A Striking Effect of Ionic‐Liquid Anions in the Extraction of Sr2+ and Cs+ by Dicyclohexano‐18‐Crown‐6

Abstract

The nature of the ionic‐liquid (IL) anion has been found to have a remarkable effect on the solvent extraction of Sr²⁺ and Cs⁺ by dicyclohexano‐18‐crown‐6 dissolved in ionic liquids. In particular, the extraction efficiency increases with the hydrophobicity of the IL anion as reflected by the solubility in water of ILs having a common cation. Since a cation‐exchange mechanism is operating in these systems, the influence of the IL anion is in large part attributable to an expected Le Chatelier effect in which a greater aqueous concentration of IL cation, obtained when using an IL anion of lower hydrophobicity, opposes cation exchange. This dependence is opposite to that found for IL cations, indicating a significant advantage of using ILs with hydrophobic anions for cation extraction. Furthermore, the extraction selectivity for Sr²⁺ over Na⁺, K⁺, and Cs⁺ can be significantly improved through the use of hydrophobic anions for the ILs containing 1‐ethyl‐3‐methylimidazolium or 1‐butyl‐3‐methylimidazolium cations.     

Fundamental Chemistry of Cesium Extraction from Acidic Media by HCCD in FS‐13

Abstract

We previously published a model for cesium extraction from acidic media by the protonated form of the hexachlorinated derivative of the chloro‐protected cobalt bis(dicarbollide), HCCD, dissolved in trifluoromethylphenyl sulfone, FS‐13. The model indicated that Cs extraction proceeds through a series of ion‐paired and/or dissociated extraction equilibria. Additional Cs distribution ratio data has been obtained and the model refined and simplified. It is demonstrated that the equilibrium exclusively involving the exchange of proton for cesium by formation of ion‐paired CsCCD models the Cs distribution data very well, particularly for the concentrations of HCCD greater than ～0.0005 M (0.5 mM). Finally, activity corrections for the aqueous phase to the Cs distribution data results in good agreement to the theoretical value of ?1 for slope (log‐log) analysis of the data over a wide range of HNO₃ and HCCD concentrations.     

Application of Synchrotron Radiation for Studying Detonation and Shock‐Wave Processes

A new method of remote investigation of detonation and shockwave processes with the use of synchrotron radiation is proposed. The facility used for the first experiments with measurement of density and smallangle xray scattering in detonation of condensed explosives is described. The high time and spatial resolution of the techniques proposed allows one to determine the character and mechanism of destruction of the condensed phase and the growth dynamics of new structures, including crystalline ones, in detonation flows. The capabilities of the new technique are described.     

Ultra‐selective epoxidation of styrene on pure Cu{111} and the effects of Cs promotion

Styrene undergoes efficient epoxidation to styrene epoxide on the Cu{111} surface. At the optimum condition (Θ_o = 0.03 ML) ∼20% of the styrene is converted to the epoxide with almost 100% selectivity. Comparison with Ag{111} shows that the epoxidation activity and selectivity of Cu greatly exceed those of Ag. Incipient oxidation of the Cu{111} surface does not suppress the adsorption of styrene, but the oxidised metal is catalytically inert. Submonolayer amounts of Cs enhance styrene uptake and increase conversion to the epoxide without adversely affecting epoxidation selectivity. This effect is due to inhibition of Cu oxidation by Cs. Our findings are discussed in the light of current understanding of Ag‐catalysed alkene epoxidation. This revised version was published online in July 2006 with corrections to the Cover Date.     

