A REVIEW OF THIRD PHASE FORMATION IN EXTRACTION OF ACTINIDES BY NEUTRAL ORGANOPHOSPHORUS EXTRACTANTS

ABSTRACT

Data are reviewed on the formation of third phase in the extraction of acti-nide(IV.VI) nitrates by neutral organophosphorus extractants, mainly tributyl phosphate. The data are critically evaluated and the effect of variables on the third phase formation is discussed. The variables are the concentrations of nitric acid and the extractant, temperature, the nature of diluent, addition of modifiers and the ionic strength of the aqueous phase. Also discussed are systems involving two extracted actinide ions.     

有机相微生物活细胞催化羰基不对称还原反应的研究进展

介绍了近１０年来在有机介质中以微生物活细胞作为生物催化剂催化羰基化合物不对称还原反应的最新进展,分析了有机相中影响微生物催化及立体选择性的因素,并列举了一些反应实例。     

INTERMOLECULAR INTERACTION AND PARTITION CONSTANTS OF METAL 77rJS-ACETYLACETONATES A SHORT THEORETICAL REVIEW

ABSTRACT

Predicting the effectiveness of liquid-liquid extraction of metal chelates and choosing optimal extraction reagents requires several characteristics of the components of the extraction system to be taken into consideration. This paper provides an analysis of the factors that affect the value of the partition constant of a chelate and the possibilities to predict the value of the partition constant from the nature of the metal ion, the structure of the chelating reagent, and the organogenic elements, one might have expected these techniques to be capable to predict the partition constants of chelates as well. However, the problem of determining the increments of metals turned out to be very difficult even in the case of relatively simple complexes. An analysis of the partition constants of coordinatively-saturated metal acetylacetonates has shown that the values depend on a large number of parameters, some of which are correlated. The central metal atom modifies the donor properties of the heteroatoms in the extraction reagent molecule to such a great extent that one cannot assign them the increments valid for the free reagent molecule.

Obviously, much more sophisticated models are needed for properly determining the contribution of each fragment in this complex system with numerous inner relations. Such models cannot ignore various intermolecular interactions occurring in the extration systems and will inevitably use the theories that describe them quantitatively, some of which have been reviewed in this paper.     

POLYNITROGEN REAGENTS,IN METAL SEPARATION. PART 5 THE EXTRACTION OF URANIUM(VI) FROM SULPHURIC,NITRIC AND HYDROCHLORIC ACID MEDIA WITH ALKYLDIAMHONIUM EXTRACTANTS.

ABSTRACT

A variety of a1kyldiammonium extractants (tertiary and quaternary) were used to extract uranium(VI) from sulphuric, nitric and hydrochloric acid media. The performance of these extractants was compared with that of Aliquat-336 and Alamine-336. Extractions from dilute uranium(VI) solutions were carried out in order to simulate conditions employed in the local mining industry     

A REVIEW OF THE INDUSTRIAL AND RECENT POTENTIAL APPLICATIONS OF TRIOCTYLPHOSPHINE OXIDE

ABSTRACT

The industrial applications of trioctylphosphine oxide, more commonly known as TOPO, make use of its complexing powers with metals and with hydrogen donor organic compounds. Commercial uses as a solvent extraction reagent are in the recovery of uranium from wet process phosphoric acid and in the recovery of byproduct acetic acid and furfural generated during sulphite wood pulping. Recently investigated potential uses include the separation of niobium from tantalum and the extraction of organic compounds, such as citric acid, from fermentation broths. Each process is discussed briefly.     

APPLICATION OF EXTRACTION AND ION EXCHANGE CHROMATOGRAPHIC TECHNIQUES FOR THE SEPARATION OF METAL ION MIXTURES: PROBLEMS AND PERSPECTIVES

ABSTRACT

This paper describes new perspectives for the development and wider application of extraction and ion-exchange chromatography for separation of metal ion mixtures. The stabilization of extraction chromatographic materials by different techniques, the evaluation of changes in the behaviour of immobilized reagents (extractants or water-soluble ligands) as compared to those in their “free” state, and the combination of extraction and ion-exchange within one fractionation technique are considered and discussed along with some related problems.     

