Lætitia H. Delmau

Calix[4]pyrrole: A New Ion-Pair Receptor As Demonstrated by Liquid-Liquid Extraction

Solvent-extraction studies provide confirming evidence that meso-octamethylcalix[4]pyrrole acts as an ion-pair receptor for cesium chloride and cesium bromide in nitrobenzene solution. The stoichiometry of the interaction under extraction conditions from water to nitrobenzene was determined from plots of the cesium distribution ratios vs cesium salt and receptor concentration, indicating the formation of an ion-paired 1:1:1 cesium:calix[4]pyrrole:halide complex. The extraction results were modeled to evaluate the equilibria inherent to the solvent-extraction system, with either chloride or bromide. The binding energy between the halide anion and the calix[4]pyrrole was found to be about 7 kJ/mol larger for cesium chloride than for the cesium bromide. The ion-pairing free energies between the calix[4]pyrrole-halide complex and the cesium cation are nearly the same within experimental uncertainty for either halide, consistent with a structural model in which the Cs+ cation resides in the calix bowl. These results are unexpected since nitrobenzene is a polar solvent that generally leads to dissociated complexes in the organic phase when used as a diluent in extraction studies of univalent ions. Control studies involving nitrate revealed no evidence of ion pairing for CsNO3 under conditions identical to those where it is observed for CsCl and CsBr.

A ROBUST ALKALINE-SIDE CSEX SOLVENT SUITABLE FOR REMOVING CESIUM FROM SAVANNAH RIVER HIGH LEVEL WASTE#

ABSTRACT A robust solvent suitable for extracting cesium from alkaline nitrate media like that of the high-level liquid waste stored at the U.S. Department of Energy Savannah River Site has been developed. The solvent is composed of the cesium extractant calix[4]arene-bis-(tert-octylbenzo-crown-6) (“BOBCalixC6”) at 0.01 M, the modifier l-(2,2,3,3-tetrafluoropropoxy)-3-(4-sec-butylphenoxy)-2-propanol (“Cs-7SBT”) at 0.50 M, trioctylamine (“TOA”) at 0.001 M, and the aliphatic diluent Isopar® L. The solvent holds up exceptionally well under various stresses, such as sustained contact with waste simulant and dilute nitric acid; repeated extraction, scrubbing, and stripping cycles; and excessive loading. The behavior of the solvent in batch-equilibrium flowsheet tests conducted at 15, 25, and 45 °C is presented. Flowsheet calculations show that the Savannah River Site requirements for a decontamination factor of 40,000 and a cesium concentration factor of 12 could be met in a 22-stage bank of 25-cm centrifugal contactors at 25 °C with conservative assumptions regarding hydrodynamics and stage efficiency. Exploiting the temperature dependence of extraction and stripping could reduce the number of stages to 18.

Rigidified Calixarenes Bearing Four Carbamoylmethylphosphineoxide or Carbamoylmethylphosphoryl Functions at the Wide Rim

Conformationally rigidified tetraCMPO derivatives have been prepared from calix[4]arene bis(crown ether) 4a in which adjacent oxygens are bridged at the narrow rim by two diethylene glycol links. Acylation of the tetraamine 4c with the CMPO-active ester 5b gave the tetraphosphine oxide 6a, while the tetraphosphinate 6b and the tetraphosphonate 6c were obtained by Arbuzov reaction of tetrabromoacetamido derivative 7 with PhP(OEt)2 or P(OEt)3. The extraction ability of these CMPO derivatives was checked for selected lanthanides and actinides and compared with the analogous compounds 1b, 10b and 10d derived from calix[4]arene tetrapentyl ether. All rigidified bis(crown ether) ligands are more effective extractants than their pentyl ether counterparts and require only 1/10 of the concentration (cL= 10 4M) to obtain the same distribution coefficients, while with CMPO itself a 2,000-fold concentration is necessary. This could be a consequence of a better preorganisation of the ligating functions owing to the rigidity which on the other hand did not change the observed selectivity for americium (DAm/DEu=9-19) and for light lanthanides over heavy ones. NMR relaxivity titration curves show that the complex of Gd3+ with ligand 6a is highly oligomerised in anhydrous acetonitrile over a large range of ligand:metal concentration ratios. Nuclear magnetic relaxation dispersion (NMRD) profiles also showed that large oligomers were formed, and their mean tumbling times were deduced from the Solomon-Bloembergen-Morgan equations. The NMR spectra of dia- and paramagnetic lanthanide complexes with 6a agreed with the presence of two conformers with an elongated calix[4]arene skeleton in which the distances between opposite methylene groups are different. Contrary to what was observed with ligand 2a, the addition of nitrate ions does not labilize the metal complexes, presumably because of the rigidification effect of the ether bridges. Single-crystal X-ray structures were obtained for the active ester 5b and for diphenylphosphorylacetic acid 5a.

