NDLI: Chromium(III) Hydroxide Solubility in the Aqueous K$^{+}$-H$^{+}$-OH$^{−}$-CO$_{2}$-HCO 3 − -CO 3 2− -H$

Content Provider	Springer Nature Link
Author	Rai, Dhanpat Moore, Dean A. Hess, Nancy J. Rosso, Kevin M. Rao, Linfeng Heald, Steve M.
Copyright Year	2007
Abstract	Chromium(III)-carbonate reactions are expected to be important in managing high-level radioactive wastes. Extensive studies on the solubility of amorphous Cr(III) hydroxide solid in a wide range of pH (3–13) at two different fixed partial pressures of CO$_{2}$(g) (0.003 or 0.03 atm.), and as functions of K$_{2}$CO$_{3}$ concentrations (0.01 to 5.8 mol⋅kg$^{−1}$) in the presence of 0.01 mol⋅dm$^{−3}$ KOH and KHCO$_{3}$ concentrations (0.001 to 0.826 mol⋅kg$^{−1}$) at room temperature (22±2 °C) were carried out to obtain reliable thermodynamic data for important Cr(III)-carbonate reactions. A combination of techniques (XRD, XANES, EXAFS, UV-Vis-NIR spectroscopy, thermodynamic analyses of solubility data, and quantum mechanical calculations) was used to characterize the solid and aqueous species. The Pitzer ion-interaction approach was used to interpret the solubility data. Only two aqueous species [Cr(OH)(CO$_{3}$) 2 2− and Cr(OH)$_{4}$CO 3 3− ] are required to explain Cr(III)-carbonate reactions in a wide range of pH, CO$_{2}$(g) partial pressures, and bicarbonate and carbonate concentrations. Calculations based on density functional theory support the existence of these species. The log $_{10}$ K° values of reactions involving these species [{Cr(OH)$_{3}$(am) + 2CO$_{2}$(g)⇌Cr(OH)(CO$_{3}$) 2 2− +2H$^{+}$} and {Cr(OH)$_{3}$(am) + OH$^{−}$+CO 3 2− ⇌Cr(OH)$_{4}$CO 3 3− }] were found to be −(19.07±0.41) and −(4.19±0.19), respectively. No other data on any Cr(III)-carbonato complexes are available for comparisons.
Starting Page	1261
Ending Page	1285
Page Count	25
File Format	PDF
ISSN	00959782
Journal	Journal of Solution Chemistry
Volume Number	36
Issue Number	10
e-ISSN	15728927
Language	English
Publisher	Springer US
Publisher Date	2007-09-01
Publisher Place	Boston
Access Restriction	One Nation One Subscription (ONOS)
Subject Keyword	Thermodynamics Cr(OH)$_{3}$(am) Solubility Carbonate complexes Ion-interaction parameters Cr(III)-carbonate complexes Cr(OH)(CO$_{3}$) 2 2− Cr(OH)$_{4}$CO 3 3− Quantum mechanics Condensed Matter Inorganic Chemistry Oceanography Geochemistry Industrial Chemistry/Chemical Engineering Physical Chemistry
Content Type	Text
Resource Type	Article
Subject	Biochemistry Molecular Biology Biophysics Physical and Theoretical Chemistry

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