Use of Di(n-butyl) and Di(iso-butyl)dithiophosphoric Acids as Complexing Agents in the TLC Separation of Some d and f Transition Metal Ions

The thin layer chromatographic behavior of U(VI), Th(IV), lanthanides(III), Co(II), Ni(II), and Cu(II) on silica gel H with di(n-butyl) and di(iso-butyl)dithiophosphoric acids as complexing agents in the organic mobile phase has been investigated. The results obtained show that the dithiophosphate anion has a substantial effect on the migration of these metal ions. The presence of electron-donor solvents in the mobile phase increases retention, especially for U(VI), Th(IV), and lanthanides(III). The effect is explained on the basis of greater solubility of the metal chelates of the dithiophosphoric anions in the organic mobile phase, because of a solvation process. Separation was investigated for three groups of metal ions — actinides, lanthanides, and d transition metals. By choice of an appropriate organic mobile phase, separation of the pairs Th(IV)-U(VI), Pr(III)-Sm(III), Sm(III)-Gd(III), and Gd(III)-Er(III) was achieved, as was separation of Co(II), Ni(II), and Cu(II) from each other. A complex separation mechanism based on adsorption-desorption, cation exchange, and extraction is suggested.

     

Quantitative Separation of Pd(II) by TLC of Metal Ions on Cerium (IV) Antimonate

Abstract

A quantitative TLC separation of metal ions using cerium (IV) antimonate as the solid phase are described. Using an acetonitrile- HNO₃ solvent Pb²⁺ can be separated quantitatively (2–10 μg) from several other ions. A quantitative spectrophotometric assay using p-nitroso-dimethylaniline is proposed.     

Iron Extraction with Di(2-Ethylhexyl)dithiophosphoric Acid and a Binary Extractant Based on It

Iron(III) extraction with trioctylmethylammonium di(2-ethylhexyl)dithiophosphate and di(2- ethylhexyl)dithiophosphoric acid was studied. It was shown that di(2-ethylhexyl)dithiophosphoric acid extracts iron in the form of the complex FeA₂, regardless of the oxidation state of iron in the initial aqueous solution. It was also shown that the iron(III) extraction with trioctylmethylammonium di(2-ethylhexyl)dithiophosphate over a wide acidity range occurs primarily to produce extractable substance (R₄N)FeCl₄; and at pH > 1, iron(II) dialkyldithiophosphate is also extracted into the organic phase. It was established that, in a system with a binary extractant, iron can be efficiently stripped from the organic phase with water or diluted solutions of mineral acids.     

Separation of Selected Transition Metal Ions and Divalent Metal Ions by HPLC Using UV-VIS Detection

Abstract

The use of ethylenediaminetetraacetic acid, disodium salt, (pH 3-5) has been investigated as an eluant for the separation and detection of nanogram levels of selected divalent and trivalent metal ions. The effect of pH and eluant concentration upon the retention times and resolution of the system are given and the ability to alter the eluant characteristics to optimize the chromatographic results in different situations will be discussed. The method is less complicated than the method frequently used for transition metal ion determinations which uses a post-column derivitization reagent. This method is applicable to a wider range of metal ions and provides detection limits which are generally within two orders of magnitude of the post-column derivitization method.     

二（2-乙基己基）二硫代磷酸溶剂萃取铊的热动力学

在Tl₂SO₄＋Na₂SO₄＋二（2-乙基己基）二硫代磷酸＋n-C₈H₁₈＋水体系中， 测定了0.1－2.0 mol•kg^－1离子强度范围内Tl^＋ 的平衡摩尔浓度。水相中电解质Na₂SO₄ 控制溶液离子强度， 有机相中萃取剂取278.15 K至303.15 K范围内的恒定摩尔浓度。通过外推法和多项式近似得到了不同温度下的标准萃取常数K⁰，计算了萃取过程的热动力学量。     

高价金属离子在结晶锑酸-磺胺偶氮氯膦浸渍板上的薄层色谱研究

本文报导了一种新的薄层色谱法,研究了稀土(Ⅲ)、钛(Ⅳ)、锆(Ⅳ)、铌(Ⅴ)和铀(Ⅳ)的TLC行为,有效地分离了一系列二元及三元混合物.方法简便、快速、直观.根据实验结果,推荐了镧系元素的原子序数(Z)、离子裸半径(r°)与R_f值的经验公式.计算了在各种展开剂中曲线的截距、斜率和线性相关系数(r).     

Sorption Studies in DMSO-NITRIC Acid and DMSO-Acetic Acid Systems and Separation of Metal Ions on TIN(IV)-Iodophosphate

Abstract

Some new samples of tin(IV)-iodophosphate have been synthesized and their ion exchange properties have been studied. Adsorption behaviour of different metal ions on tin(IV)-iodophosphate (TIP₅), in H⁺ form, in different solvent systems have been examined. Kd values of few metal ions, in 4M DMSO medium, have also been determined on the same ion-exchanger in NH⁺ ₄ form. Effect of particle size of tin(IV)-iodophosphate (TIP₅), in H⁺ form, on the Kd values of metal ions has been studied. Separations of a number of metal ions have been achieved on tin(IV)-iodophosphate (TIP₅) columns.     

