Untersuchungen zur adsorptiven anreicherung von elementspuren an adsorberharzen

Summary The mechanisms of the adsorption of neutral compounds, ion associates and metal halogeno-complexes from aqueous solutions on Amberlite XAD-2, XAD-4, XAD-7 and XAD-8 resins are studied in the light of adsorption isotherms and of the pH-dependence of the adsorption. The similarity in the behaviour of adsorption systems to corresponding solvent extraction processes and the regularities of the sorption from aqueous solution on a solid surface are discussed by use of a simple model.

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Herrn Prof. Dr. G. Tölg zum 60. Geburtstag gewidmet

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Teil IV: Fresenius Z Anal Chem (1989) 335:483–488     

Untersuchungen zur adsorptiven Anreicherung von Elementspuren an Adsorberharzen

Summary The adsorption behaviour of trace amounts of As(III), As(V), Fe(II), Hg(II), Pd(II), Pt(IV), Sb(V), Sn(II), Sn(IV) and Tl(III) from hydrochloric and hydrobromic acid solutions on Amberlite XAD-4 and XAD-7 resins by use of a chromatographic method was investigated. As expected, in certain acid concentrations, all of the elements are adsorbed partly or quantitatively. Furthermore, the adsorbability of 23 elements from sulphuric or hydrochloric acid solutions containing iodide or thiocyanate was examined. In accordance with analogous results for chloro- and bromocompounds it was found that the distribution behaviour of iodo- and thiocyanato-compounds is similar to that of corresponding solvent extraction systems. The adsorbed species of the trace compounds were estimated by comparison of the dependence of sorption rate on ligand concentration with the species distribution in the solution. The similarity of adsorbable and extractable species was discussed.

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Teil II: Fresenius Z Anal Chem (1988) 331:588     

Separation of humic acid with XAD resins

Summary Separation of humic acid with different XAD resins has been studied. The effect of pH on the adsorption of humic acid by XAD resins and effect of pH on the distribution coefficient constant in a system of XAD resin and humic acid solution are reported. The XAD-12 was found to be the most efficient resin to remove humic acid from a solution at pH 5.0.

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Zusammenfassung Die Abtrennung von Huminsäure mit verschiedenen XAD-Harzen (Amberliten) wurde untersucht. Über den Einfluß des pH auf die Adsorption der Huminsäure an XAD-Harzen und auf den Verteilungskoeffizienten in einem System aus XAD-Harz und Huminsäure-Lösung wurde berichtet. XAD-12 erwies sich als das am besten wirksame Harz, um Huminsäure bei pH 5 aus einer Lösung zu entfernen.

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This study was supported by Office of Water Research and Technology, U. S. Department of Interior.     

Preparation and characterization of chelating resins loaded with 2-(5-bromo-2-pyridylazo)-5-(diethylamino)phenol for preconcentration of rare earth elements

 Chelating resins prepared by sorption of 2-(5-bromo-2-pyridylazo)-5-(diethylamino)phenol (5-BrPADAP) on macroporous resins (Amberlite XAD-4 and XAD-7) were characterized. The adsorption properties (amount of chelating agent adsorbed per gram of resin, sorption kinetics, retention capacity, etc.) and the thermodynamic quantities of each adsorption process were determined. The retention of some rare earth elements (e.g. Er, Yb and Lu) on these chelating resins was studied in order to preconcentrate them for their determination by X-Ray fluorescence spectrometry. Received: 7 September 1995/Revised: 2 January 1996/Accepted: 10 January 1996     

