Ion exchange extraction of platinum(IV) and palladium(II) from hydrochloric acid solutions

Sorption concentration of platinum(II, IV) and palladium(II) from freshly prepared and aged two-yearold hydrochloric acid solutions by a series of anion exchangers with different functional groups and of different physical structure of Purolite and CYBBER grades was studied. The high sorption ability of the ion exchangers in relation to the extracted chlorocomplexes of noble metals is shown. It was demonstrated that palladium(II) from all tested ion exchangers can be completely desorbed with thiourea solutions acidified with hydrochloric acid, while complete desorption of platinum is achieved only from Purolite S 985 anion exchanger of the complexforming type and Purolite A 111 weak base anion exchanger.     

Ion exchange equilibria in simultaneous extraction of platinum(II,IV) and rhodium(III) from hydrochloric solutions

Regularities of sorption extraction of platinum(II, IV) and rhodium(III) by anion exchangers of various physical and chemical structure in the presence of hydrochloric media were studied. It is established that AM-2B, Purolite A 500, and Purolite S 985 ionites adsorb complex anions of platinum metals employing mixed mechanism. A high affinity of the studied anionites for the studied complex anions of platinum and rhodium is established.     

Sorption recovery of platinum(II, IV) from chloride and sulfate-chloride solutions

Sorption of platinum(II, IV) from chloride and sulfate-chloride solution on anion exchangers of varied chemical structure (various functional groups and varied basicity) was studied. It was found that sulfate-chloride systems have high efficiency comparable with that of chloride systems in sorption of platinum by AM-2B, Purolite S 985, and Lewatit MP 600 WS anion exchangers.     

Ion-exchange recovery of palladium(II) from multicomponent chloride solutions

Ion-exchange sorption of palladium(II) from both concentrated aqueous hydrochloric acid solution containing Fe(III), Sn(II), Zn(II), and Cu(II) and weakly acidic concentrated aqueous ammonium chloride solution containing Zn(II) and Cu(II) was studied. The Purolite S920, Purolite S924, and Purolite S984 macroporous resins with the thiourea, thiol, and polyethylenepolyamine functional groups, respectively, were used as sorbents. Strongly basic Purolite A500 anion exchanger was also tested. The desorption of palladium(II) with aqueous ammonia, hydrochloric acid, and acidified aqueous thiourea was examined.     

Separation of platinum and palladium from base metals with a weakly basic cellulose ion exchanger

Platinum(IV) and palladium (II) are strongly adsorbed on the weakly basic cellulose ion exchanger DEAE from dilute thiocyanate media, while most other metal ions do not show any marked tendency to adsorb from the same media. It is possible to separate and concentrate the noble metal ions from a large quantity of base metals such as iron, cobalt, nickel, copper, zinc and lead. As little as 1 mg of platinum(IV) and/or palladium (II) can be quantitatively separated from as much as 20–25 g of base metals on a small column of DEAE (thiocyanate form). The noble metal ions adsorbed are easily stripped from DEAE.     

Sorption of Rhenium(VII) on Gel and Macroporous Anion Exchangers of Different Basicities from Solutions of Mineral Acids and Their Ammonium Salts

Equilibrium sorption of rhenium on strongly basic gel-like anion exchanger Purolite A600, on weakly acidic anion exchangers Purolite A170 and A172 with macroporous and gel structures and on composite anion exchanger Purolite SIM202, which is a synthetic sorbent based on super-cross-linked polystyrene impregnated with trialkylamine Alamine 336, was studied in a wide range of concentrations of sulfuric, hydrochloric, and nitric acids and of their ammonium salts.     

Macroporous anion exchanger purolite A-500 loaded with ferron for palladium(II) recovery

A systematic study on interaction of Pd(II) with 7-iodo-8-hydroxyquinoline-5 sulfonic acid (Ferron) and the strongly basic anion exchange resin Purolite A-500 in its chloride form was carried out. It was found that for Ferron/resin ratio ranging from 0.15 to 0.70 mmol g-1, the retention of chelating reagent on the investigated ion exchanger is practically quantitative. The sorption increase of Pd(II) on Ferron-loaded resin was observed for higher values of parameters like: pH solution, initial concentration and temperature. It was observed that the equilibrium distribution of Pd(II) between sorbent and solution could adequately be described by the Langmuir model with two parameters. The thermodynamic quantities characteristic of Pd(II) sorption process (ΔG = -18.4 kJ mol^-1; ΔH = 11.7 kJ mol^-1; ΔS = 104.4 J mol^-1 K^-1) suggest a strong affinity between Ferron-loaded resin and the tested cation.     

Sorption recovery of platinum(II) and platinum(IV) chloro complexes with a heterochain sulfur-containing sorbent

The recovery of platinum(II) and platinum(IV) chloro complexes from hydrochloric acid and chloride solutions with a new heterochain S,N-containing sorbent, MITKhAT, was studied. The suggested mechanism of formation of platinum(II) mercapto-thio ether complexes in the course of sorption was confirmed by DFT calculations. The results of group and selective recovery of platinum metals with MITKhAT sorbent from simulated and real industrial solutions are reported.     

