Extractive spectrophotometric determination of palladium from acidic high activity nuclear waste

A simple and rapid method for spectrophotometric determination of palladium from highly acidic and highly radioactive nuclear waste using -benzoin oxime (ABO) as extractant and isobutyl methyl ketone (hexone) as diluent has been developed. The method can be employed over a wide range of nitric acid concentrations and for palladium concentrations in the range of 1·10^–5M to 4·10^–4M in the organic phase. The molar absorptivity was found to be 4·10³l·mol^–1·cm^–1. Influence of various heavy metal ions, fission products and corrosion products was studied. The method was found to give a precision and accuracy better than 4% at 100 g of palladium.     

Separation of trace amounts of palladium (II) with crown ether from hydrochloric acid and potassium thiocyanate media

A new method for the separation of trace amounts of palladium from hydrochloric acid and potassium thiocyanate media has been established based on the formation of an ion-pair complex of palladium thiocyanate anion Pd(SCN)₄ ^2– and the cationic potassium complex of dicyclohexyl-18-crown-6 (DC18C6) in chloroform. The effect of various factors (solvent, crown ether, potassium thiocyanate, hydrochloric acid, reagent concentration, shaking time, phase volume ratio, composition of the extracted species, foreign ions, etc.) on the extraction and back-extraction of palladium has been investigated. The method can be combined with subsequent FAAS determination of palladium. The procedure was applied to determine palladium traces in chloroplatinic acid and rhodium chloride.     

Palladium(II) and platinum(II) complexes of Schiff bases derived from 2,6-diacetylpyridine and S-methyldithiocarbazate and the X-ray crystal structure of the [Pd(mdapsme)Cl] complex

Condensation of 2,6-diacetylpyridine (dap) with S-methyldithiocarbazate (smdtc) in a 1:2 molar ratio yields a bicondensed pentadentate Schiff base (H₂dapsme) which reacts with K₂MCl₄ (M = Pd^II, Pt^II) giving stable complexes of empirical formula, [M(dapsme)] · 0.5Me₂CO. These complexes have been characterized by a variety of physico-chemical techniques. Condensation of dap with smdtc in a 1:1 molar ratio also yields the bicondensed Schiff base (H₂dapsme) as the major product, but a mono-condensed one-armed Schiff base (Hmdapsme) is also obtained as a minor product. The latter reacts with K₂PdCl₄ in an EtOH–H₂O mixture yielding a crystalline complex of empirical formula, [Pd(mdapsme)Cl], the crystal structure of which has been determined by X-ray diffraction. The complex has a distorted square-planar structure in which the ligand is coordinated to the palladium(II) ion as a uninegatively charged tridentate chelating agent via the pyridine nitrogen atom, the azomethine nitrogen atom and the thiolate sulfur atom; the oxygen atom of the acetyl group does not participate in coordination.     

Homogeneous liquid-liquid extraction method for the selective separation and preconcentration of ultra trace molybdenum

A new simple and efficient homogeneous liquid-liquid extraction method for the selective separation and preconcentration of molybdenyl ions was developed. α-Benzoin oxime (ABO) was investigated as a complexing ligand, and perfluorooctanoate ion (PFOA⁻) was applied as a phase-separator agent under strongly acidic conditions. Under the optimal conditions ([ABO] = 2.1 × 10⁻³ M, [PFOA⁻] = 1.8 × 10⁻² M, [HNO₃] = 1.7 M, [acetone] = 11.8% (v/v)), 10 μg of molybdenum in 5 ml aqueous phase could be extracted quantitatively into 40 μl of the sedimented phase. The maximum concentration factor was 125-fold. Thiocyanate was applied as a chromogenic reagent for the direct spectrophotometric determination of molybdenum in the sedimented phase. The reproducibility of the proposed method is at the most 2.4%.The influence of the type and concentration of acid solution, the concentration of ABO, the type and volume of the water-miscible organic solvent, the concentration of PFOA⁻, and the effect of different diverse ions on the extraction and determination of molybdenum(VI) were investigated. The proposed method was applied to the extraction and determination of molybdenum(VI) in natural water, Spinach, and Lucerne samples. A satisfactory agreement exists between the results obtained by the proposed method and those reported by GF-AAS.     

