Solvent extraction of lanthanide ions with 1-phenyl-3-methyl-4-benzoyl-pyrazolone-5 (HPMBP)

The solvent extraction of Er(III), Yb(III) and Lu(III) by 1-phenyl-3-methyl-4-benzoyl-pyrazolone-5 (HPMBP or HL) in carbon tetrachloride has been studied as a function of thepH of the aqueous phase and the concentration of the extractant in the organic phase. The equation for the extraction reaction has been suggested as: $$Ln^{3 + } + 3HL_{(0)} \rightleftharpoons LnL_{3(0)} + 3H^ + \left( {Ln^{3 + } = Er,Yb, Lu} \right)$$ The extraction equilibrium constants (K _ex ) and two-phase stability constants (β ₃ ^x ) for theLnL ₃ complexes have been evaluated.     

Synergistic complexes of uranyl ion with 1-phenyl-3-methyl-4-acetyl-pyrazolone-5 and some oxo-donors

Complexes of uranyl ion with 1-phenyl-3-methyl-4-acetyl-pyrazolone-5(PMAP) and various oxo-donors such as aliphatic sulphoxides [R₂SO, where R = i-C₅H₁₁(DISO), n-C₆H₁₃(DHSO), n-C₇H₁₅(DSSO), n-C₈H₁₇(DOSO), n-C₉H₁₉(DNSO), n-C_1OH₂₁(DDSO), n-C₁₁H₂₃(DUDSO) and n-C₄H₉(DBUSO)] tributylphosphate (TBP) and tri-n-octyl phosphine oxide (TOPO) have been synthesised and characterized. Analytical data establish that they have the stoichiometry UO₂(PMAP)₂X where X is the oxo-donor. The IR spectra of the sulphoxide complexes in the SO stretching region indicate that the ligands R₂SO are O-bonded. The methyl protons of the pyrazole ring and acetyl group in the PMAP ligand are equivalent giving rise to a single sharp peak in the PMR spectra, whereas in the synergistic complexes with the oxo-donors, two deshielded peaks of equal intensity are observed which indicate the non-equivalence of the methyl groups. The peak which is more deshielded has been ascribed to the methyl of the acetyl group. The higher deshielding of these methyl protons arises due to the transfer of electron density to the metal atom on complexation.     

Synergistic extraction of uranyl ion with 1-phenyl-3-methyl-4-benzoylpyrazolone-5 (HPMBP) and diphenyl sulfoxide (DPSO), tri-n-butyl phosphate (TBP) or tri-n-octylphosphine oxide (TOPO)

Synergistic extraction of uranyl ion with 1-phenyl-3-methyl-4-benzoyl-pyrazolone-5 (HPMBP) and oxo donors with widely varying basicity, viz. diphenyl sulfoxide (DPSO), tri-n-butyl phosphate (TBP) and tri-n-octylphosphine-oxide (TOPO) has been studied at various fixed temperatures. Results indicate that the equilibrium constants in the organic phase for addition reactions (K_S) with these donors follow their order of basicity (K_H) viz. DPSO (0.033)<TBP (0.16)TOPO (8.9) with log K_S values of 3.70, 4.28 and 6.45, respectively. The thermodynamic parameters associated with the formation of these systems have been evaluted by the temperature coefficient method. The results indicate that the complex in the organic phase for DPSO and TBP is stabilized only by enthalpy, whereas both enthalpy and entropy contribute to the stabilization of the TOPO complex. Also, enthalpy contribution is more prominent as compared with the UO ₂ ²⁺ /HTTA/TOPO system, where both enthalpy and entropy contribute almost equally.     

Thermodynamic parameters for the extraction of some lanthanides with 1-phenyl-3-methyl-4-benzoyl-pyrazolone-5 and trioctylamine

The synergistic extraction of Pr, Gd and Yb with a mixture of 1-phenyl-3-methyl-4-benzoyl-pyrazolone-5 and trioctylamine diluted in C₆H₆, CHCl₃ and CCl₄ at 288 K, 298 K, 308 K and 318 K has been investigated. The values of the equilibrium constants as well as of H°, S° and G° have been calculated. The thermodynamic parameters indicate that the adduct formed becomes stable on the account of the enthalpy change which exceeds the antistabilizing effect of the entropy factor. A comparison is made to the extraction of the same elements with thenoyltrifluoroacetone.

