Increased selectivity for electrochromatography by dynamic ion exchange

The separation of compounds with similar mobilities is expect to be difficult with capillary zone electrophoresis. Increased selectivity is shown for compounds of this type when other modes of separation are added to the system. A capillary coated with a hydrophobic stationary phase is shown to be a dynamic ion exchanger when a quaternary ammonium compound is added to the running buffer. Compounds are shown to have a decrease in retention when the concentration of the buffer ions is increased. The effect of adding an organic modifier and the influence of the concentration of the surface active reagent are also studied.     

Thermodynamic study of ion exchange reaction to predict ionic selectivity using ion exchange resin Indion-850

The thermodynamic study was carried out to predict the selectivity behaviour of ion exchange resin Indion-850 towaed various inorganic anions like chloride, iodide, sulfate, and oxalate. The equilibrium constant K _std values for the ion exchange reactions were calculated at different temperatures from which the enthalpy values where obtained. The K _std values were observed to increase with the rise in temperature, indicating endothermic ion exchange reactions. The thermodynamic data obtained here reveal that iodide ions were more strongly retained on the resin surface compared to chloride ions. Also the low enthalpy and high equilibrium constant values for oxalate ions indicate the greater selectivity of ion exchange resin for oxalate ions as compared to sulfate ions.     

离子交换纤维的交换动力学研究

本文研究了VS-1型强酸性阳离子交换纤维的交换动力学.在有限浴条件下,用放射性示踪法,研究了温度,搅拌速度,溶液浓度及pH 值对该离子交换纤维的异相同位素交换反应的影响.并推导出离子交换纤维的交换动力学方程,计算出不同条件下的粒内扩散系数D及液膜中的传输系数D/δ.从机理上明确了交换纤维的交换反应速率远比球形树脂快的原因     

Asymmetric ion exchange mosaic membranes with unique selectivity

In this paper, we describe the investigation of membranes to concentrate aqueous low molecular weight (<500 Da) organics streams, while removing electrolytes including divalent salts such as sodium sulfate. Such membranes would be useful in many industrial applications as currently used pressure driven process such as nanofiltration (NF) or electrical processes such as electric dialysis (ED) cannot achieve such separations and concentrations. An analysis of ion/water transport in different membranes and, selectivity and flux requirements indicated that ion exchange mosaics in the form of integrally skinned asymmetric structures could achieve the required performance. The relationship between the internal structure of the mosaic membrane elements and the required separation properties was further analyzed as a development guide. It was found that such membranes could be made by casting a homogenous solution of two mutually incompatible polymers in a common solvent, containing non-solvents and additives, followed by a chemical modification. The process of forming such membranes involves phase separation between the two polymers and the phase inversion of each polymer. In this study the membrane consists of a cation exchange asymmetric membrane with a uniform distribution of anion exchange particles in the dense integrally skin layer. The choice of polymeric materials, their molecular weights, solvent combinations and surfactants determined the membranes’ surface morphology, mosaic dimensions and particle density. In this way membranes were formed with ∼1 μm sized anion exchange particles uniformly dispersed in a thin (∼1.0 μm) cation exchange selective layer of an asymmetric membrane. The best performance to date: Fluxes of 500+LMD, 10% rejection to sodium sulfate, 90% to sucrose and >98% rejection to 400 molecular weight organic ions. The membranes also show a mosaic effect of decreasing sulfate rejection with decreasing sulfate concentration. The membranes also show a musaic effect of decreasing sulfate rejection with decreasing sulfate concentration, which is desired to perform effectively the removal of mono and bivalent ions during diafiltration.     

Equilibria in aqueous cadmium-chloroacetate-glycinate systems. A convolution-deconvolution cyclic voltammetric study

Summary Stability constants and composition of cadmium-glycinate binary complexes were determined using cyclic voltammetry. Furthermore, binary and ternary complex equilibria for chloroacetates and glycinate with cadmium in 0.1M aqueous KNO₃ atpH 10.4 and 298 K were investigated. Cadmium forms binary complexes with chloroacetates of low stability and ternary ones with chloroacetate-glycinate of significant stability.

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Gleichgewichte in wäßrigen Cadmium-Chloroacetat-Glycinat-Systemen. Untersuchungen mittels zyklischer Voltammetrie

Zusammenfassung Gleichgewichtskonstanten und Zusammensetzung binärer Cadmium-Glycinat-Komplexe wurden mittels zyklischer Voltammetrie bestimmt. Weiters wurden binäre und ternäre Gleichgewichte von Chloroacetaten und Glycinat mit Cadmium in 0.1M KNO₃ beipH 10.4 und 298 K untersucht. Cadmium bildet binäre Komplexe geringer Stabilität mit Chloroacetaten und ternäre Komplexe von beträchtlicher Stabilität mit Chloroacetaten und Glycinat.