Hydration of purolite S950 ion exchanger in deprotonated forms

A quantitative evaluation of the degree of hydration, including the ratios of water with different energies in the phase of the aminophosphonic exchanger Purolite S950 in sodium, copper, and nickel forms is conducted. The changes in the Gibbs free energy and enthalpies of hydration and dehydration are determined. It is found that the amount of bound water decreases upon the transition from nickel to copper, especially to the sodium forms of the ion exchanger, and that changes in the Gibbs energy and enthalpy are greatest upon the hydration of the sodium form of polyampholytes.     

Extraction chromatographic separation of platinum(IV) from real samples and associated elements

 The extraction behavior of platinum(IV) was studied with N-n-octylaniline as a function of different parameters, such as pH, concentrations of weak acids, mineral acids, reagents and elution time. A selective method was developed for the extraction chromatographic studies of platinum(IV) and its separation from several metal ions with N-n-octylaniline (liquid anion exchanger) as a stationary phase on silica gel. The quantitative extraction of platinum(IV) was observed with 0.067 mol/L N-n-octylaniline and 0.015 mol/L ascorbic acid at pH 1.0. Metal ion was stripped from the column with water and determined spectrophotometrically with stannous chloride method. The proposed method is free from the interference of a large number of cations and anions. Platinum(IV) was separated from pharmaceutical preparations, alloys and synthetic mixtures. Mutual separation scheme was developed for platinum(IV), palladium(II) and gold(III). The log-log plot of N-n-octylaniline concentration versus the distribution ratio indicates that the probable extracted species is ［RR′NH+2 ］· Pt(C6H7O6)－3.     

Specific features of rhenium desorption from weakly basic anion exchangers Purolite A170 and Purolite A172 with ammonia solutions

Equilibrium, kinetics, and dynamics of rhenium desorption from weakly basic macroporous (Purolite A170) and gel anion (Purolite A172) exchangers with ammonia solutions were studied. The effective diffusion coefficients of rhenium in its desorption from these anion exchangers and the activation energy of rhenium desorption from the gel anion exchanger were estimated.     

Rearrangement of a (dithiolato)platinum(II) complex formed by reaction of cyclic disulfide 7,8-dithiabicyclo[4.2.1]nona-2,4-diene with a platinum(0) complex: oxidation of the rearranged (dithiolato)platinum(II) complex

Reaction of the title bicyclic disulfide 16 with [(Ph3P)2Pt(eta2-C2H4)] (2) yielded the corresponding (dithiolato)platinum(II) complex 17 by oxidative addition. The initial product 17 isomerized at room temperature in a [1,5]-sulfur rearrangement to give another (dithiolato)platinum(II) complex 18 in high isolated yield. Oxidation reactions of 18 with dimethyldioxirane (DMD) provided (sulfenato-thiolato)platinum(II) 23, (sulfinato-thiolato)platinum(II) 24, (sulfenato-sulfinato)platinum(II) 25, and (disulfinato)platinum(II) 26 complexes, the structures of which were elucidated by NMR spectroscopy and X-ray crystallography. The oxidation process took place regioselectively in the first step and chemoselectively in the second. The selectivities are discussed.     

Extraction of platinum with Astrafloxin FF from aqueous-organic solutions: Separative extraction-spectrophotometric determination of platinum(II) and platinum(IV) species

The optimum conditions of the extraction of the ion associates of platinum with the thiocyanate ions and the polymethine basic dye Astrafloxin FF by aromatic hydrocarbons and acetic acid esters from aqueous and aqueous-organic solutions were studied. The introduction of water-soluble donor-active solvents (hexamethylphosphoric triamide, N,N-diethylacetamide, N,N-dimethylformamide, and N,N-diethylformamide) leads to a considerable increase in the extraction of the ion associates of platinum and the simultaneous suppression of the extraction of the simple dye salt. The molar absorption coefficients of the extracts of ion associates are as high as (8.1?C13.3) × 10⁴. 84?C96% platinum is extracted in the form of ion associates by a single extraction. The conversion of platinum into ion associates makes it possible to separate platinum from many elements, including Cu, Cd, Ni, Co, Cr, Pb, In, Ag, Pd, Ir, Rh, and Ru, by extraction. In this case, platinum(II) is extracted in the form of ion associates under standard conditions, whereas platinum(IV) is extracted only after the preliminary thermal treatment of the test sample. A new procedure was developed for the extraction-spectrophotometric determination of the trace amounts of platinum(II) and platinum(IV), in particular, in their mixtures.     