Separating Behaviors of Heavier Rare Earth Metal Ions in Centrifugal Partition Chromatography with Di(2-Ethylhexyl) Phosphoric Acid

Abstract

The separating behaviors of SmCl₃, EuCl₃, GdCl₃, TbCl₃, DyCl₃, HoCl₃, ErCl₃, TmCl₃, YbCl₃, and LuCl₃ in Centrifugal Partition Chromatography with the stationary phase containing a separator, Di(2-ethylhexyl) phosphoric acid (D2EHPA), are examined. The separation trends of these heavier rare earth metal ions were found to be almost as expected from the observations reported for the lighter rare earth metal ions. And the separator is also useful for mutual separation of these heavier rare earth metal ions.     

Liquid Membrane Transport of Heavier Rare Earth Metal Ions Based on CPC Results with Di(2-Ethylhexyl) Phosphoric Acid

Abstract

The behaviors of heavier rare earth metal ions in bulk liquid membrane transport systems were examined for Gd³⁺, Tb³⁺, Dy³, Ho³⁺, Er³⁺, Tm³, Yb³⁺ and Lu³⁺ ions. The liquid membrane transport system was constructed by aq. HCl/CHCl₃ containing Di (2-ethylhexyl) phosphoric acid/aq. HCl. The optimum concentration of HCl in the aqueous phase with respect to the rate of transport for these ions increased with the atomic number of the rare earth elements. This trend of transport behaviors was on the same line observed for lighter rare earth ions in the preceding work. Difference in the rate of transport can be used for selective liquid membrane transport of several sets of combination with these ions.     

甲基膦酸二甲庚酯萃取色谱法分离金、铂的研究

本文研究了以4.0mol/L H_2SO_4-0.50mol/L MgSO_4 为流动相,以硅烷化硅球负载的甲基膦酸二甲庚酯(P350)作固定相。萃取色谱法使微量铂、金与常见贱金属分离,富集在色谱柱上的铂和金分别用0.10mol/L HCl和1.0％Na_2SO_2溶液洗脱进行连续分离与测定。经实际样品的试用考核,结果令人满意。     

Electrochromatography of Metal Ions on Zirconium(IV) Phosphoantimonate Papers: Quantitative Separation of Platinum(IV) from Platinum Group and Other Metal Ions

Abstract

Zirconium (IV) phosphoantimonate impregnated papers have been used to study the electrochromatographic behaviour of 29 metal ions in buffers of weak organic acids with their corresponding ammonium salts as background electrolytes at fixed voltage and time intervals. As a result of these investigations, the variation in the average mobility of metal ions with the ionisation constants of the organic acids used in buffers and other parameters such as atomic numbers and charge on the metal ions has been studied. On the basis of the differential mobilites of the metal ions, which depends on the ion exchange properties of Zr(IV) phosphoantimonate and the nature of the complexes formed with the electrolytes, some binary, ternary and quarternary separation have been achieved. Besides microgram separations (25 μg-100 μg) of Pt(TV) from Pt group and other metal ions have also been achieved.     

离子相互作用色谱法分离金属离子的研究

离子相互作用色谱在无机离子的分离和分析中潜力很大。它通过离子相互作用试剂,能容易控制或改变柱交换容量或分析物的保留值,分离效率高,可快速完成多组分的同时分离。 在ODS固定相上涂敷阳离子型的十六烷基吡啶(CPI),使金属离子成为阴离子型的氨羧络合物,因不同金属氨羧络合物与CPI的作用程度不同从而可使金属离子分离。金属氨羧络合物亲水性很强,在键合相上的吸附作用可忽略,流动相中不需加入有机溶剂,因此络合物     

毛细管电泳法间接测定茶水、矿泉水中金属离子

采用毛细管电泳间接紫外检测技术测定了茶水、矿泉水中金属离子的含量,研究了电泳液组成和最佳实验条件.结果表明:采用pH=4.82含有浓度为6.0 mmol/L咪唑的乙酸缓冲液作为电泳液,压力进样(30 mbar×5 s),未涂层石英毛细管柱75μm×50 cm,分离电压12 kV,检测波长210 nm,柱温为25℃实验条件下,6 min内实现K+、Ca2+、Na+、Mg2+、Zn2+5种离子的分离和测定.保留时间的相对标准偏差(RSD)小于0.5%,峰面积RSD小于5%(n=7),最低检测限依次为0.002、0.001、0.001、0.010和0.050 mg/L.该方法用于茶水、矿泉水中金属离子含量的测定.回收率95.6%～108.6%,结果良好.     

