A green strategy for lithium isotopes separation by using mesoporous silica materials doped with ionic liquids and benzo-15-crown-5

Three new mesoporous silica materials IL15SGs (HF15SG, TF15SG and DF15SG) doped with benzo-15-crown-5 and imidazolium based ionic liquids (C₈mim⁺PF₆ ^?, C₈mim⁺BF₄ ^? or C₈mim⁺NTf ₂ ^? ) have been prepared by a simple approach to separating lithium isotopes. The formed mesoporous structures of silica gels have been confirmed by transmission electron microscopy image and N₂ gas adsorption–desorption isotherm. Imidazolium ionic liquids acted as templates to prepare mesoporous materials, additives to stabilize extractant within silica gel, and synergetic agents to separate the lithium isotopes. Factors such as lithium salt concentration, initial pH, counter anion of lithium salt, extraction time, and temperature on the lithium isotopes separation were examined. Under optimized conditions, the extraction efficiency of HF15SG, TF15SG and DF15SG were found to be 11.43, 10.59 and 13.07 %, respectively. The heavier isotope ⁷Li was concentrated in the solution phase while the lighter isotope ⁶Li was enriched in the gel phase. The solid–liquid extraction maximum single-stage isotopes separation factor of ⁶Li–⁷Li in the solid–liquid extraction was up to 1.046 ± 0.002. X-ray crystal structure analysis indicated that the lithium salt was extracted into the solid phase with crown ether forming [(Li_0.5)₂(B15)₂(H₂O)]⁺ complexes. IL15SGs were also easily regenerated by stripping with 20 mmol L^?1 HCl and reused in the consecutive removal of lithium ion in five cycles.     

Study of isotope effect upon lithium iodide complexation with benzo-15-crown-5 in water–chloroform extraction system

Extraction characteristics of chloroform–water system in lithium iodide extraction with benzo-15-crown-5 (B15C5) were studied. The complexation of the crown ether with LiI in organic phase was shown by IR spectroscopy. Isotope effect multiplication was performed by extraction chromatography technique. The magnitude of isotope separation factor (α) for ⁶Li-⁷Li pair was 1.017. The light lithium isotope is concentrated in organic phase.     

The role of organic acids on <Superscript>226</Superscript>Ra transfer factor in corn (<Emphasis Type="Italic">Zea mays</Emphasis> L.)

Enrichment of lithium isotopes by displacement chromatography on strong acid cation exchanger was investigated. Narrow particle fraction of Dowex 50 WX 2 cation exchanger having diameter of 150–200 µm and total exchange capacity of 1.31 meq mL^?1 was used as stationary phase. As a mobile phase, 1 mol L^?1 solution of ammonium nitrate solution was used. Shape and position of Li chromatographic peak, was determined by atomic emission spectroscopy (AES). Isotope ratio was estimated by ICP–MS after 1, 8 and 10 enrichment steps. Value of separation factor for ⁶Li in one step was determined to be 1.027.     

X-ray fluorescence determination of pre-extracted aluminium and gallium in waste-waters

The extraction of aluminium and gallium into a molten commercial C₁₇–C₂₀ fatty acid mixture without and with addition of di-2-ethylhexylphosphoric acid (DEHP) is described. Almost quantitative extraction is achieved within 3 min at about pH 1 with 0.15–0.6 mol l^?1 DEHP in the fatty acid mixture for organic/aqueous phase ratios of 1:5–1:100. The solidified melts are suitable for x-ray fluorescence spectrometry. The method is appropriate for waste-waters.     

Studies of high linear energy transfer dosimetry by 10B(n,α)7Li reactions in aqueous and organic solvents

Advanced chemical treatment processes such as aqueous separation techniques can be used to separate the reusable materials from used nuclear fuel, reducing the radiotoxicity and storage time of the remaining waste. The degradation of chemicals in these processes has been studied utilizing gamma radiation. However, radiolytic degradation by internal alpha emitters has not been as widely investigated due to the difficulty of finding appropriate internal sources. This work presents results using a method to produce alpha particles in situ in aqueous and organic solvents representative of liquid–liquid extraction systems. The method is based on the widely studied ¹⁰B(n,α)⁷Li reaction which has previously been studied in aqueous solutions. Neutrons were supplied from the UCI TRIGA^® nuclear reactor. Comparisons were also made to gamma radiation from a ¹³⁷Cs source. We report that the method is useful for inducing high linear energy transfer (LET) doses in aqueous and organic solutions. We used the classic iron sulfate-based Fricke dosimeter for dosimetry in aqueous solutions and methyl red (2-[(4-dimethylaminophenyl)diazenyl]benzoic acid) dissolved in n-dodecane for organic solvents. High LET doses in both aqueous and organic solvents are well described and a simple linear relationship was found based on the neutron flux and total boron concentration. We have established, using spectroscopic determination, that methyl red degrades in a linear fashion with absorbed dose up to 80 kGy and G-values for the methyl red degradation in n-dodecane were found to be 4.66 × 10^?4 μmol/J for external ¹³⁷Cs gamma radiation and 3.0 × 10^?5 μmol/J for ¹⁰B(n,α)⁷Li induced high LET radiation.     

