Extraction kinetics and kinetic separation of La(Ⅲ),Gd(Ⅲ),Ho(Ⅲ) and Lu(Ⅲ) from chloride medium by HEHEHP

Acco rding to the tetrad-effect,14 elements of lanthanides can be divided into four groups.In our previous study,a new approach was proposed for the kinetic separation of four rare earth ions La(Ⅲ),Gd(Ⅲ),Ho(Ⅲ) and Lu(Ⅲ) coming from four groups.In that study,four rare-earth ions were kinetically separated from their coexisting mixed aqueous solutions,by performing liquid-column elution using the aqueous solution containing four lanthanide rare-earth ions as the stationary phase and the dispersed organic oil droplets containing HEHEHP(2-ethyl hexyl phosphonic acid mono 2-ethyl hexyl ester) extractant as the mobile phase.The study of extraction kinetics is very important for understanding the kinetic separation of rare earth ions,which was carried out in this paper.The extraction kinetics of La(Ⅲ),Gd(Ⅲ),Ho(Ⅲ) and Lu(Ⅲ) by HEHEHP diluted in heptane were investigated using single drop method.The different parameters affecting the extraction rate such as column length,specific interfacial area,rare earth ion concentration,extractant concentration,hydrogen ion concentration and temperature were separately studied and the rate equations are deduced.It is first order with respect to rare earth ion and HEHEHP concentrations,and negative first order with respect to hydrogen ion concentrations.The rate constants at 293.15 K are 10~(-6.23),10~(-5.73),10~(-5.58) and 10~(-5.43),respectively.The experimental results demonstrate that the extraction rate of La(Ⅲ), Gd(Ⅲ),Ho(Ⅲ) or Lu(Ⅲ) is diffusion-controlled,and the extraction reaction takes place at the interface rather than in the bulk phase.The extraction model was proposed.Besides,the kinetic separation of rare earth ions by HEHEHP oil drops was discussed.     

Study on the adsorption of lanthanum(Ⅲ) from aqueous solution by bamboo charcoal

The adsorption behaviors of La(Ⅲ) ion on bamboo charcoal were investigated with various chemical methods and IR spectrometry. Parameters studied include the effects of pH,average particle size,initial ion concentration,contact time and temperature by batch method. The results showed that bamboo charcoal could remove La(Ⅲ) ions effectively from aqueous solution. The loading of La(Ⅲ) ions was strongly dependent on pH of the medium and the optimal adsorption condition was in HNO3-TEA medium with pH value of 7.20. In the batch system,the modified bamboo charcoal exhibited the highest La(Ⅲ) ion uptake as 120 mg/g at 298 K,at an initial pH value of 7.20. The adsorption kinetics were tested with Lagergren-first-order model and pseudo-second-order model. The adsorption data were conformed to the Langmuir and Freundlich isotherms,and the correlation coefficients had been evaluated. Thermodynamic parameters such as free energy(ΔG) ,which were all negative,indicated that the adsorption of La(Ⅲ) ion onto bamboo charcoal was spontaneous and the positive value of enthalpy(ΔH) showed that the adsorption was endothermic in nature. Thomas model was applied to experimental column data to determine the characteristic parameters of column useful for process design. The characterization of both before and after adsorption of La(Ⅲ) ion on bamboo charcoal was undertaken using IR spectroscopic technique. The results revealed that bamboo charcoal was a good choice as a biosorbent for the recovery of lanthanum from aqueous solution.     

A preliminary study of polymer inclusion membrane for lutetium(Ⅲ)separation and membrane regeneration