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Die thermodynamischen Parameter für die Extraktion einiger Lanthaniden mit 1-Phenyl-3-methyl-4-benzoyl-5-pyrazolon und Trioctylamin

Zusammenfassung Es wurde die synergistische Extraktion von Pr, Gd und Yb mit einer Mischung von 1-Phenyl-3-methyl-4-benzoyl-5-pyrazolon mit Trioctylamin in C₆H₆, CHCl₃ und CCl₄ bei 288 K, 298 K, 308 K und 318 K bestimmt. Die Gleichgewichtskonstanten und die Werte für H°, S° und G° wurden berechnet. Die thermodynamischen Parameter legen den Schluß nahe, daß die Stabilität des gebildeten Addukts in Änderungen der Enthalpie begründet ist, wobei der destabilisierende entropische Effekt übertroffen wird. Die Ergebnisse werden mit der Extraktion mittels Thenoyltrifluoraceton verglichen.

     

Influence of the temperature on the extraction of some lanthanides with 1-phenyl-3-methyl-4-benzoyl-pyrazolone-5

The extraction of Pr, Gd and Yb with 1-phenyl-3-methyl-4-benzoyl-pyrazolone-5 (HPMBP) diluted in CHCl₃, C₆H₆, and CCl₄ at 288 K, 298 K, 308 K, and 318 K has been investigated. A compound of the typeMe(PMBP)₃HPMBP is formed in the organic phase. The values of the thermodynamic constants as well as of the parameters H°, S° and G° have been determined.

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Der Temperatureinfluß auf die Extraktion einiger Lanthaniden mit 1-Phenyl-3-methyl-4-benzoyl-5-pyrazolon

Zusammenfassung Es wurde die Extraktion von Pr, Gd und Yb mit 1-Phenyl-3-methyl-4-benzoyl-5-pyrazolon (HPMBP) in CHCl₃, C₆H₆ oder CCl₄ als verdünnendes Lösungsmittel bei 288 K, 298 K, 308 K und 318 K untersucht. Es wird eine Verbindung des TypsMe(PMBP)₃HPMBP in der organischen Phase gebildet. Die thermodynamischen Konstanten und auch die Parameter H°, S° und G° wurden bestimmt.

     

Solvent extraction of lanthanide ions with 1-phenyl-3-methyl-4-benzoyl-pyrazolone-5 (HPMBP), II. Extraction of erbium(III), ytterbium(III) and lutetium(III) by HPMBP from aqueous-methanol solutions

The solvent extraction of lanthanides(III) (Ln=Er, Yb, Lu) by 1-phenyl-3-methyl-4-benzoylpyrazolone-5 (HL) in carbon tetrachloride from aqueous-methanol phase was investigated. The equilibrium constants for the extraction from aqueous –50% (v/v) methanol phase (K _ex ), two-phase stability constants of the complexesLnL ₃ ( ₃ ^* ) and stability constants of complexesLnL ²⁺,LnL ₂ ⁺ ,LnL ₃ ( _n ) (Ln=Yb, Lu) were calculated. It was confirmed that the addition of methanol to the aqueous phase causes a synergistic effect. The influence of methanol on the dissociation constant of HPMBP (K _a ) and the distribution constant of HPMBP (p _HL ) between carbon tetrachloride and water-methanol solutions was investigated.

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Extraktion von Seltenerdmetall-Ionen mit 1-Phenyl-3-methyl-4-benzoyl-pyrazolon-5 (HPMBP), II. Extraktion von Er(III), Yb(III) und Lu(III) aus Wasser-Methanol-Lösungen

Zusammenfassung Die Extraktion von Lanthaniden (Ln=Er, Yb, Lu) mittels 1-Phenyl-3-methyl-4-benzoyl-pyrazolon-5 (HL) in Kohlenstofftetrachlorid aus Wasser-Methanol Phase wurde untersucht. Die Werte der Gleichgewichtskonstante für Extraktion aus Wasser –50% (v/v) Methanol-Phase (K _ex ), der zweiphasigen Beständigkeitskonstante für die KomplexeLnL ₃ ( ₃ ^* ), sowie der Stabilitätskonstante des KomplexesLnL ²⁺,LnL ₂ ⁺ undLnL ₃ ( _n ) (Ln=Yb, Lu), wurden berechnet. Es wurde festgestellt, daß die Zugabe von Methanol zur wäßrigen Phase einen synergistischen Effekt hat. Der Einfluß von Methanol auf die Dissoziationskonstante von HPMBP (K _a ) und die Verteilungskonstante des HPMBP (p _HL zwischen organischer und wäßrig-methanolischer Phase wurde untersucht.