Mechanism for Solvent Extraction of Lanthanides from Chloride Media by Basic Extractants

The solvent extraction of lanthanides from chloride media to an organic phase containing an anion exchanger in the chloride form is known to show low extraction percentages and small separation factors. The coordination chemistry of the lanthanides in combination with this kind of extractant is poorly understood. Previous work has mainly used solvent extraction based techniques (slope analysis, fittings of the extraction curves) to derive the extraction mechanism of lanthanides from chloride media. In this paper, EXAFS spectra, luminescence lifetimes, excitation and emission spectra, and organic phase loadings of lanthanides in dry, water-saturated and diluted Aliquat 336 chloride or Cyphos IL 101 have been measured. The data show the formation of the hydrated lanthanide ion [Ln(H₂O)_8–9]³⁺ in undiluted and diluted Aliquat 336 and the complex [LnCl₆]^3? in dry Aliquat 336. The presence of the same species [Ln(H₂O)_8–9]³⁺ in the aqueous and in the organic phase explains the small separation factors and the poor selectivities for the separation of mixtures of lanthanides. Changes in separation factors with increasing chloride concentrations can be explained by changes in stability of the lanthanide chloro complexes in the aqueous phase, in combination with the extraction of the hydrated lanthanide ion to the organic phase. Finally, it is shown that the organic phase can be loaded with 107 g·L^?1 of Nd(III) under the optimal conditions.     

Separation of lithium isotope by azacrown tetramerrifield peptide resin

A study on the separation of lithium isotope was carried out with N₄O azacrown ion exchange resin. The lighter⁶Li isotope concentrated in the solution phase, while the heavier⁷Li isotope is enriched in the resin phase. Upon column chromatography (0.3 cm I.D.×15.5cm height) using 0.5M NH₄Cl as an eluent, single separation factor, α=1.00127 was obtained.     

Relation between immersion enthalpies of activated carbons in different liquids,textural properties,and phenol adsorption

The immersion enthalpies in benzene, cyclohexane, water, and phenol aqueous solution with a concentration of 100 mg L^?1 are determined for eight activated carbons obtained from peach seeds (Prunus persica) by thermal activation with CO₂ at different temperatures and times of activation. The results obtained for the immersion enthalpy show values between ?4.0 and ?63.9 J g^?1 for benzene, ?3.0 and ?47.9 J g^?1 for cyclohexane, ?10.1 and ?43.6 J g^?1 for water, and ?11.1 and ?45.8 J g^?1 for phenol solution. From nitrogen adsorption isotherms, the surface area, micropore volume, and average pore diameter of the activated carbons were obtained. These parameters are related with the immersion enthalpies, and the obtained trends are directly proportional with two first parameters in the nonpolar solvents, which is a behavior of microporous activated carbons with hydrophobic character. Phenol adsorption from aqueous solution on activated carbons is proportional to their surface area and their immersion enthalpy in the solution.     

Kinetics and Thermodynamics of Ethanol Production by Saccharomyces cerevisiae MLD10 Using Molasses

In this study, we have used ultraviolet (UV) and γ-ray induction to get a catabolite repression resistant and thermotolerant mutant with enhanced ethanol production along with optimization of sugar concentration and temperature of fermentation. Classical mutagenesis in two consecutive cycles of UV- and γ-ray-induced mutations evolved one best catabolite-resistant and thermotolerant mutant Saccharomyces cerevisiae MLD10 which showed improved ethanol yield (0.48?±?0.02 g g^?1), theoretical yield (93?±?3 %), and extracellular invertase productivity (1,430?±?50 IU l^?1 h^?1), respectively, when fermenting 180 g sugars l^?1 in molasses medium at 43 °C in 300 m³ working volume fermenter. Ethanol production was highly dependent on invertase production. Enthalpy (ΔH*) (32.27 kJ M^?1) and entropy (ΔS*) (?202.88 J M^?1 K^?1) values at 43 °C by the mutant MLD10 were significantly lower than those of β-glucosidase production by a thermophilic mutant derivative of Thermomyces lanuginosus. These results confirmed the enhanced production of ethanol and invertase by this mutant derivative. These studies proved that mutant was significantly improved for ethanol production and was thermostable in nature. Lower fermentation time for ethanol production and maintenance of ethanol production rates (3.1 g l^?1 h^?1) at higher temperature (43 °C) by this mutant could decrease the overall cost of fermentation process and increase the quality of ethanol production.     