This paper reports on the selective transport of Lu(Ⅲ) from La(III) and Sm(III) through a polymer inclusion membrane(PIM) composed of 40 wt% di(2-ethylhexyl) phosphinic acid(P227) and 60 wt%poly(vinylidene fluoride)(PVDF).Basically,the changes in surface morphology,thickness and water contact angle of this PVDF-based PIM containing P227(P227@PVDF PIM) with different polymer concentrations were investigated.By solvent extraction experiments,it is found that Lu(Ⅲ) can be selectively extracted from La(Ⅲ) and Sm(Ⅲ) at pH 1.5 in hydrochloric acid solution.According to this result,P227@PVDF PIM was used to selectively transport Lu(Ⅲ) from hydrochloric acid feed solution containing similar concentration of La(Ⅲ) and Sm(Ⅲ).The recovery factor of Lu(III) is 91% after 36 h,and about 5% of Sm(Ⅲ) was also transported through the PIM.The concentration of La(III) in the feed solution and the stripping solution does not change.Furthermore,to overcome the ubiquitous decline of transport efficiency caused by the loss of carrier or the damage of membrane structure after long-term use of PIMs,a process for regenerating PIMs was first proposed and implemented.By comparison of the regenerated PIM with the normal PIM,there is almost no difference in the SEM image,ATR-FTIR spectrum and Lu(III)transport efficiency.It is expected that P227@PVDF PIMs have the potential to be applied to the grouped separation of rare earth elements(REEs),and this study also can be as an inspiration for the further study on the PIMs regeneration process.     

Sonication method synergism with rare earth based nanocatalyst:preparation of NiFe_(2–x)Eu_xO_4 nanostructures and its catalytic applications for the synthesis of benzimidazoles,benzoxazoles,and benzothiazoles under ultrasonic irradiation

A simple and practical ultrasonically synthetic strategy for the preparation of rare-earth based catalyst, nanostructured NiFe_(2–x)Eu_xO_4 was developed. The structure of NiFe_(2–x)Eu_xO_4 was characterized by various analyses such as X-ray diffraction(XRD), scanning electron microscopy(SEM) and fourier transform infrared spectroscopy(FT-IR). The catalytic performance of NiFe_(2–x)Eu_xO_4 was evaluated for the synthesis of benzimidazoles, benzoxazoles and benzothiazoles under ultrasonic irradiation. All reactions were completed in short times and all products were obtained in good to excellent yields in presence of the rare-earth based catalyst. Besides, NiFe_(2–x)Eu_xO_4 could be recovered for 6 times without noticeably decreasing the catalytic activity.     

Synthesis and characterization of calcium and manganese-doped rare earth oxide La_(1-x)Ca_xFe_(0.9)Mn_(0.1)O_(3-δ) for cathode material in IT-SOFC

In order to develop novel cathode materials with high performance for intermediate temperature SOFC(IT-SOFC),Ca and Mn doped rare earth oxides La1-xCaxFe0.9Mn0.1O3-δ(x=0.1,0.3 and 0.5,denoted as LCFM9191,LCFM7391 and LCFM5591) were synthesized by solid state reaction(SSR) method.The formation process,phase structure and microstructure of the synthesized samples were characterized using thermogravimetry/differential scanning calorimetry(TG/DSC),X-ray diffraction(XRD) and scanning electron microscopy(SEM).The thermal expansion coefficients(TEC) of the samples were analyzed at 100-900 oC by thermal dilatometry.The electrical conductivities of the samples were measured with direct current(DC) four-terminal method from 300 to 850 oC.The results indicated that the samples(x=0.1 and 0.3) exhibited a single phase with orthorhombic and cubic perovskite structure,respectively after being sintered at 1200 oC for 3 h.The electrical conductivity of the samples increased with temperature up to a maximum value,and then decreased.The small polaron hopping was regarded as the conducting mechanism for synthesized samples at T≤600 oC.The negative temperature dependence occurring at higher temperature was due to the creation of oxygen vacancies for charge balance.LCFM7391 had higher mixed conductivity(>100 S/cm) at intermediate temperature and could meet the demand of cathode material for IT-SOFC.In addition,the average TECs of LCFM9191 and LCFM7391 were 11.9×10-6 and 13.1×10-6 K-1,respectively,which had good thermal match to the common electrolytes.     