Mono‐ and dinuclear oxime palladacycles bearing diphosphine ligands: An unusual coordination mode for dppe

Three new oxime‐based palladacycles, namely [Pd{C,N‐C₆H₄{C(Me)?NOH}‐2}(dppm)]ClO₄ ( 1 ), [Pd₂{C,N‐C₆H₄{C(Me)?NOH}‐2}₂(dppe)₂(μ‐dppe)](ClO₄)₂ ( 2 ) and [Pd{C,N‐C₆H₄{C(Me)?NOH}‐2}(dppmS₂)]ClO₄ ( 3 ), were synthesized by the reaction of dinuclear oxime complex [Pd{C,N‐C₆H₄{C(Me)?NOH}‐2}(μ‐Cl)]₂ with different diphosphine ligands (dppm, dppe and dppmS₂). The synthesized complexes were characterized using Fourier transform infrared, ³¹P NMR, ¹H NMR and ¹³C NMR spectroscopic methods and elemental analyses, and their molecular structures were elucidated using X‐ray crystallography. The structure of 2 is worthy of note as it is the first oxime palladacycle where there are both bridging (P–) and chelating (P^P) dppe ligands, giving rise to a dinuclear complex. The palladium atom is in a five‐coordinate, square pyramidal P₃NC environment, while in 3 the palladium atom is in a distorted square planar environment, coordinated by the oxime ligand and a chelating (S^S) dppmS₂ ligand. These complexes were employed as efficient catalysts for the Suzuki–Miyaura cross‐coupling reaction of several aryl bromides with phenylboronic acid. The in vitro cytotoxicity of the compounds was also evaluated against human tumour cell lines (HT29, A549 and HeLa) using the MTT assay method. The results indicate that the dinuclear complex 2 has greater catalytic and anticancer activity in comparison with the mononuclear complexes 1 and 3 .     

Liquid-Liquid Extraction of Indium(III) from the HCl Medium by Ionic Liquid A327H+Cl− and Its Use in a Supported Liquid Membrane System

Ionic liquid A327H⁺Cl⁻ was generated by reaction of tertiary amine A327 and HCl, and the liquid-liquid extraction of indium(III) from the HCl medium by this ionic liquid dissolved in Solvesso 100 was investigated. The extraction reaction is exothermic. The numerical analysis of indium distribution data suggests the formation of A327H⁺InCl₄⁻ in the organic phase. The results derived from indium(III) extraction have been implemented in a supported liquid membrane system. The influence of the stirring speed (600–1200 min⁻¹), carrier concentration (2.5–20% v/v) in the membrane phase, and indium concentration (0.01–0.2 g/L) in the feed phase on metal transport have been investigated.     

β羟肟萃取钯(Ⅱ)取代反应中的动力学催化作用

β羟肟、硫醚等在盐酸介质中萃取钯(Ⅱ)的配位取代反应具有较高的选择性,有实用意义^[1-5]。Cleare等^[1]曾提出加入胺类化合物以加快β羟肟萃钯的速度。本文在研究β羟肟萃钯(Ⅱ)机理^[2,3]的基础上考察了加入伯胺后2-羟基-4-(1-甲基庚氧基)二苯甲酮肟(HL)萃取钯(Ⅱ)的热力学和动力学行为以及界面特性,试图阐明伯胺对该取代反应的加速机理。试验所用伯胺N1923(Am)为混合支链伯胺,上海有机所实验厂生产。水相中伯胺含量用溴酚兰分光光度法测定^[6],其它实验方法参见[3]。     

An imidazolium ionic liquid having covalently attached an oxime carbapalladacycle complex as ionophilic heterogeneous catalysts for the Heck and Suzuki-Miyaura cross-coupling

An oxime carbapalladacycle, analogous to that used as catalyst in homogeneous phase, has been derivatized to increase its ionophilicity by introducing an imidazolium group covalently attached through a chain at the complex. The resulting complex is soluble in 1-butyl-3-methylimidazolium ionic liquid (bmimPF₆) and not extractable by ether. The catalytic activity of this palladium complex in bmimPF₆ is, however, unsatisfactory and only increases marginally in bmimPF₆/supercritical CO₂. This limitation has been overcome by supporting this imidazolium palladium complex on high surface area Al/MCM-41 aluminosilicate, whereby a solid active catalyst for the Suzuki cross-coupling has been obtained. Reusability and stability over reuse for this Al/MCM-41-supported catalyst have been studied.     