Electrochemical Reduction Behavior and Polarographic Determination of Methoxy Triazine Herbicides in Environmental Samples

The electrochemical reduction behavior of 1,3,5-triazine herbicides, Atraton (AN), Prometon (PN), Secbumeton (SN), and Terbumeton (TN) at mercury electrodes was studied in aqueous Britton Robinson buffer (BR) solutions by using different voltammetric techniques. The nature of the electrode process was examined. Number of electrons involved in the reduction process of all the four compounds was evaluated and a reduction mechanism was proposed. The electrolysis products were separated and identified by IR spectra. For analytical purposes, BR buffer of pH 4.0 was chosen as working medium for all the four analytes. The detection limits were found to be 1.5 × 10^?8 mol l^?1, 2 × 10^?8 mol l^?1, 2.8 × 10^?8 mol l^?1, and 1 × 10^?8 mol l^?1 for AN, PN, SN, and TN, respectively. A differential pulse voltammetric method was developed for the determination of these compounds in agricultural formulations, water, and soil samples. The interference from the ions and other herbicides were also evaluated.     

Preparation and thermal properties of palmitic acid/polyaniline/copper nanowires form-stable phase change materials

Form-stable phase change materials (PCMs) with high thermal conductivity are essential for thermal energy storage systems, which in turn are indispensible in solar thermal energy applications and efficient use of energy. In this paper, a new palmitic acid (PA)/polyaniline (PANI) form-stable PCMs were prepared by surface polymerization. The highest loading of PA in the form-stable PCMs was 80 mass% with the phase change enthalpy (ΔH _melting) of 175 J g^?1. Copper nanowires (Cu NWs) were introduced to the form-stable PCM by mixing the Cu NWs with PA and ethanol prior to the emulsifying of PA in surfactant solution. The Cu NWs would remain intact in case the ethanol was eliminated before the PA/Cu NWs mixture was mixed with surfactant solution. Otherwise, the Cu NWs would be partially oxidized under the attack of ethanol and ammonium persulfate. The ΔH _melting of the form-stable PCMs containing Cu NWs decreased linearly with the increasing of Cu NWs loading. The ΔH _melting of the form-stable PCMs doped with 11.2 mass% Cu NWs was 149 J g^?1. The thermal conductivity of the form-stable PCMs could be effectively improved by Cu NWs. By adding 11.2 mass% Cu NWs, the thermal conductivity of the form-stable PCM could attain 0.455 W m^?1 K^?1.     

In Situ Biphasic Extractive Fermentation for Hexanoic Acid Production from Sucrose by Megasphaera elsdenii NCIMB 702410

Hexanoic acid production by a bacterium using sucrose as an economic carbon source was studied under conditions in which hexanoic acid was continuously extracted by liquid–liquid extraction. Megasphaera elsdenii NCIMB 702410, selected from five M. elsdenii strains, produced 4.69 g l^?1 hexanoic acid in a basal medium containing sucrose. Production increased to 8.19 g l^?1 when the medium was supplemented by 5 g l^?1 sodium butyrate. A biphasic liquid–liquid extraction system with 10 % (v/v) alamine 336 in oleyl alcohol as a solvent was evaluated in a continuous stirred-tank reactor held at pH 6. Over 90 % (w/w) of the hexanoic acid in a 0.5 M aqueous solution was transferred to the extraction solvent within 10 h. Cell growth was not significantly inhibited by direct contact of the fermentation broth with the extraction solvent. The system produced 28.42 g l^?1 of hexanoic acid from 54.85 g l^?1 of sucrose during 144 h of culture, and 26.52 and 1.90 g l^?1 of hexanoic acid was accumulated in the extraction solvent and the aqueous fermentation broth, respectively. The productivity and yield of hexanoic acid were 0.20 g l^?1 h^?1 and 0.50 g g^?1 sucrose, respectively.     

