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Review

Endeavour

Vol.28 No.2 June 2004

Elements in the history of the Periodic


Table
Dennis H. Rouvray
Department of Chemistry, University of Georgia, Athens, Georgia 30602, USA

Discovery of the Periodic Table was rendered possible


only after four decisive prerequisites had been
achieved. These were (i) the abandonment of the metaphysical and occult notions of elements that typified
the alchemical era; (ii) the adoption of a modern and
workable definition of an element; (iii) the development
of analytical chemical techniques for the isolation of the
elements and determination of their properties; and (iv)
the devising of a means of associating each element
with a characteristic natural number. The Periodic Table
made its appearance on cue almost as soon as these
preconditions had been fulfilled.
The discovery of the Periodic Table of the chemical
elements in the 1860s was one of the greatest scientific
breakthroughs ever made. It can certainly be ranked in
importance with the classification of plant species by
Linnaeus in the 1750s or the systematization of the
subnuclear particles by the physicists Gell-Mann and
Neeman in the 1950s. The Periodic Table is the fundamental classificatory scheme for all of the elements and
may be said to summarise the whole realm of chemistry
[1]. Every element has its rightful place in the Table and
even artificial elements that have not yet been synthesized have spaces allocated for them. Simply knowing
the position of an element in the Periodic Table tells us a
good deal about its properties and is usually enough to
predict how the element will behave in a wide variety of
different situations. We are also able to make reliable
predictions of the properties of all of the compounds that the
element forms. The Periodic Table thus affords us access to a
potential mine of information. It is not at all surprising
therefore that during the 20th century the Periodic Table
became a universally recognized scientific icon.
The development of the Periodic Table in the 19th
century had been agonisingly slow. Once several crucially
important issues were settled, however, the Periodic Table
made its appearance as if on cue. Thus, although the
gestational era was long and drawn out, the actual birth of
the Table was fairly rapid. The Periodic Table was
undoubtedly an idea whose time had come. In fact, during
the 1860s, the idea occurred to several different people at
roughly the same time, and we now recognize that the
Periodic Table had no fewer than six independent
discoverers [2]. These pioneers the Frenchman Alexandre Beguyer de Chancourtois (1862), the two Britons
John Newlands (1864) and William Odling (1864), the
Danish American Gustavus Hinrichs (1867), the German

Lothar Meyer (1868), and the Russian Dmitrii Mendeleev


(1869) certainly underscore its international patrimony.
But why did this sudden burst of creative activity take
place in the 1860s and not in some other decade? The
fundamental reason is that certain preconditions had to be
fulfilled before the ultimate breakthrough to the Periodic
Table became feasible. All of the preconditions were
concerned with our understanding of the nature of the
chemical elements and, until this area had been sufficiently investigated, no significant progress could be made.
First, ancient ideas about the elements deriving from the
alchemical era had to be swept away; second, a new and
workable definition of an element was needed; third,
suitable analytic chemical techniques were required to
isolate and characterize the elements; and fourth, it was
necessary to devise a method of labelling every element
with a characteristic natural number.
Some alchemical notions
Although the earliest speculations on the nature and
existence of the elements are now lost in the mists of time,
some of the first were made by various ancient Greek
philosophers. Initially, it was postulated that the world
was comprised of only one element, though there was no
agreement on what it might be. Thales (640 546 BC)
believed that it was water, whereas Anaximenes
(560 500 BC) thought it was air, and Heraclitus
(536 470 BC) maintained that it was fire. Since these
ancient beginnings, the number of elements has steadily
increased. Even as early as 440 BC, Empedocles
(492 432 BC) put forward the doctrine that everything in
the cosmos can be traced back to four roots air, earth, fire
and water. This conjecture was the origin of the much
celebrated notion of the four terrestrial elements, a
concept that was to dominate scholastic thinking for the
next two millennia [3]. A fifth element called the ether was
introduced either by Philolaos (ca. 460 400 BC) or by
Plato (427 347 BC) and this was thought to constitute the
celestial matter forming the heavens.
Plato was the first of the ancient Greeks to associate the
five elements with the five regular polyhedra (Fig. 1a). Fire
was identified with the tetrahedron, air with the octahedron, water with the icosahedron, earth with the cube,
and the ether with the dodecahedron, a conceptual
framework that remained well into the 17th century
(Fig. 1b). Plato assumed that each of the four terrestrial
elements was cut out of space and constructed from two
different types of right-angled triangle that were so small

