Extraction of hafnium(IV) with organophosphorus reagents from solutions of mineral acids mixtures

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.

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.


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.


1988 ◽  
Vol 127 ◽  
Author(s):  
A. Chatt ◽  
R. R. Rao

ABSTRACTThe equilibrium extraction behavior of Eu(III) studied in chloroform solutions containing l-nitroso-2-naphthol (HA), either alone or combined with 2, 2'-dipyridyl, 1, 10-phenanthroline (phen), or trioctylphosphine oxide (TOPO) shows that the metal ion is extracted as either EuA, EuA3.2, 2'-dipyridyl, EuA3·phen, or EuA3·2TOPO, respectively. The synergic effect of phen or TOPO on the extraction of Eu(III) with l-nitroso-2-naphthol is more pronounced over that of 2, 2'-dipyridyl. The carbonate complexation of Eu(III) has been studied in 1.0 M ionic strength solutions at pH 8.0–9.0 and 25 °C using the synergic extraction system of 1-nitrşso-2-naphthol and pheo. The following complexes have been identified: EuCO34, Eu(CO3)2-, Eu(CO3)33-, and Eu(CO3)45- the results suggest that the first two species predominate at carbonate concentrations and pH similar to those found in most groundwaters. The formation constants of these species have been calculated at zero ionic strength using both SIT and ion pairing models.


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.


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.


2019 ◽  
Vol 54 (4) ◽  
pp. 339-346
Author(s):  
AK Karmakar ◽  
RK Biswas ◽  
MF Khatun

The present work reports the extraction behaviors of mineral acids: HClO4, HNO3, HCl and H2SO4 (commonly found in acidic bleed solutions from the hydrometallurgical route of metal extraction processes) by tri-n-octylamine (TOA) dissolved in distilled colorless kerosene. The systems have been investigated as functions of various experimental parameters, such as time, [acid], [TOA], temperature, extraction stage and the organic to aqueous phase volume ratio (O/A). Strippings was also examined. Equilibration time is less than 60 min. The acid concentration in the organic phase at equilibrium is increased with increasing initial acid concentration in the aqueous phase for all systems. However, the is after %extraction decreased with increasing initial acid concentration in the aqueous phase. The % extraction increased remarkably with increasing [TOA] for all cases. Being the ratio of the [acid] in the organic to aqueous phase at equilibrium equal to extraction ratio, D; the log D vs. log [TOA] plot is almost a curve with slope 1 at lower concentration region and with slope ~2 at higher concentration region. The extraction efficiency of TOA varies in the order: HClO4> HNO3> HCl > H2SO4. The acid-base-neutralization (extraction) reactions are exothermic with ΔH value much higher than -57 kJ/mol obtainable for of a strong acid - strong base neutralization. The loading capacity of extractant (g per 100 g TOA) for acids varied in the order: HClO4 (30.69) > HNO3 (20.49) > H2SO4 (17.87) > HCl (10.31). On using lower organic to aqueous phase volume ratio (O/A), the organic phase saturated with acid can be obtained on stage-wise extraction. The extracted organic phase, for all systems (excepting H2SO4-system) under investigation, can be stripped effectively in a single stage by 0.10 g eq/L NaOH solution to the extents of more than 96%. However, for H2SO4-system, two-stage stripping will be found effective. Bangladesh J. Sci. Ind. Res.54(4), 339-346, 2019


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


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.


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.


Sign in / Sign up

Export Citation Format

Share Document