Metal-Solvate Stoichiometry Evaluation in Extractions by Solvating Type Neutral Extractants-a Novel Approach

Srinivasan, T. G.; Suresh, A.; Prasanna, Rohit; Jayanthi, N.; Rao, P. R. Vasudeva

doi:10.1080/07366299608918349

Cited by 19 publications

(11 citation statements)

References 7 publications

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“…The metal-solvate stoichiometry for the extraction of Th(IV) by TBP, TiBP, TsBP, TAP, and TiAP has been evaluated by Srinivasan et al [21] and found to be 3 in all the cases. In the present study, the solvation number for the extraction of Th(IV) by T2MBP and TsAP has been evaluated by the same method.…”

Section: Metal-solvate Stoichiometry For the Extraction Of Th(iv) Andmentioning

confidence: 99%

“…It is reported that U(VI) forms a disolvate with TBP in the extraction from nitric acid media. [21,32] TBP 0.187 [21] 0.256 [21] (i) Th(NO 3 ) 4 . 2TalP Th ½ max org~0 :367 TiBP 0.185 [21] 0.263 TsBP 0.181 [21] -(ii) Th(NO 3 ) 4 .…”

Section: Metal-solvate Stoichiometry For the Extraction Of Th(iv) Andmentioning

confidence: 99%

“…The expected Th ½ max org values for the disolvate (0.367 mol/L) and tetrasolvate (0.138 mol/L) formation in the extraction of Th(IV) by trialkyl phosphates, given in Table 11, do not match with the observed values and this confirms the trisolvate formation in the extraction of Th(IV). Figure 16 depicts the data that have been used to determine the solvation number for the extraction of U(VI) by 1.1 M T2MBP/ndodecane at 303 K by the method developed by Srinivasan et al [21] The data that have been used to determine the solvation number for the extraction of U(VI) by 1.1 M solutions of other trialkyl phosphates Table 12. In all the cases, U ½ max org value is close to the value corresponding to the solvation number of 2, and the results are summarized in Table 11.…”

Section: Metal-solvate Stoichiometry For the Extraction Of Th(iv) Andmentioning

confidence: 99%

“…The solvation number (x), for metal-solvates of U(VI) and Th(IV) with various trialkyl phosphates has been determined by a method developed by Srinivasan et al [21] In this method, variation of D values for the extraction of metal salt from an aqueous medium with near-zero free acidity is measured as a function of metal concentration. For the extraction of metal salts by neutral solvating type extractants from aqueous media with zero free acidity, the stoichiometry was evaluated using Eq.…”

Section: Extraction Of Th(iv) and U(vi) As A Function Of Metal Concenmentioning

confidence: 99%

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The Effect of the Structure of Trialkyl Phosphates on their Physicochemical Properties and Extraction Behavior

Suresh

Srinivasan

Rao

2009

Solvent Extraction and Ion Exchange

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The density of various trialkyl phosphates (TalP) such as tri-n-butyl phosphate (TBP), tri-iso-butyl phosphate (TiBP), tri-sec-butyl phosphate (TsBP), tri-n-amyl phosphate (TAP), tri-2-methylbutyl phosphate (T2MBP), tri-iso-amyl phosphate (tri-3-methylbutyl phosphate, TiAP), tri-sec-amyl phosphate (tri-2-amyl phosphate, TsAP), tri-cyclo-amyl phosphate (TcyAP), tri-n-hexyl phosphate (THP), and 1.1 M solutions of some of these phosphates in various diluents, solubility of water in trialkyl phosphates, and the aqueous solubility of trialkyl phosphates have been measured. Extraction of nitric acid, Th(IV), and U(VI) by trialkyl phosphates has also been studied by the batch extraction method. Metalsolvate stoichiometry in the extraction of Th(IV) and U(VI) by some of the phosphates has been evaluated. Data on the extraction of U(VI) by various trialkyl phosphates as a function of equilibrium aqueous-phase nitric acid concentration at 303 K are presented in this paper. Data on the extraction of Th(IV) and U(VI) from 1 M and 5 M HNO 3 by trialkyl phosphates as a function of equilibrium aqueous-phase metal concentration at 303 K are also presented in this paper. The effects of the structure of trialkyl phosphates on their physicochemical properties and extraction behavior are described in this paper.

