The Determination of the Solubility of Amorphous UO2 (Sn and the Mononuclear Hydrolysis Constants of Uranium(IV) at 25° C.

1986 ◽  
Vol 84 ◽  
Author(s):  
Jordi Bruno ◽  
Ignasi Casas ◽  
Bo Lagerman ◽  
Maria Munoz
Keyword(s):  
Stability Constants ◽  
Solubility Data ◽  
Hydrolysis Constants ◽  
Reducing Conditions ◽  
Wide Ph Range ◽  
The Stability ◽  
Ph Range ◽  
Good Agreement

AbstractWe have measured the solubility 8f amorphous UO2in a wide pH range (2 to 10.5), in 0.5 M NaClO, at T=25 C. The species responsible for the solubility are U(OH) + and U'0H)h, with the stability constants lo:1,3=-1.1± 0.1 and log, 4 =- 5.4_.O. 2, respectively. No evidence for U(OH) is f6und up to pH=10.5. The same model explains satisfactorily the solubility data obtained by Parks and Pohl(5) at T=1000 C., in the pH range 1 to 10. The measured solubility of amorphous UO2 (s) in the pH_ýange 6 to 10.5, under reducing conditions, is rather high,. U(IV) =5 10 mols/l. This is in good agreement with previous data of Gayer and Leider(6) and Galkin and Stepanov(9).

scholarly journals Tales of the Unexpected: The Case of Zirconium(IV) Complexes with Desferrioxamine

Molecules ◽  
2019 ◽  
Vol 24 (11) ◽  
pp. 2098 ◽  
Author(s):  
Matteo Savastano ◽  
Carla Bazzicalupi ◽  
Giovanni Ferraro ◽  
Emiliano Fratini ◽  
Paola Gratteri ◽  
...  
Keyword(s):  
Stability Constants ◽  
Density Functional ◽  
Maldi Mass Spectrometry ◽  
Binuclear Complexes ◽  
X Ray Scattering ◽  
Complex Solutions ◽  
The Stability ◽  
Ph Range ◽  
First Time

The Zr4+ complexes with desferrioxamine (H3DFO) and its derivatives are the only 89Zr-based imaging agents for proton emission tomography (PET) that have been used so far in clinical trials. Nevertheless, a complete speciation of the Zr4+/H3DFO system in solution has never been performed and the stability constants of the relevant complexes are still unknown. Here we report, for the first time, the speciation of this system in water, performed by potentiometric titrations, and the determination of the stability constants of all complexes formed in the pH range 2.5–11.5. Surprisingly, although desferrioxamine gives rise to very stable 1:1 complexes with Zr4+ (logK = 36.14 for Zr4+ + DFO3− = [ZrDFO]+), 2:2 and 2:3 ones are also formed in solution. Depending on the conditions, these binuclear complexes can be main species in solution. These results were corroborated by small-angle X-ray scattering (SAXS) and MALDI mass spectrometry analyses of complex solutions. Information on complex structures was obtained by means of density functional theory (DFT) calculations.

scholarly journals Potentiometric studies on complexes of Cr (Ⅲ) and Zr (IV)with some carboxylic acids

2015 ◽  
Vol 3 (1) ◽  
pp. 25 ◽  
Author(s):  
Abdalazeem Omar ◽  
Elmugdad Ali
Keyword(s):  
Stability Constants ◽  
Transition Elements ◽  
Ph Titration ◽  
Oxalacetic Acid ◽  
The Stability ◽  
Titration Technique ◽  
Metal Ligand ◽  
Sensitive Method ◽  
Good Agreement

<p>The present work, deals with the study of proton-ligand (pK) and metal-ligand (logK) of acetic acid, oxalic acid, and oxalacetic acid with Cr (Ⅲ) and Zr (IV) by potentiometric titration technique. The stoichiometries and stability constants of these complexes were evaluated, usingCalvin-Bjerrum pH-titration technique as adopted by Irriving and Rossotti.</p><p>Graphic and algebraic methods have been employed, for determination of the stability constants, in purpose to select the most accurate and sensitive method. Furthermore, aiming to determine, the factor that effectingthe precision of those methods under investigation, and to compare the complexes of these ligands with first and second series transition elements of D-block Cr and Zr taken as an example. The obtained results were in a good agreement with each other.</p>

Polarographic and spectrophotometric behaviour of some N-p-phenyl substituted benzamidines

1991 ◽  
Vol 56 (12) ◽  
pp. 2791-2799 ◽  
Author(s):  
Juan A. Squella ◽  
Luis J. Nuñez-Vergara ◽  
Hernan Rodríguez ◽  
Amelia Márquez ◽  
Jose M. Rodríguez-Mellado ◽  
...  
Keyword(s):  
Spectrophotometric Study ◽  
Absorption Bands ◽  
Electrochemical Parameters ◽  
Wide Ph Range ◽  
Group A ◽  
Substituent Constants ◽  
Ph Range ◽  
The Waves

