Traité Élémentaire de Chimie'' (''Elementary Treatise of Chemistry''), which is considered to be the first modern
textbook
A textbook is a book containing a comprehensive compilation of content in a branch of study with the intention of explaining it. Textbooks are produced to meet the needs of educators, usually at educational institutions. Schoolbooks are textbook ...
about
chemistry. Lavoisier defined an element as a substance whose smallest units cannot be broken down into a simpler substance. Lavoisier's book contained a list of "simple substances" that Lavoisier believed could not be broken down further, which included
oxygen
Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements as ...
,
nitrogen
Nitrogen is the chemical element with the symbol N and atomic number 7. Nitrogen is a nonmetal and the lightest member of group 15 of the periodic table, often called the pnictogens. It is a common element in the universe, estimated at se ...
,
hydrogen
Hydrogen is the chemical element with the symbol H and atomic number 1. Hydrogen is the lightest element. At standard conditions hydrogen is a gas of diatomic molecules having the formula . It is colorless, odorless, tasteless, non-toxic ...
, phosphorus, mercury, zinc and sulfur, which formed the basis for the modern list of elements. Lavoisier's list also included '
light
Light or visible light is electromagnetic radiation that can be perceived by the human eye. Visible light is usually defined as having wavelengths in the range of 400–700 nanometres (nm), corresponding to frequencies of 750–420 te ...
' and '
caloric', which at the time were believed to be material substances. He classified these substances into metals and nonmetals. While many leading
chemist
A chemist (from Greek ''chēm(ía)'' alchemy; replacing ''chymist'' from Medieval Latin ''alchemist'') is a scientist trained in the study of chemistry. Chemists study the composition of matter and its properties. Chemists carefully describe t ...
s refused to believe Lavoisier's new revelations, the ''Elementary Treatise'' was written well enough to convince the younger generation. However, Lavoisier's descriptions of his elements lack completeness, as he only classified them as metals and non-metals.
In 1808–10, British natural philosopher
John Dalton published a method by which to arrive at provisional
atomic weights
Relative atomic mass (symbol: ''A''; sometimes abbreviated RAM or r.a.m.), also known by the deprecated synonym atomic weight, is a dimensionless physical quantity
A physical quantity is a physical property of a material or system that can be ...
for the elements known in his day, from
stoichiometric
Stoichiometry refers to the relationship between the quantities of reactants and products before, during, and following chemical reactions.
Stoichiometry is founded on the law of conservation of mass where the total mass of the reactants equ ...
measurements and reasonable inferences. Dalton's
atomic theory
Atomic theory is the scientific theory that matter is composed of particles called atoms. Atomic theory traces its origins to an ancient philosophical tradition known as atomism. According to this idea, if one were to take a lump of matter ...
was adopted by many chemists during the 1810s and 1820s.
In 1815, British physician and chemist
William Prout
William Prout FRS (; 15 January 1785 – 9 April 1850) was an English chemist, physician, and natural theologian. He is remembered today mainly for what is called Prout's hypothesis.
Biography
Prout was born in Horton, Gloucestershire in ...
noticed that atomic weights seemed to be multiples of that of hydrogen.
In 1817, German physicist
Johann Wolfgang Döbereiner
Johann Wolfgang Döbereiner (13 December 1780 – 24 March 1849) was a German chemist who is best known for work that foreshadowed the periodic law for the chemical elements, and for inventing the first lighter, which was known as the Döbere ...
began to formulate one of the earliest attempts to classify the elements. In 1829, he found that he could form some of the elements into groups of three, with the members of each group having related properties. He termed these groups ''
triads''.
Definition of Triad law
"Chemically analogous elements arranged in increasing order of their atomic weights formed well marked groups of three called Triads in which the atomic weight of the middle element was found to be generally the arithmetic mean of the atomic weight of the other two elements in the triad.
#
chlorine
Chlorine is a chemical element with the symbol Cl and atomic number 17. The second-lightest of the halogens, it appears between fluorine and bromine in the periodic table and its properties are mostly intermediate between them. Chlorine i ...
,
bromine
Bromine is a chemical element with the symbol Br and atomic number 35. It is the third-lightest element in group 17 of the periodic table ( halogens) and is a volatile red-brown liquid at room temperature that evaporates readily to form a simi ...
, and
iodine
#
calcium
Calcium is a chemical element with the symbol Ca and atomic number 20. As an alkaline earth metal, calcium is a reactive metal that forms a dark oxide-nitride layer when exposed to air. Its physical and chemical properties are most similar t ...
,
strontium, and
barium
#
sulfur,
selenium
Selenium is a chemical element with the symbol Se and atomic number 34. It is a nonmetal (more rarely considered a metalloid) with properties that are intermediate between the elements above and below in the periodic table, sulfur and tellurium, ...
, and
tellurium
Tellurium is a chemical element with the symbol Te and atomic number 52. It is a brittle, mildly toxic, rare, silver-white metalloid. Tellurium is chemically related to selenium and sulfur, all three of which are chalcogens. It is occasionall ...
#
lithium
Lithium (from el, λίθος, lithos, lit=stone) is a chemical element with the symbol Li and atomic number 3. It is a soft, silvery-white alkali metal. Under standard conditions, it is the least dense metal and the least dense solid ...
,
sodium
Sodium is a chemical element with the symbol Na (from Latin ''natrium'') and atomic number 11. It is a soft, silvery-white, highly reactive metal. Sodium is an alkali metal, being in group 1 of the periodic table. Its only stable ...
, and
potassium
Potassium is the chemical element with the symbol K (from Neo-Latin ''kalium'') and atomic number19. Potassium is a silvery-white metal that is soft enough to be cut with a knife with little force. Potassium metal reacts rapidly with atmosph ...
"
In 1860, a revised list of elements and atomic masses was presented at a conference in
Karlsruhe
Karlsruhe ( , , ; South Franconian: ''Kallsruh'') is the third-largest city of the German state (''Land'') of Baden-Württemberg after its capital of Stuttgart and Mannheim, and the 22nd-largest city in the nation, with 308,436 inhabitants. ...
. It helped spur creation of more extensive systems. The first such system emerged in two years.
Comprehensive formalizations
French geologist
Alexandre-Émile Béguyer de Chancourtois noticed that the elements, when ordered by their atomic weights, displayed similar properties at regular intervals. In 1862, he devised a three-dimensional chart, named the "telluric helix", after the element
tellurium
Tellurium is a chemical element with the symbol Te and atomic number 52. It is a brittle, mildly toxic, rare, silver-white metalloid. Tellurium is chemically related to selenium and sulfur, all three of which are chalcogens. It is occasionall ...
, which fell near the center of his diagram.
With the elements arranged in a spiral on a cylinder by order of increasing atomic weight, de Chancourtois saw that elements with similar properties lined up vertically. The original paper from Chancourtois in ''
Comptes rendus de l'Académie des Sciences'' did not include a chart and used geological rather than chemical terms. In 1863, he extended his work by including a chart and adding
ion
An ion () is an atom or molecule with a net electrical charge.
The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by conve ...
s and
compounds.
The next attempt was made in 1864. British chemist
John Newlands presented in ''Chemical News''
a classification of the 62 known elements. Newlands noticed recurring trends in physical properties of the elements at recurring intervals of multiples of eight in order of mass number;
[John Newlands, ''Chemistry Review'', November 2003, pp. 15-16.] based on this observation, he produced a classification of these elements into eight groups. Each group displayed a similar progression; Newlands likened these progressions to the progression of notes within a musical scale.
[ Newlands's table left no gaps for possible future elements, and in some cases had two elements at the same position in the same octave. Newlands's table was ignored or ridiculed by some of his contemporaries.][ The ]Chemical Society
The Chemical Society was a scientific society formed in 1841 (then named the Chemical Society of London) by 77 scientists as a result of increased interest in scientific matters. Chemist Robert Warington was the driving force behind its creation.
...
refused to publish his work. The president of the Society, William Odling
William Odling, FRS (5 September 1829 in Southwark, London – 17 February 1921 in Oxford) was an English chemist who contributed to the development of the periodic table.
In the 1860s Odling, like many chemists, was working towards classifying ...