Extraction of Organic Compounds from Aqueous Media by Amberlite XAD Resins

Abstract

Three Amberlite polymeric resins, XAD-2, XAD-4 and XAD-7, were evaluated for extraction efficiency from aqueous media of several organic compounds representing pesticides, polyaromatic hydrocarbons, phenols and phthalate esters. The three resins exhibited different extraction characteristics. The extraction efficiency of the resins was found to be dependent on pH conditions and, on the average, was best at pH7. At this pH the XAD-2 and XAD-4 resins yielded quantitative recoveries in the 90–100% range for most compounds at the 20–200ppb level. Recoveries by XAD-7 resins were lower for several compounds. The recovery of aldrin and o, p DDT under all conditions was relatively low (>68%) and showed a higher degree of variability than that obtained for the other compounds. Alkaline pH conditions were generally unfavourable for the extraction of phenolic compounds but acidification to pH2 was not found to be a necessary step for the quantitative extraction of the phenolic compounds. Acidification to pH2 further led to a decrease in the recovery of most compounds for XAD-4 resins. A combined resin column yielded extraction efficiencies comparable to the XAD-2 column at pH 7, but since the three resins possess different extraction characteristics, a mixture comprising all three is recommended for the preconcentration of organic compounds from environmental water samples containing a wide range of compounds.     

Untersuchungen zur adsorptiven Anreicherung von Elementspuren an Adsorberharzen

Summary Because of the purity and of the adsorption properties, the Amberlite XAD-4 resin is an adsorbent suitable for multielement preconcentration from aqueous solutions. Adsorbed trace compounds can easily be eluted from the resin by use of 1 M HNO₃ in acetone and subsequently be determined by AAS. In this paper the adsorptivity of complexes of 15 elements with different chelate forming reagents was investigated. Besides of multielement preconcentration, selective trace separation procedures are possible by suitable selection of complex reagents and pH-adjustment of the sample solution. In many cases the resin XAD-4 can advantageously be used as a trace collector instead of activated carbon. The advantages and disadvantages in the application of the two adsorbents are discussed.     

Isolierung und Anreicherung von Chlorphenoxyessigsäuren aus Wasser mit makroretikulären Adsorberharzen XAD-2 und XAD-7

Herbicide chlorophenoxy acetic acids can be isolated by the macroreticular adsorbing resins Dowex Amberlite XAD-2, XAD-4, XAD-7 and XAD-8. The adsorption of phenoxy acetic acids reaches an optimum at pH 2 and flow rates of about 5 bed-volumes per minute. Elution depends on the polarity and contact time of the eluent. A quantitative isolation of chlorophenoxy acids in the 25 ppb range in water can be achieved by adsorption at the divinylstyrolresin XAD-2 following elution with acetone. Further concentration of the eluate is possible by standard methods.     

An Investigation on the Concentration Efficiencies of Some Macroreticular and Ambersorb Resins Using Radio-Labelled Organic Contaminants Commonly Encountered in Water

Abstract

The extraction efficiencies of the three commercially available Ambersorb®, carbonaceous, polymeric resins, XE-340, XE-347 and XE-348 were evaluated for their use as sorbents for environmental pollutants using four model, radio-labelled water-borne organic contaminants. Their accumulation behaviour was compared with that of the thoroughly-studied Amberlite®, macroreticular XAD-2 (hydrophobic) and XAD-7 (hydrophilic) resins. These model compounds were desorbed from the resins using known volumes of commonly-used solvents to select the solvent for a particular resin(s). In this preliminary study, at <4 μg/L concentrations of the labelled compounds in aqueous solution (pH 5.78), the order of extraction efficiency of the resins was found to be XAD-2 > XAD-7 > XE-340?-347?-348 for organics. Several inherent impurities originally present in the carbonaceous resins were desorbed by solvents during elution. These resins therefore required exhaustive soxhlet purification prior to use. Most of the impurities were identified by gas chromatography/mass spectrometry.     

2-噻吩乙酸在三种不同树脂上的吸附热力学和动力学研究

通过静态吸附实验,研究了XAD-4,NDA-100和ND-90吸附树脂对水溶液中2-噻吩乙酸的吸附热力学及动力学特性,结果表明,2-噻吩乙酸在XAD-4树脂上是单层吸附,符合Langmuir等温吸附方程,吸附过程符合准一级动力学吸附方程.2-噻吩乙酸在NDA-100和ND-90树脂上的吸附也能用Langmuir等温吸附方程表示,但并不只是单层吸附,而主要是由毛细管凝聚和微孔填充作用造成的吸附,吸附过程可分为大孔和中孔区的吸附以及微孔区的吸附两个阶段,两个阶段都符合准一级动力学吸附方程.     

