首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 62 毫秒
1.
IR spectroscopy was used to study the structure and composition of Eu(III) and Sr(II) complexes formed by cation-exchange extraction of these metals from their aqueous nitrate solutions with dichlorethane solutions of mixtures of chlorinated cobalt(III) dicarbollide (CCD) as a superacid with diphenyldiphosphine dioxides containing a methyl (Me-DPDO), ethyl (Et-DPDO), or polyoxyethylene bridge between two phosphorus atoms of phosphine oxide groups. At molar ratios DPDO/CCD ≤ 1, [Eu(H2O)nL4]3+ complexes are formed in organic phases, whereas with an excess of DPDO relative to CCD, Eu(NO3)L 4 2+ complexes are formed, where L = Me-or Et-DPDO. Polyoxyethylenediphosphine dioxide forms anhydrous complexes of composition Eu:L = 1:1 and 1:2 with Eu(III) and outer-spheric complexes of composition Sr:L = 1:1 and 1:2 with Sr(II), where the organic ligand molecules envelop the hydrated Sr(H2O) n 2+ cation. The peculiarities of extraction of the complexes are explained based on data about their composition and structure.  相似文献   

2.
The extraction behavior of Sm(III), Eu(III) and Dy(III) with 1-nitroso-2-naphthol (HA) and trioctylphosphine oxide (TOPO) in methyl isobutyl ketone (MIBK) from aqueous NaClO4 solutions in the pH range 4–9 at 0.1M ionic strength has been studied. The equilibrium concentrations of Sm and Dy were measured using their short-lived neutron activation products,155Sm and165mDy, respectively. In the case of Eu, the concentrations were assayed through the152,154Eu radiotracer. The distribution ratios of these elements were determined as a function of pH, 1-nitroso-2-naphthol and TOPO concentrations. The extractions of Sm, Eu and Dy were found to be quantitative with MIBK solutions in the pH range 5.9–7.5, 5.6–7.5 and 5.8–7.5, respectively. Quantitative extraction of Eu was also obtained between pH 5.8 and 8.8 with chloroform solutions. The results show that these lanthanides (Ln) are extracted as LnA3 chelates with 1-nitroso-2-naphthol alone, and in the presence of TOPO as LnA3(TOPO) and LnA3(TOPO)2 adducts. The extraction constants and the adduct formation constants of these complexes have been calculated.  相似文献   

3.
Strontium(II) bis (oxalato) strontium(II) trihydrate, Sr[Sr(C2O4)2]·3H2O and mercury(II) bis (oxalato) mercurate(II) hexahydrate, Hg[Hg(C2O4)2]·6H2O have been synthesized and characterized by elemental analysis, reflectance and IR spectral studies. Thermal decomposition studies (TG, DTG and DTA) in air showed SrCO3 was formed at ca. 500°C through the formation of transient intermediate of a mixture of SrCO3 and SrC2O4 around 455°C. Sharp phase transition from γ-SrCO3 to β-SrCO3 indicated by a distinct endothermic peak at 900°C in DTA. Mercury(II) bis (oxalato) mercurate(II) hexahydrate showed an inclined slope followed by surprisingly steep slope in TG at 178°C and finally 98.66% of weight loss at 300°C. The activation energies (E *) of the dehydration and decomposition steps have been calculated by Freeman and Carroll and Flynn and Wall's method and compared with the values found by DSC in nitrogen. A tentative reaction mechanism for the thermal decomposition of Sr[Sr(C2O4)2]·3H2O has been proposed.  相似文献   

4.
The equilibrium extraction behavior of Sm(III), Eu(III) and Dy(III) from aqueous NaClO4 solutions in the pH range of 4–9 at 0.1 M ionic strength into organic solutions of 1-nitroso-2-naphthol (HA) and 1,10-phenanthroline (Phen) has been studied. The equilibrium concentrations of Eu were assayed through the 344 keV photopeak of the152Eu radiotracer used. The concentrations of Sm and Dy were measured by irradiating one mL portions of the organic extract and analyzing the 104 and 108 keV photopeaks of the short-lived neutron activation products,155Sm and165mDy, respectively. Quantitative extraction of Eu with 5×10–2 M HA alone was obtained in the pH range of 6.7–7.8 with n-butanol, 7.4–8.5 with chloroform, 8.0–8.7 with ethyl acetate, 7.7–8.5 with isoamyl alcohol and 6.1–8.0 with methyl isobutyl ketone (MIBK). But, Eu was extracted only to a maximum of 78% and 83% in the pH range of 8.3–8.9 and 7.4–8.1 with carbon tetrachloride and xylene, respectively. The extraction of Sm and Dy were found quantitative in the pH range of 6.3–7.0 and 6.6–7.1, respectively, with 5×10–2 M HA alone in MIBK solutions. The synergistic extraction of Eu was quantitative in the pH range of 6.6–9.8 with chloroform, 7.8–8.9 with ethyl acetate, 7.7–8.5 with isoamyl alcohol and 6.0–9.6 with MIBK when 1×10–2 M each of HA and Phen were employed. Sm and Dy were quantitatively extracted into MIBK solutions containing 5×10–2 M each of HA and Phen in the pH range 6.0–7.5 and 6.1–7.5, respectively. The distribution ratios of these lanthanides (Ln) were determined as a function of pH, and HA and Phen concentrations. The analysis of the data suggests that these Ln are extracted as LnA3 chelates when HA alone is used. In the presence of HA and Phen, both LnA3(Phen) and LnA3(Phen)2 adducts are formed only in the MIBK system while LnA3(Phen) complexes are the predominant ones in all other solvent systems studied. The extraction constants and the adduct formation constants of these complexes have been calculated.  相似文献   