Ion imprinted cryogel-based supermacroporous traps for selective separation of cerium(Ⅲ) in real samples

This study demonstrates the preparation and characterization of a novel ion imprinted cryogel which exhibits high affinity and selectivity towards Ce(Ⅲ) ions in aqueous solutions and bastnasite ore samples.2-Hydroxyethyl methacrylate(HEMA) and N-methacryloylamido antipyrine(MAAP) were used as functional monomers for the preparation of Ce(Ⅲ) imprinted cryogel. The effects of various factors such as initial Ce(Ⅲ) concentration, flow rate, pH, interaction time and ionic strength on the Ce(Ⅲ) binding to the prepared ion imprinted cryogels were also studied. The binding equilibrium for Ce(Ⅲ) is obtained in30 min at the flow rate of 0.5 mL/min. The maximum binding capacity of the prepared ion imprinted cryogel towards Ce(Ⅲ) is obtained as 36.58 mg/g at optimum conditions. The selectivity of the prepared ion imprinted cryogel towards Ce(Ⅲ) in the presence of other possible interfering lanthanide ions such as La(Ⅲ) and Nd(Ⅲ) were also performed. The obtained results showed that the prepared ion imprinted cryogel exhibits high selectivity and sensitivity towards Ce(Ⅲ) ions. The limit of detection(LOD) was found as 50 μg/L.     

Critical parameters near the phase transition temperature in La0.67-xDyxPb0.33MnO3

La0.67–xDyxPb0.33MnO3(x=0.00 and x=0.10) were elaborated by the solid state method and checked by X-ray diffraction. Close to magnetic temperature transition, the order transition and the critical behavior were investigated by dc magnetization measurements versus x composition. The critical properties were investigated through various techniques such as modified Arrott plot(MAP), Kouvel-Fisher(KF) method and critical isotherm(CI) analysis based on the data of static magnetic measurements recorded around the Curie temperature TC. The values of critical exponents(β and γ) estimated were found to lie between those predicted for a 3D-Ising model for x=0.00 and those of 3D-Heisenberg model for x=0.10. The reliability of the critical exponent’s values was confirmed by the Widom scaling relation and the universal scaling hypothesis. The change in the universality class should be due to the increase of the Dy content.     

Determination of Trace Metal Impurities in Cerium Oxide by Fluorination-Assisted ETV-ICP-AES after HPLC Separation

A new method for the separation and detection of trace metal impurities in cerium oxide (CeO2) using HPLC combined with electrothermal vaporization (ETV)-ICP-AES was developed. This combination links the high separation power of HPLC and high sensitivity of ETV-ICP-AES. The 2-ethylhexyl hydrogen 2-ethylhexylphosphate (P507) resin was used as stationary phase for the separation of metallic impurities in order to eliminate severe spectral interferences of the matrix. The dilute nitric acid was adopted as mobile phase for eluting Cu, Mn, Ni and La. The separation process can be accomplished in about 30 min. After concentrating the eluate by evaporation, the trace impurities were determined by using ETV-ICP-AES with the addition of 6% PTFE slurry as chemical modifier. The proposed method was applied to the analysis of CeO2 with satisfactory recoveries.     

Comparative studies on Y(Ⅲ)and Dy(Ⅲ)extraction from hydrochloric and nitric acids by Cyanex 572 as a novel extractant

Extraction of Y(III) and Dy(III) from hydrochloric and nitric acids by Cy-572 in kerosene was studied. The factors affecting the extraction were separately investigated. The stoichiometry of the extracted species was deduced on the basis of slope analysis method. Evaluation of extraction equilibrium and stripping investigation was studied as well as saponification effect of Cy-572. The composition of the extracted metal species in the organic phase was found to be [MA_3·(HA)_3] for Y(III) or Dy(III) in both media.1.0 mol/L HCI is the best stripping agent for each metal ion from the studied acidic media in one step.Saponified Cy-572 does not exhibit any selectivity towards the extraction of Y(III) or Dy(III) from both HCI and HNO_3 solutions. Based on the obtained results, the data were compared and the separation feasibility between lanthanides and Y(III) in the two media was discussed.     

