Thermodynamics of complex formation of indium metal ion with mercapto, hydroxy and amino substituted succinic acid

doi:10.1016/0022-1902(72)80438-X

Journal of Inorganic and Nuclear Chemistry

Volume 34, Issue 2, February 1972, Pages 581-590

https://doi.org/10.1016/0022-1902(72)80438-X Get rights and content

Abstract

Potentiometric studies on the free ligands and the metal complexes of indium(III) with thiomalic, malic and aspartic acid have yielded stepwise protonation constant of the ligands and the formation constants of the complexes. Thermodynamic formation constants have been obtained by extrapolation of the values at various ionic concentrations. The values of overall changes in ΔG°, ΔH°, ΔS° accompanying the reactions have been evaluated at 35°. The trend in the stability constant values of indium(III) complexes has been found to be thiomalic > malic > aspartic.

References (12)

R.A. Bailey et al.
J. Chromatog.
(1965)
D. Cozzi et al.
Z. elektrochem.
(1954)
J. Bjerrum
Metal Ammine Formation in Aqueous Solution
(1941)
M. Calvin et al.
J. Am. chem. Soc.
(1945)
H. Irving et al.
J. chem. Soc.
(1954)
Erdey László
International Series of Monographs on Analytical Chemistry
(1965)

There are more references available in the full text version of this article.

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Thermodynamics of complex formation of indium metal ion with mercapto, hydroxy and amino substituted succinic acid

Abstract

J. Chromatog.

Z. elektrochem.

Metal Ammine Formation in Aqueous Solution

J. Am. chem. Soc.

J. chem. Soc.

International Series of Monographs on Analytical Chemistry