5.
One three-dimensional Sr(II) coordination polymer [C6(MIm)2][Sr3(1,4-NDC)4] (I) (C6(MIm)2 = 1,3-bis(3-methylimidazolium-1-yl)hexyl, 1,4-H2NDC = 1,4-naphthalenedicarboxylate acid) has been synthesized using an ionothermal method and structurally characterized by IR spectroscopy, UV-Vis spectroscopy, XRPD, and X-ray single-crystal structure analysis (СIF file CCDC 1033958). Two types of strontium centers are bridged by two coordination modes of 1,4-H2NDC ligands to form a Sr(II) chain. Each Sr(II) chain is crossconnected to four other chains to generate a 3D coordination polymer, in which C6(MIm) 2 2+ cations as charge balancing species are filled in the channels of the anionic framework. The polymeric solid of I exhibits strong luminescent emission at room temperature.  相似文献   

6.
Synthesis and Characterization of six novel N,N-dioctylsuccinamate based room temperature ionic liquids (RTILs) bearing imidazolium, pyridinium, ester imidazolium, and quaternary ammonium cations is reported. Extraction of Pb(II) and Co(II) by these RTILs has been investigated. Ionic liquids (ILs) synthesized were [C4mim][N88SA], [C8mim][N88SA], [C4Py][N88SA], [C8Py][N88SA], [α-mim-ester][N88SA] and [N2244][N88SA] termed as L1, L2, L3, L4, L5 and L6 respectively. Liquid-liquid extraction was performed and all the six systems showed excellent extractability results for both Pb(II) and Co(II). During the process of extraction several factors i.e., nature of cation, pH of the aqueous phase, equilibration time, and initial metal ion concentration were investigated. The extraction efficiency of above 98 % for all types of extractants was observed. The nature of cation its concentration, equilibration time, and pH of the aqueous phase significantly influenced the extraction efficiency. Maximum extraction was observed at pH values between 4 and 8 and optimum contact time was observed to be 40–45 min. Increasing the metal ion concentration decreased the extraction efficiency. The extraction efficiency of both metal ions decreased in the order [N88SA][C8mim] (L2) > [α-mim-Ester][N88SA] (L5) > [N88SA][C4mim] (L1). This is evident from the order of extraction behaviour that increasing the bulkiness of cation, results in stronger complexation, hence increasing extraction.  相似文献   

7.
A simple back-extraction method was developed for the separation and preconcentration of trace levels of zinc from different matrices. Ethyl-2-(4-methoxybenzoyl)-3-(4-methoxyphenyl)-3-oxopropanoylcarbamate (EMPC) was used as a new complexing agent for the extraction of zinc(II) from the aqueous sample phase to the methyl isobutyl ketone (MIBK) phase as Zn(EMPC)2 complexes. The Zn(II) can be selectively stripped with 1?mL of 0.5?mol?L?1 HCl from Mn+(EMPC)n complexes [Ag(I), Al(III), Cd(II), Cr(III), Cu(II), Fe(II), Fe(III), Mn(II), Ni(II), Pb(II) and Pd(II)] which dissolved in MIBK phase. Some experimental parameters, which are important for the whole extraction process, including pH, sample volume, shaking time, amount of the EMPC reagent, amount of MIBK, ionic strength, and type of back-extractant were investigated. The recovery for Zn(II) was greater than 95%. The detection limit of the method was found to be 0.2?µg?L ? 1 and the relative standard deviation as 6.4%. The concentrations of Zn(II) in the certified reference materials (LGC6019 river water and NIST-1547 peach leaves) by the presented method were in good agreement with the certified values. The proposed method was succesfully applied to the determination of zinc in some natural waters, rice, hair, soil, and tea samples.  相似文献   

