Thermodynamic and Spectroscopic Studies on Am(III) and Eu(III) in the Extraction System of N,N,N',N'-Tetraoctyl-3-Oxapentane-1,5-Diamide in n-Dodecane/Nitric Acid

Abstract

Thermodynamic parameters (ΔG, ΔH, and ΔS) for the extraction of trivalent f-elements, M(III) (M = Am, Eu), with N,N,N',N'-tetraoctyl-3-oxapentane-1,5-diamide (TODGA) were determined in nitric acid/n-dodecane extraction system. The extraction of M(III) with TODGA was more exothermic than those with octyl(phenyl)-N,N-diisobutylcarbamoylmethyl phosphine oxide (CMPO) and dihexyl-N,N-diethylcarbamoylmethyl phosphonate (DHDECMP). The difference in ΔH between the extractants was attributed to the difference in the binding mode between them, i.e. tridentate (TODGA) and bidentate (CMPO and DHDECMP). In addition, from the results of luminescence lifetime measurement, it was found that the inner-sphere of extracted Eu(III) was dehydrated completely, and occupied by TODGA and/or NO₃ ^?.     

Carrier Facilitated Transport of Europium(III) Across Supported Liquid Membranes Containing N,N,N′,N′-tetra-2-ethylhexyl-3-oxapentane-diamide (T2EHDGA) as the Extractant

Studies on the solvent extraction and pertraction behavior of europium(III) was carried out from acidic feed solutions using N,N,N′,N′-tetra-2-ethylhexyl-3-oxapentane-diamide (T2EHDGA) in n-dodecane as the solvent. The nature of the extracted species from the solvent extraction studies conformed to Eu(NO₃)₃ · 3T2EHDGA which is in variance with the analogous Eu(III) – TODGA (linear homolog of T2EHDGA) extraction system. The transport behavior of Eu(III) was investigated from a feed containing 3.0 M HNO₃ into a receiver phase containing 0.01 M HNO₃ across a PTFE flat sheet supported liquid membrane (SLM) containing 0.2 M T2EHDGA in n-dodecane as the carrier solvent and 30% iso-decanol as the phase modifier. Effects of feed acidity, carrier extractant concentration, membrane pore size, and Eu concentration in the feed on the transport rates of Eu(III) were also investigated. Membrane diffusion coefficient (D _o) for the pertracted species was calculated using the Wilke-Chang equation as 4.25 × 10^?6 cm² · s^?1. The influence of Eu concentration on the flux was also investigated. The role of temperature on the transport rates was investigated and the thermodynamic parameters were calculated.     

Extraction Behavior of Am(III) and Eu(III) from Nitric Acid Medium in Tetraoctyldiglycolamide-Bis(2-Ethylhexyl)Phosphoric Acid Solution

The extraction behavior of Am(III) and Eu(III) in a solution of tetra-octyldiglycolamide (TODGA), bis(2-ethylhexyl)phosphoric acid (HDEHP), and n-dodecane (n-DD) was studied to understand the role of TODGA and HDEHP in the combined solvent system. The extraction behavior of these metal ions was compared with those observed in TODGA/n-DD and HDEHP/n-DD. The effect of various parameters such as concentrations of HNO₃, TODGA, and HDEHP on the distribution ratio of Am(III) and Eu(III) was studied. Synergistic extraction of both the metal ions observed at lower acidities (<2.0 M) was attributed to the involvement of TODGA and HDEHP for extraction. However, the extraction of Am(III) and Eu(III) in the combined solvent was comparable with that observed in TODGA at higher acidities. The slope analysis of the extraction data confirmed the involvement of both the extractants at all acidities investigated in the present study.     