, defended the Society's decision by saying that such 'theoretical' topics might be controversial;[ From p. 38: "The reason or rejecting Newlands's paper, which wasgiven by Odling, then the president of the Chemical Society, was that they made a rule not to publish theoretical papers, and this on the quite astonishing grounds that ''such papers lead to a correspondence of controversial character''."] there was even harsher opposition from within the Society, suggesting the elements could have been just as well listed alphabetically. Later that year, Odling suggested a table of his own but failed to get recognition following his role in opposing Newlands's table.
German chemist Lothar Meyer
Julius Lothar Meyer (19 August 1830 – 11 April 1895) was a German chemist. He was one of the pioneers in developing the earliest versions of the periodic table of the chemical elements. Russian chemist Dmitri Mendeleev (his chief rival) and he ...
also noted the sequences of similar chemical and physical properties repeated at periodic intervals. According to him, if the atomic weights were plotted as ordinates (i.e. vertically) and the atomic volumes as abscissas (i.e. horizontally)—the curve obtained is a series of maximums and minimums—the most electropositive
Electronegativity, symbolized as , is the tendency for an atom of a given chemical element to attract shared electrons (or electron density) when forming a chemical bond. An atom's electronegativity is affected by both its atomic number and the ...
elements would appear at the peaks of the curve in the order of their atomic weights. In 1864, a book of his was published; it contained an early version of the periodic table containing 28 elements, and classified elements into six families by their valence—for the first time, elements had been grouped according to their valence. Works on organizing the elements by atomic weight had until then been stymied by inaccurate measurements of the atomic weights. In 1868, he revised his table, but this revision was published as a draft only after his death.[ In a paper dated December 1869 which appeared early in 1870, Meyer published a new periodic table of 55 elements, in which the series of periods are ended by an element of the alkaline earth metal group. The paper also included a line chart of relative atomic volumes, which illustrated periodic relationships of physical characteristics of the elements, and which assisted Meyer in deciding where elements should appear in his periodic table. By this time he had already seen the publication of Mendeleev's first periodic table, but his work appears to have been largely independent.
In 1869, Russian chemist Dmitri Mendeleev arranged 63 elements by increasing ]atomic weight
Relative atomic mass (symbol: ''A''; sometimes abbreviated RAM or r.a.m.), also known by the deprecated synonym atomic weight, is a dimensionless physical quantity defined as the ratio of the average mass of atoms of a chemical element in a giv ...
in several columns, noting recurring chemical properties across them. It is sometimes said that he played "chemical solitaire" on long train journeys, using cards with the symbols and the atomic weights of the known elements. Another possibility is that he was inspired in part by the periodicity of the Sanskrit
Sanskrit (; attributively , ; nominally , , ) is a classical language belonging to the Indo-Aryan branch of the Indo-European languages. It arose in South Asia after its predecessor languages had diffused there from the northwest in the late ...
alphabet, which was pointed out to him by his friend and linguist Otto von Böhtlingk
Otto von Böhtlingk (russian: Оттон Николаевич Бётлингк, ''Otton Nikolayevich Byotlingk''; 30 May 1815 – 1 April 1904) was a Russian-German Indologist and Sanskrit scholar. His '' magnum opus'' was a Sanskrit-German dict ...
. Mendeleev used the trends he saw to suggest that atomic weights of some elements were incorrect, and accordingly changed their placements: for instance, he figured there was no place for a trivalent
In chemistry, the valence (US spelling) or valency (British spelling) of an element is the measure of its combining capacity with other atoms when it forms chemical compounds or molecules.
Description
The combining capacity, or affinity of an ...
beryllium with the atomic weight of 14 in his work, and he cut both the atomic weight and valency of beryllium by a third, suggesting it was a divalent element with the atomic weight of 9.4. Mendeleev widely distributed printed broadsheets of the table to various chemists in Russia and abroad. Mendeleev argued in 1869 there were seven types of highest oxides. Mendeleev continued to improve his ordering; in 1870, it gained a tabular shape, and each column was given its own highest oxide, and in 1871, he further developed it and formulated what he termed the "law of periodicity". Some changes also occurred with new revisions, with some elements changing positions.
File:Periodic table Meyer 1864.png, Meyer's periodic table, published in "Die modernen Theorien der Chemie", 1864[Meyer, Julius Lothar; Die modernen Theorien der Chemie (1864)]
table on page 137
File:Newlands periodiska system 1866.png, Newlands's law of octaves, 1866
File:1869-periodic-table.jpg, Mendeleev's first ''Attempt at a system of elements'', 1869
File:Dmitry Mendeleyev Osnovy Khimii 1869-1871 first periodic table.jpg, Mendeleev's ''Natural system of the elements'', 1870
File:Mendelejevs periodiska system 1871.png, Mendeleev's periodic table, 1871
Priority dispute and recognition
Mendeleev's predictions and inability to incorporate the rare-earth metals
Even as Mendeleev corrected positions of some elements, he thought that some relationships that he could find in his grand scheme of periodicity could not be found because some elements were still undiscovered, and that the properties of such undiscovered elements could be deduced from their expected relationships with other elements. In 1870, he first tried to characterize the yet undiscovered elements, and he gave detailed predictions
A prediction (Latin ''præ-'', "before," and ''dicere'', "to say"), or forecast, is a statement about a future event or data. They are often, but not always, based upon experience or knowledge. There is no universal agreement about the exact ...
for three elements, which he termed ''eka-boron'', ''eka-aluminium'', and ''eka-silicium''; he also more briefly noted a few other expectations. It has been proposed that the prefixes ''eka'', ''dvi'', and ''tri'', Sanskrit for one, two, and three, respectively, are a tribute to Pāṇini
, era = ;;6th–5th century BCE
, region = Indian philosophy
, main_interests = Grammar, linguistics
, notable_works = ' ( Classical Sanskrit)
, influenced=
, notable_ideas=Descriptive linguistics
(Devanaga ...
and other ancient Sanskrit grammar
The grammar of the Sanskrit language has a complex verbal system, rich nominal declension, and extensive use of compound nouns. It was studied and codified by Sanskrit grammarians from the later Vedic period (roughly 8th century BCE), culminati ...
ians for their invention of a periodic alphabet. In 1871, Mendeleev expanded his predictions further.
Compared to the rest of the work, Mendeleev's 1869 list misplaces seven then known elements: indium
Indium is a chemical element with the symbol In and atomic number 49. Indium is the softest metal that is not an alkali metal. It is a silvery-white metal that resembles tin in appearance. It is a post-transition metal that makes up 0.21 parts ...
, thorium
Thorium is a weakly radioactive metallic chemical element with the symbol Th and atomic number 90. Thorium is silvery and tarnishes black when it is exposed to air, forming thorium dioxide; it is moderately soft and malleable and has a high ...
, and five rare-earth metals
The rare-earth elements (REE), also called the rare-earth metals or (in context) rare-earth oxides or sometimes the lanthanides (yttrium and scandium are usually included as rare earths), are a set of 17 nearly-indistinguishable lustrous silve ...
: yttrium
Yttrium is a chemical element with the symbol Y and atomic number 39. It is a silvery-metallic transition metal chemically similar to the lanthanides and has often been classified as a " rare-earth element". Yttrium is almost always found in co ...
, cerium
Cerium is a chemical element with the symbol Ce and atomic number 58. Cerium is a soft, ductile, and silvery-white metal that tarnishes when exposed to air. Cerium is the second element in the lanthanide series, and while it often shows the +3 ...
, lanthanum
Lanthanum is a chemical element with the symbol La and atomic number 57. It is a soft, ductile, silvery-white metal that tarnishes slowly when exposed to air. It is the eponym of the lanthanide series, a group of 15 similar elements between lant ...
, erbium
Erbium is a chemical element with the symbol Er and atomic number 68. A silvery-white solid metal when artificially isolated, natural erbium is always found in chemical combination with other elements. It is a lanthanide, a rare-earth element, or ...
, and didymium
Didymium ( el, , twin) is a mixture of the elements praseodymium and neodymium. It is used in safety glasses for glassblowing and blacksmithing, especially with a gas ( propane)-powered forge, where it provides a filter that selectively block ...
. The last two were later found to be mixtures of two different elements; ignoring those would allow him to restore the logic of increasing atomic weight. These elements (all thought to be divalent at the time) puzzled Mendeleev as they did not show a regular increase in valency despite their seemingly consequential atomic weights. Mendeleev grouped them together, thinking of them as of a particular kind of series. In early 1870, he decided that the weights for these elements must be wrong and that the rare-earth metals should be trivalent (which accordingly increased their predicted atomic weights by half). He measured the heat capacity
Heat capacity or thermal capacity is a physical property of matter, defined as the amount of heat to be supplied to an object to produce a unit change in its temperature. The SI unit of heat capacity is joule per kelvin (J/K).
