Extraction of strontium with dicarbolide in the presence of polyethylene glycol

1979 ◽  
Vol 44 (1) ◽  
pp. 157-166 ◽  
Author(s):  
Petr Vaňura ◽  
Jiří Rais ◽  
Pavel Selucký ◽  
Miroslav Kyrš

The extraction of microquantities of 85Sr in the presence of 3 . 10-4 - 0.25 mol l-1 polyethylene glycol (PEG 400) (L) with solutions of dicarbolide ({(π-(3)-1,2-B9C2H11)2Co}-) in nitrobenzene (10-3 - 10-2M) was investigated. The occurrence of the maxima (up to one order of magnitude) on the plots of the strontium distribution ratio vs the total PEG concentration was explained in terms of the competition between the charged strontium-PEG complex (SrL2+) and protonized PEG (HL+) during the balancing of the dicarbolide electrostatic charge in the organic phase. Theoretical relations were derived for the shape of this dependence, for the effect of the acid concentration in the aqueous phase and that of the dicarbolide concentration in the organic phase, as well as for the positions of the corresponding maxima. The theoretical dependences are in accordance with the experimental data. The values of the concentration equilibrium constants of the reactions Sr2+ + L + 2 H+ ##e SrL2+ + 2 H+ (Kex(SrL2+)) and H+ + L ##e HL+ (Kex(HL+)) (for variable ionic strength) are Kex(SrL2+) = 3.26 . 108 and Kex(HL+) = 538 at 25 °C.

1984 ◽  
Vol 49 (6) ◽  
pp. 1367-1381 ◽  
Author(s):  
Petr Vaňura ◽  
Marie Benešová ◽  
Emanuel Makrlík ◽  
Miroslav Kyrš ◽  
Jiří Rais

Extraction of microamounts of 152, 154 Eu from the aqueous solutions of perchloric acid (c(HClO4) = 0.1-0.5 mol l-1) was studied in the presence of 3 . 10-4 -0.3 mol l-1 of polyethylene glycol PEG 400 (L) by the nitrobenzene solutions of Co(III)-dicarbolide (3.3'-commo-bis(undecahydro-1,2-dicarba-3-cobalta-closo-dodecarborate) (-1), {(π-(3)-1,2-B9C2H11)2Co}-, henceforth only B-) of the concentration c(dicarbolide) = 10-3-10-1 mol l-1. Maxima of the Eu distribution ratio dependence on the concentration of polyethylene glycol are explained by the competition reactions between the positively charged europium complexes (EuL3+, EuLH-12+, and EuL23+, EuL2H-22+, or EuL33+) and protonized polyethylene glycol (HL+) in the organic phase. The respective equilibrium extraction constants were determined.


1982 ◽  
Vol 47 (5) ◽  
pp. 1444-1464 ◽  
Author(s):  
Petr Vaňura ◽  
Emanuel Makrlík ◽  
Jiří Rais ◽  
Miroslav Kyrš

Extraction of microamounts of Sr2+ and Ba2+ from 0.2-1.0M-HClO4 by the nitrobenzene solutions of dicarbolide H+[Co(C2B9H11)2]- in the presence of polyethylene glycols (PEG) (Mr = 200, 300, 400) has been investigated. It has been found that the extraction of the protonized polyethylene glycol molecule (H+ + L ##e HL+, where the bar denotes species present in the organic phase) and the extraction of the complex between the extracted ion and polyethylene glycol, i.e., M2+ +L + 2 H+ ##e ML2+ + 2 H+, are the predominant reactions in this system. The respective equilibrium constants have been determined. The hydration numbers of HL+ and ML2+ ions in the organic phase have been obtained from the determination of water content by Karl Fischer titration method. The extraction constants and stability constants in the organic phase increase in the sequence H+ < Sr2+ < Ba2+ and PEG 200 < PEG 300 < PEG 400, while the hydration numbers decrease in the same sequence. Correlations between the hydration numbers and the extraction constants for these cations have been found.


