Effect of ring size variation within lipophilic crown ether carboxylic acids on the selectivity and efficiency of competitive alkali-metal cation solvent extraction into chloroform

Competitive solvent extraction of alkali-metal cations from aqueous solutions into chlororform by a series of lipophilic crown ether carboxylic acids with varying ring sizes is reported. Extraction selectivity for Li{sup +} is observed for lipophilic crown ether carboxylic acids with 12-15-membered polyether rings containing four oxygen atoms. For lipophilic 14-crown-4-carboxylic acids, very high Li{sup +}/Na{sup +} selectivity coefficients of 17-20 are observed with no detectable extraction of K{sup +}, Rb{sup +}, or Cs{sup +}. Lipophilic crown ether carboxylic acids which contain 15-crown-5, 18-crown-6, and 21-crown-7 rings exhibit good selectivities for Na{sup +}, K{sup +}, and Cs{sup +}, respectively. In contrast, poor extraction selectivity is observed for lipophilic crown ether carboxylic acids with 24-crown-8, 27-crown-9, and 30-crown-10 rings.