Heat capacity ...
of indium, uranium, and cerium to demonstrate their higher assumed valency (which was soon confirmed by Prussian chemist Robert Bunsen
Robert Wilhelm Eberhard Bunsen (;
30 March 1811
– 16 August 1899) was a German chemist. He investigated emission spectra of heated elements, and discovered caesium (in 1860) and rubidium (in 1861) with the physicist Gustav Kirchhoff. The Bu ...
). Mendeleev treated the change by assessing each element to an individual place in his system of the elements rather than continuing to treat them as a series.
Mendeleev noticed that there was a significant difference in atomic mass between cerium and tantalum
Tantalum is a chemical element with the symbol Ta and atomic number 73. Previously known as ''tantalium'', it is named after Tantalus, a villain in Greek mythology. Tantalum is a very hard, ductile, lustrous, blue-gray transition metal that ...
with no element between them; his consideration was that between them, there was a row of yet undiscovered elements, which would display similar properties to those elements which were to be found above and below them: for instance, an eka-molybdenum would behave as a heavier homolog of molybdenum and a lighter homolog of wolfram (the name under which Mendeleev knew tungsten
Tungsten, or wolfram, is a chemical element with the symbol W and atomic number 74. Tungsten is a rare metal found naturally on Earth almost exclusively as compounds with other elements. It was identified as a new element in 1781 and first isol ...
). This row would begin with a trivalent lanthanum, a tetravalent cerium, and a pentavalent didymium. However, the higher valency for didymium had not been established, and Mendeleev tried to do so himself. Having had no success in that, he abandoned his attempts to incorporate the rare-earth metals in late 1871 and embarked on his grand idea of luminiferous ether
Luminiferous aether or ether ("luminiferous", meaning "light-bearing") was the postulated medium for the propagation of light. It was invoked to explain the ability of the apparently wave-based light to propagate through empty space (a vacuum), so ...
. His idea was carried on by Austrian-Hungarian chemist Bohuslav Brauner
Bohuslav Brauner (May 8, 1855 – February 15, 1935) was a Czech chemist from the University of Prague, who investigated the properties of the rare earth elements, especially the determination of their atomic weights. Brauner predicted the ...
, who sought to find a place in the periodic table for the rare-earth metals; Mendeleev later referred to him as to "one of the true consolidators of the periodic law".
In addition to the predictions of scandium, gallium, and germanium that were quickly realized, Mendeleev's 1871 table left many more spaces for undiscovered elements, though he did not provide detailed predictions of their properties. In total, he predicted eighteen elements, though only half corresponded to elements that were later discovered.
Priority of discovery
None of the proposals was accepted immediately, and many contemporary chemists found it too abstract to have any meaningful value. Of those chemists that proposed their categorizations, Mendeleev strove to back his work and promote his vision of periodicity, Meyer did not promote his work very actively, and Newlands did not make a single attempt to gain recognition abroad.
Both Mendeleev and Meyer created their respective tables for their pedagogical needs; the difference between their tables is well explained by the fact that the two chemists sought to use a formalized system to solve different problems. Mendeleev's intent was to aid composition of his textbook, ''Foundations of Chemistry'', whereas Meyer was rather concerned with presentation of theories. Mendeleev's predictions emerged outside of the pedagogical scope in the realm of journal science, while Meyer made no predictions at all and explicitly stated his table and his textbook it was contained in, ''Modern Theories'', should not be used for prediction in order to make the point to his students to not make too many purely theoretically constructed projections.
Mendeleev and Meyer differed in temperament, at least when it came to promotion of their respective works. Boldness of Mendeleev's predictions was noted by some contemporary chemists, however skeptical they may have been. Meyer referred to Mendeleev's "boldness" in an edition of ''Modern Theories'', whereas Mendeleev mocked Meyer's indecisiveness to predict in an edition of ''Foundations of Chemistry''.
Recognition of Mendeleev's table
Eventually, the periodic table was appreciated for its descriptive power and for finally systematizing the relationship between the elements, although such appreciation was not universal. In 1881, Mendeleev and Meyer had an argument via an exchange of articles in British journal ''Chemical News'' over priority of the periodic table, which included an article from Mendeleev, one from Meyer, one of critique of the notion of periodicity, and many more. In 1882, the Royal Society
The Royal Society, formally The Royal Society of London for Improving Natural Knowledge, is a learned society and the United Kingdom's national academy of sciences. The society fulfils a number of roles: promoting science and its benefits, re ...
in London awarded the Davy Medal
The Davy Medal is awarded by the Royal Society of London "for an outstandingly important recent discovery in any branch of chemistry". Named after Humphry Davy, the medal is awarded with a monetary gift, initially of £1000 (currently £2000).
H ...
to both Mendeleev and Meyer for their work to classify the elements; although two of Mendeleev's predicted elements had been discovered by then, Mendeleev's predictions were not at all mentioned in the prize rationale.
Mendeleev's ''eka-aluminium'' was discovered in 1875 and became known as gallium; ''eka-boron'' and ''eka-silicium'' were discovered in 1879 and 1886, respectively, and were named scandium
Scandium is a chemical element with the symbol Sc and atomic number 21. It is a silvery-white metallic d-block element. Historically, it has been classified as a rare-earth element, together with yttrium and the Lanthanides. It was discovered in ...
and germanium. Mendeleev was even able to correct some initial measurements with his predictions, including the first prediction of gallium, which matched ''eka-aluminium'' fairly closely but had a different density. Mendeleev advised the discoverer, French chemist Paul-Émile Lecoq de Boisbaudran
Paul-Émile Lecoq de Boisbaudran, also called François Lecoq de Boisbaudran (18 April 1838 – 28 May 1912), was a French chemist known for his discoveries of the chemical elements gallium, samarium and dysprosium.
He developed methods for s ...
, to measure the density again; de Boisbaudran was initially skeptical (not least because he thought Mendeleev was trying to take credit from him) but eventually admitted the correctness of the prediction. Mendeleev contacted all three discoverers; all three noted the close similarity of their discovered elements with Mendeleev's predictions, with the last of them, German chemist Clemens Winkler
Clemens Alexander Winkler (December 26, 1838 – October 8, 1904) was a German chemist who discovered the element germanium in 1886, solidifying Dmitri Mendeleev's theory of periodicity.
Life
Winkler was born in 1838 in Freiberg, Kingdom ...
, admitting this suggestion was not first made by Mendeleev or himself after the correspondence with him, but by a different person, German chemist Hieronymous Theodor Richter
Hieronymus Theodor Richter (21 November 1824 – 25 September 1898) was a German chemist.
He was born in Dresden. In 1863, while working at the Freiberg University of Mining and Technology, he co-discovered indium with Ferdinand Reich. He was al ...
. Some contemporary chemists were not convinced by these discoveries, noting the dissimilarities between the new elements and the predictions or claiming those similarities that did exist were coincidental. However, success of Mendeleev's predictions helped spread the word about his periodic table. Later chemists used the successes of these Mendeleev's predictions to justify his table.
By 1890, Mendeleev's periodic table had been universally recognized as a piece of basic chemical knowledge. Apart from his own correct predictions, a number of aspects may have contributed to this, such as the correct accommodation of many elements whose atomic weights were thought to have wrong values but were later corrected. The debate on the position of the rare-earth metals helped spur the discussion about the table as well. In 1889, Mendeleev noted at the Faraday Lecture to the Royal Institution in London that he had not expected to live long enough "to mention their discovery to the Chemical Society of Great Britain as a confirmation of the exactitude and generality of the periodic law".
Inert gases and ether
Inert gases
British chemist Henry Cavendish
Henry Cavendish ( ; 10 October 1731 – 24 February 1810) was an English natural philosopher and scientist who was an important experimental and theoretical chemist and physicist. He is noted for his discovery of hydrogen, which he termed "infl ...
, the discoverer of hydrogen
Hydrogen is the chemical element with the symbol H and atomic number 1. Hydrogen is the lightest element. At standard conditions hydrogen is a gas of diatomic molecules having the formula . It is colorless, odorless, tasteless, non-toxic ...
in 1766, discovered that air is composed of more gases than nitrogen
Nitrogen is the chemical element with the symbol N and atomic number 7. Nitrogen is a nonmetal and the lightest member of group 15 of the periodic table, often called the pnictogens. It is a common element in the universe, estimated at se ...
and oxygen
Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements as ...