DEVELOPMENT OF A SOLVENT EXTRACTION PROCESS FOR CESIUM REMOVAL FROM SRS TANK WASTE

An alkaline-side solvent extraction process was developed for cesium removal from Savannah River Site (SRS) tank waste. The process was invented at Oak Ridge National Laboratory and developed and tested at Argonne National Laboratory using singlestage and multistage tests in a laboratory-scale centrifugal contactor. The dispersion number, hydraulic performance, stage efficiency, and general operability of the process flowsheet were determined. Based on these tests, further solvent development work was done. The final solvent formulation appears to be an excellent candidate for removing cesium from SRS tank waste.

Development of Effective Solvent Modifiers for the Solvent Extraction of Cesium from Alkaline High‐Level Tank Waste

Abstract A series of novel alkylphenoxy fluorinated alcohols were prepared and investigated for their effectiveness as modifiers in solvents containing calix[4]arene‐bis‐(tert‐octylbenzo)‐crown‐6 for the extraction of cesium from alkaline nitrate media. The structure of the fluorinated portion of the modifier influences the chemical stability, and a modifier that contained a terminal 1,1,2,2‐tetrafluoroethoxy group was found to decompose following long‐term exposure to warm alkaline solutions. However, replacement of the tetrafluoroethoxy group with a 2,2,3,3‐tetrafluoropropoxy group led to a series of modifiers that possessed the alkaline stability required for a solvent extraction process. Within this series of modifiers, the structure of the alkyl substituent (tert‐octyl, tert‐butyl, tert‐amyl, and sec‐butyl) of the alkylphenoxy moiety was found to have a profound impact on the phase behavior of the solvent in liquid–liquid contacting experiments, and hence on the overall suitability of the modifier for a solvent extraction process. The sec‐butyl derivative [1‐(2,2,3,3‐tetrafluoropropoxy)‐3‐(4‐sec‐butylphenoxy)‐2‐propanol] (Cs‐7SB) was found to possess the best overall balance of properties with respect to third phase and coalescence behavior, cleanup following degradation, resistance to solids formation, and cesium distribution behavior. Accordingly, this modifier was selected for use as a component of the solvent employed in the Caustic‐Side Solvent Extraction (CSSX) process designed for the removal of cesium from high‐level nuclear waste (HLW) at the U.S. Department of Energys (DOE) Savannah River Site. In batch equilibrium experiments, this solvent has also been successfully shown to extract cesium from both simulated and actual solutions generated from caustic leaching of HLW tank sludge stored in tank B‐110 at the DOEs Hanford Site.

Supramolecular Chemistry of Environmentally Relevant Anions

Publisher Summary This chapter discusses supramolecular chemistry of environmentally relevant anions. The ultimate goal of the studies on the basic chemical aspects of anion receptor design of functional pH-independent systems is to target selective binding of anions of environmental significance. In applications-oriented aspects of the research on the design of separations, strategies for selective and efficient removal of targeted anions have been a major long-term goal. The chapter discusses (1) some of the first synthetic sulfate-selective anion-binding agents; (2) simple, structure-based methods for modifying the intrinsic anion selectivity of a given class of anion receptors; and (3) the first system capable of extracting sulfate anion from acidic, nitrate-containing aqueous media. These initial findings point the way to more effective systems involving receptors with higher selectivity, binding strength, and solubility. The evolution of anion-binding ligands from simple ammonium-based systems through mixed amide/amine and thioamide/amine receptors is reviewed. Thus, the emphasis is largely on synthetic design strategy carried out in the Bowman–James group.