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Fig. 1. Representations of the elements. (a) An early mediaeval depiction of the four elements that incorporates also the four seasons, the four ages of humans, the 12
months, and the signs of the zodiac. The world is being viewed here as a harmonious whole. Image supplied courtesy of the President and Scholars of St. Johns Baptist
College, Oxford. (b) A representation of the elements, depicted here as the five Platonic solids reproduced with permission from The Harmony of the World by Johannes
Kepler, translated into English with an Introduction and Notes by E.J. Aiton, A.M. Duncan, and J.V. Field. Memoirs of the American Philosophical Society, Volume 209
(1997). American Philosophical Society, Philadelphia.

as to be invisible. By rearrangement of the triangles, it was


believed that the elements air, fire and water could be
converted into one another [4]. This idea eventually
evolved into the alchemical notion of transmutation of
the elements [5]. Plato referred to the elements as the
stoicheia, meaning the shapes, assuming that these
entities took on shapes or forms when they were
constituted from amorphous primary matter. The Latin
equivalent of this word is elementa and it was first used by
the Roman poet Lucretius (ca. 97 55 BC) [6].
The alchemical period lasted from at least the 5th
century BC to the end of the 18th century CE. In the
second half of this period, several new entities were
claimed to be elements. Thus, the Arab alchemist Jabir ibn
Hayyan (ca. 721 815) propagated the idea that all metals
are composed of the elements mercury and sulphur,
thereby augmenting the five elements of the Greeks by
two. The elements he introduced were, however, not
substances but were deemed to be metaphysical in nature
and therefore could not be isolated in a laboratory. Another
metaphysical essence was put forward by the mediaeval
alchemist Theophrastus von Hohenheim (1493 1541),
known as Paracelsus. He espoused the concept of the
tria prima, namely the three principles of sulphur (the
combustible principle), mercury (the liquidity principle),
and salt (the incombustible principle). These three
principles were thought to be present in all substances,
with mercury representing the spirit, sulphur the soul,
and salt the physical body of the substance. Toward the
end of the alchemical era the predilection to view matter in
terms of metaphysical principles gradually began to
decline [7].
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The four preconditions


The advent of the scientific era, at least as far as the
elements were concerned, had its beginnings in the middle
of the 17th century. From about the 1630s certain
alchemists started to question the conventional wisdom
of their time that elements were metaphysical entities.
A prime example of such an alchemist was the German
Joachim Jungius (1587 1657) who conceived of elements
not only as corpuscular in structure but also as comprised
of pure, simple substances [8]. In an attempt to deny the
existence of the metaphysical elements of his time, Robert
Boyle (1627 1691) put forward in his iconoclastic book
The Sceptical Chymist published in 1661 what is now
usually accepted as the first modern definition of a
chemical element (Fig. 2). He asserted that elements are
primitive and simple, or perfectly unmingled bodies;
which not being made of any other bodies, or of one
another, are the ingredients of which all of those called
perfectly mixed bodies are immediately compounded, and
into which they are ultimately resolved. [9]. Although
Boyles definition was largely disregarded over the next
100 years, by the end of the 18th century, it was recognized
that alchemical notions of the elements had to be
abandoned. The first of the preconditions necessary for
the discovery of the Periodic Table had been met.
The second and third of the preconditions were fulfilled
largely as a result of the pioneering endeavours of one of
the most celebrated chemists, Antoine-Laurent Lavoisier
(1743 1794) who is often referred to as the father of
modern chemistry. Although working roughly a century
after Boyle, he followed in the latters footsteps by taking
elements to be the last point which analysis is capable of

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Vol.28 No.2 June 2004

71

Fig. 2. A portrait of the chemist Robert Boyle, painted in0 the year 1689 by Johann
Kerseboom. Reproduced, with permission, from the National Portrait Gallery,
London.