. He recorded these findings in 1784 and 1785; among them, he found a then-unidentified gas less reactive than nitrogen. Helium
Helium (from el, ἥλιος, helios, lit=sun) is a chemical element with the symbol He and atomic number 2. It is a colorless, odorless, tasteless, non-toxic, inert, monatomic gas and the first in the noble gas group in the periodic table. ...
was first reported in 1868; the report was based on the new technique of spectroscopy; some spectral lines in light emitted by the Sun did not match those of any of the known elements. Mendeleev was not convinced by this finding since variance of temperature led to change of intensity of spectral lines and their location on the spectrum; this opinion was held by some other scientists of the day. Others believed the spectral lines could belong to an element that occurred on the Sun but not on Earth; some believed it was yet to be found on Earth.
In 1894, British chemist William Ramsay
Sir William Ramsay (; 2 October 1852 – 23 July 1916) was a Scottish chemist who discovered the noble gases and received the Nobel Prize in Chemistry in 1904 "in recognition of his services in the discovery of the inert gaseous element ...
and British physicist Lord Rayleigh
John William Strutt, 3rd Baron Rayleigh, (; 12 November 1842 – 30 June 1919) was an English mathematician and physicist who made extensive contributions to science. He spent all of his academic career at the University of Cambridge. Am ...
isolated argon
Argon is a chemical element with the symbol Ar and atomic number 18. It is in group 18 of the periodic table and is a noble gas. Argon is the third-most abundant gas in Earth's atmosphere, at 0.934% (9340 ppmv). It is more than twice as ...
from air and determined that it was a new element. Argon, however, did not engage in any chemical reactions and was—highly unusually for a gas—monatomic; it did not fit into the periodic law and thus challenged the very notion of it. Not all scientists immediately accepted this report; Mendeleev's original response was that argon was a triatomic form of nitrogen rather than an element of its own. While the notion of a possibility of a group between that of halogens and that of alkali metals had existed (some scientists believed that several atomic weight values between halogens and alkali metals were missing, especially since places in this half of group VIII remained vacant), argon did not easily match the position between chlorine and potassium because its atomic weight exceeded those of both chlorine and potassium. Other explanations were proposed; for example, Ramsay supposed argon could be a mixture of different gases. For a while, Ramsay believed argon could be a mixture of three gases of similar atomic weights; this triad would resemble the triad of iron, cobalt, and nickel, and be similarly placed in group VIII. Certain that shorter periods contain triads of gases at their ends, Ramsay suggested in 1898 the existence of a gas between helium and argon with an atomic weight of 20; after its discovery later that year (it was named neon), Ramsay continued to interpret it as a member of a horizontal triad at the end of that period.
In 1896, Ramsay tested a report of American chemist William Francis Hillebrand, who found a stream of an unreactive gas from a sample of uraninite
Uraninite, formerly pitchblende, is a radioactive, uranium-rich mineral and ore with a chemical composition that is largely UO2 but because of oxidation typically contains variable proportions of U3O8. Radioactive decay of the uranium causes ...
. Wishing to prove it was nitrogen, Ramsay analyzed a different uranium mineral, cleveite, and found a new element, which he named krypton. This finding was corrected by British chemist William Crookes
Sir William Crookes (; 17 June 1832 – 4 April 1919) was a British chemist and physicist who attended the Royal College of Chemistry, now part of Imperial College London, and worked on spectroscopy. He was a pioneer of vacuum tubes, inventing t ...
, who matched its spectrum to that of the Sun's helium. Following this discovery, Ramsay, using fractional distillation to separate the components air, discovered several more such gases in 1898: metargon, krypton
Krypton (from grc, κρυπτός, translit=kryptos 'the hidden one') is a chemical element with the symbol Kr and atomic number 36. It is a colorless, odorless, tasteless noble gas that occurs in trace amounts in the atmosphere and is often ...
, neon, and xenon
Xenon is a chemical element with the symbol Xe and atomic number 54. It is a dense, colorless, odorless noble gas found in Earth's atmosphere in trace amounts. Although generally unreactive, it can undergo a few chemical reactions such as the ...
; detailed spectroscopic analysis of the first of these demonstrated it was argon contaminated by a carbon-based impurity. Ramsay was initially skeptical about the existence of gases heavier than argon, and the discovery of krypton and xenon came as a surprise to him; however, Ramsay accepted his own discovery, and the five newly discovered inert gases (now noble gases
The noble gases (historically also the inert gases; sometimes referred to as aerogens) make up a class of chemical elements with similar properties; under standard conditions, they are all odorless, colorless, monatomic gases with very low ch ...
) were placed in a single column in the periodic table. Although Mendeleev's table predicted several undiscovered elements, it did not predict the existence of such inert gases, and Mendeleev originally rejected those findings as well.
Changes to the periodic table
Although the sequence of atomic weights suggested that inert gases should be located between halogens and alkali metals, and there were suggestions to put them into group VIII coming from as early as 1895, such placement contradicted one of Mendeleev's basic considerations, that of the highest oxides. Inert gases did not form any oxides, and no other compounds at all, and as such, their placement in a group where elements should form tetroxides was seen as merely auxiliary and not natural; Mendeleev doubted inclusion of those elements in group VIII. Later developments, particularly by British scientists, focused on correspondence of inert gases with halogens to their left and alkali metals to their right. In 1898, when only helium, argon, and krypton were definitively known, Crookes suggested these elements be placed in a single column between the hydrogen group and the fluorine group. In 1900, at the Prussian Academy of Sciences
The Royal Prussian Academy of Sciences (german: Königlich-Preußische Akademie der Wissenschaften) was an academy established in Berlin, Germany on 11 July 1700, four years after the Prussian Academy of Arts, or "Arts Academy," to which "Berlin ...
, Ramsay and Mendeleev discussed the new inert gases and their location in the periodic table; Ramsay proposed that these elements be put in a new group between halogens and alkali metals, to which Mendeleev agreed. Ramsay published an article after his discussions with Mendeleev; the tables in it featured halogens to the left of inert gases and alkali metals to the right. Two weeks before that discussion, Belgian botanist Léo Errera had proposed to the Royal Academy of Science, Letters and Fine Arts of Belgium
The Royal Academy of Science, Letters and Fine Arts of Belgium (french: Académie royale des sciences, des lettres et des beaux-arts de Belgique, sometimes referred to as ') is the independent learned society of science and arts of the French Comm ...
to put those elements in a new group 0. In 1902, Mendeleev wrote that those elements should be put in a new group 0; he said this idea was consistent with what Ramsay suggested to him and referred to Errera as to the first person to suggest the idea. Mendeleev himself added these elements to the table as group 0 in 1902, without disturbing the basic concept of the periodic table.
An English translation appeared as
In 1905, Swiss chemist Alfred Werner resolved the dead zone of Mendeleev's table. He determined that the rare-earth element
The rare-earth elements (REE), also called the rare-earth metals or (in context) rare-earth oxides or sometimes the lanthanides ( yttrium and scandium are usually included as rare earths), are a set of 17 nearly-indistinguishable lustrous silv ...
s ( lanthanides), 13 of which were known, lay within that gap. Although Mendeleev knew of lanthanum
Lanthanum is a chemical element with the symbol La and atomic number 57. It is a soft, ductile, silvery-white metal that tarnishes slowly when exposed to air. It is the eponym of the lanthanide series, a group of 15 similar elements between lant ...
, cerium, and erbium
Erbium is a chemical element with the symbol Er and atomic number 68. A silvery-white solid metal when artificially isolated, natural erbium is always found in chemical combination with other elements. It is a lanthanide, a rare-earth element, or ...
, they were previously unaccounted for in the table because their total number and exact order were not known; Mendeleev still could not fit them in his table by 1901.[ This was in part a consequence of their similar chemistry and the imprecise determination of their atomic masses. Combined with the lack of a known group of similar elements, this rendered the placement of the lanthanides in the periodic table difficult.] This discovery led to a restructuring of the table and the first appearance of the 32-column form.