Preconcentration of beryllium via octadecyl silica gel microparticles doped with aluminon, and its determination by flame atomic absorption spectrometry

A simple and sensitive method is presented for solid phase extraction (SPE) and preconcentration of trace quantities of beryllium using octadecyl silica gel modifed with aurin tricarboxylic acid (aluminon). Beryllium is then determined by flame atomic absorption spectroscopy. Parameters affecting SPE such as pH, sample solution and eluent flow rate, type, concentration and volume of eluent, interfering ions and breakthrough volume, were investigated. Under optimal conditions, the beryllium ions were retained on the sorbent at pH 6–6.7, while 3.0 mL of 0.05 mol L^?1 HNO₃ is sufficient to elute the ions. The limit of detection (LOD) based on 3σ was 0.8 µg L^?1 for 250 mL sample solution and 5 mL 0.05 mol L^?1 HNO₃ as eluent. The LOD can reach 0.1 µg L^?1 for 1 L sample solution and 3 mL of 0.05 mol L^?1 HNO₃. The accuracy and precision (RSD %) of the method is >90% and <10%, respectively. The method was applied to the determination of beryllium in aqueous samples.     

Kinetic study on reactive extraction for chiral separation of phenylsuccinic acid enantiomers

The kinetics of the extraction of phenylsuccinic acid (PSA) enantiomers by hydroxypropyl-β-cyclodextrin (HP-β-CD) in a modified Lewis cell was studied, in which HP-β-CD dissolved in 0.1 mol L^?1 NaH₂PO₄/H₃PO₄ buffer solution (pH = 2.5) was selected as the chiral extractant. PSA enantiomers were extracted from organic phase to aqueous phase in the extraction module. The theory of extraction accompanied by a chemical reaction has been used to obtain the intrinsic kinetics of this extraction module. The different parameters affecting the extraction rate such as agitation speed, interfacial area, initial concentration of PSA enantiomers in organic phase as well as HP-β-CD concentration in aqueous phase were separately studied. The experimental results demonstrate that the extraction reactions are fast. The reactions were found to be first order with respect to PSA and second order with respect to HP-β-CD with forward rate constants of 3.4 × 10^?2 m⁶ mol^?2 s^?1 for R-PSA and 9.96 × 10^?3 m⁶ mol^?2 s^?1 for S-PSA. These data will be useful in the design of extraction processes.     

Separation of no-carrier-added 113,117mSn and 113m,114mIn from alpha particle irradiated natural cadmium target

A natural cadmium foil was irradiated by 42 MeV α-particles to produce ^113,117mSn, ^{111,113m,114m}In simultaneously in the target matrix. After the complete decay of short lived radionuclides, long-lived NCA products were separated sequentially from the bulk cadmium by liquid–liquid extraction using di-(2-ethylhexyl)phosphoric acid (HDEHP) dissolved in cyclohexane as organic phase and HCl as aqueous phase. At the optimum condition, 10^?2 M HCl and 5 % HDEHP, NCA In along with NCA Sn radionuclides (75 %) were separated from the bulk Cd resulting to high separation factors of 2.7 × 10⁴ (D _In/D _Cd) and 500 (D _Sn/D _Cd), respectively. The NCA In was stripped back completely to the aqueous phase by 6 M HCl leaving NCA Sn in the HDEHP phase with a separation factor (D _Sn/D _In) of 3.94 × 10⁶.     

An enhanced poly(vinylidene fluoride) matrix separator with high density polyethylene for good performance lithium ion batteries

A sponge-like poly(vinylidene fluoride)/high density polyethylene (PVDF/HDPE) separator exhibiting high ionic conductivity and transference number of Li⁺ ion for lithium ion battery has been prepared by non-solvent induced phase separation (NIPS) method. HDPE fillers with size smaller than 250 nm are prepared with moderated reverse phase emulsion. The ion conductivity of PVDF/HDPE separator saturated with 1.0 M LiPF₆–ethylene carbonate (EC)/dimethyl carbonate (DMC)/ethyl methyl carbonate (EMC) (1:1:1, v/v/v) can be up to 2.54 mS cm^?1 at 25 °C, which is higher than that of pristine PVDF separator (1.85 mS cm^?1). The transference number of lithium ion with PVDF/HDPE separator is 0.495, better than that with commercial PP separator (0.33) and pristine PVDF separator (0.27). What is more, LiCoO₂/Li cells assembled with PVDF/HDPE separator show good C-rate and cycling performance which indicates great potential in serving as a good candidate of polymer separator for lithium ion batteries application.     

