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Mendeleev
on Periodicity: 1

The Periodic Law was announced by D I Mendeleev (1834 - 1907) at the first meeting of
the Russian Chemical
Society in March 1869, the paper from which the following is an
extract being published in the Journal of the
Russian Chemical Society, 1:
60-77 (1869). The Periodic Table was almost immediately reprinted in Zeitschrift
fur
Chemie, 12, 405 (1869); it appears also on Mendeleev's Memorial in
St Petersburg. The driving force for
Mendeleev's work was probably the writing of his
famous 'Principles of Chemistry', published between 1868
and 1870. This appeared in three
editions in English alone, as well as eight in Russian and some in French and
German.

The famous predictions of then unknown elements were the subject of a second paper in
1871: see 'Mendeleev
and Peridicity: 2'.

THE RELATION BETWEEN THE PROPERTIES AND ATOMIC WEIGHTS

OF THE ELEMENTS.

In undertaking to prepare a textbook called "Principles of

Chemistry," I wished to establish somesort of system
of simple bodies in which their
distribution is not guided by chance, as might be thought instinctively, but by
some sort
of definite and exact principle. We previously saw that there was an almost complete
absence of
numerical relations for establishing a system of simple bodies, but in the end
any system based on numbers
which can be determined exactly will deserve preference over
other Systems which do not have numerical
support, since the former leave little room for
arbitrary choices. The numerical data for simple bodies are limited
at the present time.
If for some of them the physical properties are determined with certainty, yet this
applies
only to a very small number of the elementary bodies. For example, such properties
as optical, or even electrical
or magnetic, ones, cannot in the end serve as a support for
a system because one and the same body can show
different values for these properties,
depending on the state in which they occur. In this regard, it is enough to
recall
graphite and diamond, ordinary and red phosphorus, and oxygen and ozone. Not only do we
not know the
density in the vapour state for most of them, by which to determine the
weight of the particles of the simple
bodies, but this density is subject to alteration
exactly like those polymeric alterations which have been noted for
complex bodies. Oxygen
and sulphur show this effect positively, but the relations between nitrogen, phosphorus,
and arsenic offer further confirmation because these similar elements have particle
weights of N2, P4, and As4,
unequal in the number of
atoms among themselves. A number of the properties of the simple bodies must
change with
these polymeric changes. Thus we cannot be sure that for any element, even for platinum,
there may
not occur another state, and the location of an element in a system based on its
physical properties would then be
changed. Besides this, anyone understands that no matter
how the properties of a simple body may change in the
free state, something remains constant, and when the elements form compounds, this something has a material
value and establishes the characteristics of the
compounds which include the given element. In this respect, we
know only one constant
peculiar to an element, namely, the atomic weight. The size of the atomic weight, by the
very essence of the matter, is a number which is not related to the state of division of
the simple body but to the
material part which is common to the simple body and all its
compounds. The atomic weight belongs not to coal
or the diamond, but to carbon. The
property which Gerhardt and Cannizzaro determined as the atomic weight of
the elements is
based on such a firm and certain assumption that for most bodies, especially for those
simple
bodies whose heat capacity in the free state has been determined, there remains no
doubt of the atomic weight,
such as existed some years ago, when the atomic weights were
so often confused with the equivalents and
determined on the basis of varied and often
contradictory ideas.

This is the reason I have chosen to base the system on the size of the atomic weights
of the elements.

The first attempt which I made in this way was the following: I selected the bodies
with the lowest atomic
weights and arranged them in the order of the size of their atomic
weights. This showed that there existed a
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period ih the properties of the simple bodies,

and even in terms of their atomicity the elements followed each
other in the order of
arithmetic succession of the size of their atoms:

Li = 7; Be =  9.4; B = 11; C = 12; N= 14; O = 16; F = 19;

Na = 23; Mg = 24; Al = 27.4; Si = 28; P= 31; S = 32; Cl = 35.3
K = 39; Ca = 40; ...... Ti = 50; V = 51

In the arrangement of elements with atoms greater than 100, we meet an entirely
analogous continuous order:

Ag = 108; Cd = 112; Ur 116; Sn = 118; Sb = 122; Te = 128;

I = 127.

It has been shown that Li, Na, K, and Ag are related to each other, as are C, Si, Ti,
Sn, or as are N, P, V, Sb, etc.
This at once raises the question whether the properties of
the elements are expressed by their atomic weights and
whether a system can be based on
them. An attempt at such a system follows.