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.


1986 ◽  
Vol 51 (3) ◽  
pp. 498-515 ◽  
Author(s):  
Emanuel Makrlík ◽  
Petr Vaňura

Extraction of Eu3+ and Ce3+ microamounts from 0.1-0.4M perchloric acid by the nitrobenzene solution of dicarbolide H+[Co(C2B9H11)2]- in the presence of polyethylene glycols (Mr = 200, 300, 400) has been studied. The equilibrium data and the typical maxima on the dependence of the metal distribution ratio on the total analytical concentration of polyethylene glycol in the system can be explained assuming that the species ML3+org, ML3+2org, ML3+3org, MLH2+-1org, and HL+org (where M3+ = Eu3+, Ce3+; L = polyethylene glycol) are extracted into the organic phase. The values of extraction and equilibrium constants in the organic phase were determined and the effect of the polyethylene glycol molecular weight on the equilibrium constants and on the abundances of individual species in the organic phase is discussed. It has been found that the addition of polyethylene glycol to the acid - nitrobezene - dicarbolide system increases the values of the separation factors αCe/Eu.


1982 ◽  
Vol 35 (11) ◽  
pp. 2345 ◽  
Author(s):  
R Paimin ◽  
RW Cattrall

The extraction of cobalt(II) by Aliquat 336R from 7 M lithium chloride solutions involves two species from the aqueous phase, COCl42 and CoCl3-, with the former being the predominant one. The equilibrium constants for the formation of the extracted complexes (R3MeN+)2 CoCl42- and R3MeN+CoCI3- are: logKll 5.01 and logK12 9.55. From the results of experiments by means of the single-drop technique, a mechanism is proposed based on the formation of interfacial complexes by fast ion-exchange with a rate-determining step which involves the replacement at the interface of the complex (R3MeN+)2 COCl42- by two molar proportions of reagent from the bulk organic phase.


1980 ◽  
Vol 45 (11) ◽  
pp. 3116-3129 ◽  
Author(s):  
Petr Vaňura ◽  
Libor Kuča

The composition of Fe(III) complexes extracted from the aqueous phase of constant ionic strength (1M-(H3,Na3,Fe)A, where H3A denotes citric acid) by the toluene solution of trilaurylamine (TLA) has been determined and the respective extraction constants have been calculated. In the concentration range cFe < 10-2 mol l-1 FeA(TLA)2 and FeA(TLA)4(H3A)2-4 are the predominant complexes in the organic phase. The abundance of the (FeA)3(TLA)6(H3A)2 complex in the organic phase increases at higher equilibrium concentrations of Fe(III) in the aqueous phase and at higher concentrations of TLA.


2014 ◽  
Vol 1665 ◽  
pp. 111-116 ◽  
Author(s):  
I. Puigdomènech ◽  
E. Colàs ◽  
M. Grivé ◽  
I. Campos ◽  
D. García

ABSTRACTA set of computer programs has been developed to draw chemical-equilibrium diagrams. This new software is the Java-language equivalent to the Medusa/Hydra software (developed some time ago in Visual basic at the Royal Institute of Technology, Stockholm, Sweden). The main program, now named “Spana” calls Java programs based on the HaltaFall algorithm. The equilibrium constants that are needed for the calculations may be retrieved from a database included in the software package (“Database” program). This new software is intended for undergraduate students as well as researchers and professionals.The “Spana” code can be easily applied to perform radionuclide speciation and solubility calculations of minerals, including solubility calculations relevant for the performance assessment of a nuclear waste repository. In order to handle ionic strength corrections in such calculations several approaches can be applied. The “Spana” code is able to perform calculations based on three models: the Davies equation; an approximation to the model by Helgeson et al. (HKF); and the Specific Ion-Interaction Theory (SIT). Default SIT-coefficients may be used, which widens the applicability of SIT significantly.A comparison is made here among the different ionic strength approaches used by “Spana” (Davies, HKF, SIT) when modelling the chemistry of radionuclides and minerals of interest under the conditions of a geological repository for nuclear waste. For this purpose, amorphous hydrous Thorium(IV) oxide (ThO2(am)), Gypsum (CaSO4·2H2O) and Portlandite (Ca(OH)2) solubility at high ionic strengths have been modelled and compared to experimental data from the literature. Results show a good fitting between the calculated values and the experimental data especially for the SIT approach in a wide range of ionic strengths (0-4 M).