Titanium dioxide/graphene oxide composite and its application as an anode material in non-flammable electrolyte based on ionic liquid and sulfolane

A composite of aminosilane-grafted TiO₂ (TA) and graphene oxide (GO) was prepared via a hydrothermal process. The TiO₂/graphene oxide-based (TA/GO) anode was investigated in an ionic liquid electrolyte (0.7 M lithium bis(trifluoromethanesulfonyl)imide (LiNTf₂)) in ionic liquid (N-methyl-N-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide (MPPyrNTf₂)) at room temperature and in sulfolane (1 M lithium hexafluorophosphate (LiPF₆) in tetramethylene sulfolane (TMS)). Scanning and transmission electron microscopy (SEM and TEM) observations of the anode materials suggested that the electrochemical intercalation/deintercalation process in the ionic liquid electrolyte with vinylene carbonate (VC) leads to small changes on the surface of TA/GO particles. The addition of VC to the electrolyte (0.7 M LiNTf₂ in MPPyrNTf₂ + 10 wt.% VC) considerably increases the anode capacity. Electrodes were tested at different current regimes in the range 5–50 mA g^?1. The capacity of the anode, working at a low current regime of 5 mA g^?1, was ca. 245 mA g^?1, while a current of 50 mA g^?1 resulted in a capacity of 170 mA g^?1. The decrease in anode capacity with increasing current rate was interpreted as the result of kinetic limits of electrode operation. A much lower capacity was observed for the system TA/GO│1 M LiPF₆ in TMS + 10 wt.% VC│Li.     

Preparation and thermal reliability of <Emphasis Type="Italic">N</Emphasis>-butyl stearate/methyl palmitate composite phase change material

In this study, a series of binary mixtures of N-butyl stearate (nBS) and methyl palmitate (MP) were used to produce a novel composite phase change material (CPCM) for potential application in the eastern China, and their thermal properties were investigated by differential scanning calorimetry (DSC). The results of DSC indicated that the mixture consisting of 10 mass% nBS and 90 mass% MP is optimum as the CPCM in terms of the phase change temperature ranges (T _f = 19.74–5.59 °C; T _m = 18.34–33.80 °C) and latent heats (ΔH _f = 176.8 J g^?1; ΔH _m = 189.3 J g^?1). On the other hand, the thermal reliability and chemical stability of the CPCM after 120, 180, 240, 300, 360 and 500 accelerated thermal cycling tests were studied by DSC and fourier transform infrared (FTIR) analysis. The results demonstrated that the CPCM had good thermal reliability and chemical stability.     

Low-temperature thermodynamic properties of L- and DL-valines

Heat capacities C _p(T) of L-valine and DL-valine were measured in the temperature range 6–300 K with an adiabatic calorimeter; thermodynamic functions were calculated based on these measurements. At 298.15 K, the values of heat capacity, C _p; entropy, S _m ⁰ (T) ? S _m ⁰ (0); enthalpy, H _m ⁰ (T) ? H _m ⁰ (0) of L-valine are equal, respectively, to 167.9 ± 0.3 J K^?1 mol^?1; 178.5 ± 0.4 J K^?1 mol^?1; and 27510 ± 60 J mol^?1. For DL-valine, these values are equal, respectively, to 167.3 ± 0.3 J K^?1 mol^?1, 174.4 ± 0.3 J K^?1 mol^?1, and 27000 ± 50 J mol^?1. The difference between the heat capacities of enantiomer and racemate has been calculated and compared with the similar data for serines, cysteines, and phenylglycines.     

Extraction of gadolinium from El-Garra El-Hamra rare-earth cake,South Western Desert,Egypt

The study area of El-Garra El-Hamra is one of the igneous masses located in the southern part of the Western Desert of Egypt. This work has been carried out to investigate the process of gadolinium separation from REEs cake obtained from El-Garra El-Hamra ore concentrate. It is considered as a new approach in the Nuclear Materials Authority of Egypt. Firstly; the optimum leaching conditions achieved are 200 gm/L H₂SO₄, 1/2 solid/liquid ratio, 4 h agitation time,?125 mesh size and at 90 ^°C temperature. Then by solvent extraction method using 1 mol/L D2EHPA middle REEs were extracted. The organic extractant was stripped by using 2 mol/L HCl and Gd pregnant solution was obtained. Then, the relevant optimum factors were 0.3 mol/L D2EHPA diluted by kerosene, 10 min contact time, and 4/1 organic/aqueous ratio giving 87 % Gd extraction. Then, the scrubbing of the loaded extractant was by 1 mol/L HCL followed by Gd stripping using 5 M HCl, contact time of 30 min and 1/3 organic/aqueous ratio. The strip solution was subjected to evaporation and little amount was dried to obtain GdCl₃ powder having a purity of about 81 % associated with YCl₃ 4 %.