Influence of the Steric Hindrance,Ligand Hydrophobicity,and DN of solvents on Structure and Extraction of Cu(II) Complexes of 1‐Alkyl‐2‐Ethylimidazoles

Abstract

Formation of Cu(II) complexes of 1‐alkyl‐2‐ethylimidazoles (where alkyl=propyl, butyl, pentyl, hexyl, and octyl) has been studied by using the liquid‐liquid partition method, at 25°C and a fixed ionic strength of the aqueous phase (I=0.5; (HL)NO₃, KNO₃). The complexes were extracted with 2‐pentanone, 2‐butanol, isoamyl alcohol, 2‐ethyl‐1‐hexanol, dichloromethane, trichloromethane, and toluene. The length of the 1‐alkyl group and the nature of solvent have been shown to influence the extraction process. Extraction curves (log D_M vs. pH) are displaced towards lower pH's with increasing chain length of the 1‐alkyl substituent and donor number of the solvents. Stability constants of the complexes in aqueous solution were determined as well as their partition ratios between the aqueous and organic phase. The stability of the Cu(II) complexes increased with increasing 1‐alkyl chain length. The stability constants are comparable with β_n ones for the Cu(II) complexes of 1‐alkyl‐2‐methylimidazoles, but smaller than those of the Cu(II)–1‐alkylimidazole counterparts. The P_c‐partition ratios of the 1‐alkyl‐2‐ethylimidazole complexes with Cu(II) are high, and increased with increasing 1‐alkyl chain length and the donor number of the solvents. Both the strong steric effect of the ethyl substituent at position 2 and the bulkiness of the 1‐alkyl‐2‐ethylimidazole molecules as well as the strong electron‐donating properties of the solvent molecules have an effect on the change of the coordination number of Cu(II) from 6 to 4. The 4‐coordinate Cu(II) complexes (distorted tetrahedron) are more readily extractable by organic solvent than are the 6‐coordinate ones and for this reason their partition constants, P_c, are high. This finding offers the possibility of extraction of the Cu(II) ions from a mixture cations.     

Influence of Extractant Aggregation on the Extraction of Trivalent f‐Element Cations by a Tetraalkyldiglycolamide

Abstract

The influence of nitric acid extraction on the aggregation state of 0.10 M N,N,N′,N′‐tetra‐n‐octyl‐3‐oxapentane‐1,5‐diamide (TODGA) in n‐octane or n‐heptane was studied by small‐angle neutron scattering (SANS) and vapor pressure osmometry (VPO). When the equilibrium concentration of nitric acid in the aqueous phase is less than 0.7 M, TODGA exists as a mixture of monomers and dimers. As the aqueous phase acidity is increased, the extractant molecules form higher aggregates containing up to an average of seven molecules of TODGA. The formation of the larger TODGA aggregates takes place over the same range of aqueous acidities where the extraction of trivalent f‐element cations displays a hyperstoichiometric sixth power nitric acid dependence. This suggests that acid‐driven aggregation of TODGA is responsible for the unusual acid and extractant dependencies observed for the extraction of trivalent metal nitrates with this ligand.     

Microgels for the Intensification of Liquid-Liquid Extraction Processes – Feasibility and Advantages

Microgels are cross-linked polymers with a high application potential in liquid-liquid systems due to their surface activity and switchable stabilization properties. A process concept utilizing microgels in extraction processes is presented. The microgels are located at the drop surface and prevent coalescence, enabling monodisperse operation. At the column top, the stabilization is switched off by temperature shift. The switchable stabilization and the absence of additional mass transfer resistance are crucial requirements for the concept and tested experimentally. The results provide the basis for the model-based evaluation of the process performance, revealing a broader operating window, capacity increase at equal height equivalent of theoretical stage (HETS) for high loads, and reduced HETS for small loads.     