1980 ◽  
Vol 45 (4) ◽  
pp. 1221-1226 ◽  
Author(s):  
Oldřich Navrátil ◽  
Pavel Linhart

The partition of 1-phenyl-3-methyl-4-benzoylpyrazolone-5 (HA) between aqueous solutions of HClO4 and NaClO4, ionic strength 0.1, and Freon 113 or its 2 : 1 mixture with benzene was studied. The logarithms of the HA distribution constants are 2.84 ± 0.10 and 3.39 ± 0.15 for the two organic phases, respectively. The extraction curves of cerium(III) and europium(III) revealed that in dependence on the pH of the aqueous phase, the metals are transferred into the organic phase in the form of the MA3 complexes (M = Ce, Eu). The stability constants of the complexes MAn in the aqueous phase were determined along with their distribution and extraction constants. For cobalt, zinc, and hafnium, a part of the extraction curves could only be studied, only the extraction constants were therefore determined. The sparing solubility of HA in Freon 113 can be circumvented by using a Freon-benzene mixture 2 : 1, which is still practically incombustible.


2013 ◽  
Vol 2013 ◽  
pp. 1-7 ◽  
Author(s):  
Nazan Karapinar ◽  
Emin Karapinar ◽  
Emine Ozcan

Liquid-liquid extraction of various alkalis (Li+, Na+, K+, and Cs+), transition metals (Co2+, Ni2+, Cu2+, Zn2+, Cd2+, and Hg2+), and Pb2+cations with phenylglyoxime (L1), p-tolylglyoxime (L2),N′-(4′-Benzo[15-crown-5])phenylaminoglyoxime (L3), andN′-(4′-Benzo[15-crown-5])-p-tolylaminoglyoxime (L4) from the aqueous phase into the organic phase was carried out. For comparison, the corresponding two glyoximes and their macrocyclic glyoxime ether derivatives were also examined. Crown ether groups having ligands (L3,L4) carry especially Na+cation from aqueous phase to organic phase. The extraction equilibrium constants (Kex) for complexes of ligands with Cu2+and Hg2+metal picrates between dichloromethane and water have been determined at 25°C. The values of the extraction constants (logKex) were determined to be 12.27, 13.37, 12.94, and 12.39 for Cu2+and 10.29, 10.62, 11.53, and 11.97 for Hg2+with L1–L4, respectively.


2006 ◽  
Vol 985 ◽  
Author(s):  
Teodora Valeria Retegan ◽  
Christian Ekberg ◽  
Anna Fermvik ◽  
Gunnar Skarnemark

AbstractA screening experiment was carried out where the organic phase consisted of different concentrations of 2,6-bis-(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-benzo[1,2,4]triazy-3-yl)-[2,2']bipyridinyl (CyMe4-BTBP) [1], which is the extracting molecule, dissolved in different diluents. The aqueous phase consisted of 0.01 M HNO3 and was spiked with trace amounts of 241Am and 152Eu acting as analogues for actinides and lanthanides. The ionic strength was kept constant at 1.0 M using NaNO3. Three of the selected diluents used to dissolve CyMe4-BTBP were abandoned: n-hexane, TPH and TBB. Another extraction experiment screened out anisole, 1,1,2,2-tetrachloroethane and benzaldehyde.A kinetic experiment was then performed. Three very different kinetic behaviors were observed in three different organic systems. For a proper understanding of the kinetic mechanism, further investigations are needed.


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