     

Differential-pulse anodic-stripping voltammetric determination of traces of lead in high-purity copper after its separation by ion exchange

Trace amounts of lead in copper can be determined by differential-pulse anodic-stripping voltammetry after separating it from the matrix. Lead was quantitatively retained on a small Dowex 1-X4 ion-exchange column, without retaining copper when present as a copper-amine complex in solutions containing 0.2 M sodium hydroxide. Subsequent desorption was done with 2 M nitric acid. After deposition for 1 min on a hanging mercury drop electrode and subsequent stripping, the limit of detection was 2 ng ml^?1 and the limit of quantification was 6.6 ng ml^?1. Recoveries of lead were checked by standard addition to copper solution.     

A study of ion exchange equilibria using radioactive isotopes

The ion exchange equilibrium was determined for Fe, Mn, Ni, Co, Sr, Rb, Ba, and Cs ions using tracer technique. Based on these data column operations were carried out. The barium—caesium and strontium—rubidium ions can be separated with good effiency.     

The effect of multi-component adsorption on selectivity in ion exchange displacement systems

This paper examines chemically selective displacement chromatography using affinity ranking plots, batch displacer screening experiments, column displacements, multi-component adsorption isotherms and spectroscopy. The affinity ranking plot indicated that the displacers, sucrose octasulfate (SOS) and tatrazine, should possess sufficient affinity to displace the proteins amyloglucosidase and apoferritin over a wide range of operating conditions. In addition, the plots indicated that the separation of these proteins by displacement chromatography would be extremely difficult. Further, the two proteins were shown to have very similar retention times under shallow linear gradient conditions. When batch displacement experiments were carried out, both tartrazine and SOS exhibited significant selectivity differences with respect to their ability to displace these two proteins, in contrast to the affinity ranking plot results. Column displacement experiments carried out with sucrose octasulfate agreed with the predictions of the affinity ranking plots, with both proteins being displaced but poorly resolved under several column displacement conditions. On the other hand, column displacement with tartrazine as the displacer resulted in the selective displacement and partial purification of apoferritin. Single- and multi-component isotherms of the proteins with or without the presence of displacers were determined and were used to help explain the selectivity reversals observed in the column and batch displacement experiments. In addition, fluorescence and CD spectra suggested that the displacers did not induce any structural changes to either of the proteins. The results in this paper indicate that multi-component adsorption behavior can be exploited for creating chemically selective displacement separations.     

Study of ion exchange selectivity of organic ions by using (31)P NMR spectroscopy

Ion exchange distribution of the phenylphosphoric acid has been studied on various types of chloride form strong base resins as a function of pH at 25 °C, at 0.1 M ionic strength. Equilibrium measurements were supplemented by the study of pH dependence of the ³¹P NMR spectra of the resin-phase phenylphosphate species. Equations were derived to describe the pH dependence of the overall distribution coefficient and the chemical shift of the resin-phase solute species. Experimental data were evaluated by using these model equations and the values of the individual distribution coefficients, ion exchange selectivity coefficients and the resin-phase ³¹P chemical shifts of the mono- and divalent ions have been calculated. Comparison of distribution data of the individual species corroborated the significance of the role of hydrophobic interaction in the selectivity of organic ion exchange processes. A well-defined correlation between the ion exchange selectivity and the resin-phase ³¹P NMR chemical shift data has been pointed out.     

二茂铁衍生物LB膜修饰Pt电极的循环伏安法性能

本文研究了单取代二茂铁酯和双取代亚麻酸二茂铁酯LB膜修饰Pt电极的循环伏安法性能,用修饰电极的循环伏安模型对实验结果进行拟合,计算了在转移压力分别为20,30,40mN·m^-^1下LB膜修饰Pt电极的覆盖度,并分析和讨论了不同转移压力下修饰的二茂铁LB膜的电荷转移中介作用     

Aqueous-phase ion solvation and the selectivity of anion exchange resins for monovalent ions

This research examines and quantifies the influence of ion solvation parameters on the affinity of monovalent anions for strong-base anion resins. A data set comprising resin selectivity coefficients and solvation parameters from the literature is statistically analyzed using correlation and multiple regression techniques. The affinity of monovalent anions for the resin phase correlated well to ionic radii. Solvation parameters such as the hydration number, and entropy, enthalpy and free energy of hydration are also strongly correlated to selectivity. Using the stepwise regression procedure on subsets of independent variables, the entropy of hydration, which characterizes the structure-influencing nature of ions in solution, is incorporated as the sole parameter in the predictive model for resin selectivity. The data are best correlated by the exponential form of the regression equation, and the physical meaning of the correlation is shown to be reasonable. A simple rule for categorizing ions as structure-makers and structure-breakers is proposed, and the results are consistent with conventional classifications.     

