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Crystal structures of synthetic 7 Å and 10 Å manganates substituted by mono- and divalent cations

Published online by Cambridge University Press:  05 July 2018

Kenshi Kuma ,
Akira Usui ,
William Paplawsky ,
Benjamin Gedulin  and
Gustaf Arrhenius
Kenshi Kuma
Affiliation:
Department of Chemistry, Faculty of Fisheries, Hokkaido University, 3-1-1 Minato-cho, Hakodate, Hokkaido 041, Japan
Akira Usui
Affiliation:
Marine Geology Department, Geological Survey of Japan, 1-1-3 Higashi, Tsukuba, Ibaraki 305, Japan
William Paplawsky
Affiliation:
Scripps Institution of Oceanography, University of California at San Diego, La Jolla, CA 92093, USA
Benjamin Gedulin
Affiliation:
Scripps Institution of Oceanography, University of California at San Diego, La Jolla, CA 92093, USA
Gustaf Arrhenius
Affiliation:
Scripps Institution of Oceanography, University of California at San Diego, La Jolla, CA 92093, USA
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Abstract

The crystal structures of synthetic 7 Å and 10 Å manganates, synthetic birnessite and buserite, substituted by mono- and divalent cations were investigated by X-ray and electron diffractions. The monoclinic unit cell parameters of the subcell of lithium 7 Å manganate, which is one of the best ordered manganates, were obtained by computing the X-ray powder diffraction data: a = 5.152 Å, b = 2.845 Å, c = 7.196 Å, β = 103.08°. On the basis of the indices obtained by computing the X-ray diffraction data of Li 7 Å manganate, monovalent Na, K and Cs and divalent Be, Sr and Ba 7 Å manganates were interpreted as the same monoclinic structure with β = 100–103° as that of Li 7 Å manganate, from their X-ray diffraction data. In addition, divalent Mg, Ca and Ni 10 Å manganates were also interpreted as the same monoclinic crystal system with β = 90–94° The unit cell parameters, especially a, c and β, change possibly with the type of substituent cation probably because of the different ionic radius, hydration energy and molar ratio of substituent cation to manganese. However, these diffraction data, except for those of Sr and Ba 7 Å and Ca and Ni 10 Å manganates, reveal only some parts of the host manganese structure with the edge-shared [MnO6] octahedral layer. On the other hand, one of the superlattice reflections observed in the electron diffractions was found in the X-ray diffraction lines for heavier divalent cations Sr and Ba 7 Å and Ca and Ni 10 Å manganates. The reflection presumably results from the substituent cation position in the interlayer which is associated with the vacancies in the edge-shared [MnO6] layer and indicates that the essential vacancies are linearly arranged parallel to the b-axis. Furthermore, the characteristic superlattice reflection patterns for several cations, Li, Mg, Ca, Sr, Ba and Ni, manganates were interpreted that the substituent cations are regularly distributed in the interlayer according to the exchange percentage of substituent cation to Na+. In contrast, the streaking in the a-direction observed strongly in the electron diffractions for heavier monovalent cations, K and Cs, manganates probably results from the disordering of their cations in the a-direction in the interlayer.

Keywords

7 Å manganate10 Å manganateX-ray diffractionelectron diffractioncrystal structure
Type
Mineralogy
Information
Mineralogical Magazine , Volume 58 , Issue 392 , September 1994 , pp. 425 - 447
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 1994

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