Fundamental Chemistry of Cesium Extraction from Acidic Media by HCCD in FS‐13

Abstract We previously published a model for cesium extraction from acidic media by the protonated form of the hexachlorinated derivative of the chloro‐protected cobalt bis(dicarbollide), HCCD, dissolved in trifluoromethylphenyl sulfone, FS‐13. The model indicated that Cs extraction proceeds through a series of ion‐paired and/or dissociated extraction equilibria. Additional Cs distribution ratio data has been obtained and the model refined and simplified. It is demonstrated that the equilibrium exclusively involving the exchange of proton for cesium by formation of ion‐paired CsCCD models the Cs distribution data very well, particularly for the concentrations of HCCD greater than ∼0.0005 M (0.5 mM). Finally, activity corrections for the aqueous phase to the Cs distribution data results in good agreement to the theoretical value of −1 for slope (log‐log) analysis of the data over a wide range of HNO3 and HCCD concentrations.

EXTRACTION OF TRIVALENT LANTHANIDES AND ACTINIDES BY “CMPO-LIKE” CALIXARENES

ABSTRACT Extractive properties of calix[4]arenes bearing carhamoylmethylphosphine oxide moieties on their upper rim toward trivalent lanthanide and actinide cations were investigated. The study revealed that these molecules selectively extract light lanthanides and actinides from heavy lanthanides. All parameters present in the extraction system were varied to determine the origin of the selectivity. It was found that this selectivity requires a calix[4]arene platform and acetamidophosphine oxide groups containing phenyl substituents on the four phosphorus atoms.

A solution to stripping problems caused by organophilic anion impurities in crown-ether-based solvent extraction systems: a case study of cesium removal from radioactive wastes

Abstract A problem related to stripping efficiency has been identified in the use of crown ether derivatives to extract alkali metal salts, and a simple solution is proposed. Focusing on the specific case of cesium extraction from simulants of alkaline nuclear waste by a calix-crown ether, calix[4]arene-bis( tert -octylbenzo-crown-6) (BOBCalixC6), it has been shown that low concentrations of a common surfactant, dodecylsulfonate, seriously impairs stripping. This surfactant has been identified as a trace component in laboratory simulants and was subsequently studied in experiments in which it was added in controlled amounts. Computer modeling of stripping behavior is consistent with the formation of a 1:1:1 organic-phase complex of the calix-crown with cesium and its nitrate counterion. In the presence of an organophilic surfactant anion, cesium ion can only effectively be stripped from the solvent until its organic-phase concentration becomes equivalent to that of the surfactant anion. Cleanup of nuclear waste requires a high decontamination factor for 137 Cs, and insufficient stripping therefore leads to process failure. This difficulty raises a generic issue for use of crown ethers for waste decontamination or for other hydrometallurgical applications. However, remediation is possible by simply adding an alkylamine to the solvent. The alkylamine in its ammonium form acts as a counterion of the organophilic anion, suppressing the deleterious effects of the organophilic anion and allowing the cesium cation to be stripped efficiently. Trioctylamine (TOA) at a concentration of only 1 mM was found effective at restoring stripping performance while not affecting extraction. Ultimately, this solvent amendment enabled the development of a robust solvent for the Caustic-Side Solvent Extraction (CSSX) process and its successful demonstration on actual nuclear waste.

SOLVATOCHROMIC SOLVENT POLARITY MEASUREMENTS OF ALCOHOL SOLVENT MODIFIERS AND CORRELATION WITH CESIUM EXTRACTION STRENGTH

Solvatochromic solvent polarity measurements reveal that the cesium extraction strength afforded by solutions composed of calix[4]arene-bis-(tert-octylbenzocrown-6) at 0.005 M in 1,2-dichloroethane containing a variety of novel alcohol phase modifiers at 0.25 M correlates well with the hydrogen-bond donor (HBD) ability of the alcohol. The alcohols comprise a small library of derivatives of 2-(4-tert-octylphenoxy)-1-ethanol, in which the alcohol carbon atom contains a substituent of variable electron-withdrawing ability. The betaine dye 4-(2,4,6-triphenylpyridinium)-2,6-diphenylphenoxide, also known as Dimroth-Reichardt dye #30, was used to obtain ET(30) and ET N values. Alcohols containing substituents with fluorine atoms gave rise to both higher ET N values and higher cesium distribution values. The trend observed in HDB parallels the expected trend in alcohol acidity. †This research was sponsored by the Office of Science, Office of Basic Energy Sciences, U.S. Department of Energy, under contract number DE-AC05-00OR22725 with Oak Ridge National Laboratory, managed and operated by UT-Battelle, LLC.