A method for selective separation of scandium (III) from yttrium and a number of rare-earth elements for its subsequent determination

2018 ◽  
Vol 84 (11) ◽  
pp. 23-27
Author(s):  
M. I. Degtev ◽  
A. A. Yuminova ◽  
A. S. Maksimov ◽  
A. P. Medvedev

The possibility of using an aqueous stratified system of antipyrine — sulfosalicylic acid — water for the selective isolation of scandium macro- and microquantities for subsequent determination is studied. The proposed extraction system eliminates the usage of toxic organic solvents. The organic phase with a volume of 1.2 to 2.0 ml, resulting from delamination of the aqueous phase containing antipyrine and sulfosalicylic acid is analysed to assess the possibility of using such systems for metal ions extraction. Condition necessary for the formation of such a phase were specified: the ratio of the initial components, their concentration, presence of inorganic salting out agents. The optimum ratio of antipyrine to sulfosalicylic acid is 2:1 at concentrations of 0.6 and 0.3 mol/liter in a volume of the aqueous phase of 10 ml. The obtained phase which consists of antipyrinium sulfosalicylate, free antipyrine and water, quantitatively extracts macro- and microquantities of scandium at pH = 1.54. Macro- and microquantities of yttrium, terbium, lanthanum, ytterbium and gadolinium are not extracted under the aforementioned conditions thus providing selective isolation of scandium from the bases containing yttrium, ytterbium, terbium, lanthanum, and gadolinium.

Author(s):  
Mikhail I. Degtev ◽  
Aleksandra A. Yuminova

The possibilities of an aqueous delaminating system containing antipyrine (AP) and sulfosalicylic acid (SSA) for extracting macro - and microamounts of thorium (IV) were studied. The proposed extraction system eliminates the use of toxic organic solvents. The dependences of the distribution of metal from nitrate solutions between phases on the concentration of reagents, acidity of the medium, the amount of inorganic salting-out agent (NaNO3, NH4NO3, Na2SO4) and the volume of the aqueous phase are determined, and optimal conditions for extraction are found. It is shown that in the organic phase with a volume of 1.6 ml at room temperature, macro-and microamounts of thorium (IV) are extracted by 88 and 90%, respectively. The maximum extraction of the cation is achieved at the ratio of AP: SSA = 2.0 : 1.0 and their concentration, mol/l: 0.6: 0.3, while the acidity of the medium created by nitric acid should be equal to 0.015 mol/l (pHequ. = 1.8-1.9). The extraction of thorium (IV) becomes quantitative if inorganic salts (sodium sulfate, sodium nitrate) are introduced into the AP – SSA – 0,015 mol/l HNO3 – H2O system, which, by reducing the activity of water, increase the concentration of reagents in the aqueous phase. The concentration of salting-out agents should correspond to 1.0 and 2.5 mol/l. A mechanism for the distribution of a mixed thorium (IV) complex containing AP, SSA, nitrate ions, solvated with a salt of antipyrinium sulfosalicylate is proposed. The extract is mixed in any relationship with distilled water, providing the use of various instrumental methods of analysis. A method for extraction-photometric determination of thorium (IV) with a toron indicator has been developed. The limit for the fulfillment of the Bouguer-Lambert-Beer law is established. The apparent coefficient of light absorption is calculated (ε = 1.7∙104).


Author(s):  
Alexander V. Val'kov ◽  
Nadezhda D. Khmelevskaya

Results of studying of extraction of nitrates of rare-earth elements (REE) and trialkylmetylammoniya nitrate (TAMAN) are given by mixes of isomers of tributyl phosphate (TBP). Tri-iso-butylphosphate and tri - sec-butylphosphate are investigated as isomers of normal tributylphosphate. The water phase contained 8 mol/dm3 nitrate of ammonium and 5.10-4 mol/dm3 of neodymium nitrate at рН = 2-3. The content of extractants in isomolar series was varied in the range of 0-0.3 mol/dm3. It was established that synergistic effect decreases in a series of TBP> TIBP> TvtBP. Synergistic effect is calculated as the distribution coefficient relation at extraction by mix of extractants to the sum of coefficients of distribution at extraction by each of extractants. Synergistic effect reaches its maximum value at the ratio: [NPOC] : [TAMAN] = 2 : 1 for TBP and 4-5 : 1 for TiBP, TvtBP, and the absolute value fluctuates within 10-50 at extraction of microconcentration of REE. It is noted that the method of isomolar series is applied incorrectly in many researches with the violation of the fundamental requirements (variable concentration of rare earth metals and acid in the aqueous phase, an assumption of a possibility of simultaneous existence of several solvate, variable concentration of salting-out owing to extraction into the organic phase, the association and polymerization in the organic phase, etc..), which must be followed when using this method. Мultiple saturation method (MSM) is offered for a correct application of the method of isomolar series. The method consists in the fact that the organic phase is saturated repeatedly (5-6 times) with the original aqueous solution until a constant composition of the aqueous phase at all points of  isomolar series. It is possible to believe that the organic phase is responsible for the deviation from the additivity in this case. It was established that synergistic effect tends to unity or virtually disappears in the extraction of REE macroamounts method of ofisomolar series of multiple saturation. It is shown that value of synergistic effect approaches unity at gadolinium nitrate extraction by isomolar mix in the MSM mode. Synergistic effect for a mixture of rare earth elements is close to unity in the extraction of REE mixtures macroamounts of TiBP and TAMAN, and the individual elements are distributed in accordance with the extraction characteristics of each of the extractants alone: synergistic effect for several elements of cerium is greater than one, and yttrium - somewhat less than one. It is suggested that if there is free extragent the formation of mixed solvate may be explained by the steric effect, which disappears at saturation of extracgent.Forcitation:Val'kov A.V., Khmelevskaya N.D. Extraction of rare-earth elements by mixes of isomers of tributylphosphate with nitrate trialkylmethylammonium. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2018. V. 61. N 7. P. 54-60