reaching. Lavoisier was thus the practitioner who put


Boyles definition into practice and in his groundbreaking
lementaire de Chimie, Lavoisier drew up a
book Traite E
table of simple substances that he claimed were elements
[10] (Fig. 3), many of which we still consider to be elements
today. Lavoisiers insistence on the systematic use of the
balance and other precision instruments, coupled with his
rigorous accounting for all of the products of chemical
reactions, set new standards for the way in which
chemistry was practised at this time and rendered the
quantitative approach to analysis the norm. Moreover, his
rejection of the notion of phlogiston afforded a much more
realistic interpretation of the reactions entered into by the
elements.
The key step toward fulfillment of the fourth precondition was taken by the English chemist John Dalton
(1766 1844) in the year 1803. On the basis of the known
combining weights of different pairs of elements, and
assuming that the hydrogen atom had unit weight, Dalton
was able to deduce a relative weight for each atom. Thus,
because by weight 12.6 parts of hydrogen combine with
87.4 parts of oxygen, Dalton concluded that the weight of
the oxygen atom relative to that of the hydrogen atom was
87.4/12.6, which yields 7 when rounded to the nearest
integer. Dalton had succeeded in assigning a number the
atomic weight to each element. Unfortunately, however,
he made the assumption that the formula of water was HO
and that of ammonia was HN. This meant that the list of
atomic weights he published [11] contained many errors
(Fig. 4). The confusion was to continue for another 50 years
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Fig. 3. A table of simple substances that were claimed to be elements. Published in


Traite Elementaire de Chimie by Antoine-Laurent Lavoisier in 1789.

until the famous Karlsruhe Congress, held in September


1860, after which the problem was finally resolved. One of
the participants, the Italian chemist Stanislao Cannizzaro
(1826 1910) had shown how accurate atomic weights
could be calculated using a reformulation of the wellknown law enunciated in 1811 by his compatriot Amadeo
Avogadro (1776 1856). The amended law stated that the
different quantities of the same element contained in
different molecules are all whole multiples of one and the
same quantity, which, always being entire, has the right to
be called an atom [12].
Grouping the elements
The discovery that patterns of behaviour were to be
discerned among the elements was made by the German
chemist Johann Dobereiner (1780 1849). He carried out
detailed studies of individual groups of three elements that
exhibited analogous behaviour. The first group he investigated consisted of the trio calcium-strontium-barium
and he was able to demonstrate that these elements not
only had similar chemical characteristics but also that
they were interconnected by a mathematical relationship.
The relationship was that the equivalent weight of

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magnesium-calcium-strontium-barium
and
oxygensulphur-selenium-tellurium. Many other relationships
were also found during the 1850s. One of these was
that pentads of elements could exist, the pentad
nitrogen-phosphorus-arsenic-antimony-bismuth
being
announced in 1858 [17] by the French chemist Jean
Dumas (1800 1884).
The scene was thus set for the first attempt to assign all
of the elements to natural families, and this was achieved
by the English chemist William Odling (1829 1921) as
early as 1857 [18]. Odling took great pains to ensure that
only those elements that had been rigorously shown to
have many properties in common be admitted to any of his
13 different groups. As a consequence, most of Odlings
groups now have a very familiar sound to them. Thus, in
group I he included fluorine, chlorine, bromine and iodine;
in group II oxygen, sulphur, selenium and tellurium; and
in group III nitrogen, phosphorus, arsenic, antimony and
bismuth. In constructing such a scheme, Odling came
within a whisker of devising the Periodic Table, a feat he
was able to accomplish some seven years later in 1864. By
this time, however, two other workers had already
developed rudimentary versions of the Periodic Table.

Fig. 4. One of the earliest listings of the elements with their atomic weights by
John Dalton. The table dates from 1810 and this replica was produced in 1925
from the original held by the Manchester Literary and Philosophical Society.
Image supplied by and reproduced courtesy of the Science Museums Science and
Society Picture Library.

strontium oxide was almost exactly the average of the


equivalent weights of calcium oxide and barium oxide. In
several other respects too the element strontium appeared
to possess properties that placed it precisely between the
elements calcium and barium. These results, published in
1817 [13], were followed up by additional studies on other
groups of three elements, including the trios lithiumsodium-potassium, chlorine-bromine-iodine, and sulphurselenium-tellurium, and in each case the same kind of
relationship was established [14]. Trios of analogous
elements were referred to as triads and the relationship
that they satisfied was called the law of triads.
Around the middle of the 19th century several
new insights were gained in the various ways in which
the elements were interrelated. In 1843 the German
chemist Leopold Gmelin (1788 1853) pointed out [15]
that while there were triads like chromium-manganeseiron whose atomic weights differed hardly at all, other
triads such as chlorine-bromine-iodine showed much
greater differences. In 1850 the German chemist
Max von Pettenkofer (1818 1901) discovered that some
triads, e.g. fluorine-chlorine-bromine, did not satisfy
the law of triads [16]. He went on to formulate the concept
of the tetrad of elements and studied the tetrads
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Discovery of the Periodic Table


