Mixed-metal hydroxycarboxylic acid complexes.  Chromium(III) inhibition of the solvent extraction of indium(III)

Gilbert, T. W.; Newman, L.; Klotz, P.

doi:10.1021/ac50158a032

Cited by 17 publications

(6 citation statements)

References 22 publications

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“…For the special case where the number of aqueous phases is equal to the number of organic phases used (i.e., a = c), the value of f is 0.5, and eqn. ( 5) for this "symmetrical" case reduces to rsym = (DADBr!/- (6) which is the same result obtained by Bush and Densen. It is interesting to note that the "diamond" design used by these authors is different from the one under consideration here.…”

Section: Selection Of the Phase Volume Ratio Rsupporting

confidence: 88%

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The "push through" design for solvent extraction separation

Gilbert¹

1974

J. Chem. Educ.

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Section: Selection Of the Phase Volume Ratio Rsupporting

confidence: 88%

“…In some cases these effects 2The computer output for 80 values of rD between 0.01 and 100, and c = 1-5, a = 1-12, may be obtained from the author. may be predicted, but in others they may be entirely unexpected (6).…”

Section: Independence Of Distribution Ratiosmentioning

confidence: 94%

The "push through" design for solvent extraction separation

Gilbert¹

1974

J. Chem. Educ.

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“…On the basis of spectrophotometric evidence, Gilbert et uZ. 13 suggested the structure (111) for the mixed-metal complex between Cr"', In'" and malic acid.…”

Section: Mixed-me Tal Complexesmentioning

confidence: 99%

Mixed-metal hydroxycarboxylic acid complexes. Formation constants of complexes of UVI with FeIII, AlIII, InIII and CuII

Manzurola¹,

Apelblat²,

Markovits³

et al. 1989

J. Chem. Soc., Faraday Trans. 1

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Formation constants for mixed-metal complexes, K,,,, between uranium(vI), as the central metal ion, and each one of the metal ions iron(III), aluminium(rrI), indium(1rr) and copper(1r) have been determined using data from potentiometric measurements. In each case one of the hydroxycarboxylic acids, citric, tartaric or malic, was used as a ligand. At 298.15 K the values of -log K,,, for the investigated systems are uranyl iron@) citrate, 2.45 ; uranyl iron(II1) malate, 7.37 ; uranyl aluminium(II1) citrate, 8.21 ; uranyl aluminium(1rr) tartarate, > 12; uranyl aluminium(1n) malate, 8.06; uranyl indium(rr1) citrate, 1 1.3 ; uranyl indium(Ir1) tartarate, 7.88 ; uranyl indium(II1) malate, 7.45 ; uranyl copper(I1) citrate -1.41 ;uranyl copper(I1) tartarate, -1.17 ; and uranyl copper(I1) malate, -1.1 1.Previous investigations 1-3 have shown that at pH 4.0 uranium(v1) forms mixed-metal complexes with some other metal ions when a hydroxycarboxylic acid is present. The spectrophotometric data1 indicate formation of complexes with a metal-metal ratio of 1 : 1 and 1 : 2 with Al'I', In ''I and Cu" and a ratio of ligand to total metal ion of 1 : 1 with citric, tartaric and malic acids, have the predominant stoichiometry of 1 : 1 : 2. From calorimetric measurements2 it was concluded that Fe'" also forms mixed-metal complexes with uranium(v1) in the presence of these acids. The formation constants of uranyl indium(Ir1) systems with citric, tartaric and malic acids were reported pre-viously4* using potentiometric and solvent-extraction methods.In the present study a model for evaluation of formation constants for the mixedmetal complexes from potentiometric data is proposed, and the values of Kmmc are reported. ExperimentalAqueous solutions of Cu", AlII', In''' and Fe'" were prepared from the metals, of at least 99% purity (all Merck), by dissolving the weighted metals in HCl and HNO, (Merck). The solutions were then evaporated to dryness and diluted to final volume with distilled water. Indium and aluminium were determined gravimetrically as oxides, copper was determined electrogravimetrically and iron was determined complexometrically with EDTA (Merck). Aqueous solutions of uranium(v1) were prepared from UO,(NO,),, 6 H 2 0 (Merck) and standardized gravimetrically as U,O,. Fresh aqueous solutions of citric, tartaric and malic acids were prepared from analytical-grade reagents (Merck) and standardized potentiometrically, using standard NaOH (Merck) solutions.All solutions contained 0.5 mol dm-, NaNO, (Merck), to maintain a constant ionic strength. The pH of the solutions was measured with an El-Hama combined electrode t Represents part of the Ph.D. thesis submitted by Emanual Manzurola to Ben Gurion University of the Negev.

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“…It forms soluble metal-citrate complexes with transition metals and actinides (3,4). In the presence of more than one metal, a ternary complex is formed with citric acid due to the bonding of the metals with both the carboxyl and hydroxyl groups (5). The bioavailability of metals may be affected by the formation of mixed-metal complexes (6,7).…”

Section: Introductionmentioning

confidence: 99%

“…The bioavailability of metals may be affected by the formation of mixed-metal complexes (6,7). Several metals such as Cr with In(III) (5); Cd with Ni, Mn, or Zn (8); and U(VI) with Al, Cu, Fe(III), and In(III) (9,10) were reported to form mixed-metal complexes with citric acid.…”

Section: Introductionmentioning

confidence: 99%

Biotransformation of Binary and Ternary Citric Acid Complexes of Iron and Uranium

Dodge

Francis

1997

Environ. Sci. Technol.

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Citric acid forms ternary mixed-metal complexes with various metal ions involving the hydroxyl and carboxyl groups of citric acid. The coordination of the metal to citric acid has been shown to affect the biodegradation of the metal−citrate complexes and metal mobility in the environ ment. We investigated the formation and biodegradation of the ternary mixed metal Fe−U−citric acid complex. The presence of 1:1:2 Fe−U−citric acid in solution was confirmed by potentiometric titration, UV−vis spectrophotometry, gel-filtration chromatography, and extended X-ray absorption fine structure (EXAFS) analysis. Comparison of the EXAFS spectra shows that the 1:1:2 Fe−U−citric acid complex has structural characteristics similar to the 1:1 U−citric acid complex. Biotransformation studies of Fe(III)−citrate, U(VI)−citrate, and Fe−U−citrate complexes by Pseudomonas fluorescens showed that the binary 1:1 Fe−citric acid was readily biodegraded, whereas the 1:1 U−citric acid complex and the ternary 1:1:2 Fe−U−citric acid complexes were recalcitrant. Adding excess citric acid to the 1:1 U−citric acid complex resulted in the formation of a 2:3 U−citric acid complex after metabolism of the excess citric acid. When 1-fold excess citric acid was added to the 1:1:2 Fe−U−citric acid complex, the excess citric acid was completely degraded with no change in the stoi chiometry of the complex. However, in the presence of 2-fold excess citric acid, a 1:1:1 Fe−U−citric acid complex remained in solution after the excess citric acid had been biodegraded.

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Mixed-metal hydroxycarboxylic acid complexes. Chromium(III) inhibition of the solvent extraction of indium(III)

Cited by 17 publications

References 22 publications

The "push through" design for solvent extraction separation

The "push through" design for solvent extraction separation

Mixed-metal hydroxycarboxylic acid complexes. Formation constants of complexes of UVI with FeIII, AlIII, InIII and CuII

Biotransformation of Binary and Ternary Citric Acid Complexes of Iron and Uranium

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