Contributions to the chemistry of highly concentrated aqueous electrolyte solutions. XXV. Ionophoretic investigation of the association of Al3+, Sc3+, Ga3+ and In3+ ions in concentrated solutions of NaClO4 and LiCl

Šmirous, F.; Celeda, J.; Palek, M.

doi:10.1135/cccc19713891

Cited by 8 publications

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“…Scandium(III) is slightly adsorbed by an anion exchanger column from 7 to 12 M HCl, indicating the presence of an anionic species at high chloride concentration . From an ionophoretic investigation, Šmirous et al invoked the electro neutral ScCl 3 species and ScCl 4 - in ScCl 3 solutions with an excess of Cl - . It should be mentioned that these physicochemical methods detect besides the inner-sphere complex also complexes of an outer-sphere type.…”

Section: Resultsmentioning

confidence: 99%

Raman Spectroscopic Measurements of Scandium(III) Hydration in Aqueous Perchlorate Solution and ab Initio Molecular Orbital Studies of Scandium(III) Water Clusters: Does Sc(III) Occur as a Hexaaqua Complex?

Rudolph

Pye

2000

J. Phys. Chem. A

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We have shown that Sc(III) in aqueous perchlorate solution occurs as a hexaaqua cation. The weak, polarized Raman band assigned to the ν1(a1g)(ScO6) mode of the hexaaqua Sc(III) ion has been studied as a function of concentration. Besides the isotropic component at 442 cm-1, two weak depolarized modes at 295 and 410 cm-1 were measured in the Raman effect. These two modes of the ScO6 unit were assigned to ν5(f2g) and ν2(eg), respectively. The infrared active mode,ν3(f1u), was found at 460 cm-1. The Raman spectroscopic data suggest that the hexaaqua Sc(III) ion is stable in perchlorate solution within the concentration range measured. Furthermore, the frequency data confirm the centrosymmetry of the Sc(III) aqua complex, contrary to earlier Raman results. The ScO6 unit possesses O h symmetry (water seen as point mass). These findings are in contrast to ScCl3 solutions, where chloride replaces water in the first hydration sphere and forms one or more chloro complexes. Gas-phase structures, binding energies, and enthalpies are reported for small [Sc(OH2) n ]3+ clusters, with one to nine water molecules in the first sphere. Ab initio molecular orbital calculations were performed at the HF and MP2 levels of theory using different basis sets up to 6-31+G*. The water molecules in these clusters coordinate the Sc3+ in highly symmetric arrangements that tend to enhance electrostatic charge−dipole interactions while minimizing ligand−ligand repulsion. The Sc−O bond length for the [Sc(OH2)6]3+ cluster reproduces the experimentally determined bond length (EXAFS) of 2.18 Å. The theoretical binding energy for the [Sc(OH2)6]3+ ion was calculated and accounts for ca. 54−59% of the experimental single ion hydration enthalpy of Sc(III). The stability of the hexaaquascandium(III) cluster could be demonstrated by comparing the stability of the [Sc(OH2)6(OH2)]3+ cluster with the [Sc(OH2)7]3+ cluster, resulting in the stability of the former. The frequencies of ν1(ScO6) of the [Sc(OH2)6]3+ cluster are ca. 11% lower than the experimental frequency. The reason for this discrepancy was discussed and found to lie in the lack of the second hydration sphere which was subsequently modeled as the [Sc(OH2)18]3+ cluster, denoted Sc[6+12]. Frequencies of the ScO6 unit for the Sc[6+12] cluster were calculated and agree with the experimental values. The binding enthalpy resembles that of the single ion hydration enthalpy.

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Section: Resultsmentioning

confidence: 99%

Raman Spectroscopic Measurements of Scandium(III) Hydration in Aqueous Perchlorate Solution and ab Initio Molecular Orbital Studies of Scandium(III) Water Clusters: Does Sc(III) Occur as a Hexaaqua Complex?

Rudolph

Pye

2000

J. Phys. Chem. A

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“…These fairly well known provisions are fully confirmed for indium perchlorate, which is proved by various research methods [3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19]. The absence of coordination interaction of acid ions in the "In 3 + -ClO 4 − -H 2 O" system is indicated by the spectra of Raman scattering [5][6][7][8][9][10][11].…”

Section: Ionic State Of Indium In Perchlorate Solutionsmentioning

confidence: 79%

“…There is no evidence of the complexing effect of the highly concentrated electrolyte NaClO 4 1.1÷9.1 M and by electrophoresis [19]. Spectrophotometrically in the ultraviolet region of the spectrum, there were no significant signs of direct interaction in aqueous solutions of In(ClO 4 ) 3 salts [20].…”