Aqueous Two‐Phase Partitioning of Glucose Isomerase from Actinoplanes missouriensis in the Presence of PEG‐Derivatives and its Immobilization on Chitosan Beads

Abstract

Purification of glucose isomerase by its partitioning in a PEG‐salt aqueous two‐phase system (ATPS) in the presence of PEG derivatives has been studied. Selective partitioning of the proteins was observed towards the PEG phase containing PEG‐benzoate and PEG‐palmitate, enriching glucose isomerase in the salt phase. Cross‐current extraction in 4 stages in the presence of PEG‐palmitate gave an enrichment factor of ～5 for the enzyme. After initial purification with ATPS, glucose isomerase was immobilized on cross‐linked chitosan beads. The immobilized enzyme was stable over a wider pH range (5.2–9.0) and showed an optimum pH of 6.5     

The Solvent Extraction of Boron with Synthesized Aliphatic 1,3‐Diols: Stripping and Extraction Behavior of Boron by 2,2,5‐Trimethyl‐1,3‐hexanediol

Abstract

A variety of aliphatic 1,3‐diols (4a–c, 5a–c, 6a–c) was synthesized from β‐hydroxy carbonyl compounds (1–3) for potential use in the solvent extraction of boron. Primary‐secondary and primary‐tertiary alcohol structures of 1,3‐diols substituted with isopropyl, isobutyl, and isopentyl groups have been demonstrated to be very efficient for the solvent extraction of boric acid from aqueous solutions. The extraction ability of 2,2,5‐trimethyl‐1,3‐hexanediol (5b) was investigated as a function of 5b concentration, solution pH, solvent properties, and stripping conditions. Extraction efficiency increased with increasing concentration of 5b, and the best extraction of boron (96.8%) was found to be at an equilibrium pH of 2 with 0.5 M of 5b. Chloroform, toluene, chlorobenzene, 2‐octanol, and n‐amyl alcohol were found to be suitable solvents for the solvent extraction of boron. The boron complex can be recovered from the organic phase by treatment with an aqueous solution of sodium hydroxide. The highest ratio (96.7%) of boron was recovered by 0.1 M of sodium hydroxide solution.     

Effect of a Gas‐Phase Reaction on the Combustion Performance of a Sandwich Layered System

This paper considers a sandwich layered combustion model (an oxidizer and a fuel) that takes into account condensed and gasphase chemical reactions and transverse heat and mass transfer. Under particular simplifications, algebraic expressions are obtained for the burning rates of the components and the temperature and concentration of gaseous reagents on the burning surface. Calculated dependences of the burning rate on the sandwich size agree with experiments.     

Vapour phase O‐methylation of 2‐naphthol over the solid bases alkali‐loaded silica and Cs‐loaded MCM‐41

O‐alkylation of 2‐naphthol has been investigated in the vapour phase over alkali‐loaded fumed silica and Cs‐MCM‐41. Both SiO₂ and MCM‐41 had low C‐alkylation activities and no O‐alkylation activity. The introduction of alkali ions considerably increases 2‐naphthol conversion with 2‐methoxynaphthalene being the major product. The activity of the catalysts increases with alkali loading and the basicity of the metal (Cs > K > Na > Li). Very high conversion (∼99%) of 2‐naphthol and selectivity (>95%) for 2‐methoxynaphthalene are obtained over Cs‐loaded fumed silica and MCM‐41. A small amount of 1‐methyl‐2‐hydroxynaphthalene is also formed over the Li‐, Na‐ and K‐loaded silica. This revised version was published online in July 2006 with corrections to the Cover Date.     

Trans‐Lanthanide Extraction Studies in the TALSPEAK System: Investigating the Effect of Acidity and Temperature

A recent review of the TALSPEAK (Trivalent Actinide ‐ Lanthanide Separation by Phosphorous reagent Extraction from Aqueous Komplexes) process summarized previous research characterizing the performance of this system. Attempts were made in that report to develop correlations between the previous separations data and the thermodynamic data that describes the interactions among the components of the separation system. However, the diversity of observations and the breadth of conditions employed in the many studies from the literature make comparisons between the TALSPEAK system performance and existing thermodynamic data challenging. To better test the adequacy of the available thermodynamic database for modeling this system, an internally consistent set of observations of lanthanide extraction under TALSPEAK conditions is offered in this report. The extraction of the lanthanides from La through Lu (excluding Pm) plus Y, and that of Am³⁺ from buffered lactic acid solutions containing diethylenetriamine‐N,N,N′,N″,N″‐pentaacetic acid (DTPA) into organic solutions of bis‐(2‐ethylhexyl)phosphoric acid (HDEHP) solutions in 1,4‐diisopropylbenzene has been investigated as a function of temperature, pH, and ionic strength. Extraction of both lanthanides and Am³⁺ decreases with increasing pH and with temperature. At the same time, separation factors remain approximately constant. Calculations based on an internally consistent thermodynamic data set confirm the prior conclusion that the existing thermodynamic data do not predict the observed decline in partitioning with increased pH, though the data do support the constancy of the separation factors. The relationship between the basic thermodynamic data, calculated speciation, and the performance of the separation system is discussed.     