     

Recovery of neptunium from macroamounts of uranium by extraction with 1-phenyl-3-methyl-4-benzoyl-pyrazolone-5

Conditions for neptunium recovery from nitrate solution containing large amounts of uranium by extraction with 1-phenyl-3-methyl-4-benzoyl-pyrazolone-5 (PMBP), and a mixture of PMBP with di-2-ethyl-hexylphosphoric acid (HDEHP) were studied. A two-stage technique, based on removal of uranium macroamounts at the first stage by means of extraction of uranium with PMBP and HDEHP mixture, and neptunium extraction by PMBP at the second stage, was suggested.     

Synergistic extraction of uranium(VI) with 1-phenyl-3-methyl-4-acylpyrazolone-5 and neutral extractants

The synergistic extraction of uranium(VI) from hydrochloric acid solution with five chelating agents: 1-phenyl-3-methyl-4-benzoylpyrazolone-5 (PMBP), 1-phenyl-3-methyl-4-acetylpyrazolone-5 (PMAP), 1-phenyl-3-methyl-4-(2-chlorobenzoyl)pyrazolone-5 (PMCBP), 1-phenyl-3-methyl-4-(p-nitrobenzoyl)pyrazolone-5 (PMNBP) and 1-phenyl-3-methyl-4-trifluoroacetylpyrazolone-5 (PMTFP) plus the neutral extractants tributylphosphate (TBP), dioctyl sulfoxide (DOSO) and trioctylphosphine oxide (TOPO) in chloroform has been investigated. The extraction coefficients have been found to be greater for such mixtures than the individual component. The formulas of the extracted species have been determined to be UO₂A₂B (where HA = chelating agent, B = neutral extractant). Extraction power of these chelating agents increases as follows: PMCBP>PMNBP>PMTFP=PMBP>PMAP. Synergistic extraction power of the neutral extractants increases as follows: TOPO>DOSO>TBP. The extraction equilibrium constants have been calculated. The mechanism of the synergistic extraction and possible structure of the extracted species are discussed.     

Solvent extraction of Hf(IV) and Zr(IV) with some 1-phenyl-3-methyl-4-acylpyrazolones-5

The distribution of Hf, Zr and Nb between aqueous solutions of mineral acids and solutions of 1-phenyl-3-methyl-4-acylpyrazolones-5 (acyl=acetyl, ethoxycarbonyl, butyryl, capronyl, capryl and benzoyl) in various organic solvents has been studied. The dependence of the distribution ratio of metal on the acidity of the aqueous phase, the analytical concentrations of reagents and metals, and on the organic solvent was investigated. The composition of the complex extracted is MeP₄ for Hf and Zr. The conditions for the separation of Zr, Hf and Nb are defined, and a comparison is made with extractions by means of thenoyltrifluoroacetone.     

Mixed-ligand chelate extraction of trivalent lanthanides and actinides with 1-phenyl-3-methyl-4-benzoyl-pyrazolone-5 and dihexyl-N,N-diethylcarbamoylmethyl phosphonate

Mixed-ligand chelate extraction of trivalent lanthanides such as La, Eu and Lu and a trivalent actinide, Am into xylene with mixtures of 1-phenyl-3-methyl-4-benzoyl-pyrazolone-5 (HPMBP) and dihexyl-N,N-diethylcarbamoylmethylphosphonate (CMP) has been studied by tracertechniques. These trivalent metal ions are found to be extracted from 0.01 mol/dm³ chloroacetate buffer solutions as M(PMBP)₃·HPMBP type self adducts with HPMBP alone and in the presence of CMP as M(PMBP)₃·CMP (where M=La, Eu, Lu and Am) into the organic phase. The equilibrium constants of the above species are deduced by non-linear regression analysis. The synergistic constants of trivalent lanthanides do not increase monotonically with atomic number but have a maximum at Eu and that of Am was found to lie between that of La and Eu.     