8.
Solvent extraction of Cr(VI), Mo(VI), W(VI) and Hf(IV) with 1-phenyl-3-methyl-4-caproyl-pyrazolone-5 (PMCP) in methyl isobutylketone (MIBK), xylene and chloroform (CHCl3) from mineral acid solutions was studied. Chromium(VI) is not extracted from any of the acids studied (HCl, H2SO4 and HClO4). Molybdenum(VI) is quantitatively extracted by the reagent in xylene and CHCl3 from HClO4 and HNO3 solutions. It is also extracted quantitatively by the reagent in MIBK from HCl, HNO3 and H2SO4 solutions but the participation of the diluent as extractant is considerable. Tungsten(VI) is quantitatively extracted in xylene from 9M HClO4 solution. MIBK used as diluent also affects its extraction with PMCP. Hafnium(IV) is not extracted from H2SO4 solutions while it extracts more than 99% at 3M HNO3 and above. The extracted species likely are: MoO2(PMCP)2, WO2(PMCP)2 and Hf(PMCP)4, respectively.  相似文献   

9.
Summary Equimolar quantities of [MI2(CO)3(NCMe)2] (M = Mo or W) and C3H4N2 (pyrazole) react in CH2C12 at room temperature to give the iodo-bridged dimers [M(μ-I) (CO)3(C3H4N2)]2 (1) and (2). Two equivalents of C3H4N2 react with [MI2(CO)3(NCMe)2] (M = Mo or W) to give the bis(pyrazole) complexes [MI2(CO)3(C3H4N2)2] (3) and (4) in good yield. Three and four equivalents of pyrazole react with [MoI2(CO)3(NCMe)2] to give the cationic complexes [MoI(CO)3(C3H4N2)3]I (5) and [MoI(CO)2(C3H4N2)4]I (6), respectively. The mixed ligand complexes [MI2(CO)3(C3H4N2)L] (M = Mo or W; L = PPh3, AsPh3 or SbPh3) (7)-(12) are prepared by reacting equimolar amounts of [MI2(CO)3(NCMe)2] and L in CH2C12 at room temperature, followed by an in situ reaction with one equivalent of C3H4N2. The MoSnCl3 complex [MoCl(SnCl3)(CO)3(C3H4N2)2] (13) is prepared in an analogous manner using acetone as the solvent, whilst the mixed ligand compound [MoCl(SnQ3)(CO) 3(C3H4N2)(PPh3)] (14) was prepared by treating the dimeric complex [Mo(μ-Cl)(SnCl3)(CO)3(PPh3)]2 with two equivalents of C3H4N2. All the new complexes were characterised by elemental analysis (carbon, hydrogen and nitrogen), i.r. and 1H n.m.r. spectroscopy.  相似文献   

10.
Different solvents including cyclohexane, dichloromethane, chloroform, toluene, 1-octanol, and methyl isobutyl ketone (MIBK) have been evaluated in extracting copper(II) from nitrate medium by salicylideneaniline. Extracted species differs from solvent to solvent: CuL2 in cyclohexane, toluene, 1-octanol, and methyl isobutyl ketone. However, in dichloromethane or chloroform, there are two complexes of the type CuL2 and CuL2(HL). The extraction constants and percentage of extraction (%E) are calculated for different solvents. Solvent played an important role in recovering copper(II) from the aqueous solution, thus affecting the extraction equilibrium and extraction efficiency. The nonpolar solvent showed better performance than the polar solvent. The maximum extraction efficiency was 85.75% at pH?=?4.5, which was from cyclohexane.  相似文献   

11.
A new type of silica-based chelating extraction resin, DtBuCH18C6/SiO2-P, was prepared by impregnating a crown ether derivative, 4,4,(5)-di(tert-butylcyclohexano)-18-crown-6 (DtBuCH18C6), into the porous silica/polymer composite particles (SiO2-P). The adsorption of Sr(II) and some other fission product elements was investigated by a batch adsorption experiment in HNO3 medium. It was found that Sr(II) exhibits a strong adsorption onto the extraction resin, while the other fission product elements show almost no or only weak adsorption. The adsorption kinetics of Sr(II) was explained by assuming as the rate-controlling step the complex-formation reaction between Sr(II) and DtBuCH18C6 contained in the extraction resin. The rate equation of Sr(II) adsorption was determined as:-d[Sr(II)]/dt = k[Sr(II)][DtBuCH18C6][NO3 ]0.5.  相似文献   