Simultaneous determination of platinum(II) and platinum(IV) by controlled-reagent coulometry

Both platinum(II) and the total amount of platinum were determined in the 5-μmole range with a precision of 0.3%. First, platinum(II) was determined dy oxidation with electrogenerated bromine,the equivalent quantity of electricity being measured. After reduction to platinum(II) with electrogenarated tin(II), the total amount of platinum was determined by a second oxidation with electrogenerated bromine.The reduction with tin(II) was too slow for manual control, and an electronic coulometric titrator was used.The construction of the tritator is described. The underlying coulometric principle, called controlled-reagent coulometry, and its adventages are discussed. A number of other substances were also tested.     

Synthesis and characterization of a platinum(II) complex with N-acetyl-L-cysteine

Synthesis and spectroscopic studies in the solid-state of a platinum(II) complex with N-acetyl-L-cysteine are described. Elemental analyses are consistent with composition Pt₂(C₅H₈NO₃S)₄ · 3H₂O. Solid-state ¹³C NMR, infrared, and U-Vis spectroscopic results are consistent with coordination of the ligand to platinum(II) through sulfur. Thermal analyses confirmed water in the complex composition. Final residue of the thermal treatment was identified by powder X-ray diffractometry as metallic platinum.     

双马来腈二亚胺合铂与DNA的作用

本文以紫外-可见光谱、荧光光谱及黏度法研究了双马来腈二亚胺合铂与DNA的作用。紫外-可见光谱的研究表明,与DNA作用后,双马来腈二亚胺合铂在可见区的吸收显示出了减色效应,并伴随着吸收峰的蓝移。Scatchard图的分析结果表明,双马来腈二亚胺合铂与DNA的作用位点与溴化乙锭不同。黏度法实验表明,双马来腈二亚胺合铂与DNA作用后降低了DNA的相对黏度。这些研究结果表明,双马来腈二亚胺合铂以静电作用方式与DNA结合。本研究有助于深入理解双马来腈二亚胺合铂的作用机理并开发这种潜在的新型光动力治疗剂。     

Cyclometallated platinum(II) complexes: oxidation to, and C-H activation by, platinum(IV)

A series of cyclometallated phenylpyridine platinum(II) complexes have been synthesised with a systematic variation in both the phenylpyridine and the ancillary ligand. Oxidation of one of the cyclometallated species leads to a number of isomeric platinum(IV) complexes, all of which eventually isomerize to a single compound. The route to these new compounds has been demonstrated to involve an initial slow oxidation followed by a rapid C-H activation to give doubly cyclometallated complexes. The solid state structures of a number of both the platinum(II) and the platinum(IV) species have been solved; many of the structures exhibited extended interactions that result in complex three dimensional packing.     

Liquid-liquid extraction of platinum(II) with cyclic tetrathioethers

The liquid-liquid extraction of platinum(II) with 12-, 14- and 16-membered cyclic tetrathioethers from chloride solution was studied. Bromocresol Green ion as a counter anion and 1,2-dichloroethane as an extraction solvent were used. The effect of thiourea on the extraction rate of platinum(II) was examined. Platinum(II) was hardly extracted with macrocyclic tetrathioethers in the absence of thiourea because of the slow extraction rate. The extraction rate of platinum(II) was considerably enhanced by the addition of thiourea. The extraction rate of platinum(II) with 16-membered cyclic tetrathioether was faster than that with 12- and 14-membered ones. Platinum(II) was quantitatively extracted with 16-membered cyclic tetrathioether into 1,2-dichloroethane within 5 h in the presence of thiourea.     

Structural features of a new dinuclear platinum(II) complex with significant antiproliferative activity

A novel dinuclear platinum(II) complex, [Pt(2)-N,N'-bis(2-dimethylaminoethyl oxamide)Cl(4)], showing peculiar structural features, has been prepared and characterized. X-ray diffraction data reveal that the two platinum ions are simultaneously bound to the N,N'-bis(2-dimethylaminoethyl) oxamide ligand, on opposite sides. The coordination environment of both platinum centers is square planar, with identical NOCl(2) donor sets. The complex is poorly soluble within a physiological buffer but moderately soluble in DMSO. Preliminary in vitro studies point out that this dinuclear platinum complex exhibits significant growth-inhibiting properties on a panel of cultured human tumor cell lines, although less pronounced than those of cisplatin.     

The thermal decomposition of platinum(II) and (IV) complexes

The decomposition characteristics of Pt(II) and Pt(IV) complexes in hydrogen, air and argon were investigated by thermal gravimetric and differential thermal analysis. Based on weight-loss measurements, the thermal stability in hydrogen increased in the order: hexachloroplatinic acid<platinum acetyl acetonate<platinum diamino dinitrite<tetrammine platinous hydroxide<tetrammine platinous chloride<platinum phthalocyanine; whereas in air, the order was: hexachloroplatinic acid<tetrammine platinous hydroxide<platinum acetyl acetonate<platinum diamino dinitrite<tetrammine platinous chloride. The platinum complexes were more stable in air than in hydrogen where decomposition was observed in all platinum samples at temperatures below 200°C.