Solvent extraction of gold(III) with 1-phenyl-3-methyl-4-trifluoroacetylpyrazolone-5

A simple, rapid and selective separation procedure of gold based on its extraction with 1-phenyl-3-methyl-4-trifluoroacetylpyrazolone-5 has been developed. The dependence of the distribution ratio of gold on the pH of aqueous solutions, concentration of hydrochloric, nitric and perchloric acids and the organic solvents has been investigated. Decontamination factors for a number of metal ions with respect to gold are reported. Excellent separation of gold is obtained from many elements including noble metals. Citrate, cyanide, iodide, thiosulfate and thiourea completely mask gold, whereas oxalate does not interfere. Solutions of 1 M HCl, 0.2 M KCN, and the buffer of pH 0.8 readily strip gold from the organic phase. Some useful analytical applications of this procedure are discussed.     

1-苯基-3-甲基-4-苯甲酰基-吡唑啉酮-5镉配合物的合成和晶体结构

1苯-基-3甲-基-4苯-甲酰基-吡唑啉酮-5(HPMBP)是一类含有氮杂环的β-二酮螯合剂,现在已经广泛应用于金属离子的分离和分析[1-4]。它与许多金属离子生成的配合物的生物活性明显增强,显示了广谱的抗菌、抗病毒和抗肿瘤等性质,引起了化学家对它与金属离子的配位作用以及配合物的晶     

Synergistic extraction of uranium(VI) with 1-phenyl-3-methyl-4-(2′-chlorobenzoyl)-pyrazolone-5 and acidic organophosphorus reagents

A study of the synergistic extraction of uranium(VI) from sulphuric acid solution with 1-phenyl-3-methyl-4-(2-chlorobenzoyl)-pyrazolone-5 (PMCBP) together with di-(2-ethylhexyl)-phosphoric acid (HDEHP) and also mono-(2-ethylhexyl)-2-ethylhexyl-phosphate (HEHEHP) is described. The results suggest that the compositions of the extracted species is UO₂XHA₂ and UO₂X₂H₂A₂ respectively. Models for the extraction mechanism is also discussed.     

Studies on extraction of manganese(II) with 1-phenyl-3-methyl-4-acyl-5-pyrazolone

The extraction of Mn(II) with 1-phenyl-3-methyl-4-acyl-5-pyrazolone (HA) in MIBK has been studied. Mn(II) is extracted as MnA(2). The extraction constant for each 4-acyl compound was calculated. The effect of temperature on the extraction of Mn(II) has also been investigated.     

Studies on extraction of copper(II) with 1-phenyl-3-methyl-4-acyl-5-pyrazolone

The extraction of Cu(II) with 1-phenyl-3-methyl-4-acyl-5-pyrazolone (HA), in different organic solvents has been studied. The extraction mechanism of Cu(II) and the composition of the extracted species has been determined. Cu(II) was extracted as CuA₂, or in the presence of TOPO, as CuA₂TOPO. The extraction constants do not change regularly with increasing the length of acyl chain in the 1-phenyl-3-methyl-4-acyl-5-pyrazolone derivatives. The effect of the temperature on the extraction of Cu(II) has also been investigated.     

Synergistic solvent extraction of lanthanides with mixtures of 1-phenyl-3-methyl-4-benzoyl-pyrazol-5-one and aliphatic amines: Influence of the ammonium salt ions

Summary The synergistic solvent extraction of Pr, Gd, and Yb with mixtures of 1-phenyl-3-methyl-4-benzoyl-pyrazol-5-one (HP) and tridodecylammonium (TDAHA), trioctylammonium (TOAHA), and dioctylammonium (DOAHA) salts (A ^–=Cl^–, NO ₃ ^– , and ClO ₄ ^– ) in C₆H₆ has been studied. The composition of the extracted species has been determined asAmH⁺[LnP ₄]^– (AmH⁺: ammonium salt cation). The values of the equilibrium constant have been calculated. The influence of the ammonium salt ions on the extraction process is discussed.

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Synergetische Extraktion von Lanthaniden mit Mischungen aus 1-Phenyl-3-methyl-4-benzoyl-pyrazol-5-on und aliphatischen Aminen: Einfluß der Ammoniumsalzionen

Zusammenfassung Die synergetische Extraktion von Pr, Gd und Yb mit Mischungen aus 1-Phenyl-3-methyl-4-benzoyl-pyrazol-5-on (HP) und Tridodecylammonium-(TDAHA), Trioctylammonium-(TOAHA) und Dioctylammoniumsalzen (DOAHA) (A ^–=Cl^–, NO ₃ ^– und ClO ₄ ^– ) in C₆H₆ wurde untersucht. Die Zusammensetzung der Extraktionskomplexverbindungen wurde zuAmH⁺[LnP ₄]^– bestimmt; die Gleichgewichtskonstanten wurden berechnet. Der Einfluß der Ionen des Ammoniumsalzes auf die Extraktion wird diskutiert.