12.
The extraction of Nd(III), Tb(III) and Lu(III) as representatives of lanthanide(III) ions with picrolonic acid (HPA) in methylisobutylketone (MIBK) has been studied from pH 1-2 buffer solutions. The composition of the organic species formed in the organic phase after extraction has been determined by slope analysis to be M(PA)3 [M = Nd(III), Tb(III) and Lu(III)]. The equilibrium constant values, log k ex This revised version was published online in July 2006 with corrections to the Cover Date.  相似文献   

13.
Diaqua oxalato strontium(II) complex [Sr(C2O4)(H2O)2] was prepared via a precipitation reaction. Thermal treatment of the as-synthesized precursor at 550?°C resulted in formation of strontium carbonate (SrCO3) nanocrystals. A new composite of silver nanoparticles decorated with strontium carbonate (Ag-NPs@SrCO3) was fabricated by heating a mixture of silver oxalate and strontium carbonate in air at 150?°C for 2?h. The spectral, morphological and thermal properties of the materials have been studied using different physicochemical techniques such as X-ray diffraction (XRD), scanning electron microscopy (SEM) with energy dispersive X-ray spectroscopy (EDX), high-resolution transmission electron microscopy (HR-TEM), Fourier infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), diffrential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). From the Debye–Scherrer equation the calculated particle size of Sr(C2O4)(H2O)2], SrCO3 and Ag-NPs@SrCO3 are 62.1, 58.7, and 58.5?nm, respectively. The SEM and TEM images indicate tetragonal structure of [Sr(C2O4)(H2O)2] while SrCO3 and Ag-NPs@SrCO3 appeared as cubic structures. The calculated energy band gap of SrCO3 and Ag-NPs@SrCO3 using the Tauc equation are estimated at 5.9 and 4.7?eV, respectively. The adsorption capacity of the materials is tested for the adsorption of Congo red anionic dye and exhibited promising results. The adsorption capacity followed the order Ag-NPs@SrCO3>SrCO3>?[Sr(C2O4)(H2O)2] with efficiencies of 73.90, 67.55, and 60.50%, respectively.  相似文献   

14.
Selective separation of Co(II) from aqueous acidic solutions containing thiocyanate ions has been achieved by using 2-benzylpyridine (BPy) dissolved in benzene. Optimum conditions of extraction by 0.1M BPy are: 0.05M (HCl, HNO3) or 0.01M H2SO4+1 M KSCN. Ascorbate and sulfate ions do not affect the extraction of cobalt(II), whereas acetate, citrate and oxalate ions lower the extraction. Separation of cobalt(II) from Mn, Cr, Hf, Fe, Y, Ce, Cd, Sr, Cs and several rare earth elements can be achieved in a single extraction. Slope analysis by log-log plot reveals that neutral cobalt-thiocyanate species is extracted with the probable formula of the extracted complex as Co(BPY)3 (SCN)2.  相似文献   

15.
Summary Stoichiometric stability constants of Cu(II), Ni(II), Zn(II), Co(II), UO2(II) and Th(VI) phthalate have been determined by paper electrophoresis. Phthalic acid (0.005 mol dm−3) was added to the background electrolyte: 0.1 mol dm−3 HClO4. The proportions of C6H5C2O 4 and C6H4C2O 4 = were varied by changing the pH of the electrolyte. These anions yielded the complexes, Cu C6H5C2O 4 + , Cu C6H4C2O4, Zn C6H5C2O 4 + , Co C6H5C2O 4 + , Ni C6H5C2O 4 + , UO2 C6H5C2O 4 + , UO2 (C6H4C2O4) 2 = and Th (C6H4C2O4)2 whose stability constants are found to be 103.0, 104.7, 102.6, 102.5, 102.3, 103.5, 1012.6 and 1013.4 respectively (μ=0.1, temp 40°C).  相似文献   

16.
Fe(CH3)2(PMe3)4 reacts with 1-(diphenylphosphino)naphthalene or benzyldiphenylphosphine within 4 h at 20 °C to give the novel metallated methyl iron complexes Fe(CH3){P(C6H5)2(C10H6)}(PMe3)3 (1) and Fe(CH3){(C6H4)CH2P(C6H5)2}(PMe3)3 (3), respectively, via selective activation of the C-H bond of the pre-chelating ligands. The complexes are thermally unstable releasing metal through a reductive elimination of the aromatic backbone and leading to a C,C-coupling product that is regiospecifically methylated, namely 8-methyl(diphenylphosphino)naphthalene (2). Carbonylation (1 bar, 20 °C, 1 h) of complex 1 effects monosubstitution of a trimethylphosphine ligand trans to the metallated 8-C atom to afford Fe(CH3){P(C6H5)2(C10H6)}(CO)(PMe3)2 (4). The remaining methyl group in the parent complex 1 reacts with trimethylsilylethyne and tert-butylethyne affording the new complexes 5 and 6 bearing an alkynyl substituent trans to the diphenylphosphino anchoring group. The complexes 1 and 3-6 are diamagnetic and possess octahedral coordination geometry. All novel complexes were fully characterized by spectroscopic methods and by X-ray diffraction.  相似文献   

