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Chemical Valency: Its Impact on the Proposal of the Periodic System and Some Thoughts About Its Current Significance

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The Periodic Table I

Part of the book series: Structure and Bonding ((STRUCTURE,volume 181))

Abstract

Mendeleev’s proposal of the periodic table was the final step in what happened to be a long series of attempts by leading chemists of the day to devise a “modern” system for the chemical elements and their compounds following on from Dalton’s notion of atoms in the early nineteenth century. While most of the early systems (including, finally, Mendeleev’s) were based on an ordering of the known elements by atomic weight, the (then) new concept of “valency” introduced by Frankland, Kekulé and others in the 1850s inspired many of the significant contributions (inter alia by Lothar Meyer) in the final decade before 1869. This chapter will begin with a summary of some key developments of chemical concepts during the first half of the nineteenth century and will emphasize the key role played by the Congress at Karlsruhe in 1860 and the way it shaped the development towards a periodic table of the chemical elements. We will then briefly recapitulate the role that “valency” played in the evolution towards a periodic table of the elements and how it has impacted the development of chemistry subsequently. The principal value of the valence concept is its role as an ordering principle for the elements, their compounds and their chemical structures. As chemists expanded the number of elements and their numerous compounds, it has become apparent that it also has significant limitations, and since its origins were based on a very limited view of chemical bonding and no structural information, it has had to adapt significantly during the last 150 years. Modern concepts generalizing structure formation and bonding capabilities of molecular fragments are generally based on qualitative frontier orbital models, which are guided by increasingly accurate quantum mechanical calculations. The difficulties encountered in the establishment of relationships between concepts of chemical bonding and quantum chemical modelling of the chemical bond are illustrated for metal–metal bond polarity in oligonuclear complexes at the end of the chapter.

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Notes

  1. 1.

    Based on the “information” of prime matter (hyle) with a combination of the four elementary properties hot/cold, wet/dry [which in turn gave rise to the four elements fire, water, earth and air].

  2. 2.

    For monoatomic hydrogen and oxygen, the result would have been 1 volume of water (H2O).

  3. 3.

    In fact, Kekulé had approached both Wurtz and August W. Hofmann, then at the Royal College of Chemistry in London about the proposed meeting. Whereas Wurtz accepted with enthusiasm, Hofmann wrote back that “he was not one to fight in the vanguard and would not wish to place himself among the leaders of such a meeting”.

  4. 4.

    Karlsruhe had also been the venue of a very successful meeting of the Deutsche Gesellschaft der Naturforscher und Ärzte 2 years before.

  5. 5.

    Also spelt Karl Weltzien. Weltzien had been born in 1813 in St. Petersburg to ethnic German parents and was raised in Germany from the age of 10 onwards.

  6. 6.

    Later the Technische Hochschule Karlsruhe and nowadays the Karlsruher Institut für Technologie (KIT).

  7. 7.

    Dated “Paris, 5 April 1860”.

  8. 8.

    Altogether delegates from 12 countries are listed in the minutes of the meeting prepared by Wurtz [1,2,3].

  9. 9.

    “.. was impressed by the clarity with which the piece treated the most important issues. It was as though the scales fell from my eyes, the doubts dissolved and made way for a feeling of calmest certainty…..”

  10. 10.

    As opposed to developments which may be viewed as “scientific revolutions” as claimed in Kuhn’s epistemology [34]. This has been pointed out by E. R. Scerri, [10]. p. xviii.

  11. 11.

    The omission of graphical representations of the element spiral was due to the editor’s refusal to print them. Privately distributed separates of the scheme subsequent to the appearance of the articles failed to make a significant impact at the time and were only rediscovered later.

  12. 12.

    See Table 5.5 in Ref. [5, p. 142].

  13. 13.

    This term appeared in the first publication of his periodic system in Russian in 1869 but was not translated as such for a German version of this work which was the more widely read publication. This subsequently led to a dispute between Mendeleev and Meyer, who also began to use this term from 1870 onwards, about who had first published it. While the works of both protagonists in the development of a complete periodic table were clearly conducted independently, it appears that Mendeleev employed this terminology earlier than Meyer.

  14. 14.

    It is based on the “central field approximation” for the potential energies of the electrons but, beyond that, is independent of the quantum chemical approximation employed.

  15. 15.

    The reduction of the periodic table to quantum mechanical principles has been challenged inter alia by Scerri who pointed out, e.g. that the designation of electron configurations within the aufbau principle is based on a one-electron picture of the many electron systems which can only be justified by comparison with the experiment. However, as argued here, the specific pattern arising from the orbital description (and its role for the construction of the many particle wave functions) may be traced to the symmetry properties of the rotational group representing to a good approximation of the potential energies of the electrons experiencing the shielded Coulomb field of the nucleus.

  16. 16.

    Coordination number = number of atoms bonded to the given atom.

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Acknowledgements

LHG would like to thank H. Wadepohl for advice and helpful discussions.

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  1. Anorganisch-Chemisches-Institut, Universität Heidelberg, Heidelberg, Germany

    Lutz H. Gade

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  1. Lutz H. Gade
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Correspondence to Lutz H. Gade .

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  1. Inorganic Chemistry Laboratory, University of Oxford, Oxford, UK

    D. Michael P. Mingos

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Gade, L.H. (2019). Chemical Valency: Its Impact on the Proposal of the Periodic System and Some Thoughts About Its Current Significance. In: Mingos, D. (eds) The Periodic Table I. Structure and Bonding, vol 181. Springer, Cham. https://doi.org/10.1007/430_2019_40

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