X-Ray Diffraction Studies of the Structures of Hydrated Divalent Transition-Metal Ions in Aqueous Solution

Ohtaki, Hitoshi; Yamaguchi, Toshio; Maeda, Masunobu

doi:10.1246/bcsj.49.701

Cited by 228 publications

(76 citation statements)

References 40 publications

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“…The parameters referring to the manganese ion confirm its octahedral coordination by six oxygen atoms, with a value for the Mn-0 distance, 2.20 Ä, very close to that found in the crystal structures of MnS04-5H20 and of Mn(N03)2 • 4H20 [28], The same value was also found in the solutions of MnS04 [10] and Mn(C104)2 [29].…”

Section: Resultssupporting

confidence: 78%

See 1 more Smart Citation

A Comparative X-Ray Diffraction Study of Aqueous MnSO₄ and Crystals of MnSO₄·5H₂O

Caminiti

Marongiu

Paschina

1982

Zeitschrift Für Naturforschung A

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X-ray single crystal analysis of MnS04 • 5H2O shows that the manganese atoms are octahedral ly coordinated by oxygen atoms, four of which belong to water molecules and two to sulphate groups.A model derived from the crystal structure was fitted to the X-ray scattering intensities from aqueous MnS04. Good agreement with experimental data is achieved using a model in which Mn(H20)6-2(0S03)z +2 " 2z interacts with about ten water molecules and each sulphate ion with about seven water molecules.Analysis of X-ray [1-3] and neutron [4] diffraction data from concentrated aqueous salt solutions gives details about the environment of the ions and information about the geometry of the coordination polyhedra. This is particularly useful in the case of direct interaction between the anion and the cation, since information about their relative orientation cannot be obtained through other experimental techniques than diffraction; in the last several years contributions to the knowledge of complex-formation in solution have been provided by the analysis of halogen salt solutions [1,3,5] and recently by that of some sulphate salts, i.e. Shapovalow and Radchenko [10] examined diffraction data of dilute MnS04 solutions; their analysis was, however, limited to the first hydration sphere and no mention was made of cation-anion interaction, although an indication for its presence is suggested by the values of equilibrium constants [11]. We therefore undertook a detailed analysis of the diffraction data of two concentrated MnS04 solutions, which is reported in this paper, together with the single crystal structure determination of MnS04-5H20. Experimental and Data ProcessingMnS04 • H20 (Merck reagent grade) was dissolved in water to give a 2M (Sol. A) and a saturated Reprints request to Dr. Ruggero Caminiti, Istituto Chimico, Universitä di Cagliari, Via Ospedale 72, 09100 Cagliari, Italy.(Sol. B) solution. Mn + + and SO^-contents were determined by titrations with standard EDTA [12] and with a cation exchange resin (Dowex 50W-X8). The analytical results are given in Table 1. X-ray scattering data were obtained at 20i 1°C on a $ -& diffractometer using Moka radiation (wavelength X = 0.7107 Ä). A divergent beam was diffracted at the horizontal surface of the sample and then monochromatized by reflection from a curved quartz crystal. The observed range of scattering angles (2$) was from 3° to 134°, corresponding to the range 0.46 Ä -1 ^ 16.3 A -1 , where s= (4tt/A) sin $ is the scattering variable. The measured intensities were corrected for background, polarization and absorption [13], and smoothed by fourth differences [14], The Compton contribution was evaluated by a semiempirical method [15] in order to account for the monochromator discrimination. The corrected intensities were scaled to the independent scattering factor for the solution using both the analytical method

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Section: Resultssupporting

confidence: 78%

“…The possibility of a second hydration shell around the cation was taken into account neither by Ohtaky in the case of Mn(C104)2 [29] solution nor by Shapolow and Radchenko for MnS04 [10].…”

Section: Resultsmentioning

confidence: 99%

A Comparative X-Ray Diffraction Study of Aqueous MnSO₄ and Crystals of MnSO₄·5H₂O

Caminiti

Marongiu

Paschina

1982

Zeitschrift Für Naturforschung A

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“…This is the case for the Zn 2+ ion; indeed the investigations of Wertz et al [2,3] aimed at determining the degree of Zn 2+ -Cl~ complex formation. Information on the hydration of Zn 2+ ions has been obtained in solutions of oxy-anions like N03~ (Boi et al, [4]), C1<V and S04 2 " (Ohtaki et al, [5]). However, these studies are not systematic and information on the hydration of Zn 2+ is not as detailed as, for example, that concerning Ni 2+ , Co 2+ , Fe 3+ and Cr 3+ .…”

Section: Introductionmentioning

confidence: 99%

X-ray Diffraction Study of Aqueous Solutions of ZnSO₄

Licheri

Paschina

Piccaluga

et al. 1982

Zeitschrift Für Naturforschung A

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Five aqueous solutions of ZnS04 of concentrations ranging from 0.6M to 3.1 M were examined by X-ray diffraction. In the correlation functions no concentration effect on structural phenomena is detectable. The same model was then successfuly used for all cases, attributing two hydration shells to Zn 2+ and one hydration shell to SO4 2-. The reliability of the structural parameters obtained is discussed.

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“…(36) An X-ray diffraction study of a series of hydrated transition metal ions (37) can also be mentioned as one of the most interesting subjects in solution chemistry and coordination chemistry in solution investigated by Japanese solution chemists during an early period in the history of X-ray diffraction studies in Japan.…”

Section: Contribution Of the Japanese Community To Solution Chemistrymentioning

confidence: 99%

History of Solution Chemistry of Japan

Ohtaki

2005

J Solution Chem

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A historical view of the solution chemistry of Japan is described for a wide range of fields of solution chemistry, which relates to physical chemistry, inorganic chemistry, analytical chemistry, biochemistry and bioinorganic chemistry, and colloid and polymer chemistry. The works by pioneers of Japanese solution chemistry are introduced, some of which are not well recognized internationally. The influences of Japanese solution chemistry on the world and vice versa are discussed on the basis of a rather personal viewpoint. Recent activities of Japanese solution chemists at the national and international levels are also reviewed.

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X-Ray Diffraction Studies of the Structures of Hydrated Divalent Transition-Metal Ions in Aqueous Solution

Cited by 228 publications

References 40 publications

A Comparative X-Ray Diffraction Study of Aqueous MnSO₄ and Crystals of MnSO₄·5H₂O

A Comparative X-Ray Diffraction Study of Aqueous MnSO₄ and Crystals of MnSO₄·5H₂O

X-ray Diffraction Study of Aqueous Solutions of ZnSO₄

History of Solution Chemistry of Japan

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X-Ray Diffraction Studies of the Structures of Hydrated Divalent Transition-Metal Ions in Aqueous Solution

Cited by 228 publications

References 40 publications

A Comparative X-Ray Diffraction Study of Aqueous MnSO4 and Crystals of MnSO4·5H2O

A Comparative X-Ray Diffraction Study of Aqueous MnSO4 and Crystals of MnSO4·5H2O

X-ray Diffraction Study of Aqueous Solutions of ZnSO4

History of Solution Chemistry of Japan

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A Comparative X-Ray Diffraction Study of Aqueous MnSO₄ and Crystals of MnSO₄·5H₂O

A Comparative X-Ray Diffraction Study of Aqueous MnSO₄ and Crystals of MnSO₄·5H₂O

X-ray Diffraction Study of Aqueous Solutions of ZnSO₄