Five N-p-phenyl substituted benzamidines were studied by DC and DP polarography in a wide pH range. Coulometric results show that the overall processes are four-electron reductions. Logarithmic analysis of the waves indicate that the process are irreversible. The influence of the pH on the polarographic parameters was also studied. A UV spectrophotometric study was performed in the pH range 2-13. In basic media some variations in the absorption bands were observed due to the dissociation of the amidine group. A determination of the pK values was made by deconvolution of the spectra. Correlations of both the electrochemical parameters and spectrophotometric pK values with the Hammett substituent constants were obtained.

Impact of sulfate on the solubility of Tc(IV) in acidic to hyperalkaline aqueous reducing systems

2021 ◽  
Vol 0 (0) ◽  
Author(s):  
Sarah B. Duckworth ◽  
Xavier Gaona ◽  
Alexander Baumann ◽  
Kathy Dardenne ◽  
Jörg Rothe ◽  
...  
Keyword(s):  
Solid Phase ◽  
Correction Factors ◽  
Mixed Salt ◽  
Ph Values ◽  
Reducing Conditions ◽  
Upper Limits ◽  
Salt Systems ◽  
Amorphous Character ◽  
Good Agreement

Abstract The solubility of 99Tc(IV) was investigated from undersaturation conditions in NaCl–Na2SO4 (0.3 M ≤ I ≤ 5.0 M), MgCl2–MgSO4 (I = 13.5 M) and CaCl2–CaSO4 (I = 13.5 M) systems with 0.001 M ≤ [SO4 2−]tot ≤ 1.0 M and 1 ≤ pH m  ≤ 12 (with pH m  = −log[H+], in molal units). Reducing conditions were set by either Sn(II) or Fe(0). Special efforts were dedicated to accurately characterize the correction factors A m required for the determination of pH m from the experimentally measured pH values in the mixed salt systems investigated, with pH m  = pHexp + A m . The combination of (pe + pH m ) measurements with Pourbaix diagrams of Tc suggests that technetium is present in its +IV redox state. This hypothesis is confirmed by XANES, which unambiguously shows the predominance of Tc(IV) both in the aqueous and solid phases of selected solubility samples. XRD and SEM–EDS support the amorphous character of the solid phase controlling the solubility of Tc(IV). EXAFS data confirm the predominance of TcO2(am, hyd) at pH m  > 1.5, whereas the formation of a Tc(IV)–O–Cl solid phase is hinted at lower pHm values in concentrated NaCl–Na2SO4 systems with ≈5 M NaCl. Solubility data collected in sulfate-containing systems are generally in good agreement with previous solubility studies conducted in sulfate-free NaCl, MgCl2 and CaCl2 solutions of analogous ionic strength. Although the complexation of Tc(IV) with sulfate cannot be completely ruled out, these results strongly support that, if occurring, complexation must be weak and has no significant impact on the solubility of Tc(IV) in dilute up to highly saline media. Solubility upper-limits determined in this work can be used for source term estimations including the effect of sulfate in a variety of geochemical conditions relevant in the context of nuclear waste disposal.

Physicochemical investigation on thiomalate complexes of nickel

1968 ◽  
Vol 21 (3) ◽  
pp. 641 ◽  
Author(s):  
RS Saxena ◽  
KC Gupta ◽  
ML Mittal
Keyword(s):  
Aqueous Medium ◽  
Stability Constants ◽  
Alternative Methods ◽  
Acid System ◽  
Kcal Mole ◽  
Physicochemical Investigation ◽  
Different Temperatures ◽  
The Stability ◽  
Ph Range ◽  
Deep Violet

Potentiometric and conductometric studies of the nickel-thiomalic acid system, in aqueous medium of 0. lM KNO3, reveal the formation of two complexes; one light violet 1 : 1 predominating at pH 6.5-7.5 and another deep violet 1 : 2 in the pH range 8.5-10.0. The stability constants of the complexes formed have been determined by applying Calvin and Melchior's extension of Bjerrum's method at three different temperatures and were further refined by using alternative methods. The logK values (final) for 1 : 1 and 1 : 2 complexes at 20, 25, and 30� have been found to be 7.86, 7.87, 7.96, and 6.24, 6.31, 6.39 respectively. The values of the overall changes in ΔG, ΔH, and ΔS accompanying the reaction have also been evaluated at 25� and found to be -19.31 kcal/mole, -8.77 kcal/mole, and +35.36 cal/deg respectively.

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