The Effects of Water and CO2 on the Reaction Kinetics in the Iron‐Based Low‐Temperature Fischer‐Tropsch Synthesis: A Literature Review

A review of kinetic models for the iron‐based Fischer‐Tropsch synthesis revealed some important areas of progress, namely (a) a transition from rate equations with a first order denominator (consistent with an Eley‐Rideal type mechanism) to Langmuir‐Hinshelwood expressions with a second order inhibition term; (b) whereas kinetic models originally specified full coverage of the catalytic surface, later models found the influence of vacant sites to be important; (c) whereas water or CO₂ was traditionally always included in the FT rate equations, the most recent lumped kinetic models do not account for any influence of water. It was further concluded that the perceived inhibiting influence of water on the FT rate may have been an indirect effect via the water‐gas‐shift reaction that changed the hydrogen and CO partial pressures.     

Effect of Anions on the Extraction of Lanthanides (III) by N,N′‐Dimethyl‐N,N′‐Diphenyl‐3‐Oxapentanediamide

Abstract

The extraction of microquantities of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y by N,N′‐dimethyl‐N,N′‐diphenyl‐3‐oxapentanediamide (DMDPhOPDA) in 1,2‐dichloroethane from aqueous media containing ClO₄ ^?, PF₆ ^?, (CF₃SO₂)₂N^? anions or by DMDPhOPDA in 1,2‐dichloroethane in the presence of 1‐butyl‐3‐methylimidazolium bis[(trifluoremethyl)sulfonyl]imide ([C₄mim][Tf₂N]) and 1‐butyl‐3‐methylimidazolium hexafluorophosphate ([C₄mim][PF₆]) from HNO₃ solutions has been studied. The effect of HNO₃ concentration in the aqueous phase and that of the extractant concentration in the organic phase on the extraction of metal ions is considered. The stoichiometry of the extracted complexes has been determined. The addition of HPF₆ and (CF₃SO₂)₂NH or their salts to the aqueous HNO₃ or HCl solutions leads to an enchancement of lanthanides (III) extraction by DMDPhOPDA. A considerable synergistic effect was observed in the presence of ionic liquids (IL) in the organic phase containing DMDPhOPDA. This effect is connected with the hydrophobic nature of the IL anion. The distribution of ILs between the equilibrium organic and aqueous phases can govern the extractability of lanthanides (III) in DMDPhOPDA‐IL systems.     

Synergistic Solvent Extraction and Separation of Lanthanide(III) Ions with 4‐Benzoyl‐3‐Phenyl‐5‐Isoxazolone and the Quaternary Ammonium Salt

The solvent extraction of the lanthanide(III) ions (without Pm) with a 4‐benzoyl‐3‐phenyl‐5‐isoxazolone(HPBI) alone and in the presence of the quaternary ammonium salt Aliquat 336 in perchlorate form (QClO₄) in C₆H₆ was investigated by the slope analysis method. The composition of the extracted species was determined as Ln(PBI)₃ and Q[Ln(PBI)₄] (Q⁺ is the quaternary ammonium salt cation). The values of the equilibrium constant were calculated. Synergistic effects were found for all lanthanide metals when they were extracted with a binary mixture of HPBI and QClO₄. The influence of the synergistic agent on the extraction process has been discussed. The parameters of the extraction process were determined. The separation factors between adjacent metals were evaluated.     