In the assumed system, the atomic weight of the element, unique to it, serves as a
basis for determining the place
of the element. Comparison of the groups of simple bodies
known up to now according to the weights of their
atoms leads to the conclusion that the
distribution of the elements according to their atomic weights does not
disturb the
natural similarities which exist between the elements but, on the contrary, shows them
directly. .

All the comparisons which I have made in this direction lead me to conclude that the
size of the atomic weight
determines the nature of the elements, just as the weight of
the molecules determines the properties and many of
the reactions of complex bodies. If
this conclusion is confirmed by further applications of this approach to the
study of the
elements, then we are near an epoch in understanding the existing differences and the
reasons for the
similarity of elementary bodies.

I think that the law established by me does not run counter to the general direction of
natural science, and that
until now it has not been demonstrated, although already there
have been hints of it. Henceforth, it seems to me,
there will be a new interest in
determining atomic weights, in discovering new elementary bodies, and in finding
new
analogies between them.

I now present one of many possible systems of elements based on their atomic weights.
It serves only as an
attempt to express those results which can be obtained in this way. I
myself see that this attempt is not final, but
it seems to me that it clearly expresses
the applicability of my assumptions to all combinations of elements
whose atoms are known
with certainty. In this I have also wished to establish a general system of the elements.
Here is this attempt:

Ti = 50 Zr = 90 ? = 180
V = 51 Nb = 94 Ta = 182
Cr = 52 Mo = 96 W = 186
Mn = 55 Rh = 104.4 Pt = 197.4
Fe = 56 Ru = 104.4 Ir = 198
               
Ni = Co = 59 Pd = 106.6 Os = 199
H=1 Cu = 63.4 Ag = 108 Hg = 200
Be = 9.4 Mg = 24 Zn = 65.2 Cd = 112
B = 11 Al = 27.4 ? = 68 Ur = 116 Au = 197?
C = 12 Si = 28 ? = 70 Sn = 118
N = 14 P = 31 As = 75 Sb = 122 Bi = 210?
O = 16 S = 32 Se = 79.4 Te = 128?

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F = 19 Cl = 35.5 Br = 80 J = 127
Li = 7 Na = 23 K = 39 Rb = 85.4 Cs = 133 Tl = 204
Ca = 40 Sr = 87.6 Ba = 137 Pb = 207
? = 45 Ce = 92
?Er = 56 La = 94
?Yt = 60 Di = 95
?In = 75.6 Th = 118?

 Periodic Table according to D I Mendeleev, 1869

…… In conclusion, I consider it advisable to recapitulate the results of the

above work.

1. Elements arranged according to the size of their atomic weights show clear periodic
properties.

2. Elements which are similar in chemical function either have atomic weights which lie
close
together (like Pt, Ir, Os) or show a uniform increase in atomic weight (like K, Rb,
Cs). The
uniformity of such an increase in the different groups is taken from previous
work. In such
comparisons, however, the workers did not make use of the conclusions of
Gerhardt, Regnault,
Cannizzaro, and others who established the true value of the atomic
weights of the elements.

3. Comparisons of the elements or their groups in terms of size of their atomic weights
establish
their so-called "atomicity" and, to some extent, differences in
chemical character, a fact which is
clearly evident in the group Li, Be, B, C, N, 0, F,
and is repeated in the other groups.

4. The simple bodies which are most widely distributed in nature have small atomic
weights, and all
the elements which have small atomic weights are characterized by the
specificity of their
properties. They are therefore the typical elements. Hydrogen, as the
lightest element, is in justice
chosen as typical of itself.

5. The size of the atomic weight determines the character of the element, just
as the size of the
molecule determines the properties of the complex body, and so, when we
study compounds, we
should consider not only the properties and amounts of the elements,
not only the reactions, but also
the weight of the atoms. Thus, for example, compounds of
S and Te, Cl and I, etc., although
showing resemblances, also very clearly show
differences.

6. We should still expect to discover many unknown simple bodies; for example,
those similar to Al
and Si, elements with atomic weights of 65 to 75.

7. Some analogies of the elements are discovered from the size of the weights of
their atoms. Thus
uranium is shown to be analogous to boron and aluminium, a fact which is
also justified when their
compounds are compared.

The purpose of my paper will be entirely attained if I succeed in turning the attention
of investigators to the
same relationships in the size of the atomic weights of
non-similar elements, which have, as far as I know, been
almost entirely neglected until
now. Assuming that in problems of this nature lies the solution of one of the most
important questions of our science, I myself, as my time will permit, will turn to a
comparative study of lithium,
beryllium, and boron.

Mendeleev on Periodicity: 2
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