Fast volatilization of some lanthanide and actinide elements from titanium surfaces

Summary The ad- and desorption of trace quantities of the lanthanide elements lanthanum, praseodymium, neodymium, samarium, europium, gadolinium, dysprosium, and ytterbium and of the actinide elements americium and curium were investigated by thermochromatographic and isothermal measurements with hot titanium columns. The adsorption enthalpies deduced from the experimental data are in reasonable agreement with calculated values which indicate considerable variations in volatility under such conditions. More volatile elements can quickly be separated from less volatile elements by heating the mixture on titanium in high vacuum.

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Schnelle Verflüchtigung einiger Lanthanidenund Aktinidenelemente von Titanoberflächen

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Dedicated to Prof. Dr. G. Tölg on the occasion of his 60th birthday

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Part of a Doctoral Thesis, Mainz 1987     

2-噻吩乙酸在3种树脂上的吸附行为研究

通过静态吸附实验 ,研究了XAD 4、NDA 10 0和ND 90吸附树脂对水溶液中 2 噻吩乙酸的吸附热力学及动力学特性 ,结果表明 ,2 噻吩乙酸在XAD 4树脂上是单层吸附 ,符合Langmuir等温吸附方程 ,吸附过程符合准一级动力学吸附方程 .2 噻吩乙酸在NDA 10 0和ND 90树脂上的吸附也能用Langmuir等温吸附方程表示 ,但并不只是单层吸附而主要是由毛细管凝聚和微孔填充作用造成的 ,吸附过程可分为大孔和中孔区的吸附以及微孔区的吸附两个阶段 ,两个阶段都符合准一级动力学吸附方程     

Comparative study of breakthrough volumes BTV on various sorbents

Summary Breakthrough volumes on ten sorbents (Chromosorb 102, 104, 105 and 106, Porapak R and S, XAD-2, XAD-7, Tenax GC and Carbosphere) have been determined for vapours of 15 volatile organic compounds (halogenated hydrocarbons, alcohols, etc.). The volumes were determined by an indirect method employing typical chromatographic parameters such as retention volume and peak width.The method seems to be useful for preliminary estimation of adsorption capacity of various sorbents. It is not suitable, however, for the investigation of the effect of various parameters on the breakthrough volume.

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Vergleichende Untersuchung des Durchbruchsvolumens an verschiedenen Sorbentien

Zusammenfassung An 10 verschiedenen Sorbentien (Chromosorb 102, 104, 105, 106; Porapak R und S; XAD-2; XAD-7; Tenax GC; Carbosphere) wurden für 15 flüchtige organische Verbindungen (halogenierte Kohlenwasserstoffe, Alkohole u. a.) die Durchbruchsvolumina bestimmt. Es wurde dafür ein indirektes Verfahren mit typischen chromatographischen Parametern (Retentionsvolumen, Peakbreite) benutzt. Die Methode erscheint nützlich für die vorläufige Abschätzung der Adsorptionskapazität von Sorbentien, eignet sich jedoch nicht für die Untersuchung des Einflusses verschiedener Parameter auf das Durchbruchsvolumen.

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Part of this research was supported by Institute of Oceanology, Polish Academy of Sciences, Gdask, grant MR. I-15.     

Die papierchromatographische Kristallisation als Methode zur Herstellung von Komplexverbindungen und zur Reinigung von seltenen Elementen, 1. Mitt.