The Influence of Alkyl Chain Length and Steric Effect on Extraction of Zinc(II) Complexes with 1‐Alkyl‐2‐Methylimidazoles

Abstract

The extraction of Zn(II) complexes with six 1‐alkyl‐2‐methylimidazoles (alkyl is from C₅H₁₁ up to C₁₂H₂₅) from nitric solution was studied as a function of pH of the aqueous phase. As the organic solvents toluene, p‐xylene and 1,2,3,4‐tetrahydronaphthalene were used. The stability constants of the complexes in the aqueous phase as well as partition constants of the extractable species were determined. It was demonstrated that both the stability constants (β_c) and the partition constants (P_c) of the complexes increased with increasing alkyl chain length. Pseudo‐tetrahedral complexes were found to dominate at the second and third complexation steps, thus increasing the stability constants and facilitating extraction of the Zn(II) complexes with 1‐alkyl‐2‐methylimidazoles.     

Development of Effective Solvent Modifiers for the Solvent Extraction of Cesium from Alkaline High‐Level Tank Waste

Abstract

A series of novel alkylphenoxy fluorinated alcohols were prepared and investigated for their effectiveness as modifiers in solvents containing calix[4]arene‐bis‐(tert‐octylbenzo)‐crown‐6 for the extraction of cesium from alkaline nitrate media. The structure of the fluorinated portion of the modifier influences the chemical stability, and a modifier that contained a terminal 1,1,2,2‐tetrafluoroethoxy group was found to decompose following long‐term exposure to warm alkaline solutions. However, replacement of the tetrafluoroethoxy group with a 2,2,3,3‐tetrafluoropropoxy group led to a series of modifiers that possessed the alkaline stability required for a solvent extraction process. Within this series of modifiers, the structure of the alkyl substituent (tert‐octyl, tert‐butyl, tert‐amyl, and sec‐butyl) of the alkylphenoxy moiety was found to have a profound impact on the phase behavior of the solvent in liquid–liquid contacting experiments, and hence on the overall suitability of the modifier for a solvent extraction process. The sec‐butyl derivative [1‐(2,2,3,3‐tetrafluoropropoxy)‐3‐(4‐sec‐butylphenoxy)‐2‐propanol] (Cs‐7SB) was found to possess the best overall balance of properties with respect to third phase and coalescence behavior, cleanup following degradation, resistance to solids formation, and cesium distribution behavior. Accordingly, this modifier was selected for use as a component of the solvent employed in the Caustic‐Side Solvent Extraction (CSSX) process designed for the removal of cesium from high‐level nuclear waste (HLW) at the U.S. Department of Energy's (DOE) Savannah River Site. In batch equilibrium experiments, this solvent has also been successfully shown to extract cesium from both simulated and actual solutions generated from caustic leaching of HLW tank sludge stored in tank B‐110 at the DOE's Hanford Site.     

Effects of various rare-earth additives on the sintering and transmittance of γ-AlON

Several rare earth elements (Sc, La, Pr, Sm, Gd, Dy, Er, and Yb) were evaluated to develop a sintering additive for transparent γ-AlON. After adding 0.2 wt. % of each of the rare earth additives to the α-Al₂O₃ and AlN starting material, hot pressing was performed at 1850 °C for 1 h under 20 MPa as a screening test, whereby the γ-AlON with Pr-nitrate showed the highest transmittance of 60.4 % at 632 nm. Two-step pressureless sintering was conducted as a separate test for the same starting material after adjusting the amount of Pr-nitrate to 0, 0.1, or 0.2 wt. % to enhance transmittance. The γ-AlON with 0.1 wt. % Pr-nitrate showed the highest transmittance of 80.36 % after 1st and 2nd sintering steps at 1610 and 1940 °C, respectively, indicating that Pr can be an alternative sintering additive to conventional Y₂O₃, MgO, and La₂O₃ for the fabrication of transparent γ-AlON.