     

Effect of inorganic aqueous anions on the synergic extraction of cadmium and zinc with 1-phenyl-3-methyl-4-benzoyl-pyrazol-5-one (HPMBP) and lipophilic ammonium salts

As a part of a systematic study of the synergic extractions of metals with mixtures of acidic chelating extractants and lipophilic anion-exchangers (B, X with X^?6 inorganic anion), the extractions of M  Cd and Zn from perchlorate, nitrate and sulphate media with 1-phenyl-3-methyl-4-benzoyl-pyrazol-5- one (HL) and tri-n-octylammonium salts (TOAH.X) or aliquat 336 (TOMA.X) in toluene have been investigated. Three key equilibria describe the extractions: (a) M²⁺+2$\text{HL}$?$\text{ML}{}_2$+2H⁺. (b) $\text{B.X}$ +$\text{HL}$?$\text{B.L}$+H⁺+X^? with B efficiency TOMA < TOAH and X efficiency ClO₄ < NO₃ < SO₄. (c) $\text{ML}{}_2$+$\text{B.L}$?$\text{B.ML}{}_3$ with B efficiency toma > TOAH and Ni ～ Co > Cd > ZN.As a consequence of the conflicting orders of efficiencies of TOMA and TOAH in equilibria b and c, TOAH.X is a better synergic extractant from perchlorate medium than TOMA.X whereas the inverse is observed from nitrate and sulphate media. Equilibrium c is independent of the inorganic anions. Constants of equilibria a, b and c are given. B.ML₃ species are not extracted in 1-octanol.     

Synergistic extraction of lanthanum(III) from chloride medium by mixtures of 1-phenyl-3-methyl-4-benzoyl-pyrazalone-5 and triisobutylphosphine sulphide

The synergistic effect of 1-phenyl-3-methyl-4-benzoyl-pyrazalone-5 (HPMBP) and triisobutylphosphine sulphide (TIBPS, B) is investigated in the extraction of lanthanum(III) from chloride solution. Lanthanum(III) is extracted by the mixture as LaCl₂·PMBP·B_0.5 instead of La(PMBP)₃·(HPMBP) which is extracted by HPMBP alone. The equilibrium constants and thermodynamic functions such as ΔG, ΔH and ΔS are determined. The extraction of other rare earth ions by mixtures of HPMBP and TIBPS is also studied and the possibility of separating rare earth ions is discussed.     

Extraction of cobalt(II) and nickel(II) with mixtures of 1-phenyl-3-methyl-4-benzoyl-pyrazol-5-one (HPMBP) and tri-n-octylamine (TOA)

The extraction of Co(II) with mixtures of 1-phenyl-3-methyl-4-benzoyl-pyrazol-5-one ((H)PMBP) and tri-n-octylamine (TOA) is investigated in order to explore the influence of diluents and inorganic anions with synergistic acidic extractant + liquid anion exchanger systems. Although it is proved that the same species [HTOA]⁺ [Co(PMBP)₃]^? is extracted from various inorganic media, with toluene as the diluent, the presence of ClO₄^? SO₄^2? or Cl^? anion modifies the distribution of the anions which are associated to (HTOA)⁺ in the organic phase, leading to different synergistic equilibria; with Cl^? or SO₄^2?: $\text{CO(PMBP)}{}_2$ + $\text{(HTOA}{}^{\mathrm{+}}$,PMBP^?) ?$\text{(HTOA}{}^{\mathrm{+}}$,Co(PMBP)₃^? (log K = 6.10) and with ClO₄^? : $\text{Co(PMBP)}{}_2$ + $\text{HPMBP}$ + $\text{(HTOA}{}^{\mathrm{+}}$,ClO₄^? ? $\text{(HTOA}{}^{\mathrm{+}}$,Co(PMBP)₃^? + H⁺ + ClO₄^? (log K = 2.34) The same synergistic equilibrium is observed for the extraction of Ni(II) from ClO₄^? medium, with a comparable value of the constant (log K = 2.45). The synergistic effect is cancelled in n-octanol.