Abstract
This work emphasizes the crucial role of polar solvating molecules known as phase modifiers in solvent‐extraction systems. The focus of these studies was the extraction of cesium by calix[4]arene‐bis(tert‐octylbenzo‐crown‐6) in dodecane modified with various lipophilic alcohols. Results of equilibrium modeling are consistent with aggregation of the alcohol molecules with each other and with the calixarene‐cesium nitrate complexes. These modeling results are supported by electrospray mass spectrometry experiments, clearly showing the alcohol:anion adducts containing several alcohol molecules. They are also supported by crystallographic evidence showing the existence of a hexameric aggregate in the solid state for a derivative of one of the alcohol modifiers used for solvent extraction, in agreement with the species giving the best modeling results.
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