Ether
By 1904, Mendeleev's table rearranged several elements, and included the noble gases along with most other newly discovered elements. It still had the dead zone, and a row zero was added above hydrogen and helium to include coronium
Coronium, also called newtonium, was the name of a suggested chemical element, hypothesised in the 19th century. The name, inspired by the solar corona, was given by Gruenwald in 1887. A new atomic thin green line in the solar corona was then con ...
and the ether, which were widely believed to be elements at the time. Although the Michelson–Morley experiment
The Michelson–Morley experiment was an attempt to detect the existence of the luminiferous aether, a supposed medium permeating space that was thought to be the carrier of light waves. The experiment was performed between April and July 188 ...
in 1887 cast doubt on the possibility of a luminiferous ether
Luminiferous aether or ether ("luminiferous", meaning "light-bearing") was the postulated medium for the propagation of light. It was invoked to explain the ability of the apparently wave-based light to propagate through empty space (a vacuum), so ...
as a space-filling medium, physicists set constraints for its properties. Mendeleev believed it to be a very light gas, with an atomic weight several orders of magnitude smaller than that of hydrogen. He also postulated that it would rarely interact with other elements, similar to the noble gases of his group zero, and instead permeate substances at a velocity of per second.
Mendeleev was not satisfied with the lack of understanding of the nature of this periodicity; this would only be possible with the understanding of composition of atom. However, Mendeleev firmly believed that future would only develop the notion rather than challenge it and reaffirmed his belief in writing in 1902.
File:Masson main table 1895.png, Main table of the periodic table published by Australian chemist David Orme Masson in 1895
File:Ramsay 1896 fragment.png, Fragment of a periodic table published by Ramsay in 1896
File:Ramsay 1900 fragment.png, Fragment of a periodic table published by Ramsay in 1900
File:Errera 1900.png, Periodic table as published by Errera in 1900
File:Mendeleev 1904 Periodic Table.png, Mendeleev's 1904 table. It includes the noble gases in group 0, and it has two reserved gaps for coronium
Coronium, also called newtonium, was the name of a suggested chemical element, hypothesised in the 19th century. The name, inspired by the solar corona, was given by Gruenwald in 1887. A new atomic thin green line in the solar corona was then con ...
and ether
In organic chemistry, ethers are a class of compounds that contain an ether group—an oxygen atom connected to two alkyl or aryl groups. They have the general formula , where R and R′ represent the alkyl or aryl groups. Ethers can again be ...
.
File:Taula periòdica de Werner (1905).gif, Werner's 32-column 1905 table. This table left spaces for many then-unknown elements, and several elements had their positions revised following advances in atomic theory.
Atomic theory and isotopes
Radioactivity and isotopes
In 1907 it was discovered that thorium and radiothorium, products of radioactive decay, were physically different but chemically identical; this led Frederick Soddy
Frederick Soddy FRS (2 September 1877 – 22 September 1956) was an English radiochemist who explained, with Ernest Rutherford, that radioactivity is due to the transmutation of elements, now known to involve nuclear reactions. He also prov ...
to propose in 1910 that they were the same element but with different atomic weights. Soddy later proposed to call these elements with complete chemical identity “isotopes“.
The problem of placing isotopes in the periodic table had arisen beginning in 1900 when four radioactive elements were known: radium
Radium is a chemical element with the symbol Ra and atomic number 88. It is the sixth element in group 2 of the periodic table, also known as the alkaline earth metals. Pure radium is silvery-white, but it readily reacts with nitrogen (rathe ...
, actinium
Actinium is a chemical element with the symbol Ac and atomic number 89. It was first isolated by Friedrich Oskar Giesel in 1902, who gave it the name ''emanium''; the element got its name by being wrongly identified with a substance An ...
, thorium
Thorium is a weakly radioactive metallic chemical element with the symbol Th and atomic number 90. Thorium is silvery and tarnishes black when it is exposed to air, forming thorium dioxide; it is moderately soft and malleable and has a high ...
, and uranium
Uranium is a chemical element with the symbol U and atomic number 92. It is a silvery-grey metal in the actinide series of the periodic table. A uranium atom has 92 protons and 92 electrons, of which 6 are valence electrons. Uranium is weak ...
. These radioactive elements (termed "radioelements") were accordingly placed at the bottom of the periodic table, as they were known to have greater atomic weights than stable elements, although their exact order was not known. Researchers believed there were still more radioactive elements yet to be discovered, and during the next decade, the decay chain
In nuclear science, the decay chain refers to a series of radioactive decays of different radioactive decay products as a sequential series of transformations. It is also known as a "radioactive cascade". Most radioisotopes do not decay dire ...
s of thorium and uranium were extensively studied. Many new radioactive substances were found, including the noble gas radon
Radon is a chemical element with the symbol Rn and atomic number 86. It is a radioactive, colourless, odourless, tasteless noble gas. It occurs naturally in minute quantities as an intermediate step in the normal radioactive decay chains through ...
, and their chemical properties were investigated.[ By 1912, almost 50 different radioactive substances had been found in the decay chains of thorium and uranium. American chemist Bertram Boltwood proposed several decay chains linking these radioelements between uranium and lead. These were thought at the time to be new chemical elements, substantially increasing the number of known "elements" and leading to speculations that their discoveries would undermine the concept of the periodic table which had long been established to obey the ]octet rule
The octet rule is a chemical rule of thumb that reflects the theory that main-group elements tend to bond in such a way that each atom has eight electrons in its valence shell, giving it the same electronic configuration as a noble gas. The rul ...
. For example, there was not enough room between lead and uranium to accommodate these discoveries, even assuming that some discoveries were duplicates or incorrect identifications. It was also believed that radioactive decay violated one of the central principles of the periodic table, namely that chemical elements could not undergo transmutations and always had unique identities.[
Soddy and ]Kazimierz Fajans
Kazimierz Fajans (Kasimir Fajans in many American publications; 27 May 1887 – 18 May 1975) was a Polish American physical chemist of Polish-Jewish origin, a pioneer in the science of radioactivity and the discoverer of chemical element protac ...
, who had been following these developments, published in 1913 that although these substances emitted different radiation, many of these substances were identical in their chemical characteristics, so shared the same place in the periodic table. They became known as isotope
Isotopes are two or more types of atoms that have the same atomic number (number of protons in their nuclei) and position in the periodic table (and hence belong to the same chemical element), and that differ in nucleon numbers (mass numb ...
s, from the Greek ' ("same place").[ Austrian chemist Friedrich Paneth cited a difference between "real elements" (elements) and "simple substances" (isotopes), also determining that the existence of different isotopes was mostly irrelevant in determining chemical properties.][
Following British physicist ]Charles Glover Barkla
Charles Glover Barkla FRS FRSE (7 June 1877 – 23 October 1944) was a British physicist, and the winner of the Nobel Prize in Physics in 1917 for his work in X-ray spectroscopy and related areas in the study of X-rays (Roentgen rays).
Life ...
's discovery of characteristic X-ray
An X-ray, or, much less commonly, X-radiation, is a penetrating form of high-energy electromagnetic radiation. Most X-rays have a wavelength ranging from 10 picometers to 10 nanometers, corresponding to frequencies in the range 30&nb ...
s emitted from metals in 1906, British physicist Henry Moseley
Henry Gwyn Jeffreys Moseley (; 23 November 1887 – 10 August 1915) was an English physicist, whose contribution to the science of physics was the justification from physical laws of the previous empirical and chemical concept of the atomic num ...
considered a possible correlation between X-ray emissions and physical properties of elements. Moseley, along with Charles Galton Darwin, Niels Bohr
Niels Henrik David Bohr (; 7 October 1885 – 18 November 1962) was a Danish physicist who made foundational contributions to understanding atomic structure and quantum theory, for which he received the Nobel Prize in Physics in 1922 ...
, and George de Hevesy
George Charles de Hevesy (born György Bischitz; hu, Hevesy György Károly; german: Georg Karl von Hevesy; 1 August 1885 – 5 July 1966) was a Hungarian radiochemist and Nobel Prize in Chemistry laureate, recognized in 1943 for his key rol ...
, proposed that the nuclear charge 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 ...
(''Z'') might be mathematically related to physical properties. The significance of these atomic properties was determined in the Geiger–Marsden experiment, in which the atomic nucleus and its charge were discovered.