The Periodic Table made its debut almost as soon as
reliable atomic weights had been determined for the
elements. As if on cue, only 18 months after the Karlsruhe
Congress, the earliest version of the Periodic Table was put
mile
forward by the French mineralogist Alexandre E
Beguyer de Chancourtois (1819 1886) in April 1862 [19].
He was seeking for a way to facilitate the classification of
geological rock specimens. His device consisted of a
continuous line of the elements ordered by their new
atomic weights. This line was wound around a right
cylinder at an angle of 458 from the top, an arrangement
that enabled analogous elements to be aligned on the same
vertical lines drawn on the surface of the cylinder. The first
complete winding through 3608 encompassed all of the
elements up to oxygen, the next winding the elements from
fluorine to sulfur, and so on until all of the 59 elements
known at the time had been accommodated. The device
was called the Telluric Screw because in Latin tellus
signifies the Earth from which the elements derive and the
specific element tellurium was located at the centre of the
device (Fig. 5).
The Periodic Table was an idea whose time had come.
No fewer than five other authors independently published
versions of the Periodic Table during the seven years
following the breakthrough by de Chancourtois. By 1869,
there was thus something of an embarrassment of riches in
that six different renditions of the Periodic Table had been
put forward [2,20,21]. In general, moreover, between 1862
and 1869, the Periodic Table developed considerably, even
though its discoverers were operating independently. Ever
more elements were being included in the Table and spaces
began to be left for elements that were unknown at the
time. Furthermore, it became increasingly manifest that
all of the discoverers were relying on the Periodic Law of
the elements to construct their various Tables. Lothar
Meyer (1839 1895) referred specifically to the existence of

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such a Law [22], which Dmitrii Mendeleev (1834 1907)


subsequently formulated [23]: When the elements are
arranged according to their atomic weights, they show an
evident periodicity in their properties, he argued.
Mendeleev was much bolder than the other discoverers
of the Periodic Table in making predictions about the
properties of elements unknown at the time and for which
he left gaps in his Table. It is for this reason and also
because Mendeleev aggressively pursued his priority
claim to discovery of the Periodic Table in spite of
being the last of its discoverers that it is he who gets most
of the credit for the discovery (Fig. 6). The gaps he left for
elements with atomic weights 45, 68 and 70 were
respectively filled within 15 years by the discovery of the
elements scandium, gallium and germanium. In each of
these cases, Mendeleevs predictions proved to be spectacularly accurate and this enhanced his reputation enormously. It should not be forgotten, however, that
Mendeleev made around 20 such predictions in all and,
apart from the three he got right, the remainder turned out
to be either fortuitous guesses or completely misconceived.
In particular, his predictions of the elements newtonium
(atomic weight 0.17) and coronium (atomic weight 0.4), as
well as six alleged new elements that existed between
hydrogen and lithium, were notably aberrant.

Fig. 5. A two-dimensional depiction of The Telluric Screw, the first version of the
Periodic Table. This was put forward by Alexandre Beguyer de Chancourtois in
1862.

Conclusion
The Periodic Table made its appearance in the 1860s
because the time was right. All of the preconditions for the
advent of the Table had been met: earlier, alchemical
notions of the elements had been abandoned; a workable,
modern definition of an element was at hand; the isolation
and characterisation of elements could be performed by
analytical techniques; and a means had been established
to assign to each element a characteristic natural number

Fig. 6. Dmitrii Mendeleevs table. (a) A Russian postage stamp of the year 1969. The picture is of Dmitrii Mendeleev set against a backgound of his handwritten version of
the Periodic Table dating from 1869. (b) The first printed version of Mendeleevs version of the Periodic Table dating from 1869. The Russian heading reads An Attempt at
a System of the Elements based on their Atomic Weight and Chemical Affinity.
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Vol.28 No.2 June 2004