Zusammenfassung Durch papierchromatographische Kristallisation ist es möglich, die Kristallisationsbedingungen für schwer kristallisierende Oxalatokomplexe des Al, Ga, In, Cr, Fe, Zr, Hf, Nb, Ta, Ti, Ge zu ermitteln und die kristallisationshemmenden Oxo- bzw. Hydroxokomplexformen quantitative zu eliminieren.Unter Ausnützung der verschieden großen Wanderungsgeschwindigkeit sowie dem unterschiedlichen Verhalten der Oxalate bzw. Oxalatokomplexe der Verunreinigungen und den dabei auftretenden Verteilungs-, Adsorptions-und Ionenaustauschvorgängen bei der papierchromatographischen Kristallisation kann diese zur Feinstreinigung einiger seltener Elemente wie z. B. Ge, Zr, Nb, Sc, U, In u. a. über Oxalate bzw. Oxalatokomplexe verwendet werden.Die Verteilung der Verunreinigungen während der papier-chromatographischen Kristallisation hat einen komplizierten Charakter und kann nicht durch Adsorption oder mechanische Einfügungen der Mutterlauge allein erklärt werden.

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Paper chromatographic crystallization, a method for the preparation of complex compounds and for the purification of rare elements, I.

With the help of the paper chromatographic crystallization technique it is possible to determine optimum crystallization conditions of the badly crystallizing oxalato complexes of Al, Ga, In, Cr, Fe, Zr, Hf, Nb, Ta, Ti and Ge and to remove quantitatively their crystallization inhibiting oxo and hydroxo complexes, resp. The different migration rates and the behavior of the oxalates and oxalato complexes of the impurities as well as the distribution, adsorption and ion exchange phenomena operative in paper-chromatographic crystallization may be used for ultra-purification of some rare elements by means of their oxalates and oxalato complexes, for instance for Ge, Zr, Nb, Sc, U, In, and others. The distribution of impurities in paper chromatographic crystallization follows a complicated mechanism and is not explainable on the basis of adsorption or mechanical interaction of mother liquors alone.

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Mit 2 Abbildungen     

Adsorption equilibrium and heat of phenol onto aminated polymeric resins from aqueous solution

Aminated polystyrene resins (NDA-101 and NDA-103) were synthesized, and their adsorption performances for phenol in aqueous solution were investigated and compared with the commercial polystyrene resin (Amberlite XAD-4) and weakly basic polystyrene resin (Amberlite IRA-96). All the associated adsorption isotherms are well described by Freundlich and Langmuir equations. The results indicated that all the four resins spontaneously adsorb phenol driven mainly by enthalpy change, and their adsorption capacities, free energy changes, enthalpy changes, and entropy changes for phenol followed the same order as: NDA-101 > NDA-103 > XAD-4 > IRA-96. Surface energy heterogeneity analysis by Do's model also suggested that the surfaces of XAD-4 and IRA-96 were more homogeneous, and the better adsorption capacity and affinity of the aminated resins (NDA-101 and NDA-103) are probably due to their multiple hydrogen bonding and π–π stacking interactions with phenol molecule.     

Adsorption of cesium using supermolecular impregnated XAD-7 composite: isotherms,kinetics and thermodynamics

As an effective cesium complex agent, calix[4]biscrown-6 (CBC) applied at a low cost way is of interest. In this study, CBC/XAD-7 was prepared by embedding CBC into XAD-7. Subsequently the as-prepared sorbent was used for the removal of cesium from aqueous solution as functions of HNO₃ concentration, contact time, temperature and initial cesium concentration. The results revealed that the nitric concentration influenced cesium adsorption by complex and protonation interaction. The most effective adsorption happened at the nitric concentration of 1.0 M. The adsorption isotherm well described with the Langmuir model illustrated a monolayer adsorption. Its maximum adsorption capacity was 24.4 mg/g in the 2 M nitric acid aqueous solution. The adsorption kinetics was in accordance with the pseudo-second order model, which indicated a chemisorption. The thermodynamic parameters demonstrated that the adsorption process was exothermal and spontaneous. In addition CBC/XAD-7 showed highly selective recognition toward cesium and good reusability. The study offered an economical and effective material for cesium removal.

     

Treatment and Determination of Organophosphorous Pesticides in Waste Water by Using Continuous Flow Methodologies Coupled On Line With High Performance Liquid Chromatography

Abstract

The treatment of waste water containing three organophosphorous pesticides: diazinon, azinphos-methyl and fenthion by using continuous flow methodologies coupled on line with HPLC-UV detection is presented.