离子交换树脂催化酯化生物油的试验研究

生物油黏稠、稳定性差、热值低、腐蚀性强,需要进行改质与品位提升,将生物油中的有机酸通过酯化的方法转化为中性的酯类可以改善生物油的性能。实验利用模型反应,筛选出了适合于生物油体系的732型和NKC-9型两种树脂作为酯化改质的催化剂。生物油和甲醇在间歇釜内以732和NKC-9为催化剂进行改质以后,酸值分别降低了88.54%和85.95%,表明生物油中的有机酸极大地转化为中性酯类。此外,热值分别提高了32.26%和31.64%,水分分别降低了27.74%和30.87%,密度均降低了21.77%,黏度降低均接近97%。732树脂固定床催化酯化生物油后,酸值降低了92.61%。加速陈化实验和铝片腐蚀性实验结果分别表明,改质生物油的稳定性和腐蚀性能得到了改善。     

Variation of selectivity of ion exchange in liquid chromatography with the use of macrocycles

The modification of active sites of a sorbent containing surface NH₂ groups by the addition of 18-crown-6 to the acidified mobile phase (acetonitrile) was studied. A relationship between the chemical structure of modified anion-exchange sites of the stationary phase and the selectivity of ion exchange in the determination of oxygen-containing benzo and dibenzo macrocycles (from 12 to 30 atoms in a cycle) and organic compounds of different classes was revealed.     

Chemometric analysis of voltammetric data on metal ion binding by selenocystine

The behavior of selenocystine (SeCyst) alone or in the presence of various metal ions (Bi(3+), Cd(2+), Co(2+), Cu(2+), Cr(3+), Ni(2+), Pb(2+), and Zn(2+)) was studied using differential pulse voltammetry (DPV) over a wide pH range. Voltammetric data matrices were analyzed using chemometric tools recently developed for nonlinear data: pHfit and Gaussian Peak Adjustment (GPA). Under the experimental conditions tested, no evidence was found for the formation of metal complexes with Bi(3+), Cu(2+), Cr(3+), and Pb(2+). In contrast, SeCyst formed electroinactive complexes with Co(2+) and Ni(2+) and kinetically inert but electroactive complexes with Cd(2+) and Zn(2+). Titrations with Cd(2+), Co(2+), Ni(2+), and Zn(2+) produced data that were reasonably consistent with the formation of stable 1:1 M(SeCyst) complexes.     

Plutonium removal by ion exchange chromatography

A study of Pu recovery at trace level from U solutions by ion exchange technique is presented. Plutonium retention >99.5% onto strong anionic resin, AG-X8, from nitric acid solutions and a 92% recovery using 0.4M HNO₃ at 60°C as eluent, were obtained. Uranium interference in Pu sorption from mixed U/Pu nitrate solutions with low U/Pu ratio (25) was not verified. However, for high U/Pu ratio solutions (10000), uranium interference in Pu retention on the resin, decreases to 59%. Selecting the loading conditions and using AG-X4 resin, 99% Pu retention was achieved. The Pu product is still contaminated with U and another purification cycle is recomended. A scheme for U/Pu first cycle separation is proposed.     

Metal ion selectivity of oligopeptides

Metal binding affinity and selectivity of peptides are reviewed with a special emphasis on the high structural variety of peptide complexes. The most common structural type of these complexes is built up by the deprotonation and metal ion coordination of subsequent amide groups in the form of fused five-membered chelate rings. The metal ion selectivity of this process and the role of various anchoring groups are discussed in detail. The highest metal binding affinity of peptides is connected to the presence of two anchoring groups in appropriate location (the "double anchor"): e.g. the NH2-Xaa-Xaa-His/Cys/Asp/Met-Xaa sequence. Among the side chain donor functions, the imidazole of histidyl and thiolate of cysteinyl residues are the most effective ligating groups and their involvement in metal binding results in a great variety of different macrochelate or loop structures and/or formation of various polynuclear complexes. Examples of these structural motifs and their possible applications have been thoroughly discussed.     

A radiochemical study of the kinetics of ion exchange on hydrous titanium dioxide

This paper reports a radiochemical study of the kinetics of ion exchange of Na⁺ and Cs⁺ with H⁺ on hydrous titanium dioxide. The experimental conditions are set to favor the particle diffusion mechanism only, and this is confirmed by the Bt versus t plots. On the basis of these studies the various physical parameters such as the effective diffusion coefficients, activation energies and entropies of activation have been evaluated. Tentative explanations are given for these results, from which some conclusions are drawn.