(its atomic weight). Moreover, there were just about the


right number of elements known in the 1860s about 60
to make recognition of the periodicity in their behaviour
feasible. Had more rare earth elements been known,
setting up the Periodic Table would have been jeopardized
and might not have occurred at all.
Over the years, changes in the shape of the Periodic
Table became necessary as ever more elements, such as the
rare gases, the lanthanides, and the actinides had to be
accommodated. Nowadays, the Periodic Table is not
regarded as having a fixed shape but rather a variety of
differing shapes, each of which is employed for a specific
purpose. Finally, the conception of an element also
changed during the 20th century. Following the lead
given by Mendeleev, an element is no longer regarded as a
simple substance that cannot be decomposed into anything
simpler. In fact, our thinking has come full circle in that an
element is now viewed as essentially an abstract entity
characterized by a mathematical integer, namely its
atomic number.
References
1 Sanderson, R.T. (1960) Chemical Periodicity, Reinhold, New York, p. 1
2 van Spronsen, J.W. (1969) The Periodic System of Chemical Elements,
Elsevier, Amsterdam, pp. 97 139
3 Morris, R. (2003) The Last Sorcerers: The Path from Alchemy to the
Periodic Table, Joseph Henry Press, Washington, D.C., p. 3
4 Multhauf, R.P. (1966) The Origins of Chemistry, Oldbourne, London,
pp. 67 68
5 Roche, J. (1986) The transition from the ancient world picture. In The
Physical Sciences since Antiquity (Harre, R., ed.), pp. 34 35, St.
Martins Press, New York
6 Lucretius Carus, T. (2001) De Rerum Natura (On the Nature of
Things), Transl. Smith, M.F., Hackett, Indianapolis, Book 1,
pp. 22 26
7 Duncan, A. (1996) Laws and Order in Eighteenth-Century Chemistry,
Clarendon Press, Oxford, pp. 27 29
8 Meinel, F. (1982) Der Begriff des chemischen Elementes bei Joachim
Jungius. Sudhoffs Archiv 66, 313 338

9 Boyle, R. (1661) The Sceptical Chymist, Caldwell, London, Reprinted


in 1911 and 1964 by Dent, London, Part 6, p. 187
lementaire de Chimie, Cuchet, Paris.
10 Lavoisier, A.L. (1789) Traite E
English transl. by Kerr, R. (1790) Elements of Chemistry, Creech,
Edinburgh, pp. 175 176
11 Dalton, J. (1803) Observations on the ultimate particles of bodies, and
their combinations. In A New View of the Origin of Daltons Atomic
Theory (Roscoe, H. E. and Harden, A., eds), pp. 26 28, Macmillan,
London, 1896. See also Dalton, J. (1808) A New System of Chemical
Philosophy, Part 1, pp. 212 215, Bickerstaff, London
12 Cannizzaro, S. (1858) Sunto di un Corso di Filosofia Chimica. Nuovo
Cim. 7, 321 366
13 Dobereiner, J.W. (1817) Folgerungen aus seinen stochiometrischen
Versuchen. Ann. Chem. (Gilbert) 57, 435 438
14 Dobereiner, J.W. (1829) Versuch zu einer Gruppirung der elementaren
Stoffe nach ihrer Analogie. Ann. Chem. (Poggendorf) 15, 301 306
15 Gmelin, L. (1843) Handbuch der Chemie (Vol. 1), 4th edn, Winter,
Heidelberg, p. 52 and p. 456
16 Pettenkofer, M. (1850) Ueber die regelmassigen Abstande der
Aequivalentzahlen der sogennanten einfachen Radicale. Gelehrte
Anzeigen Akad. Wiss. Munchen 30, 261 272
17 Dumas, J.B. (1858) Memoire sur les equivalents des corps simples.
Comptes Rendus Acad. Sci. Paris 47, 1026 1034
18 Odling, W. (1857) On the natural groupings of the elements. Phil. Mag.
[4] 13, 423 439 and 480 497
19 Beguyer de Chancourtois, A. E. (1862) Sur un classement naturel des
corps simples ou radicaux appele vis tellurique (Three Parts). Comptes
Rendus Acad. Sci. Paris 54, 757 761, 840 843, 967 971
20 Partington, J.R. (1964) A History of Chemistry (Vol. 4), Macmillan,
London, chap. 26, esp. pp. 883 898
21 Rouvray, D.H. (2004) Fact and fable in the story of the table. In The
Periodic Table: Into the Twenty-First Century (Rouvray, D. H. and
King, R. B., eds), chap. 1, esp. pp. 6 40, Research Studies Press,
Baldock, Hertfordshire, UK
22 Meyer, J.L. (1864) Die Modernen Theorien der Chemie und ihre
Bedeutung fur die Chemische Statik, 1st edn, Maruschke and Berendt,
Breslau (Wroclaw, Poland), P. 139
23 Mendeleev, D.I. (1869) Sootnoshenie soistv s atomnym vesom
elementov. Zhur. Russ. Fiz.-Khim. Obshch. 1, 60 67. English transl.
in Leicester, H.M. and Klickstein, H.S. (1952) A Source Book in
Chemistry: 14001900, Harvard University Press Cambridge, Massachusetts, pp. 438 444

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