Two continuous flow techniques: completely continuous flow and flow injection, both combined with two separation methods: liquid-liquid extraction and adsorption resins are discussed, as well as the influence of physical and chemical parameters on the analysis.

Adsorption resins seem to be more suitalbe for the treatment of waste water at low pesticide concentraions while liquid-liquid extraction is more selective.     

Trennung chemisch sehr nahe verwandter Elemente durch Fällung unter Dekomplexierung mittels Austausch-und Verdrängungsreaktionen (Displacement)

Zusammenfassung Durch einen gekoppelten Komplex-Dissoziations-Assoziationsvorgang derSE-ÄDTE-Komplexe mit Co-, Cu- oder Ni-Salzlösungen werden dieSE-Kationen beliebig langsam entwickelt und bei Anwesenheit von Fällungsmitteln dieSE-Ionen nach den Bedingungen der Fällung im homogenen Medium selektiv gefällt. Es werden wirkungsame Trennungen bzw. Reinstdarstellung der Ceriterden und insbesondere die Reindarstellung von Pr und Nd beschrieben.

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Separation of very closely related elements by precipitation and simultaneous decomplexation accompanied by exchange and displacement reactions.

Rare earth ions were found to be released from theirEDTA complexes at arbitrary rates in acoupled dissociation-association reaction with Co-, Cu- and Ni-salts, respectively. In the presence of precipiting in agents the rare earth ions are selectively precipitated in homogeneous media. Highly effective separations, preparation of ultra-pure samples of the cerite metals and the preparation of pure samples of Pr and Nd are described.

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Mit 2 Abbildungen     

Adsorption studies of tannic acid by commercial ester resin XAD-7

<正>Tannic acid and its related compounds are known as refractory organic pollutants,and it can create serious problems for the environment.The adsorption and desorption studies of tannic acid on commercial resins XAD-7 and D-201 are performed,and all data indicates resin XAD-7 can be used as an effective adsorbent for removing tannic acid during water/wastewater treatment.Furthermore,adsorption thermodynamics studies indicate different adsorption mechanisms for TA on XAD-7 and D-201.FT-IR and solid state ~(13)C-NMR spectroscopy are used to explain the adsorption force between XAD-7 and TA.It suggests that hydrogen bonding is the main adsorption force for TA.Finally,XAD-7's adsorption capacity in the presence of different metal ions is investigated,which indicates that heavy metal ions in solutions can decrease the adsorption capacity for TA on ester resin XAD-7.     

超高交联吸附树脂吸附对硝基苯乙酮的热力学研究

比较两种超高交联聚苯乙烯吸附树脂NJ-8、AM-1与Amberlite XAD-4(以下简称XAD-4)对对硝基苯乙酮的静态吸附行为，根据吸附等温线研究了吸附热力学性质．在298～318K和研究的浓度范围内，NJ-8，AM-1、XAD-4对对硝基苯乙酮的吸附平衡数据符合Freundlich吸附等温方程．结果表明：吸附为放热过程，适当降低温度有利于吸附．计算了对硝基苯乙酮在NJ-8，AM-1、XAD-4树脂上的吸附焓变、自由能变，吸附熵变．对吸附行为作了合理的解释。     

Comparative Enrichment Capabilities of Some Carbonaceous and Macroreticular Resins Using Selected Radioactive Model Compounds in Fortified Aqueous Samples

Abstract

The concentration efficiency of synthetic macroreticular resins, XAD-2 and XAD-7 and carbonaceous resins, XE-340, XE-347 and XE-348 was evaluated and compared using trace levels of eight radioactive model environmental contaminants present in aqueous medium. Influences of chemical functionalities of the solvents, physical characteristics of the sorbents, and pH of the aqueous medium on sorption of the model compounds were investigated under frontal dynamic chromatographic conditions. The elution behavior of these sorbates and desorption properties of the polymer adsorbents with respect to solvents of different polarities were studied.