Characterization of A-site excessive perovskite La0.7-xSmx＋0.02Ca0.3CrO3-δ

La0.7-xSmx+0.02Ca0.3CrO3-δ(0≤x≤0.4) powders with A-site excessive perovskite structure were synthesized by auto-ignition process and characterized. X-ray diffraction (XRD) patterns of samples after sintering at 1400℃ for 4 h were indexed as tetragonal structure. The relative densities were all above 96% although decreased slightly with the increasing content of samarium, indicating that the excessive A-site element was helpful to enhance their sinterability. Conductivities of the specimens in air increased with increasing content of samar-ium. The conductivity of La0.6Sm0.12Ca0.3CrO3-δ was 33.6 S/cm in air at 700 ℃ which was about 1.7 times as high as that of La0.7Ca0.3CrO3-δ (20.1 S/cm). Average thermal expansion coefficients (TECS) of the specimens increased from 11.06×10-6 to 12.72×10-6 K-1 when x in-creased from 0 to 0.4, and they were close to that of Y doped ZrO2 (YSZ). La0.7-xSmx+0.02Ca0.3CrO<3-δ>(0.1≤x≤0.3) were good choices for in-termediate temperature solid oxide fuel cells (IT-SOFCs) interconnect materials.     

Adsorption of Ce（ Ⅳ ） Anionic Nitrato Complexes onto Anion Exchangers and Its Application for Ce （Ⅳ） Separation from Rare Earths （ Ⅲ ）

Ceriumis one of the cheapest[1]and most abun-dant rare earths (RE) .However ,high purityis usual-ly required for its utilization in industry , where it isusedfor sulfur control insteels ,pyrophoric alloys ,ce-ramic ,catalyst support ,polishing powders ,etc .In its minerals ,as well as in the spent nuclearfuel ,ceriumis accompanied by other RE.They basi-cally exist in solution as stable RE(Ⅲ) species ,which makes their mutual separation rather difficult .In contrast to other RE, Ce(Ⅲ) can…     

Investigation on pumping oxygen characteristics of （Bi2O3）0.73（Y2O3）0.27 solid electrolyte

（Bi2O3）0.73（Y2O3）0.27 fine powders prepared by wet chemical precipitation method were cold isostatically pressed to form solid electrolyte tubes, and sintered at 900 ℃ for 10 h in the air. Their pumping oxygen characteristics in non-dehydrated Ar gas were investigated, where a ZrO2 （Y2O3 stabilized） oxygen sensor was used to measure the oxygen partial pressure Po2. The results showed that the Po2 value reached magnitudes of 1×10^-2-1×10^-10 Pa at the applied pumping oxygen voltage of 0.5 V, 1×10^-37-1×10^-27 Pa at 1.0 V and 1×10^-53-1×10^47 Pa at 2.0 V within the temperature range from 550 to 650 ℃. Moreover, no cracks were found in the tested solid electrolyte tubes. Thus, the Bi2O3-Y2O3 system might be used in solid electrolyte oxygen pump for purifying gases.     

Adsorption of rhenium(VII) on 4-amino-1,2,4-triazole resin

The adsorption properties of 4-amino-1,2,4-triazole resin (4-ATR) for Re(VII) were investigated by static and dynamic adsorption–desorption measurements with ultraviolet–visible spectroscopy. The influence of conditions such as temperature, initial solution pH and contact time on the adsorption curve was studied. It was found that the 4-amino-1,2,4-triazole resin was suitable for adsorption of Re(VII). The saturated adsorption capacity was 354 mg·g^− 1resin at pH 2.6 in HAc–NaAc medium at 298 K. The adsorption rate constant was k₂₉₈ = 8.2 × 10^− 5 s^− 1. The adsorption behavior of 4-ATR for Re(VII) obeyed the Freundlich empirical equation; whilst changes in adsorption with temperature gave an enthalpy change ΔH  = − 11.8 kJ·mol^− 1. The molar ratio of the functional group of 4-ATR to Re(VII) was about 2:1. Re(VII) adsorbed on 4-ATR was eluted by 1.0 ~ 5.0 mol·L^− 1 HCl with 100% quantitative elution in 4.0 mol·L^− 1 HCl solution. The resin can be regenerated and reused without apparent decrease in adsorption capacity.     