Electrochromatographic Separation of DMSO Complexes of Metal Ions

Abstract

Electrochromatography of DMSO complexes of fourteen metal ions have been performed in five electrolytes at 100 volts for 3 hrs. The mechanism of migration has been explained and a number of separations of metal-DMSO complexes were achieved.     

Quantitative Separation of Hg(11) From Several Metal Ions on Zr(IV) Antimonate Papers

Abstract

The chromatographic behaviour of 32 metal ions has been studied on paper Impregnated with Zirconium(IV) antimonate in aqueous HCI and mixed solvent system containing dimethyisul phoxide and dioxane. Several Important binary and ternary separations have been achieved. Quantitative separation of Hg(ll) from Ni²⁺, Pb²⁺, Pd²⁺, Ru³⁺, Rh³⁺, Bi³⁺, Co²⁺, Cd²⁺ and Gd³⁺ is described.     

Retention of Some Metal Ions and Their Separation on Silica Gel Modified with Acid Red 88

 Acid Red 88 is strongly extracted by chloroform solutions of Aliquat 336 by an ion exchange mechanism and for its reextraction from the ion pair formed, relatively high concentrations of mineral acids are required. By impregnation of silica with the ion pairs between the cation of Aliquat 336 and the anion of the dye a chelating sorbent for metal ions can be obtained. The sorbent prepared may be successfully used for separation of mixtures of various metal ions by the column extraction chromatography technique, additional purification of sodium and potassium salts from ions of heavy metals and for concentration of trace amounts of ions of various metals from aqueous solutions followed by their quantitative determination. The sorbent can be used repeatedly in the process of sorption and desorption of metal ions (especially those forming less stable complexes with the reagent) after regeneration with solutions of perchloric acid. Received January 28, 1998. Revision March 1, 1999.     

Calixarenes as Polyhapto-aromatic Ligands: Alkali Metal Ions and Sulfonated Calixarenes

Crystal structure determinations for the hexarubidium and octacesium derivatives of calix[6]arene hexasulfonic acid, as well as of a new solvate of the pentasodium derivative of calix[4]arene tetrasulfonic acid, and comparison with structural data from the literature for alkali metal complexes of sulfonated calixarenes, have provided further evidence for the importance of interactions with aromatic ~ -electrons for the heavier alkali metal cations. There is evidence as well that this interaction can be enhanced by extended ionization of the sulfonated calixarene.     

Die Dimerisierung von Di(n-butyl)fluorphosphan und seine Reaktion mit Benzaldehyd

The Dimerization of Di(n-butyl)fluorophosphane and its Reaction with Benzaldehyde The phosphorus atom of organylfluorophosphanes possesses electrophilic as well as nucleophilic properties. This dualistic character decisively determines both their disproportionation and their reaction with aldehydes. The phoshanylphoshorane n-Bu₂P? PF₂(n-Bu)₂, 1 b , has been proved to be the intermediat product of the disproportionation of n-Bu₂PF. In the presence of an equimolar amount of Et₃N an equilibrium exists between 1 b and the monomeric n-Bu₂PF. n-Bu₂PF react with benzaldehyde forming the phosphinitophoshorane n-Bu₂P′? O? CHPh? PF₂(n-Bu)₂, 3 a. Reliable information on the reaction pathway has been obtained by means of crossing experiments.     

Luminescent Properties of Europium(III) Complexes with Quinaldic Acid and Sulfur–Containing Neutral Ligands

The luminescent heteroligand complexes of europium(III) with quinaldic acid and sulfur-containing neutral ligands Eu(Quin)3∙D∙3H2O (Quin–quinaldic acid, D–dimethyl sulfoxide or dihexyl sulfoxide) and Eu(Quin)3∙3H2O have been obtained. Their composition and structure have been determined. The thermal and spectral-luminescent properties of the heteroligand europium(III) complexes have been studied. The quinaldate ion has been found to coordinate to the europium(III) ion as a bidentate ligand. The Stark structure of 5D0–7Fj (j = 0, 1, 2) transitions in the low-temperature luminescence spectra of the europium(III) complexes has been analyzed     

Structures of Metal Complexes with Anions of Di(hydroxymethyl)phosphinic and Di(chloromethyl)phosphinic Acids

This paper considers the structural features of complexes containing Ag(I), 3dmetals (Cu and Ni), and rare-earth elements (REE) such as La, Nd, Er, and Lu, alkaline-earth (Sr) or alkaline (Li, Na) metals with anions of di(hydroxymethyl)phosphinic (L¹) or di(chloromethyl)phosphinic (L²) acids with a general formula RR"PO^– ₂, where R = R" = OH and Cl for L¹and L², respectively. Different patterns of coordination between organophosphorus acids and different metals (four for each L¹and L²) are described. Structures of copper(II) complexes with L¹and L²were compared with those of Cu(II) with dialkyl- and diaryl-substituted monophosphonic and aminophosphinic acids.