Extraction of Europium(III) into W/O Microemulsion Containing Aerosol OT and a Bulky Diamide. I. Cooperative Effect

Abstract

The extraction of Eu(III) from aqueous HNO₃ solution into a water‐in‐oil (W/O) microemulsion occurring in hexane was studied. Aerosol OT (AOT^?) was used as an anionic surfactant, and a bulky diamide (DA), N,N ^′‐dioctyl‐N,N ^′‐dimethyl‐2‐(3^′‐oxapentadecyl)propane‐1,3‐diamide, was employed as an electrically neutral extractant. The combination of AOT^? and the DA shows a very strong cooperative effect on the metal extraction. The microemulsion containing AOT^? alone in hexane, equilibrated with the acidic solution, is unstable. However, in the presence of the electrically neutral extractant acting as a “masking” ligand to H⁺, the microemulsion in the hexane phase is dramatically stabilized, which enhances the distribution of Eu(III) to the organic phase. The distribution of the metal in the micellar extraction system is also greatly affected by the concentration of an electrolyte, such as HNO₃ or NaNO₃, playing two important roles, i.e., the formation of the microemulsion, “promoting” the metal extraction, and the ion‐exchange of the metal ion for the cation yielded from the electrolyte, contrarily, “suppressing” the metal extraction.     

Extraction of Lanthanides(III) and Am(III) by Mixtures of Malonamide and Dialkylphosphoric Acid

Abstract

N,N′‐dimethyl‐N,N′‐dioctylhexylethoxymalonamide, DMDOHEMA, and di‐n‐hexylphosphoric acid, HDHP, are the extractants of reference for the French DIAMEX–SANEX process for the separation of trivalent actinide ions from the lanthanide ions. In this work, the extraction of Eu³⁺ and Am³⁺ by the two extractants, alone or in mixtures, has been investigated under a variety of experimental conditions. The two cations are extracted by HDHP as the M(DHP · HDHP)₃ complexes with an Eu/Am separation factor of ～10. With DMDOHEMA, Eu³⁺ and Am³⁺ are extracted as the M(NO₃)₃(DMDOHEMA)₂ disolvate species with an Am/Eu separation factor of ～2. The metal distribution ratios measured with a mixture of the two reagents indicated that almost all lanthanides are extracted equally well. The extraction of Eu³⁺ and Am³⁺ by HDHP‐DMDOHEMA mixtures exhibits a change of extraction mechanism and a reversal of selectivity taking place at ～1 M HNO₃ in the aqueous phase. Below this aqueous acidity, HDHP dominates the metal extraction by the mixture, whereas DMDOHEMA is the predominant extractant at higher aqueous acidities. Some measurements indicated apparent modest antagonism between the two extractants in the extraction of Eu³⁺ and synergism in the extraction of Am³⁺. These data were interpreted as resulting from the formation in the organic phase of mixed HDHP‐DMDOHEMA species containing two HDHP and five DMDOHEMA molecules.     

Extraction of Lanthanides(III) from Aqueous Nitrate Media with Tetra‐(p‐tolyl)[(o‐Phenylene)Oxymethylene] Diphosphine Dioxide

A novel tridentate neutral organophosphorus compound, tetra‐(p‐tolyl)[(o‐phenylene)oxymethylene] diphosphine dioxide (I) has been synthesized and its extracting ability for microquantities of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y from HNO₃ and NH₄NO₃ aqueous solutions has been studied. The effect of HNO₃ concentration in the aqueous phase and that of the extractant concentration in the organic phase on the extraction of metal ions is considered. The stoichiometry of the extracted complexes and conditional extraction constants of Ln(III) have been determined. The extraction behavior of compound I is compared with that of the diglycolamide ligand TODGA. The potentialities of polymeric resin impregnated with compound I for the preconcentration of lanthanides(III) from nitric acid solutions are demonstrated.     

Supercritical Fluid Dissolution and Extraction of Trivalent Metal Cations from Different Matrices

Studies on the recovery of trivalent metal ions such as Nd³⁺Eu³⁺ (taken as homologs of Am(III)) from solid oxide (Nd₂O₃), Thorium concentrate (obtained from Monazite ore processing), tissue paper/surgical gloves (rubber), and plant samples have been carried out by supercritical fluid extraction (SFE) using supercritical CO₂ and ethanol/nitric acid. N,N,N’,N’-tetraoctyl diglycolamide (TODGA) was used as the extractant in these studies. The results showed that the recovery of Nd increased with TODGA concentration from 50% (no TODGA) to 70% (10% TODGA) at 3 M HNO₃ in ethanol. However, the extraction of Nd at 1 M HNO₃ was invariant with 1-3% (v/v) TODGA concentration (73 ± 4%). Interestingly, REEs recovery from Th concentrate was ? 60% even without TODGA using ethanol/3 M HNO₃ mixture. On the other hand, quantitative recovery of ^152,154Eu from tissue paper and surgical gloves sample could be achieved using 3 M HNO₃/ethanol mixture. This suggested that it would be possible to decontaminate the contaminated laboratory waste papers using SFE technique.     