离子交换膜扩散系数的测定方法评述

本文叙述了电解质通过离子交换的扩散系数，离子的相互扩散系数及自扩散系数的测定方法，原理，推导了有关公式，并对有些方法作了评述和实验上的比较。     

UPTAKE OF METAL IONS BY A NEW CHELATING ION-EXCHANGE RESIN. PART 2: ACID DEPENDENCIES OF TRANSITION AND POST-TRANSITION METAL IONS*

ABSTRACT

Diphonix^(tm)is a new dual-mechanism polyfunctional resin containing sulfonic and gem-diphosphonic acid groups. In Part 1 of this series the effectiveness of Diphonix in removing actinide ions from very acidic solutions was demonstrated. In this paper we report on the uptake of various transition and post-transition metal ions with Diphonix and two other resins for comparison. The results show that Diphonix has a very high affinity for Fe(III) and Cr(III) in very acidic solutions. From neutral solutions Diphonix exhibits a high selectivity for lead and transition metals over calcium. Conditions for efficient stripping of the investigated ions have been found.     

UPTAKE OF METAL IONS BY A NEW CHELATING ION EXCHANGE RESIN. PART 8 : SIMULTANEOUS UPTAKE OF CATIONIC AND ANIONIC SPECIES* *

ABSTRACT

The uptake of tri-, tetra- and hexa-valent actinides as well as of pertechnetate anions by some new multifunctional ion exchange resins has been investigated. The new resins, identified as Diphonix A, for anionic Diphonix, contain the same geminally substituted diphosphonic acid groups bonded to a styrenic-based polymer matrix as the regular Diphonix resin, plus strong base anion exchange groups such as the tetraalkylammonium (Diphonix A - Type 1 resins) or the quaternized pyridinium (Diphonix A - Type 2 resins) groups. Our uptake measurements have shown that the Type 2 Diphonix A resins are as effective as the regular Diphonix resin in the rapid uptake of actinides from acidic solutions, while at the same time sorbing pertechnetate anions in a manner comparable to existing commercial anion exchange resins. The failure of the Type 1 Diphonix A resins to perform equally well has been explained as a consequence of the mutual interaction of adjacent diphosphonic acid groups and tetraalkylammonium groups. Uptake data have also been obtained with Se(IV). The behavior of the Diphonix A resins toward Se(IV) uptake in acidic solutions is comparable to that of commercial anion exchange resins.     

CORRELATION OF THE EXTRACTION OF STRONTIUM NITRATE BY A CROWN ETHER WITH THE WATER CONTENT OF THE ORGANIC PHASE*

A simple correlation has been observed between the extraction of strontium nitrate from nitric acid solution by cis-dicyclohexano-18-Crown-6 dissolved in a variety of oxygenated, aliphatic diluents and the molarity of water present in the organic phase. This correlation is attributed to the extraction of the hydrated nitrate ion and its solvation by the diluent, facilitated by the high concentration of dissolved water. Of the solvents studied, ketones yield the largest values of the extraction constant for a given water content, although C₅ and C₆ alcohols give the highest overall values.     

NEW XANTHIC ACID DERIVATIVES AS POTENTIAL REAGENTS IN THE SOLVENT EXTRACTION OF PRECIOUS METAL IONS: EXTRACTION OF PALLADIUM(II) WITH 13-BIS(0-BUTYLXANTHATO)PROPANE

ABSTRACT

Two series of new xanthic acid derivatives namely, the bis (O-butylxanthato) alkanes ( abbreviated as BBXAs or simply as bis-xanthates in this paper) have been synthesized in connection with the solvent extraction of precious metal ions. From an aqueous medium containing 0.1 M NaC10₄ (1 M=l mol dm^-3), these compounds exhibited high selectivity for extraction of Pd(II) and Ag(I) in dichloroethane, over most of the base metals as well as Pt(IV) and Au(III) ions. Towards Pd(II) and Ag(I) ions, the bis compounds act as SS chelating agents where the stabilities of the extractable complexes are determined by the length of the alkylene chain existing between the donor atoms. Pd(II) extraction has been studied in detail taking 13-bis(O-n-butylxanthato)propane (BnBXP) as the representative member of the series of bis-xanthates synthesized in this work. The extraction of palladium(II) was found to be quite slow in pure chloride medium. But, a mixed acid medium containing H₂SO₄ or HNO₃ in the presence of smaller amount of chloride ion provided optimum reversible extraction of palladium in dichloroethane, where Pd(II) forms 1:1 extractabic complexes with BnBXP. Pd(II) extraction is described in terms of the aqueous phase compositions, extraction and back-extraction data, extraction equilibrium, selectivity considerations and probable mechanisms of extraction.     