Rutherford model and atomic number
In 1913, amateur Dutch physicist Antonius van den Broek was the first to propose that the atomic number
The atomic number or nuclear charge number (symbol ''Z'') of a chemical element is the charge number of an atomic nucleus. For ordinary nuclei, this is equal to the proton number (''n''p) or the number of protons found in the nucleus of every ...
(nuclear charge) determined the placement of elements in the periodic table. He correctly determined the atomic number of all elements up to atomic number 50 (tin
Tin is a chemical element with the symbol Sn (from la, stannum) and atomic number 50. Tin is a silvery-coloured metal.
Tin is soft enough to be cut with little force and a bar of tin can be bent by hand with little effort. When bent, t ...
), though he made several errors with heavier elements. However, Van den Broek did not have any method to experimentally verify the atomic numbers of elements; thus, they were still believed to be a consequence of atomic weight, which remained in use in ordering elements.[
Moseley was determined to test Van den Broek's hypothesis.][ After a year of investigation of the ]Fraunhofer lines
In physics and optics, the Fraunhofer lines are a set of spectral absorption lines named after the German physicist Joseph von Fraunhofer (1787–1826). The lines were originally observed as dark features (absorption lines) in the optical spectru ...
of various elements, he found a relationship between the X-ray wavelength
In physics, the wavelength is the spatial period of a periodic wave—the distance over which the wave's shape repeats.
It is the distance between consecutive corresponding points of the same phase on the wave, such as two adjacent crests, t ...
of an element and its atomic number. With this, Moseley obtained the first accurate measurements of atomic numbers and determined an absolute sequence to the elements, allowing him to restructure the periodic table. Moseley's research immediately resolved discrepancies between atomic weight and chemical properties, where sequencing strictly by atomic weight would result in groups with inconsistent chemical properties. For example, his measurements of X-ray wavelengths enabled him to correctly place argon
Argon is a chemical element with the symbol Ar and atomic number 18. It is in group 18 of the periodic table and is a noble gas. Argon is the third-most abundant gas in Earth's atmosphere, at 0.934% (9340 ppmv). It is more than twice as ...
(''Z'' = 18) before potassium
Potassium is the chemical element with the symbol K (from Neo-Latin ''kalium'') and atomic number19. Potassium is a silvery-white metal that is soft enough to be cut with a knife with little force. Potassium metal reacts rapidly with atmosph ...
(''Z'' = 19), cobalt
Cobalt is a chemical element with the symbol Co and atomic number 27. As with nickel, cobalt is found in the Earth's crust only in a chemically combined form, save for small deposits found in alloys of natural meteoric iron. The free element, p ...
(''Z'' = 27) before nickel
Nickel is a chemical element with symbol Ni and atomic number 28. It is a silvery-white lustrous metal with a slight golden tinge. Nickel is a hard and ductile transition metal. Pure nickel is chemically reactive but large pieces are slow ...
(''Z'' = 28), as well as tellurium
Tellurium is a chemical element with the symbol Te and atomic number 52. It is a brittle, mildly toxic, rare, silver-white metalloid. Tellurium is chemically related to selenium and sulfur, all three of which are chalcogens. It is occasionall ...
(''Z'' = 52) before iodine (''Z'' = 53), in line with periodic trends
Periodic trends are specific patterns that are present in the periodic table that illustrate different aspects of a certain element. They were discovered by the Russian chemist Dmitri Mendeleev in the year 1863. Major periodic trends include atom ...
. The determination of atomic numbers also clarified the order of chemically similar rare-earth elements; it was also used to confirm that Georges Urbain Georges Urbain (12 April 1872 – 5 November 1938) was a French chemist, a professor of the Sorbonne, a member of the Institut de France, and director of the Institute of Chemistry in Paris. Much of his work focused on the rare earths, isolating a ...
's claimed discovery of a new rare-earth element ( celtium) was invalid, earning Moseley acclamation for this technique.[
Swedish physicist Karl Siegbahn continued Moseley's work for elements heavier than gold (''Z'' = 79), and found that the heaviest known element at the time, ]uranium
Uranium is a chemical element with the symbol U and atomic number 92. It is a silvery-grey metal in the actinide series of the periodic table. A uranium atom has 92 protons and 92 electrons, of which 6 are valence electrons. Uranium is weak ...
, had atomic number 92. In determining the largest identified atomic number, gaps in the atomic number sequence were conclusively determined where an atomic number had no known corresponding element; the gaps occurred at atomic numbers 43 (technetium
Technetium is a chemical element with the symbol Tc and atomic number 43. It is the lightest element whose isotopes are all radioactive. All available technetium is produced as a synthetic element. Naturally occurring technetium is a spontaneous ...
), 61 ( promethium), 72 (hafnium
Hafnium is a chemical element with the symbol Hf and atomic number 72. A lustrous, silvery gray, tetravalent transition metal, hafnium chemically resembles zirconium and is found in many zirconium minerals. Its existence was predicted by Dmitri M ...
), 75 (rhenium
Rhenium is a chemical element with the symbol Re and atomic number 75. It is a silvery-gray, heavy, third-row transition metal in group 7 of the periodic table. With an estimated average concentration of 1 part per billion (ppb), rhenium is one ...
), 85 (astatine
Astatine is a chemical element with the symbol At and atomic number 85. It is the rarest naturally occurring element in the Earth's crust, occurring only as the decay product of various heavier elements. All of astatine's isotopes are short-li ...
), and 87 ( francium).[
]
Electron shell and quantum mechanics
In 1888, Swedish physicist Johannes Rydberg working from the 1885 Balmer formula noticed that the atomic numbers of the noble gases was equal to doubled sums of squares of simple numbers: 2 = 2·12, 10 = 2(12 + 22), 18 = 2(12 + 22 + 22), 36 = 2(12 + 22 + 22 + 32), 54 = 2(12 + 22 + 22 + 32 + 32), 86 = 2(12 + 22 + 22 + 32 + 32 + 42). This finding was accepted as an explanation of the fixed lengths of periods and led to repositioning of the noble gases from the left edge of the table, in group 0, to the right, in group VIII. Unwillingness of the noble gases to engage in chemical reaction was explained in the alluded stability of closed noble gas electron configurations; from this notion emerged the octet rule
The octet rule is a chemical rule of thumb that reflects the theory that main-group elements tend to bond in such a way that each atom has eight electrons in its valence shell, giving it the same electronic configuration as a noble gas. The rul ...
originally referred to as Abegg’s Rule of 1904. Among the notable works that established the importance of the periodicity of eight were the valence bond theory, published in 1916 by American chemist Gilbert N. Lewis and the octet theory of chemical bonding, published in 1919 by American chemist Irving Langmuir. The chemists' approach during the period of the Old Quantum Theory (1913 to 1925) was incorporated into the understanding of the electron shells and orbitals under current quantum mechanics
Quantum mechanics is a fundamental theory in physics that provides a description of the physical properties of nature at the scale of atoms and subatomic particles. It is the foundation of all quantum physics including quantum chemistr ...
. A real pioneer who gave us the foundation for our current model of electrons is Irving Langmuir. In his 1919 paper, he postulated the existence of "cells", which we now call orbitals, which could each only contain two electrons, and these were arranged in "equidistant layers" which we now call shells. He made an exception for the first shell to only contain two electrons. These postulates were introduced on the basis of Rydberg's rule which Niels Bohr
Niels Henrik David Bohr (; 7 October 1885 – 18 November 1962) was a Danish physicist who made foundational contributions to understanding atomic structure and quantum theory, for which he received the Nobel Prize in Physics in 1922 ...
had used not in chemistry, but in physics, to apply to the orbits of electrons around the nucleus. In the Langmuir paper, he introduced the rule as 2N2 where N was a positive integer.
The chemist Charles Rugeley Bury
Charles Rugeley Bury (29 June 1890 – 30 December 1968) was an English physical chemist who proposed an early model of the atom with the arrangement of electrons, which explained their chemical properties, alongside the more dominant model of Nie ...
made the next major step toward our modern theory in 1921, by suggesting that eight and eighteen electrons in a shell form stable configurations. Bury’s scheme was built upon that of earlier chemists and was a chemical model. Bury proposed that the electron configurations in transitional elements depended upon the valency electrons in their outer shell. In some early papers, the model was called the "Bohr-Bury Atom". He introduced the word ''transition'' to describe the elements now known as transition metal
In chemistry, a transition metal (or transition element) is a chemical element in the d-block of the periodic table (groups 3 to 12), though the elements of group 12 (and less often group 3) are sometimes excluded. They are the elements that ca ...
s or transition elements.
