contain one or more orbitals. Each orbital can contain up to two electrons: they are distinguished by a quantity known as spin, conventionally labeled “up” or “down”. In a cold atom (one in its ground state), electrons arrange themselves in such a way that the total energy they have is minimised by occupying the lowest-energy orbitals available. Only the outermost electrons (so-called valence electrons) have enough energy to break free of the nucleus and participate in chemical reactions with other atoms. The others are called core electrons.

Elements are known with up to the first seven shells occupied. The first shell contains only one orbital, a spherical s orbital. As it is in the first shell, this is called the 1s orbital. This can hold up to two electrons. The second shell similarly contains a 2s orbital, and it also contains three dumbbell-shaped 2p orbitals, and can thus fill up to eight electrons (2×1 + 2×3 = 8). The third shell contains one 3s orbital, three 3p orbitals, and five 3d orbitals, and thus has a capacity of 2×1 + 2×3 + 2×5 = 18. The fourth shell contains one 4s orbital, three 4p orbitals, five 4d orbitals, and seven 4f orbitals, thus leading to a capacity of 2×1 + 2×3 + 2×5 + 2×7 = 32. Higher shells contain more types of orbitals that continue the pattern, but such types of orbitals are not filled in the ground states of known elements. The subshell types are characterised by the quantum numbers. Four numbers describe an orbital in an atom completely: the principal quantum number n, the azimuthal quantum number ℓ (the orbital type), the magnetic quantum number m_ℓ, and the spin quantum number s.

The order of subshell filling

The sequence in which the subshells are filled is given in most cases by the Aufbau principle, also known as the Madelung or Klechkovsky rule (after Erwin Madelung and Vsevolod Klechkovsky respectively). This rule was first observed empirically by Madelung, and Klechkovsky and later authors gave it theoretical justification. The shells overlap in energies, and the Madelung rule specifies the sequence of filling according to:1s ≪ 2s < 2p ≪ 3s < 3p ≪ 4s < 3d < 4p ≪ 5s < 4d < 5p ≪ 6s < 4f < 5d < 6p ≪ 7s < 5f < 6d < 7p ≪ …

Here the sign ≪ means “much less than” as opposed to < meaning just “less than”. Phrased differently, electrons enter orbitals in order of increasing n + ℓ, and if two orbitals are available with the same value of n + ℓ, the one with lower n is occupied first. In general, orbitals with the same value of n + ℓ are similar in energy, but in the case of the s-orbitals (with ℓ = 0), quantum effects raise their energy to approach that of the next n + ℓ group. Hence the periodic table is usually drawn to begin each row (often called a period) with the filling of a new s-orbital, which corresponds to the beginning of a new shell. Thus, with the exception of the first row, each period length appears twice:2, 8, 8, 18, 18, 32, 32, …

The overlaps get quite close at the point where the d-orbitals enter the picture, and the order can shift slightly with atomic number and atomic charge.

Starting from the simplest atom, this lets us build up the periodic table one at a time in order of atomic number, by considering the cases of single atoms. In hydrogen, there is only one electron, which must go in the lowest-energy orbital 1s. This electron configuration is written 1s¹, where the superscript indicates the number of electrons in the subshell. Helium adds a second electron, which also goes into 1s, completely filling the first shell and giving the configuration 1s².

Starting from the third element, lithium, the first shell is full, so its third electron occupies a 2s orbital, giving a 1s² 2s¹ configuration. The 2s electron is lithium’s only valence electron, as the 1s subshell is now too tightly bound to the nucleus to participate in chemical bonding to other atoms. Thus the filled first shell is called a “core shell” for this and all heavier elements. The 2s subshell is completed by the next element beryllium (1s² 2s²). The following elements then proceed to fill the 2p subshell. Boron (1s² 2s² 2p¹) puts its new electron in a 2p orbital; carbon (1s² 2s² 2p²) fills a second 2p orbital; and with nitrogen (1s² 2s² 2p³) all three 2p orbitals become singly occupied. This is consistent with Hund’s rule, which states that atoms usually prefer to singly occupy each orbital of the same type before filling them with the second electron. Oxygen (1s² 2s² 2p⁴), fluorine (1s² 2s² 2p⁵), and neon (1s² 2s² 2p⁶) then complete the already singly filled 2p orbitals; the last of these fills the second shell completely.

Starting from element 11, sodium, the second shell is full, making the second shell a core shell for this and all heavier elements. The eleventh electron begins the filling of the third shell by occupying a 3s orbital, giving a configuration of 1s² 2s² 2p⁶ 3s¹ for sodium. This configuration is abbreviated [Ne] 3s¹, where [Ne] represents neon’s configuration. Magnesium ([Ne] 3s²) finishes this 3s orbital, and the following six elements aluminium, silicon, phosphorus, sulfur, chlorine, and argon fill the three 3p orbitals ([Ne] 3s² 3p¹ through [Ne] 3s² 3p⁶). This creates an analogous series in which the outer shell structures of sodium through argon are analogous to those of lithium through neon, and is the basis for the periodicity of chemical properties that the periodic table illustrates: at regular but changing intervals of atomic numbers, the properties of the chemical elements approximately repeat.