17.
Carbamoyl and alkoxycarbonyl complexes of palladium(II) and platinum(II) of the type M(pnp)(CONHR)Cl (pnp = 2,6-bis(diphenylphosphinomethyl)pyridine; M Pd, R  C6H5, p-CH3C6H4, p-CH3OC6H4, C6H11, t-Bu; M  Pt, R  C6H5), Pd(pnp)[CON(Pr)2]Cl (Pr = propyl), M(pnp)(COOR)Cl (M  Pd, R  C6H5, CH3; M  Pt, R  CH3), Pd(pnp)(COOCH3)2 result from reaction of M(pnp)Cl2 with carbon monoxide and amines or alkoxides at room temperature and atmospheric pressure.The carbamoyl complexes react with bases to give urethane or diphenylurea depending upon the experimental conditions.  相似文献   

18.
Extraction of Am(III) and Ln(III) from NaClO4 medium with di(2-ethylhexyl)dithiophosphoric acid (DEHDTP), di(2-ethylhexyl)monothiophosphoric acid (DEHMTP), di(2-ethylhexyl)monothiophosphinic acid (DEHMTPI), dihexyldithiophosphinic acid (DHXDTPI), diheptyldithiophosphinic acid (DHPDTPI), dioctyldithiophosphinic acids (DODTPI), dinonyldithiophosphinic acid (DNDTPI), di(1-methylheptyl)dithiophosphinic acid (DMHDTPI) and di(2-ethylhexyl)dithiophosphinic acid (DEHDTPI) in xylene has been investigated. The order of the extraction selectivity for Am(III) is DEHDTPI > DEHDTP > DEHMTPI > DEHMTP, DHPDTPI > DODTPI > DHXDTPI > DNDTPI, DMHDTPI > DEHDTPI > DODTPI, for extractants with 2-ethylhexyl alkyl, straight chain alkyl, branch chain alkyl, respectively. Using 0.1 mol/l NaClO4 solution as aqueous phase, the slope values of the logD-pH and logD-logC curves are not integers, and the slope values for Am(III) are slightly higher than those for Eu(III), for all extractants. The relationship between the slope value and extraction conditions can be described as: logS = alg(C HA/C M S/4)+b. In the presence of macro Eu(ClO4)3, the formula, logSF Am/Ln = B-2log(C HL-D Ln/(D Ln + 1)C Eu), can well describe the relationship between separation factor and the extraction condition. A high separation factor (SF Am/Eu = 2500) is obtained by solvent extraction with 0.5 mol/1 DEHDTPI in toluene from 1 mol/l NaNO3 solution.  相似文献   

19.
Abstract

While it might be expected that the availability of vacant coordination sites in the four coordinate acyl complexes trans[Pt(PPh3)2 (RCO)Cl] provides low energy pathways for alkyl and aryl migration and subsequent decarbonylation, the decarbonylation has been previously achieved only at elevated temperatures. The addition of SnCl2 greatly facilitates decarbonylation of [Pt(PPh3)2 (RCO)Cl] where R is CH3, C2 H5, Y[sbnd]C6 H4. Compounds of the type [Pt(PPh3)2 (RCO)SnCl3] and [Pt(PPh3)2 R(SnCl3)] have been isolated. The removal of SnCl2 from these compounds has been achieved with ethanol. A kinetic study of the decarbonylation of [Pt(PPh3)2 (RCO)SnCl3] (where R is CH3, C2 H5, Y[sbnd]C6 H4 for Y=H, CH3, CH3 O, NO2, Cl) is reported. The role of 3 and 5 coordinate intermediates in alkyl-aryl migrations in Pt(II) systems is discussed.  相似文献   

20.
The extraction characteristics of some selected metals from an aqueous buffered solution by LIX 622, a commercial oxime extractant have been studied. The pH1/2 values for extracting different metals with 5 v/v% LIX 622 extractant in methyl isobutyl ketone (MIBK) have been obtained. The order of extraction of metals with LIX 622 extractant as a function of pH1/2 value is determined and results agree well with the order obtained using salicylaldoxime as chelating ligand for the extraction of these metals.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号