Synergistic Extraction of Lanthanides (III) with Mixtures of TODGA and Hydrophobic Ionic Liquid into Molecular Diluent

The extraction of lanthanides(III) from aqueous nitric acid solutions with N,N,N’,N’-tetra(n-octyl)diglycolamide (TODGA) and with mixtures of TODGA and the hydrophobic ionic liquid (IL) [C₄mim][Tf₂N] into 1,2-dichloroethane (DCE) has been investigated. The extraction efficiency of Ln(III) ions was greatly enhanced by the addition of a small amount of IL to an organic phase containing TODGA. The synergistic effect comes from the higher hydrophobicity of Ln(III) extracted species formed by TODGA and the weakly coordinating Tf₂N^? anions compared with those formed by TODGA and NO₃^? ions as the counter-anions. The partition of Tf₂N^? anions between the organic and aqueous phases is the dominant factor governing the extractability of lanthanides(III) with mixtures of TODGA and [C₄mim][Tf₂N]. The extraction of Ln(III) from aqueous nitric acid solutions by TODGA alone and its mixtures with [C₄mim][Tf₂N] into DCE can be described on the basis of the solvation extraction mechanism. However, in the extraction system with added [C₄mim][Tf₂N], the partition of Tf₂N^? between two immiscible phases and the interaction between HTf₂N and TODGA in the organic phase should be taken into account. Possible reasons of the antagonistic effect in the TODGA–[C₄mim][Tf₂N] extraction system are discussed.     

Complexation of Eu(III) with Dibutyl Phosphate and Tributyl Phosphate

Abstract

The complexation of Ln(III) with tributyl phosphate (TBP) in the presence of dibutyl phosphate (HDBP) is of importance for the smooth operation of the plutonium uranium refining extraction (PUREX) process. The time resolved laser‐induced fluorescence spectroscopy (TRLFS) and extraction experiments were employed to study the complexation of Eu(III) with TBP or HDBP and their mixture. The emphasis was on the inner‐sphere hydration numbers and emission spectra of the Eu(III) extracted complexes. The results show that the HNO₃ loading in the organic phase influences not only the distribution ratio but also the emission spectra, as well as the hydration numbers of the complexes. For the Eu‐TBP complexes, one water molecule remained at low HNO₃ loading in the organic phase, and it would be removed at enhanced HNO₃ loading. For the Eu‐HDBP complexes, one water molecule remained at low or high HNO₃ loading. For the Eu‐HDBP/TBP or Eu‐HDBP/30%TBP, more than one species formed and third phase with different chemical form appeared at low HNO₃ loading. The possible species of Eu(III) complexes formed under various conditions were proposed and discussed.     

Actinide(III)/Lanthanide(III) Separation Via Selective Aqueous Complexation of Actinides(III) using a Hydrophilic 2,6-Bis(1,2,4-Triazin-3-Yl)-Pyridine in Nitric Acid

i-SANEX is a process for separating actinides(III) from used nuclear fuels by solvent extraction: Actinides(III) and lanthanides(III) are co-extracted from a PUREX raffinate followed by selective back extraction of actinides(III) from the loaded organic phase. This step requires a complexing agent selective for actinides(III). A hydrophilic sulfonated bis triazinyl pyridine (SO₃-Ph-BTP) was synthesized and tested for selective complexation of actinides(III) in nitric acid solution. When co-extracting Am(III) and Eu(III) from nitric acid into TODGA, adding SO₃-Ph-BTP to the aqueous phase suppresses Am(III) extraction while Eu(III) is extracted. Separation factors in the range of 1000 are achieved. SO₃-Ph-BTP remains active in nitric acid up to 2 mol/L. As a result of this performance, buffering or salting-out agents are not needed in the aqueous phase; nitric acid is used to keep the lanthanides(III) in the TODGA solvent. These properties make SO₃-Ph-BTP a suitable candidate for i-SANEX process development.     