The first eighteen elements can thus be arranged as the start of a periodic table. Elements in the same column have the same number of valence electrons and have analogous valence electron configurations: these columns are called groups. The single exception is helium, which has two valence electrons like beryllium and magnesium, but is typically placed in the column of neon and argon to emphasise that its outer shell is full. (Some contemporary authors question even this single exception, preferring to consistently follow the valence configurations and place helium over beryllium.) There are eight columns in this periodic table fragment, corresponding to at most eight outer-shell electrons. A period begins when a new shell starts filling. Finally, the colouring illustrates the blocks: the elements in the s-block (coloured red) are filling s-orbitals, while those in the p-block (coloured yellow) are filling p-orbitals.

Starting the next row, for potassium and calcium the 4s subshell is the lowest in energy, and therefore they fill it. Potassium adds one electron to the 4s shell ([Ar] 4s¹), and calcium then completes it ([Ar] 4s²). However, starting from scandium ([Ar] 3d¹ 4s²) the 3d subshell becomes the next highest in energy. The 4s and 3d subshells have approximately the same energy and they compete for filling the electrons, and so the occupation is not quite consistently filling the 3d orbitals one at a time. The precise energy ordering of 3d and 4s changes along the row, and also changes depending on how many electrons are removed from the atom. For example, due to the repulsion between the 3d electrons and the 4s ones, at chromium the 4s energy level becomes slightly higher than 3d, and so it becomes more profitable to have a [Ar] 3d⁵ 4s¹ configuration than an [Ar] 3d⁴ 4s² one. A similar anomaly occurs at copper. These are violations of the Madelung rule. Such anomalies however do not have any chemical significance, as the various configurations are so close in energy to each other that the presence of a nearby atom can shift the balance. The periodic table therefore ignores these and considers only idealised configurations.

At zinc ([Ar] 3d¹⁰ 4s²), the 3d orbitals are completely filled with a total of ten electrons. Next come the 4p orbitals, completing the row, which are filled progressively by gallium ([Ar] 3d¹⁰ 4s² 4p¹) through krypton ([Ar] 3d¹⁰ 4s² 4p⁶), in a manner analogous to the previous p-block elements. From gallium onwards, the 3d orbitals form part of the electronic core, and no longer participate in chemistry. The s- and p-block elements, which fill their outer shells, are called main-group elements; the d-block elements (coloured blue below), which fill an inner shell, are called transition elements (or transition metals, since they are all metals).

The next eighteen elements fill the 5s orbitals (rubidium and strontium), then 4d (yttrium through cadmium, again with a few anomalies along the way), and then 5p (indium through xenon). Again, from indium onward the 4d orbitals are in the core. Hence the fifth row has the same structure as the fourth

The sixth row of the table likewise starts with two s-block elements: caesium and barium. After this, the first f-block elements (coloured green below) begin to appear, starting with lanthanum. These are sometimes termed inner transition elements. As there are now not only 4f but also 5d and 6s subshells at similar energies, competition occurs once again with many irregular configurations; this resulted in some dispute about where exactly the f-block is supposed to begin, but most who study the matter agree that it starts at lanthanum in accordance with the Aufbau principle. Even though lanthanum does not itself fill the 4f subshell as a single atom, because of repulsion between electrons, its 4f orbitals are low enough in energy to participate in chemistry. At ytterbium, the seven 4f orbitals are completely filled with fourteen electrons; thereafter, a series of ten transition elements (lutetium through mercury) follows, and finally six main-group elements (thallium through radon) complete the period. From lutetium onwards the 4f orbitals are in the core, and from thallium onwards so are the 5d orbitals.

The seventh row is analogous to the sixth row: 7s fills (francium and radium), then 5f (actinium to nobelium), then 6d (lawrencium to copernicium), and finally 7p (nihonium to oganesson). Starting from lawrencium the 5f orbitals are in the core, and probably the 6d orbitals join the core starting from nihonium. Again there are a few anomalies along the way: for example, as single atoms neither actinium nor thorium actually fills the 5f subshell, and lawrencium does not fill the 6d shell, but all these subshells can still become filled in chemical environments. For a very long time, the seventh row was incomplete as most of its elements do not occur in nature. The missing elements beyond uranium started to be synthesised in the laboratory in 1940, when neptunium was made. The row was completed with the synthesis of tennessine in 2010 (the last element oganesson had already been made in 2002) and the last elements in this seventh row were given names in 2016.

Electron configuration table

The following table shows the electron configuration of a neutral gas-phase atom of each element. Different configurations can be favoured in different chemical environments. The main-group elements have entirely regular electron configurations; the transition and inner transition elements show twenty irregularities due to the aforementioned competition between subshells close in energy level. For the last ten elements (109–118), experimental data is lacking and therefore calculated configurations have been shown instead. Completely filled subshells have been greyed out.

Group names and numbers

Under an international naming convention, the groups are numbered numerically from 1 to 18 from the leftmost column (the alkali metals) to the rightmost column (the noble gases). The f-block groups are ignored in this numbering. Groups can also be named by their first element, e.g. the “scandium group” for group 3. Previously, groups were known by Roman numerals. In America, the Roman numerals were followed by either an “A” if the group was in the s- or p-block, or a “B” if the group was in the d-block. The Roman numerals used correspond to the last digit of today’s naming convention (e.g. the group 4 elements were group IVB, and the group 14 elements were group IVA). In Europe, the lettering was similar, except that “A” was used if the group was before group 10, and “B” was used for groups including and after group 10. In addition, groups 8, 9 and 10 used to be treated as one triple-sized group, known collectively in both notations as group VIII. In 1988, the new IUPAC (International Union of Pure and Applied Chemistry) naming system (1–18) was put into use, and the old group names (I–VIII) were deprecated.