Zur Kenntnis der Hydrate des Mangan- und Zinksulfits. Röntgenographische, thermoanaly tische, Raman- und IR-spektroskopische Untersuchungen / Hydrates of Manganese and Zinc Sulfite. X-ray, Thermoanalytical, Raman, and IR Data

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Abstract
X-ray, IR and Raman data as well as thermoanalytical measurements (DTA, TG, and DTG) of several new hydrates, viz. MnSO3 · 2 ½ H2O, MnSO3 · 2 H2O, ZnSO3 · 3 H2O, β-ZnSO3 · 2 ½ H2O, and γ-ZnSO3 · 2 ½ H2O, and of previously reported hydrates in the systems MnSO3-H2O, ZnSO3-H2O, and MnSO3-ZnSO3-H2O are presented. Furthermore, the formation of mixed crystals is studied in the system MnSO3-ZnSO3-H2O. The following crystal data have been determined by single crystal measurements: MnSO3 · 2 ½ H2O (P41212) : a = b = 968.4(1), c = 1040.9(1) pm, Z = 8, MnSO3 · 2 H2O (P21/n): a = 650.9(1), b = 873.8(1), c = 774.7(1) pm, β = 99.80(1)°, Z = 4, ZnSO3 · 3 H2O (Pnma): a = 953.6(1), b = 553.0(1), c = 941.9(1) pm, Z = 4, β-ZnSO3 · 2 ½ H2O (P41212): a = b = 952.1(1), c = 1025.4(1) pm, Z = 8, γ-ZnSO3 · 2 ½ H2O (with small amount of Mn2+) (o-rh.): a = 1493(1), b = 1812(2), c = 753(1) pm, Z = 16, ZnSO3 · ½ H2O (mon.): a = 1326.7(5), b = 706.3(2), c = 834.4(1) pm, β = 117.41(3)°, Z = 8. The IR spectra show that, with the exception of γ-ZnSO3 · 2 ½ H2O, both weak and strong hydrogen bonds are present in the sulfite hydrates. Under an SO2 atmosphere the sulfite hydrates can be dehydrated without simultaneous dissociation to the oxide and sulfur dioxide. The isotypic hydrates β-MnSO3 · 3 H2O and ZnSO3 · 3 H2O (β-MnSO3 · 3 H2O type), and MnSO3 · 2 H2O and ZnSO3 · 2 H2O (ZnSeO3 · 2 H2O type) form complete mixed crystal series. Solid solutions are also formed from α-MnSO3 · 3 H2O (α-FeSO3 · 3 H2O type), γ-ZnSO3 · 2 ½ H2O, MnSO3 · 1 H2O, and ZnSO3 · ½ H2O. No incorporation of Mn or Zn could be observed for α-ZnSO3 · 2 ½ H2O and the isotype hydrates MnSO3 · 2 ½ H2O and β-ZnSO3 · 2 ½ H2O (CoSO3 ½ 2 ½ H2O type)

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