Extraction of U(VI), Th(IV), and Lanthanides(III) from Nitric Acid Solutions with CMPO-Functionalized Ionic Liquid in Molecular Diluents

The extraction of microquantities of U(VI), Th(IV), and lanthanides(III) from nitric acid solutions with CMPO-functionalized ionic liquid 1-[3[[(diphenylphosphinyl)acetyl]amino]propyl]-3-tetradecyl-1H-imidazol-3-ium hexafluorophosphate, CMPO-FIL(I) in molecular organic diluents has been studied. The effect of HNO₃ concentration in the aqueous phase and that of extractant concentration in the organic phase on the extraction of metal ions is considered. The stoichiometry of the extracted complexes was determined. CMPO-FIL(I) demonstrates greater extraction ability towards Ln(III) than its neutral CMPO analog, diphenylphosphorylacetic acid N-nonylamide. This inner synergistic effect increases with a decreasing organic diluent polarity. The partition of CMPO-FIL(I) between the equilibrium organic and aqueous phases is the dominant factor governing the extractability of Ln(III) ions in the extraction system.     

2,2′‐(Methylimino)bis(N,N‐dioctylacetamide) (MIDOA), A New Tridentate Extractant for Technetium(VII), Rhenium(VII), Palladium(II), and Plutonium(IV)

2,2′‐(Methylimino)bis(N,N‐dioctylacetamide) (MIDOA) was developed as a new extractant for technetium. MIDOA has a similar backbone to TODGA, N,N,N′,N′‐tetraoctyldiglycolamide, where the nitrogen atom bearing a methyl group replaces the ether oxygen in TODGA. MIDOA is highly lipophilic and ready to use in the HNO₃–n‐dodecane extraction system. The distribution ratio (D) for Tc(VII) is extremely high. In addition, Cr(VI), Re(VII), Mo(VI), W(VI), Pd(II), and Pu(IV) are well extracted by MIDOA. MIDOA has high selectivity toward certain oxometallates. The D(Tc) values decrease gradually with HNO₃, H⁺, and NO₃ ^? concentrations, and the log D vs log [MIDOA] dependence indicates the species extracted to be the 1:1 metal‐ligand complex. It is clear that MIDDA [2,2′‐(methylimino)bis(N,N‐didodecylacetamide)] and IDDA [2,2′‐(imino)bis(N,N‐didodecylacetamide)], which have structures analogous to MIDOA, have similar extraction behavior to that of MIDOA.     

Liquid – Liquid Extraction and Pertraction of Eu(III) from Nitric Acid Medium Using Several Substituted Diglycolamide Extractants

Solvent extraction and supported liquid membrane (SLM) transport properties of Eu(III) from nitric acid feed conditions were investigated using several substituted diglycolamide (DGA) extractants such as N,N,N′N′-tetra-n-octyl diglycolamide (TODGA), N,N,N′N′-tetra(2-ethylhexyl) diglycolamide (T2EHDGA), N,N,N′N′-tetra-n-hexyl diglycolamide (THDGA), N,N,N′N′-tetra-n-pentyl diglycolamide (TPDGA), and N,N,N′N′-tetra-n-decyl diglycolamide (TDDGA). Effects of feed acidity and phase modifier composition on Eu(III) extraction were investigated using the DGAs and the nature of extracted species were ascertained by slope analysis method. The Eu(III) distribution ratio (D_Eu) values were found to decrease in the presence of iso-decanol. In general, the D_Eu values decreased with increased alkyl chain length of the DGA. The extracted species contained only 2 extractant molecules when TPDGA and TDDGA were used while for TODGA about four extractant molecules were found to be present in the extracted species.

The supported liquid membrane transport of Eu(III) was studied under varying experimental conditions using the five DGA extractants. Transport studies using 0.1 M DGA as the extractant suggested the trend as TDDGA > TODGA > T2EHDGA ～ THDGA which significantly changed to TPDGA > THDGA > TODGA > TDDGA > T2EHDGA in the presence of 30% iso-decanol as the phase modifier. The permeability coefficient (P) values were also determined with membranes of varying pore sizes.     