In the 1910s and 1920s, pioneering research into quantum mechanics led to new developments in atomic theory and small changes to the periodic table. In the 19th century, Mendeleev had already asserted that there was a fixed periodicity of eight, and expected a mathematical correlation between atomic number and chemical properties. The Bohr model
In atomic physics, the Bohr model or Rutherford–Bohr model, presented by Niels Bohr and Ernest Rutherford in 1913, is a system consisting of a small, dense nucleus surrounded by orbiting electrons—similar to the structure of the Solar Syst ...
was developed beginning 1913, and championed the idea of electron configurations that determine chemical properties. Bohr proposed that elements in the same group behaved similarly because they have similar electron configurations, and that noble gases had filled valence shells; this forms the basis of the modern octet rule
The octet rule is a chemical rule of thumb that reflects the theory that main-group elements tend to bond in such a way that each atom has eight electrons in its valence shell, giving it the same electronic configuration as a noble gas. The rul ...
. Bohr's study of spectroscopy and chemistry was not usual among theoretical atomic physicists. Even Rutherford told Bohr that he was struggling "to form an idea of how you arrive at your conclusions". This is because none of the quantum mechanical equations describe the number of electrons per shell and orbital. Bohr acknowledged that he was influenced by the work of Walther Kossel
Walther Ludwig Julius Kossel (4 January 1888 – 22 May 1956) was a German physicist known for his theory of the chemical bond (ionic bond/octet rule), Sommerfeld–Kossel displacement law of atomic spectra, the Kossel-Stranski model for crysta ...
, who in 1916 was the first to establish an important connection between the quantum atom and the periodic table. He noticed that the difference between the atomic numbers 2, 10, 18 of the first three noble gases, helium, neon, argon, was 8, and argued that the electrons in such atoms orbited in "closed shells". The first contained only 2 electrons, the second and third, 8 each. Bohr's research then led Austrian physicist Wolfgang Pauli
Wolfgang Ernst Pauli (; ; 25 April 1900 – 15 December 1958) was an Austrian theoretical physicist and one of the pioneers of quantum physics. In 1945, after having been nominated by Albert Einstein, Pauli received the Nobel Prize in Physics ...
to investigate the length of periods in the periodic table in 1924. Pauli demonstrated that this was not the case. Instead, the Pauli exclusion principle
In quantum mechanics, the Pauli exclusion principle states that two or more identical particles with half-integer spins (i.e. fermions) cannot occupy the same quantum state within a quantum system simultaneously. This principle was formulat ...
was developed, not upon a mathematical basis, but upon the previous developments in alignment with chemistry. This rule states that no electrons can coexist in the same quantum state, and showed, in conjunction with empirical observations, the existence of four quantum numbers and the consequence on the order of shell filling.[ This determines the order in which ]electron shell
In chemistry and atomic physics, an electron shell may be thought of as an orbit followed by electrons around an atom's nucleus. The closest shell to the nucleus is called the "1 shell" (also called the "K shell"), followed by the "2 shell" (or ...
s are filled and explains the periodicity of the periodic table.
British chemist Charles Bury is credited with the first use of the term ''transition metal'' in 1921 to refer to elements between the main-group element
In chemistry and atomic physics, the main group is the group of elements (sometimes called the representative elements) whose lightest members are represented by helium, lithium, beryllium, boron, carbon, nitrogen, oxygen, and fluorine as arrange ...
s of groups II and III. He explained the chemical properties of transition elements as a consequence of the filling of an inner subshell rather than the valence shell. This proposition, based upon the work of American chemist Gilbert N. Lewis, suggested the appearance of the ''d'' subshell in period 4 and the ''f'' subshell in period 6, lengthening the periods from 8 to 18 and then 18 to 32 elements, thus explaining the position of the lanthanides in the periodic table.
Proton and neutron
The discovery of proton and neutron demonstrated that an atom was divisible; this rendered Lavoisier's definition of a chemical element obsolete. A chemical element is defined today as a species of atoms with a consistent number of protons and that number is now known to be precisely the atomic number of an element. The discovery also explained the mechanism of several types of radioactive decay, such as alpha decay
Alpha decay or α-decay is a type of radioactive decay in which an atomic nucleus emits an alpha particle (helium nucleus) and thereby transforms or 'decays' into a different atomic nucleus, with a mass number that is reduced by four and an at ...
.
Eventually, it was proposed that protons and neutrons were made of even smaller particles called quarks; their discovery explained the transmutation of neutrons into protons in beta decay
In nuclear physics, beta decay (β-decay) is a type of radioactive decay in which a beta particle (fast energetic electron or positron) is emitted from an atomic nucleus, transforming the original nuclide to an isobar of that nuclide. For ...
.
From short form into long form (into -A and -B groups)
Circa 1925, the periodic table changed by shifting some ''Reihen'' (series) to the right, into an extra set of columns (groups). The original groups I–VII were repeated, distinguished by adding "A" and "B". Group VIII (with three columns) remained sole.
Thus, ''Reihen'' 4 and 5 were shifted, and together formed new ''period'' 4 with groups IA–VIIA, VIII, IB–VIIB.
Later expansions and the end of the periodic table
Actinides
As early as 1913, Bohr's research on electronic structure
In quantum chemistry, electronic structure is the state of motion of electrons in an electrostatic field created by stationary nuclei. The term encompasses both the wave functions of the electrons and the energies associated with them. Electr ...
led physicists such as Johannes Rydberg to extrapolate the properties of undiscovered elements heavier than uranium. Many agreed that the next noble gas after radon would most likely have the atomic number 118, from which it followed that the transition series in the seventh period should resemble those in the sixth. Although it was thought that these transition series would include a series analogous to the rare-earth elements, characterized by filling of the 5f shell, it was unknown where this series began. Predictions ranged from atomic number 90 (thorium) to 99, many of which proposed a beginning beyond the known elements (at or beyond atomic number 93). The elements from actinium
Actinium is a chemical element with the symbol Ac and atomic number 89. It was first isolated by Friedrich Oskar Giesel in 1902, who gave it the name ''emanium''; the element got its name by being wrongly identified with a substance An ...
to uranium were instead believed to form part of a fourth series of transition metals because of their high oxidation state
In chemistry, the oxidation state, or oxidation number, is the hypothetical charge of an atom if all of its bonds to different atoms were fully ionic. It describes the degree of oxidation (loss of electrons) of an atom in a chemical compound. C ...
s; accordingly, they were placed in groups 3 through 6.
In 1940, neptunium
Neptunium is a chemical element with the symbol Np and atomic number 93. A radioactive actinide metal, neptunium is the first transuranic element. Its position in the periodic table just after uranium, named after the planet Uranus, led to it bein ...
and plutonium
Plutonium is a radioactive chemical element with the symbol Pu and atomic number 94. It is an actinide metal of silvery-gray appearance that tarnishes when exposed to air, and forms a dull coating when oxidized. The element normally exhibi ...
were the first transuranic element
The transuranium elements (also known as transuranic elements) are the chemical elements with atomic numbers greater than 92, which is the atomic number of uranium. All of these elements are unstable and decay radioactively into other elements. ...
s to be discovered; they were placed in sequence beneath rhenium
Rhenium is a chemical element with the symbol Re and atomic number 75. It is a silvery-gray, heavy, third-row transition metal in group 7 of the periodic table. With an estimated average concentration of 1 part per billion (ppb), rhenium is one ...
and osmium, respectively. However, preliminary investigations of their chemistry suggested a greater similarity to uranium than to lighter transition metals, challenging their placement in the periodic table.[ During his ]Manhattan Project
The Manhattan Project was a research and development undertaking during World War II that produced the first nuclear weapons. It was led by the United States with the support of the United Kingdom and Canada. From 1942 to 1946, the project w ...
research in 1943, American chemist Glenn T. Seaborg experienced unexpected difficulties in isolating the elements americium and curium, as they were believed to be part of a fourth series of transition metals. Seaborg wondered if these elements belonged to a different series, which would explain why their chemical properties, in particular the instability of higher oxidation state
In chemistry, the oxidation state, or oxidation number, is the hypothetical charge of an atom if all of its bonds to different atoms were fully ionic. It describes the degree of oxidation (loss of electrons) of an atom in a chemical compound. C ...
s, were different from predictions. In 1945, against the advice of colleagues, he proposed a significant change to Mendeleev's table: the actinide series
The actinide () or actinoid () series encompasses the 15 metallic chemical elements with atomic numbers from 89 to 103, actinium through lawrencium. The actinide series derives its name from the first element in the series, actinium. The inform ...