1979 ◽  
Vol 44 (12) ◽  
pp. 3656-3664
Author(s):  
Oldřich Navrátil ◽  
Jiří Smola ◽  
Rostislav Kolouch

Extraction of hafnium(IV) was studied from solutions of mixtures of perchloric and nitric acids and of perchloric and hydrochloric acids for constant ionic strength, I = 2, 4, 6, or 8, and for cHf 4 . 10-4 mol l-1. The organic phase was constituted by solutions of some acidic or neutral organophosphorus reagents or of 2-thenoyltrifluoroacetone, 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone, or N-benzoyl-N-phenylhydroxylamine in benzene, chloroform, or n-octane. A pronounced synergic extraction of hafnium proceeds only on applying organophosphorus reagents from an aqueous phase whose acidity is not lower than 3M-(HClO4 + HNO3) or 5M-(HClO4 + HCl). The synergic effect was not affected markedly by a variation of the initial concentration of hafnium in the range 1 . 10-8 -4 .10-4 mol l-1, it lowered with increasing initial concentration of the organophosphorus reagent and decreasing concentration of the H+ ions. It is suggested that the hafnium passes into the organic phase in the form of mixed complexes, the salting-out effect of perchloric acid playing an appreciable part.


2012 ◽  
Vol 65 (11) ◽  
pp. 1548 ◽  
Author(s):  
Yuki Kohno ◽  
Nobuhumi Nakamura ◽  
Hiroyuki Ohno

Mixtures of some ionic liquids (ILs) and water show reversible phase change between a homogeneous mixture and phase-separated state by a small change in temperature. Some water-soluble proteins have been migrated from the aqueous to the IL phase. When tetrabutylphosphonium 2,4,6-trimethylbenzenesulfonate was used as an IL, cytochrome c (Cyt.c) was found to be extracted from the water phase to the IL phase. Conversely, both horseradish peroxidase (HRP) and azurin remained in the aqueous phase. This selective extraction was comprehended to be due to the difference in solubility of these proteins in both phases. The separated aqueous phase contained a small amount of IL, which induced the salting-out of Cyt.c. On the other hand, condensed IL phase promoted the salting-in of Cyt.c. As a result, Cyt.c was preferably dissolved in the hydrated IL phase rather than aqueous phase. In the case of HRP, there was only a salting-out profile upon increasing the concentration of IL, which induced selective dissolution of HRP in the aqueous phase. These results clearly suggest that the profile of salting-out and salting-in for proteins is the key factor to facilitate the selective extraction of proteins from aqueous to the IL phase.


Author(s):  
Nurul Ain Ismail

Using a two-level factorial design, a study was undertaken to change the parameters impacting the recovery of rare earth from rare earth mixture. The experimental design was used to screen and identify the major contributing aspects to rare earth recovery. The experiment aims to isolate samarium from a mixture of samarium, europium, and gadolinium. Factors involved consist of pH (pH 1 and pH 6), acid type (nitric acid and hydrochloric acid) and concentration (1.0M and 5.0M), mixing duration (30 min and 120 min), feed composition (20% samarium and 80% samarium), type of diluent (hexane and chloroform), temperature (room temperature and 60°C) and organic to aqueous phase ratio (1:1 and 2:1). The results showed that the samarium recovery was in the range of 0.98% to 90.88%. Based on analysis variance (ANOVA), five factors significantly affect the samarium recovery out of eight factors explored. The five factors according to the most significant order are pH> feed composition> organic to aqueous phase ratio>acid concentration>acid type>mixing duration>type of diluent> temperature.  Statistical analysis shows that the linear model is significant, with the value of R2 is 0.9886. Based on the statistical data, five significant variables influence the separation of samarium. This research shows that two-level factorial design can anticipate significant variables impacting rare earth separation, particularly samarium, in the solvent extraction process.


1979 ◽  
Vol 44 (8) ◽  
pp. 2366-2372 ◽  
Author(s):  
Věra Jedináková ◽  
Jana Cibulková ◽  
Libor Kuča

The extraction of Am(III) with benzyldibutylamine from nitrate medium was examined in dependence on the concentration of nitric acid, kind and concentration of the salting-out agent in the aqueous phase, and on the solvent. Am(III) is extracted into the organic phase in the form of {(R3NH+)α, Am(NO3)52-}. The IR spectra of the organic phase are discussed and confronted with the results of the chemical analysis of the organic phase. The extraction of Am(III) and of lanthanoids was found to be considerably higher than that of some products of corrosion and nuclear fission (Cs, Sr, Zr, Fe), which is documented by the high values of the separation factors.


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