Extraction of Lanthanides(III) with N,N′-Bis(Diphenylphosphinyl-Methylcarbonyl)Diaza-18-Crown-6 in the Presence of Ionic Liquids

The extraction of microquantities of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y from nitric acid solutions into an organic phase containing N,N′-bis(diphenylphosphinyl-methylcarbonyl)diaza-18-crown-6 and ionic liquid (IL) 1-butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide (BMImTf₂N) has been studied. The effect of HNO₃ concentration in the aqueous phase and that of the extractant and IL concentration in the organic phase on the extraction of metal ions is considered. The stoichiometry of the extracted complexes has been determined. A considerable synergistic effect was observed in the presence of IL in the organic phase containing a neutral organophosphorus ligand. This effect is connected with the hydrophobic nature of the IL anion. The partition of IL between the equilibrium organic and aqueous phases is the dominant factor governing the extractability of lanthanide (III) ions in the extraction system. The potentialities of polymeric resin impregnated with compound I and BMImTf₂N for the preconcentration of lanthanides(III) from nitric acid solutions are demonstrated.     

Extraction Behavior of Ln(III) Ions by T2EHDGA/n-Dodecane from Nitric Acid and Sodium Nitrate Solutions

The diglycolamide extractant T2EHDGA has proven to be promising for the separation of lanthanides and minor actinides in high-level nuclear waste reprocessing. This neutral extractant has shown significant extraction capacity for HNO₃ into the nonpolar organic phase, along with hyper-stoichiometric nitrate dependence on extraction of trivalent f-elements. The transport behavior of T2EHDGA/n-dodecane toward trivalent lanthanides is not well understood. This work found a significant increase in distribution ratios for Eu(III) extracted from aqueous HNO₃ media compared with that from NaNO₃. The extraction of Eu(III) from HNO₃ results in a different thermodynamic product than predicted by classic solvent extraction of 3:1 ligand–metal complex as observed with NaNO₃ in FTIR and UV-vis spectroscopy. Experimental distribution measurements in conjunction with mass-action modeling using the solvent extraction modeling program SXLSQI suggest participation of 1 to 2 HNO₃ molecules in the Eu(III)/T2EHDGA complex upon extraction from HNO₃ media, indicative of a mechanism change responsible for the enhanced extraction behavior toward lanthanides in the presence of HNO₃.     

Synergistic Extraction of U(VI), Th(IV), and Lanthanides(III) from Nitric Acid Solutions Using Mixtures of TODGA and Dinonylnaphthalene Sulfonic Acid

The extraction of U(VI), Th(IV), and lanthanides(III) from aqueous nitric acid solutions with mixtures of N,N,N′,N′-tetra(n-octyl)diglycolamide (TODGA) and dinonylnaphtalene sulfonic acid (HDNNS) in n-decane has been investigated. The extraction efficiency of U(VI), Th(IV), and Ln(III) ions is greatly enhanced by addition of HDNNS to an organic phase containing TODGA. The synergistic effect arises from the higher hydrophobicity of U(VI), Th(IV), and Ln(III) extracted species formed by TODGA and DNNS^? anions as compared to those formed by TODGA and NO₃^? ions as counter anions. The synergistic effect for U(VI), Th(IV), and Ln(III) extraction from aqueous nitric acid solutions with mixtures of TODGA and HDNNS becomes weaker when the acidity of the aqueous phase increases. A high synergistic enhancement is accompanied with a high selectivity of Ln(III) extraction from nitric acid solutions.     

Synthesis of Pre‐Organized Bisdiglycolamides (BisDGA) and Study of their Extraction Properties for Actinides(III) and Lanthanides(III)

Bisdiglycolamides 1–9 were synthesized and studied as extracting agents for An(III) and Ln(III) from nitric acid solutions. Compounds 1d‐3 with rigid spacers as m‐xylylene and 6b‐9 with more flexible alkyl chain linkers, show higher selectivity for Eu(III) extraction over Am(III) than diglycolamides (TBDGA, DMDODGA, TODGA) in (50:50)_%Vol HPT/1‐octanol mixture. Am(III) and Eu(III) extraction kinetics are very fast and back‐extraction with more than 99% efficiency of both cations is possible after four times of contact of the loaded solvent with fresh 0.01 mol/L nitric acid solutions.     

