ABSTRACT
We studied the extraction behavior of two thioglycolate-based ionic liquids (ILs), for heavy metals from aqueous solutions; substances of interest were methyltrioctylammonium S-hexyl thioglycolate [N1888][C6SAc] and methyltrioctylphosphonium S-hexyl thioglycolate [P1888][C6SAc]. Theses ILs previously have shown very good extraction abilities towards cadmium and copper, therefore we investigated time-dependent metal removal experiments with aqueous solutions of cobalt(II), nickel(II) and zinc(II). The highest distribution ratio (RIL/Water) was determined for zinc (RIL/Water=2000). Recovery studies for zinc after extraction were performed with different stripping agents showing a successful recycling. Additionally, the two ILs were immobilized on active charcoal, displaying great potential for solid-liquid extraction. Regarding the extraction mechanism, quantum-mechanical calculations were included, which indicate that the metal extraction depends on the stability of the metal-water cluster. Ligands (water as well as ILs) are planar coordinated in nickel complexes but showed a tetrahedral configuration for zinc. As a first estimate of the ecotoxicity of the ILs, in vivo tests toward three freshwater green algae species Tetradesmus obliquus, Desmodesmus armatus and Raphidocelis subcapitata were carried out. The EC50 values (effective concentration after 72 h) confirm high toxicity of all tested ILs to all species, displaying only small differences between the species and EC50ies.
Subject(s)
Ionic Liquids/chemistry , Metals, Heavy/chemistry , Thioglycolates/chemistry , Water Pollutants, Chemical/chemistry , Chlorophyta/drug effects , Chlorophyta/growth & development , Ionic Liquids/toxicity , Thioglycolates/toxicityABSTRACT
Eight novel task-specific ionic liquids (TSILs) based on the thioglycolate anion designed for heavy metal extraction have been prepared and characterized by 1H and 13C NMR, UV-Vis, infrared, ESI-MS, conductivity, viscosity, density and thermal properties. Evaluation of their time-resolved extraction abilities towards cadmium(II) and copper(II) in aqueous solutions have been investigated where distribution ratios up to 1200 were observed. For elucidation of the IL extraction mode, crystals were grown where Cd(II) was converted with an excess of S-butyl thioglycolate. It was found by X-ray diffraction analysis that cadmium is coordinated by five oxygen and one sulfur donor atoms provided by two thioglycolate molecules and one water molecule. Leaching behavior of the hydrophobic ionic liquids into aqueous systems was studied by TOC (total dissolved organic carbon) measurements. Additionally, the immobilization on polypropylene was elucidated and revealed slower metal extraction rates and similar leaching behavior. Finally, recovery processes for cadmium and copper after extraction were performed and recyclability was successfully proven for both metals.
ABSTRACT
This study aims to develop novel ammonium and phosphonium ionic liquids (ILs) with thiosalicylate (TS) derivatives as anions and evaluate their extracting efficiencies towards heavy metals in aqueous solutions. Six ILs were synthesized, characterized, and investigated for their extracting efficacies for cadmium, copper, and zinc. Liquid-liquid extractions of Cu, Zn, or Cd with ILs after 1-24h using model solutions (pH 7; 0.1M CaCl2) were assessed using flame atomic absorption spectroscopy (F-AAS). Phosphonium-based ILs trihexyltetradecylphosphonium 2-(propylthio)benzoate [P66614][PTB] and 2-(benzylthio)benzoate [P66614][BTB] showed best extraction efficiency for copper and cadmium, respectively and zinc was extracted to a high degree by [P66614][BTB] exclusively.
ABSTRACT
Two novel maltol-based ionic liquids, namely [A336][Mal] and [C101][Mal], were synthesized as potential extracting agents for radionuclides from water. These two room temperature task-specific ionic liquids could be easily prepared by anion metathesis starting from commercially available materials. The isolated compounds were characterized by standard analytical methods. Their application as extraction agent for Unat., 234Th, 210Pb, 210Bi, 210Po and 226Ra was elucidated by liquid-liquid extraction and scintillation counting. Uranium was totally extracted by both ionic liquids over a broad pH range (2-8), while the other radionuclides were removed with differing efficacies depending on the respective pH value.