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Section: Metal-solvate Stoichiometry For the Extraction Of Th(iv) Andmentioning

confidence: 99%

Section: Metal-solvate Stoichiometry For the Extraction Of Th(iv) Andmentioning

confidence: 99%

Section: Metal-solvate Stoichiometry For the Extraction Of Th(iv) Andmentioning

confidence: 99%

Section: Extraction Of Th(iv) and U(vi) As A Function Of Metal Concenmentioning

confidence: 99%

See 2 more Smart Citations

The Effect of the Structure of Trialkyl Phosphates on their Physicochemical Properties and Extraction Behavior

Suresh

Srinivasan

Rao

2009

Solvent Extraction and Ion Exchange

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“…Our earlier studies on the evaluation of metal-solvate stoichiometry revealed that thorium nitrate forms trisolvate with TiAP [21]. In general, the distribution ratio (D) for the extraction of a metal nitrate by a neutral extractant increases with increase in the concentration of nitrate ion in the aqueous phase and also with increase in the extractant concentration in the organic phase.…”

Section: Results and Discussion Loc As A Function Of Tiap Concentratimentioning

confidence: 97%

Empirical equations for the prediction of third phase formation limits in the extraction of thorium nitrate by tri-iso-amyl phosphate (TiAP)

Suresh

Sreenivasulu

Sivaraman

et al. 2015

J Radioanal Nucl Chem

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Third phase formation in the extraction of Th(IV) by TiAP in various n-alkane diluents was investigated under different conditions. The limiting organic concentrations (LOC) for third phase formation for TiAP/nalkane/thorium nitrate systems were measured as a function of various parameters for deriving empirical equations with respect to extractant concentration, equilibrium aqueous phase nitric acid concentration ([HNO 3 ] aq,eq ), temperature and number of carbon atoms per diluent for the prediction of LOC. Our results show a very good agreement between the LOC values calculated with empirical equations derived from two different approaches.

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Structure‐Modulated Complexation of Actinides with Phosphonates: A Combined Experimental and Quantum Chemical Investigation

et al. 2018

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Phosphonates have shown promising specificity and remarkable extractability towards actinide elements. Among all the organophosphorous compounds, phosphonates have the dual advantage of simplicity in preparation coupled with the flexibility to tailor-make their carbon chain structure. In the present work the relationship between structure and metal binding affinity of phosphonates has been examined both experimentally and quantum mechanically. Symmetrical Diisobutylisobutyl, Diisoamylisoamyl and unsymmetrical Diisoamylhexyl and Diisoamylbutyl branched phosphonates were synthesised and characterised by NMR and GC-MS. These ligands were used to bind Th(IV), U(VI), Pu(IV) and Am(III) at the liquidliquid interface. The ligands also were examined for their physicochemical properties of density, viscosity, aqueous solubility and dielectric constant which are significantly affected by changes in the alkyl chain structure. A combination of physico-chemical parameters, as well as the structure modulated chemical nature of the extractants, cause variations in the distribution ratios towards metal ions. These effects have been probed in detail using Th(IV), U(VI), Pu(IV) and Am(III) ion extractions and found to correlate with the carbon chain length of the organic groups on the phosphoryl centre. Further, density functional theory was employed to understand the electronic structure of the extractants and metal complexes. The computed complexation energies in the formation of metal-ligand complexes compared well with the trends observed in the experiments. Both experiment and quantum chemistry emphasizes the importance of the carbon chain structure on the actinide binding ability of phosphonate ligands.

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Metal-Solvate Stoichiometry Evaluation in Extractions by Solvating Type Neutral Extractants-a Novel Approach

Cited by 19 publications

References 7 publications

The Effect of the Structure of Trialkyl Phosphates on their Physicochemical Properties and Extraction Behavior

The Effect of the Structure of Trialkyl Phosphates on their Physicochemical Properties and Extraction Behavior

Empirical equations for the prediction of third phase formation limits in the extraction of thorium nitrate by tri-iso-amyl phosphate (TiAP)

Structure‐Modulated Complexation of Actinides with Phosphonates: A Combined Experimental and Quantum Chemical Investigation

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