Comparison between polyethylenglycol and imidazolium ionic liquids as solvents for developing a homogeneous and reusable palladium catalytic system for the Suzuki and Sonogashira coupling

The carbapalladacycle complex of 4-hydroxyacetophenone oxime is a highly active palladium catalyst to effect the Suzuki coupling of aryl chlorides and other C-C forming reactions in water. In an attempt to develop a reusable, homogeneous system based on this complex, its stability against prolonged heating in different ionic liquids and polyethylenglycol (PEG) has been studied. It was found that the palladium complex decomposes in water, 1-butyl-1-methylimidazolium hexafluorophosphate and 1-butyl-1-methylimidazolium chloride to form palladium nanoparticles in the first two cases and PdCl₄²⁻ in the third case. In contrast, this cyclic palladium complex was stable upon extended heating in 1-butyl-2,3-dimethylimidazolium hexafluorophosphate and in PEG. The activity of this complex for the Suzuki and Sonogashira correlates with the stability of the complex, the activity in PEG being higher than any of the ionic liquids tested. Although the carbapalladacycle complex also decomposes in PEG upon reaction, the resulting Pd nanoparticles (2-5 nm size) are stabilized by PEG acting as ligand. In this way, a reusable, homogeneous system in PEG has been developed that is able to effect the Suzuki and Sonogashira couplings without the need of copper and phosphorous ligands, working at the open air.     

Structural Study of Silica Xerogel Composites Containing Pd Aggregates

Composites containing Pd aggregates dispersed in amorphous silica are of interest from both a fundamental and applied point of view because of their attractive catalytic properties. The silica powders added with palladium, prepared by the sol-gel method, were studied using X-ray diffraction, and IR- and UV-Vis-spectrophotometry. Silica xerogel samples were prepared using a ethanol/H₂O/TEOS molar ratio of 4:11.6:1 and loaded with sodium tetrachloropalladate. The silica xerogel microstructure of the powders was studied as a function of annealing temperature. Attention was paid to the evolution of the glass matrix as well as the palladium aggregates in the SiO₂ matrix. We found in our samples partial crystallization of the glass matrix in form of quartz and cristobalite phases with palladium oxide and metallic palladium phase at 1000^∘C. The Rietveld refinement method was used in order to determine the percentage of the phase contents.     

Spectrophotometric Determination of Palladium with Methylthymol Blue

A new, sensitive spectrophotometric method for the determination of palladium(II) with methylthymol blue has been developed. The palladium methylthymol blue complex has an absorption maximum at 530 nm. The colour reaction has a sensitivity of 0.005 µg of palladium/cm² and obeys Beer's Law over the range 0.4 to 3.24 ppm of palladium. The effects of concentration of perchloric acid, reagent, heating, stability of colour and diverse ions have been investigated. The ratio of metal: ligand in the complex is 1:1 and the formation constant was calculated to be 1.18×10⁴.     

Spectrophotometric determination of palladium(II) with phenylfluorone in the presence of hexadecylpyridinium bromide

Phenylfluorone reacts with palladium(II) in the presence of hexadecylpyridinium bromide to form a water-soluble chelate with an absorption maximum at 630 nm, the absorbance being constant in the pH-range of 9.0–10.2. At this wavelength Beer's law is obeyed up to 7.25 × 10^–5 mol/L palladium(II). The sensitivity is very high and the molar absorptivity is 8.5 × 10⁴ L mol^–1 cm^–1, permitting the determination of palladium(II) at µg level. The ratio of palladium to phenylfluorone in the complex is 1:1. The method has successfully been applied to the determination of palladium in titanium alloys.     

Recovery of palladium from basic reprocessing waste of spent nuclear fuel

The methods including collection method, extraction-collection method, and special extraction-collection method have been investigated for high speed and efficient recovery of palladium from high pH reprocessing waste of spent nuclear fuel. The equilibrium of the reactions can be obtained is less than 1 minute. The maximum percent recovery of Pd is about 89%, 96% and 97% for collection, extraction-collection, and special extraction-collection methods, respectively. Nearly 100% of back extraction of Pd in the organic phase can be attained by using 7.4M ammonia solution, with a phase ratio of 1:1. The purity of the Pd product is high. The percent recovery of Pd is constant, up to 5·10³ Gy of irradiation dose.     