MATHEMATICAL MODEL OF L-LACTIC ACID FERMENTATION IN A RDC COUPLED WITH PRODUCT SEPARATION BY ION EXCHANGE

A Rotating Disk Contactor (RDC) was designed to perform the L-lactic acid fermentation with a filamentous fungus, Rhizopus oryzae, which was immobilized on the surface of rotating disks. The bioreactor was operated in repeated batch or continuous modes. The growth rate of the fungi was about 1 mm/day perpendicular to the disks' surface. A weak-base anionic resin, D354, was selected which was high in selectivity for lactic acid separation. Even at low concentration, the ion exchange capability was about 0.5 g Lac/g dry resin. A coupled process of L-lactic acid fermentation and ion-exchange separation was evaluated experimentally. The results indicated that the pH value of the fermentation broth could be maintained at pH 3.5 without any addition of alkali. The conversion ratio of glucose to L-lactic acid was about 0.7 g/g and the fermentation rate was able to reach as high as 62.5g glucose per hour per square meter of the disk surface area. A mathematical model was proposed to describe the simultaneous process of L-lactic acid fermentation and separation by ion exchange, in which the thickness increase of mycelia as well as the substrate and product inhibitions were included. The model simulation was in good agreement with the experimental data.     

THE APPLICATIONS OF A GENERALIZED EQUATION OF STATE TO THE CORRELATION AND PREDICTION OF PHASE EQUILIBRIA*

Two methods of generalizing an equation of state are demonstrated and their limitations are outlined. One method involves the correlation of the equation of state constants and the second method involves a recently proposed Generalized Corresponding States Principle based on the properties of two (nonspherical) reference fluids. The PVT properties of pure fluids are represented by a new cubic equation of slate with four parameters which are obtained from vapor pressure and saturated liquid density data. It is demonstrated how a limited amount of data on key components may be used to obtain phase equilibria in mixtures.     

USE OF ALUMINUM METAL IN THE CERAMIC INDUSTRY: II,EFFECT OF COATING INSULATING FIREBRICK WITH ALUMINUM-FIRE-CLAY MIXTURES*

After insulating firebrick are reheated in service, many of them contract too much and develop large open shrinkage cracks. By first applying to the surfaces a 0.035-in. coating composed of aluminum and fire clay, these brick usually remain intact and constant in size when they are reheated. The coating also becomes hard, causing the brick to become more resistant to abrasion, slag action, permeability of gases, load at high temperatures, and sudden temperature changes. Coatings composed of 60 to 70% of fire clay and 30 to 40% of aluminum powder were found to overcome most of these deficiencies in insulating firebrick.     

THE USE OF OZONATION TO REDUCE THE POTENTIAL FOR FORMING TRIHALOMETHANE COMPOUNDS IN CHLORINATING RESORCINOL, PHLOROGLUCINOL AND 1,3 CYCLOHEXANEDIONE

This study concerns the ozonation of Resorcinol, Phloroglucinol and 1,3 Cyclohexanedione in the presence of bromide ion in a bubble column, prior to chlorination. Preozonation in aqueous solutions reduces the potential for forming chlorinated trihalomethane compounds. At organic concentrations greater than 10^-4 M a short ozonation time increases the potential for forming trihalo compounds. At longer ozonation times the reverse is true. Finally the influence of mass transfer and chemical reaction on the ozone absorption rate have been evaluated following the film theory.     

THE USE OF OZONATION TO REDUCE THE POTENTIAL FOR FORMING TRIHALOMETHANE COMPOUNDS IN CHLORINATING RESORCINOL,PHLOROGLUCINOL AND 1,3 CYCLOHEXANEDIONE

This study concerns the ozonation of Resorcinol, Phloroglucinol and 1,3 Cyclohexanedione in the presence of bromide ion in a bubble column, prior to chlorination. Preozonation in aqueous solutions reduces the potential for forming chlorinated trihalomethane compounds. At organic concentrations greater than 10^?4?M a short ozonation time increases the potential for forming trihalo compounds. At longer ozonation times the reverse is true. Finally the influence of mass transfer and chemical reaction on the ozone absorption rate have been evaluated following the film theory.