.
Seaborg's actinide concept
In nuclear chemistry, the actinide concept proposed that the actinides form a second inner transition series homologous to the lanthanides. Its origins stem from observation of lanthanide-like properties in transuranic elements in contrast to the d ...
of heavy element electronic structure proposed that the actinides form an inner transition series analogous to the rare-earth
The rare-earth elements (REE), also called the rare-earth metals or (in context) rare-earth oxides or sometimes the lanthanides (yttrium and scandium are usually included as rare earths), are a set of 17 nearly-indistinguishable lustrous silve ...
series of lanthanide elements—they would comprise the second row of the f-block (the 5f series), in which the lanthanides formed the 4f series. This facilitated chemical identification of americium and curium,[ and further experiments corroborated Seaborg's hypothesis; a spectroscopic study at the ]Los Alamos National Laboratory
Los Alamos National Laboratory (often shortened as Los Alamos and LANL) is one of the sixteen research and development laboratories of the United States Department of Energy (DOE), located a short distance northwest of Santa Fe, New Mexico, ...
by a group led by American physicist Edwin McMillan
Edwin Mattison McMillan (September 18, 1907 – September 7, 1991) was an American physicist credited with being the first-ever to produce a transuranium element, neptunium. For this, he shared the 1951 Nobel Prize in Chemistry with Glenn Seab ...
indicated that 5f orbitals, rather than 6d orbitals, were indeed being filled. However, these studies could not unambiguously determine the first element with 5f electrons and therefore the first element in the actinide series; it was thus also referred to as the "thoride" or "uranide" series until it was later found that the series began with actinium.
In light of these observations and an apparent explanation for the chemistry of transuranic elements, and despite fear among his colleagues that it was a radical idea that would ruin his reputation, Seaborg nevertheless submitted it to ''Chemical & Engineering News
''Chemical & Engineering News'' (''C&EN'') is a weekly news magazine published by the American Chemical Society, providing professional and technical news and analysis in the fields of chemistry and chemical engineering.[berkelium
Berkelium is a transuranic radioactive chemical element with the symbol Bk and atomic number 97. It is a member of the actinide and transuranium element series. It is named after the city of Berkeley, California, the location of the Lawrence Ber ...]
in 1949. It also supported experimental results for a trend towards +3 oxidation states in the elements beyond americium—a trend observed in the analogous 4f series.
Relativistic effects and expansions beyond period 7
Seaborg's subsequent elaborations of the actinide concept theorized a series of superheavy elements in a transactinide series comprising elements from 104 104 may refer to:
*104 (number), a natural number
*AD 104, a year in the 2nd century AD
* 104 BC, a year in the 2nd century BC
* 104 (MBTA bus), Massachusetts Bay Transportation Authority bus route
* Hundred and Four (or Council of 104), a Carthagin ...
to 121 and a superactinide
An extended periodic table theorises about chemical elements beyond those currently known in the periodic table and proven. , the element with the highest atomic number known is oganesson (''Z'' = 118), which completes the seventh period (row ...
series of elements from 122 122 may refer to:
*122 (number), a natural number
*AD 122, a year in the 2nd century AD
*122 BC, a year in the 2nd century BC
*122 (film), ''122'' (film), a 2019 Egyptian psychological horror film
*"One Twenty Two", a 2022 single by the American roc ...
to 153. He proposed an extended periodic table
An extended periodic table theorises about chemical elements beyond those currently known in the periodic table and proven. , the element with the highest atomic number known is oganesson (''Z'' = 118), which completes the seventh period (row ...
with an additional period of 50 elements (thus reaching element 168); this eighth period was derived from an extrapolation of the Aufbau principle and placed elements 121 to 138 in a g-block, in which a new g subshell would be filled. Seaborg's model, however, did not take into account relativistic effects resulting from high atomic number and electron orbital speed. Burkhard Fricke in 1971 and Pekka Pyykkö
Veli Pekka Pyykkö (born 12 October 1941) is a Finnish academic. He was professor of Chemistry at the University of Helsinki. From 2009–2012, he was the chairman of the International Academy of Quantum Molecular Science. He is known for his ...
in 2010 used computer modeling to calculate the positions of elements up to ''Z'' = 172, and found that the positions of several elements were different from those predicted by Seaborg. Although models from Pyykkö and Fricke generally place element 172 as the next noble gas, there is no clear consensus on the electron configurations of elements beyond 120 120 may refer to:
*120 (number), the number
* AD 120, a year in the 2nd century AD
*120 BC, a year in the 2nd century BC
*120 film, a film format for still photography
* ''120'' (film), a 2008 film
* 120 (MBTA bus)
* 120 (New Jersey bus)
* 120 (Ken ...
and thus their placement in an extended periodic table. It is now thought that because of relativistic effects, such an extension will feature elements that break the periodicity in known elements, thus posing another hurdle to future periodic table constructs.[
The discovery of ]tennessine
Tennessine is a synthetic chemical element with the symbol Ts and atomic number 117. It is the second-heaviest known element and the penultimate element of the 7th period of the periodic table.
The discovery of tennessine was officially anno ...
in 2010 filled the last remaining gap in the seventh period. Any newly discovered elements will thus be placed in an eighth period.
Despite the completion of the seventh period, experimental chemistry of some transactinides has been shown to be inconsistent with the periodic law. In the 1990s, Ken Czerwinski at University of California, Berkeley
The University of California, Berkeley (UC Berkeley, Berkeley, Cal, or California) is a public land-grant research university in Berkeley, California. Established in 1868 as the University of California, it is the state's first land-grant u ...
observed similarities between rutherfordium and plutonium and between dubnium and protactinium, rather than a clear continuation of periodicity in groups 4 and 5. More recent experiments on copernicium
Copernicium is a synthetic chemical element with the symbol Cn and atomic number 112. Its known isotopes are extremely radioactive, and have only been created in a laboratory. The most stable known isotope, copernicium-285, has a half-life of ap ...
and flerovium
Flerovium is a Transactinide element, superheavy chemical element with Chemical symbol, symbol Fl and atomic number 114. It is an extremely radioactive synthetic element. It is named after the Flerov Laboratory of Nuclear Reactions of the Joint ...
have yielded inconsistent results, some of which suggest that these elements behave more like the noble gas radon
Radon is a chemical element with the symbol Rn and atomic number 86. It is a radioactive, colourless, odourless, tasteless noble gas. It occurs naturally in minute quantities as an intermediate step in the normal radioactive decay chains through ...
rather than mercury and lead, their respective congeners. As such, the chemistry of many superheavy elements has yet to be well characterized, and it remains unclear whether the periodic law can still be used to extrapolate the properties of undiscovered elements.
See also
* Alternative periodic tables
Alternative periodic tables are tabulations of chemical elements differing in their organization from the traditional depiction of the periodic system.
Over a thousand have been devised, often for didactic reasons, as not all correlations bet ...
* History of chemistry
* Periodic systems of small molecules
Periodic systems of molecules are charts of molecules similar to the periodic table of the elements. Construction of such charts was initiated in the early 20th century and is still ongoing.
It is commonly believed that the periodic law, represen ...
* ''The Mystery of Matter: Search for the Elements'' (PBS film)
* Timeline of chemical element discoveries
The discovery of the 118 chemical elements known to exist as of 2022 is presented in chronological order. The elements are listed generally in the order in which each was first defined as the pure element, as the exact date of discovery of most el ...
Notes
References
Sources
*
*. Republished from
*. Republished from
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Further reading
*. Republished from
*
*
External links
Development of the periodic table
(part of a collection of pages that explores the periodic table and the elements) by th
Royal Society of Chemistry
*Dr. Eric Scerri'
web page
which contains interviews, lectures and articles on various aspects of the periodic system, including the history of the periodic table.
The Internet Database of Periodic Tables
– a large collection of periodic tables and periodic system formulations.
History of Mendeleev periodic table of elements as a data visualization
at Stack Exchange
Stack Exchange is a network of question-and-answer (Q&A) websites on topics in diverse fields, each site covering a specific topic, where questions, answers, and users are subject to a reputation award process. The reputation system allows th ...
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