Thermochemical Study on Ternary Solid Complex of La(Gly)2 (Ala)3 Cl3 ·2H2O (s)

The complex of lanthanum chloride with Glycine and Alanine, La(Gly)₂(Ala)₃Cl₃ · 2H₂O, was synthesized and characterized by IR, elementary analysis, thermogravimetric analysis, and chemical analysis. The dissolution enthalpies of LaCl₃ · 7H₂O(s), 2Gly(s) + 3Ala(s) and La(Gly)₂(Ala)₃Cl₃ · 2H₂O(s) were determined in 2 mol · L⁻¹ HCl by a solution-reaction isoperibol calorimeter. By designing a thermochemical cycle in terms of Hess' Law and through calculation, the reaction enthalpy of lanthanum chloride seven-hydrate with Glycine and Alanine was obtained: Δ_rH^θ_m(298.15 K) = (29.652 ± 0.504) kJ · mol⁻¹, and the standard enthalpy of formation of La(Gly)₂(Ala)₃Cl₃ · 2H₂O(s) Δ_fH^θ_m[La(Gly)₂ (Ala)₃Cl₃ · 2H₂O, s, 298.15 K] = −4467.6 ± 8.3 kJ · mol⁻¹.     

Direct Spectroscopic Determination of Europium（ Ⅱ ） Concentration During Europium（ Ⅲ ） Electro-Reduction in Hydrochloric Acid Medium

Europiumis one of the most important rare earth(RE) element .It is widely used as a component ofcathode ray tubes , with screen coated with red phos-phor ,as phosphorescent pigments ,andinlaser optics .It can also be used as neutron-absorbing material .In…     

Extraction of Fe(III) from hydrochloric acid solutions using Amberlite XAD-7 resin impregnated with trioctylphosphine oxide (Cyanex 921)

Ferric ions were efficiently removed from HCl solutions using Amberlite XAD-7 resin impregnated with trioctylphosphine oxide (Cyanex 921). Iron was removed under the form HFeCl₄ through direct binding on the resin or by extraction with Cyanex 921 involving a solvation mechanism. High concentrations of HCl and intermediary extractant loadings were required for maximum sorption efficiency and rationale use of the extractant. At intermediary extractant loading (in the range 300–450 mg Cyanex 921 g^− 1) the maximum sorption capacity increased with extractant loading. Maximum sorption capacity slightly increased with temperature, the reaction is endothermic and the enthalpy change was found close to − 30.8 kJ mol^− 1. Sorption isotherms were fitted with the Langmuir equation and maximum sorption capacity reached values as high as 20–22 mg Fe g^− 1 in 3 M HCl solutions. Despite the good fit of experimental data with the pseudo second-order rate equation, sorption kinetics was controlled by the resistance to intraparticle diffusion. The intraparticle diffusion coefficient (D_e) varying in the range 1.2 × 10^− 11–4.7 × 10^− 10 m² min^− 1 was found to increase with metal concentration and with temperature, while varying the extractant loading it reached a maximum at a loading close to 453 mg Cyanex 921 g^− 1. The desorption of Fe(III) can be achieved using 0.1 M solutions of nitric acid, sulfuric acid, sodium sulfate and even water, maintaining high efficiencies for sorption and desorption for at least 5 cycles.     

Electrochemical Behavior of Dissolved Fe2O3 in Molten CaCl2-KF

The electrochemical behavior of dissolved Fe2O2 in 82.5CaCl2-17.5KF （mole percent, %） was studied using cy clic voltammetry, chronoamperometry, and galvanostatic electrolysis at 827 ℃, and the deposits were characterized by XRD and SEM. Pure iron was deposited on a rotating cylinder （210 r/min） with a cell voltage less than -- 1.0 V. Deposition rate was controlled by diffusion on a molybdenum electrode. The diffusion coefficient of iron species Fe（ Ⅲ ） in the melt at 827 ℃ was found to be 9.7×10^-5 cm^2/s.     