A highly sensitive spectrophotometric determination of palladium with chromal blue g and cetyltrimethylammonium chloride

A new spectrophotometric method for the determination of palladium with chromal blue G (Color Index 43835) and cetyltrimethylammonium chloride is described. The sensitivity of the color reaction between palladium and chromal blue G is greatly increased in the presence of cetyltrimethylammonium chloride. The palladium complex has maximal absorbance at pH 3.2–3.8 and at 670 nm. Beer's law is obeyed over the range 0.08–1.4 p.p.m. palladium; the molar absorptivity is 1.01 · 10⁵ l mol^-1 cm^-1 at 670 nm and the sensitivity is 1·10^-3 μg Pd cm^-2. The mole ratio of palladium and chromal blue G in the complex in the presence of cetyltrimethylammonium chloride is 1:3. Only scandium interferes when sodium fluoride is used as masking agent.     

A proposed structure for the copper(ii) salts of α-acyloin oximes

The behavior of the copper (II) salts of the a-isomers of some acyloin oximes towards a series of selected amines was examined in order to study the unusual solubility relationships which these copper salts exhibit towards ammonium hydroxide. The insolubility in ammonium hydroxide of these copper salts of acyloin oximes has been attributed to their being inner complex salts. Evidence is presented which is contra y to this view. Based on the solubilities of the copper (II) salts investigated, a polymeric structure for copper (II) acyloin oximes is proposed. The study included the following α-isomers of acyloin oximes: benzoin oxime, 2,2'-furoin oxime, phenylbenzoin oxime, methylbenzoin oxime, 2,2'thenoin oxime, a-hydroxyisobutyrophenone oxime, and α-hydroxyacetophenone oxime. The last four compounds had not been examined previously as to their ability to form copper (II) salts.     

Microdetermination of palladium based on formation of ternary complex of palladium with pyrogallol red and cetylpyridinium bromide

A new spectrophotometric method was employed for the determination of microamounts of palladium(II) based on the ternary complex formation with pyrogallol red and cetylpyridinium bromide. A blue green ternary complex, whose molar absorptivities is 22500 mol^?1 cm^?1 at 650 nm, is formed. Composition (PdPGRCP₃) of the ternary complex was established by continuous variation and mole ratio methods. Beer's law range (0.1–8.5 ppm of Pd) and Sandell's sensitivity (0.001 γ/cm²) were evaluated. The conditional stability constant value (logK = 24.35) was determined by Prakash et al. 's method. A detailed study was made for the determination of microamounts of palladium in the presence of platinum metals and several other cations and anions.     

Application of thiophene-2-carbaldehyde-modified mesoporous silica as a new sorbent for separation and preconcentration of palladium prior to inductively coupled plasma atomic emission spectrometric determination

A new and efficient method was described for an easy synthesis of functionalized mesoporous silica (MCM-41) using thiophene-2-carbaldehyde. This new chemically bonded analytical reagent was used as an effective sorbent for the solid phase extraction of palladium(II) ion from aqueous solutions. Conditions for effective adsorption of trace levels of palladium concentration were optimized with respect to different experimental parameters in batch process. Thiourea solution could efficiently elute adsorbed palladium(II) ion from the surface of the sorbent which then was determined by inductively coupled plasma atomic emission spectrometer (ICP-AES).Common coexisting ions did not interfere with the separation and determination. The preconcentration factor was 100 (1 ml elution volume) for a 100 ml sample volume. The limit of detection of the proposed method is 0.2 ng ml⁻¹. The maximum sorption capacity of sorbent under optimum conditions has been found to be 5 mg of palladium per gram of sorbent. The relative standard deviation under optimum conditions was 3.2% (n = 10). Accuracy and application of the method was estimated by using test samples of natural and synthetic water spiked with different amounts of palladium(II) ion.     

