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Cherkesov: Two Periodic Tables

von Bichowsky FR, The place of manganese in the periodic system, J. Am. Chem. Soc. 1918, 40, 7, 1040–1046 Publication Date: July 1, 1918 https://doi.org/10.1021/ja02240a008 

René Vernon writes:

"In this curious article, von Bichowsky, a physical chemist (1889-1951), mounted an argument for regarding Mn as belonging to group 8 (see table 1 below) rather than group 7 (table 2). His article has effectively been assigned to the dustbin of history, having apparently gathered zero citations over the past 103 years.

"Items of note in his 24-column table:

• While Mn, 43 and 75 are assigned to group 8 they remain in alignment with group 7. Se is shown as Sc
• 14 lanthanides, from Ce to Yb, make up group 3a; If La and Lu are included, there are 16 Ln
• Gd is shown as Cd
• Positions of Dy and Ho have been reversed
• Tm and Tm2
• Po shown as "RaF"
• Ra shown as "RaEm"
• Pa shown as Ux2

von Bichowsky made his argument for Mn in group 8, on the following grounds:

• by removing the Ln from the main body of the table all of the gaps denoted by the dashes (in table 2) were removed
• the eighth group links Cr with Cu; Mo with Ag; and W with Au
• the symmetry of the table is greatly increased
• the triads are replaced by tetrads and a group of 16 Ln which accords better with "the preference of the periodic system for powers of two"
• about eight chemistry-based differences between Ti-V-Cr and Mn, including where Mn shows more similarities to Fe-Co-Ni, for example:
  • divalent Ti, V, Cr cations are all powerful reducing agents, Cr being one of the most powerful known; divalent Mn, Fe, Co, Ni are either very mild reducing agents as divalent Mn or Fe, or have almost no reducing power in the case of divalent Co or Ni;
  • metal titanates, vanadates and chromates are stable in alkaline solution and are unstable in the presence of acid whereas permanganates are more stable in acid than alkali; their oxidizing power is also widely different.

I can further add:

• Mn, Fe, and Co, and to some extent Ni, occupy the "hydrogen gap" among the 3d metals, having no or little proclivity for binary hydride formation
• the +2 and +3 oxidation states predominate among the Mn-Fe-Co-Ni tetrad (+3 not so much for Mn)
• in old chemistry, Mn, Fe, Co, and Ni represented the "iron group" whereas Cr, Mo, W, and U belonged to the "chromium group": Struthers J 1893, Chemistry and physics: A manual for students and practitioners, Lea Brothers & Co., Philadelphia, pp. 79, 123
• Tc forms a continuous series of solid solutions with Re, Ru, and Os

Moving forward precisely 100 years, Rayner-Canham (2018) made the following observations:

• Conventional classification systems for the transition metals each have one flaw: "They organise the TM largely according to one strategy and they define the trends according to that organisation. Thus, linkages, relationships, patterns, or similarities outside of that framework are ignored."
• There are two oxide series of the form MnO and Mn3O4 which encompass Mn through Ni. Here the division is not clear cut since there are also the series Mn2O3 for Ti-Cr and Fe; and MnO2 for Ti to Cr.
• Under normal condition of aqueous chemistry, Mn favours the +2 state and its species match well with those of the following 3d member, Fe.

  Rayner-Canham G 2018, "Organizing the transition metals" [a chapter in] in E Scerri & G Restrepo, Mendeleev to Oganesson: A multidisciplinary perspective on the periodic table, Oxford University Press, Oxford, pp. 195–205

I've also attached a modern interpretation of von Bichowsky’s table. It's curious how there are eight metals (Fe aside) capable of, or thought to be capable of, achieving +8. I am not sure that a table of this kind with Lu in group 3 is possible, without upsetting its symmetry."

© Mark R. Leach Ph.D. 1999 –

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