Measurements of Enthalpy Change of Reaction of Formation, Molar Heat Capacity and Constant-Volume Combustion Energy of Solid Complex Yb（Et2dtc）3（phen）

A ternary solid complex Yb(Et2dtc)3(phen) was obtained from the reaction of hydrous ytterbium chloride with sodium diethyldithiocarbamate (NaEt2dtc), and 1, 10-phenanthroline (o-phen·H2O) in absolute ethanol.The bonding characteristics of the complex were characterized by IR.The result shows Yb3 bands with two sulfur atoms in the Na(Et2dtc)3 and two nitrogen atoms in the o-phen.The enthalpy change of liquid-phase reaction of formation of the complex ΔrHθm (l), was determined as being (-24.838±0.114) kJ·mol-1 at 298.15 K, by an RD-496 Ⅲ type heat conduction microcalormeter.The enthalpy change of the solid-phase reaction of formation of the complex ΔrHθm (s), was calculated as being (108.015±0.479) kJ·mol-1 on the basis of an appropriate thermochemistry cycle.The thermodynamics of liquid-phase reaction of formation of the complex was investigated by changing the temperature during the liquid-phase reaction.Fundamental parameters, the activation enthalpy, ΔHθ≠, the activation entropy, ΔSθ≠, the activation free energy, ΔGθ≠, the apparent reaction rate constant k, the apparent activation energy E, the pre-exponential constant A, and the reaction order n, were obtained by a combination of the reaction thermodynamic and kinetic equations with the data from the thermokinetic experiments.At the same time, the molar heat capacity of the complex cm, p, was determined to be (86.34±1.74) J·mol-1·K-1 by the same microcalormeter.The constant-volume combustion energy of the complex, ΔcU, was determined to be (-17954.08±8.11) kJ·mol-1 by an RBC-Ⅱ type rotating-bomb calorimeter at 298.15 K.Its standard enthalpy of combustion, ΔcHθm, and standard enthalpy of formation, ΔfHθm, were calculated to be (-17973.29±8.11) kJ·mol-1 and (-770.36±9.02) kJ·mol-1, respectively.     

Effect of Lanthanum （Ⅲ） on Reactive Oxygen Metabolism of Soybean Seedlings under Supplemental UV-B Irradiation

The effect of lanthanum （Ⅲ） on reactive oxygen metabolism of soybean seedlings under elevated ultraviolet-B radiation（UV-B：280~320 nm）at 0.15 and 0.45 W·cm-2 levels respectively was studied through hydroponics in the laboratory.Plasmolemma permeability and contents of malonadialdehyde（MDA）,hydrogen peroxide（H2O2）,and proline gradually increased during the imposition of UV-B radiation and subsequently decreased during recovery from UV-B stress.The dynamic tendency of catalase（CAT）activity was similar to that of the above four indices.The activity of peroxidase（POD）initially increased,then remained at a high level,and finally dropped steeply when soybean seedlings were exposed to a low dosage of UV-B radiation.However,POD activity rose throughout and declined slightly on the eleventh day when soybean seedlings were stressed by a high dosage.With the addition of La （Ⅲ） of 20 mg·L-1,the rising tendency of plasmolemma permeability and contents of MDA,H2O2,and proline were slowed down during the stress period,whereas the declining speed was accelerated during the recovery period.The activities of CAT and POD were higher than those without La （Ⅲ） in all experiments.It suggested that the regulative effect of La （Ⅲ） on antioxidant enzymes such as CAT and POD could strengthen their capacities to scavenge reactive oxygen species（ROS）,decrease contents of MDA and proline,and maintain normal plasmolemma permeability.Further more,the protective potential of La （Ⅲ） was better under low UV-B radiation than under a high one.     

Nitric Oxide Alleviates Oxidative Stress Caused by Lanthanum in Rice Leaves

The effect of NO on lanthanum-induced antioxidant activities in rice was evaluated. The results showed that the uptake and translocation of La from root to shoot were obviously inhibited by 10μmol·L^-1 sodium nitropmsside （SNP）, a donor of NO, in the seedlings grown in Mura B nutrient solution with 100μmol·L^-1 La. Although the content of ascorbate acid （AsA） were scarcely affected by La or NO in our experiment, La decreased significantly the activity of SOD and content of GSH, while promoted H202 content in leaves. Furthermore, NO blocked these La effects. Taken together, the results suggested that NO relieved La toxicity in rice. A possible role for NO effects on antioxidant activity was discussed.