Section: Ionic State Of Indium In Perchlorate Solutionsmentioning

confidence: 87%

“…Spectrophotometrically in the ultraviolet region of the spectrum, there were no significant signs of direct interaction in aqueous solutions of In(ClO 4 ) 3 salts [20]. Also, no intrinsic complexation influencing the activity of In 3+ was reliably detected up to a sodium perchlorate concentration of 16 mol/kg [19,21] and with an In(ClO 4 ) 3 content of more than 4 M [6,9].…”

Section: Ionic State Of Indium In Perchlorate Solutionsmentioning

confidence: 99%

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Features of the Ionic State of Indium in Perchlorate Solutions and the Physicochemical Properties of Indium Perchlorate

Konstantinovich¹,

Anatolievich²

2021

Post-Transition Metals

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The possibility of the formation of India perchlorate and mixed ligand complexes has been studied. It is assumed that during the extraction of indium in aqueous solutions of hydrochloric acid at various concentrations and constant ionic strength maintained by the addition of perchloric acid, indium is present in the organic phase in the form of ionic aggregates HClO4 · HInCl4. To study the hydration of Ions, the method of electrical conductivity was carried out in the “In(ClO4)3 - HClO4 - H2O” system. The structure of aqueous solutions of India perchlorates was determined by IR spectroscopy. The structures of trivalent perchlorate India have been established.

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“…Scandium(III) is slightly adsorbed by an anion exchanger column from 7 to 12 M HCl indicating the presence of an anionic species at high chloride concentration [36]. From an ionophoretic investigation by Š mirous et al [37] invoked the electro neutral ScCl 3 species and ScCl 4 Ϫ in ScCl 3 solutions with excess of Cl Ϫ . It should be mentioned that these physicochemical methods detect besides the inner-sphere complex also a complex of an outer-sphere type.…”

Section: Sccl 3 Solutionmentioning

confidence: 98%

Raman Spectroscopic Studies of Scandium(III) Hydration in Aqueous Solution - about the First Hydration Sphere of Sc(III) in Solution

Rudolph¹

2000

Zeitschrift Für Physikalische Chemie

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Sc(III)-Perchlorate and -Chloride / Aqueous Solutions / Hydration / Ion Pair Formation / Raman-SpectroscopyIt has been shown conclusively that Sc(III) in aqueous perchlorate solution occurs as an hexaaqua cation. The weak, polarized Raman band assigned to the ν1(a1g) ScO6 mode of the hexaaqua-Sc(III) ion (T h symmetry for the whole complex ion or O h symmetry for the ScO 6 unit) has been studied as a function of concentration and temperature. The isotropic scattering geometry in R-format was employed in order to measure the true vibrational contribution of the band and account for the Boltzmann temperature factor B and the wavenumber factor ν. The ν1(a1g)ScO6 mode at 442 cm Ϫ1 of the hexaaqua-Sc(III) shifts only 3 cm Ϫ1 to lower wavenumbers and broadens about 20 cm Ϫ1 for a 60°C temperature increase. The Raman spectroscopic data suggest that the hexaaqua Sc(III) ion is stable in perchlorate solution within the temperature range measured.Besides the polarized component at 442 cm Ϫ1 , two weak depolarized modes at 295 cm Ϫ1 and 410 cm Ϫ1 were measured in the Raman effect. These two modes of the ScO 6 unit were assigned to ν 5 (f 2g ) and ν 2 (e g ) respectively. The infrared active mode, ν 3 (f 1u ), was measured to be at 460 cm Ϫ1 . The wavenumber data confirm the centrosymmetry of the Sc(III)aqua-complex, in opposite to earlier Raman results.These findings are also in contrast to the results found in Sc2(SO4)3 solutions, where sulfate replaces water in the first hydration sphere and forms quite strong sulfato complexes. In ScCl3 solutions weak chloro-complex(es) could be detected.

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Contributions to the chemistry of highly concentrated aqueous electrolyte solutions. XXV. Ionophoretic investigation of the association of Al3+, Sc3+, Ga3+ and In3+ ions in concentrated solutions of NaClO4 and LiCl

Cited by 8 publications

References 0 publications

Raman Spectroscopic Measurements of Scandium(III) Hydration in Aqueous Perchlorate Solution and ab Initio Molecular Orbital Studies of Scandium(III) Water Clusters: Does Sc(III) Occur as a Hexaaqua Complex?

Raman Spectroscopic Measurements of Scandium(III) Hydration in Aqueous Perchlorate Solution and ab Initio Molecular Orbital Studies of Scandium(III) Water Clusters: Does Sc(III) Occur as a Hexaaqua Complex?

Features of the Ionic State of Indium in Perchlorate Solutions and the Physicochemical Properties of Indium Perchlorate

Raman Spectroscopic Studies of Scandium(III) Hydration in Aqueous Solution - about the First Hydration Sphere of Sc(III) in Solution

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