Liquid–liquid extraction of palladium(II) and gold(III) with N-benzoyl-N′,N′-diethylthiourea and the synthesis of a palladium benzoylthiourea complex

N-Benzoylthioureas have been reported to form complexes with gold (III) and palladium (II) and other transition metals. In this study, an N-benzoyl-N′,N′-diethylthiourea (3f) ligand was used in the solvent extraction of palladium(II) and gold(III) from aqueous chloride media (0.1 mol l−1 NaCl). The distribution coefficient was determined as a function of both metal concentration in the aqueous phase and extractant concentration in the organic phase. The experimental distribution data were numerically analysed by letagrop-distr software in order to obtain the thermodynamic model corresponding to the metal extraction. It is found that pH does not affect the metal extraction process in the 1–2 pH range. Synthesis of the palladium benzoyl thiourea complexes was carried out by mixing quantities of metal and ligand solutions in methanol in a 1:2 ratio stoichiometric. Yields of 74 and 80.9% were obtained for the Pd-3c and Pd-3f complexes. In order to confirm the formation of the palladium complexes, NMR, FTIR and MS analyses were performed. From MS analyses a complex stoichiometry 1:2 (metal:ligand) was confirmed. The formation of crystals of palladium N-benzoyl-N′,N′-diethylthiourea complex (Pd-3f) in the methanolic solution allows the characterisation of the complex structure by XRD. The resulting structure is described and discussed. Bis(1,1,-diheptadecyl-3-benzoyl-thioureate)palladium(II) (Pd-3c) and bis(1,1,-diheptadecyl-3-benzoyl-thioureate)palladium(II) (Pd-3f) were used as ionophores in polymeric membrane electrodes. Their potentiometric responses to different anionic metal chlorocomplexes are evaluated and discussed taking into consideration the results obtained in the liquid–liquid distribution studies. A nernstian response was only obtained for AuCl4 − (PDL=8.8×10−8) and PdCl4 2− (PDL=1.5×10−4 M) with a selectivity coefficient of KAuCl4-, PdCl42−pot=−3.4, calculated taking AuCl4 − as being the primary anion.     

Spectrophotometric determination of palladium by adsorption of its n-butyl xanthate complex on microcrystalline naphthalene

A new reliable method for the spectrophotometric determination of trace amounts of palladium after adsorption of its n-butyl xanthate complex on microcrystalline naphthalene is developed. Palladium reacts with this reagent to form a colored water insoluble complex which can be quantitatively adsorbed on naphthalene in the pH range of 3.8 – 8.4. The mixture of the complex and naphthalene is dissolved in chloroform and the trace amount of palladium is determined spectrophotometrically. It has an adsorption maximum at 385 nm. Beer's law holds in the concentration range of 2.5–105.0 μg of palladium in 10 ml of chloroform. The molar absorptivity of the complex is found to be 1.319 × 10⁴ liters mol cm⁻¹, while the Sandlle's sensitivity is 0.008 μg cm⁻² for palladium at 385 nm. Samples containing 25 μg of palladium give a mean absorbance of 0.310 with a standard deviation of 0.0027. The effect of experimental variables such as pH, amount of reagent, aqueous phase volume, and diverse ions have been examined. The method has been applied to the determination of palladium in some alloys.     

Application of non-steroidal anti-inflammatory drugs for palladium determination

A highly sensitive spectrophotometric method for palladium determination using piroxicam and tenoxicam as new chromogenic reagents has been developed. In the presence of sodium lauryl sulfate (SLS), palladium reacts with piroxicam (PX) or tenoxicam (TX) to form stable yellow orange complexes in an acetate buffer solution of pH 5.0 at 424 nm and 426 nm with molar absorptivity of 7.16 × 10⁴ L mol⁻¹ cm⁻¹ and 1.20 × 10⁵ L mol⁻¹ cm⁻¹, respectively. Sandell sensitivity, detection, and quantitation limits were also calculated. Optimum conditions were evaluated considering pH, reagent concentration, time, temperature, and surfactant concentration. The complex system conforms to Beer’s law over the range of 0.07–1.28 μg mL⁻¹ palladium. The stoichiometric ratio and stability constant were also evaluated. Tolerance limits of many cations and anions were determined. Finally, the proposed method was applied successfully in the determination of palladium in jewellery, anode mud, synthetic mixtures, catalysts, and alloy samples.