Extraction of Trivalent Europium and Americium from Nitric Acid Solution with Bisdiglycolamides

Two bisdiglycolamides (BisDGAs) of N,N,N′′′,N′′′-tetrabutyl-N?,N′′-ethidene bisdiglycolamide (TBE-BisDGA) and N,N,N′′′,N′′′-tetrabutyl-N?,N′′-m-xylylene bisdiglycolamide (TBX-BisDGA) were synthesized. Their extraction behaviors of Eu(III) and Am(III), as well as nitric acid were investigated from nitric acid medium by using n-octanol as diluent. Nitric acid is extracted as the form of HNO₃·(BisDGAs)_0.6 by BisDGAs and the conditional acid uptake constants of TBE-BisDGA and TBX-BisDGA were 0.26 and 0.10, respectively. The distribution ratios of Eu(III) and Am(III) increased with the increase of nitric acid and extractant concentration, whilst decreased with temperature rise. TBX-BisDGA had a stronger extraction power for Eu(III) and Am(III) than TBE-BisDGA. Both of the extractants displayed a higher affinity toward Eu(III) than Am(III). In the examination of the acidity range from 0.5 to 5.0 M, a maximum separation factor SF_{Eu(III)/Am(III)} can reach 8.0 at 3.0 M HNO₃ for TBX-BisDGA; and 10 at 4.0 M HNO₃ for TBE-BisDGA, respectively. Slope analyses showed that Eu(III) and Am(III) are extracted as di-solvated species by TBX-BisDGA or TBE-BisDGA. The extraction mechanism was described and the apparent extraction equilibrium constant as well as Gibbs free energy change, enthalpy change and entropy change were presented. In addition, their Eu(III) complexes were analyzed by using infrared spectra.     

Influence of Extractant Aggregation on the Extraction of Trivalent f‐Element Cations by a Tetraalkyldiglycolamide

Abstract

The influence of nitric acid extraction on the aggregation state of 0.10 M N,N,N′,N′‐tetra‐n‐octyl‐3‐oxapentane‐1,5‐diamide (TODGA) in n‐octane or n‐heptane was studied by small‐angle neutron scattering (SANS) and vapor pressure osmometry (VPO). When the equilibrium concentration of nitric acid in the aqueous phase is less than 0.7 M, TODGA exists as a mixture of monomers and dimers. As the aqueous phase acidity is increased, the extractant molecules form higher aggregates containing up to an average of seven molecules of TODGA. The formation of the larger TODGA aggregates takes place over the same range of aqueous acidities where the extraction of trivalent f‐element cations displays a hyperstoichiometric sixth power nitric acid dependence. This suggests that acid‐driven aggregation of TODGA is responsible for the unusual acid and extractant dependencies observed for the extraction of trivalent metal nitrates with this ligand.     

Extraction of Lanthanides with N,N′‐Dimethyl‐N,N′‐diphenyl‐malonamide and ‐3,6‐dioxaoctanediamide

Abstract

The extraction properties of the trivalent lanthanides (Ln(III)) with the bidentate N,N′‐dimethyl‐N,N′‐diphenyl‐malonamide (MA) and the tetradentate N,N′‐dimethyl‐N,N′‐diphenyl‐3,6‐dioxaoctanediamide (DOODA) were investigated. These diamides formed by coupling two amide groups with methylene and/or ether groups are bidentate for the MA and tetradentate for the DOODA. By adding a previous data regarding the tridentate N,N′‐dimethyl‐N,N′‐diphenyl‐diglycolamide (DGA), these extraction results enabled us systematically study an effect of number of oxygen donor on its extraction behavior of Ln(III). The change in the distribution ratios (Ds) of Lu(III) with an increase in the HNO₃ concentration is greater than that of La(III) in both the MA and DOODA systems. Therefore, the relationship between the D and atomic number, i.e., the lanthanide pattern, changes with the HNO₃ concentration: the Ds decrease with an increasing atomic number at lower HNO₃ concentrations. The Ds of the lighter Ln(III) are similar to the Ds of the heavier Ln(III) at higher HNO₃ concentrations. The number of the extractant in the extracted species for La(III) and Lu(III) obtained from slope analysis at 4 M HNO₃ in the MA system are about 3, while those in the DOODA system are quite different, i.e., 2 for La(III) and 1.5–3 for Lu(III). The comparison of the extractability of Ln(III) by MA, DOODA, and DGA shows that the magnitude of the Ds is in the sequence of MA < DOODA ? DGA. This suggests the introduction of one ether oxygen atom to the principal chain in the diamides leads to a good extractability for the Ln(III) from HNO₃ solution.