Competitive solvent extraction of the mixure of alkali metal and alkaline earth cation from water into organic solvent containing the crown ether carboxylic acid and anlogous crown ether phosphonic acid was investigated as follows. The lipophilic group is found to strongly influence to the selective extraction in the mixed systems from only alkali metal cation for sym-(n-decyldibenzo)-16-crown-5-oxyacetic acid _1 to mostly alkaline earth metal cation for sym-bis[4(5)-tert-butylbenzo]-16-crown-5-oxyacetic acid _3. Monoethyl sym-(n-decyldibenzo)-16-crown-5-oxymethylphosphonic acid _2. and monoethyl-sym- bis]4(5)-tert-butylbenzo]-16-crown-5-oxymethylphosphonic acid _4 showed good selectivity for Na+ over Mg2+, the second extracted ion. Structural variation in the crown ether phosphonic acid somewhat was influenced to the extraction selectivity in the mixed systems. when variation of the ionized group is influenced in the mixed systems, the selectivity of Na+ as the second extracted ion was much better crown ether carboxylic acid _1 than crown ether phosphonic acid _2, while the efficiency of Na+ extraction was better _2 (83% total loading) than _1 (32%).

Competitive solvent extraction of alkaline earth metal cations from water into organic solvent containing the carboxylic acid crown ether and analogous crown ether phosphonic acid monoethyl esters were investigated. sym-(n-Decyldibenzo)-16-crown-5xyacetic acid _1 and monoethyl sym-(n-decyldibenzo)-16-crown-5-oxymethylphosphonic acid _3 are structurally identical except for the ionizable groups. Both of them provide similar extraction behavior in terms of efficiency and selectivity, but monoethyl sym-(n-decyldibenzo)-16-crown-5-oxymethylphosphonic acid _3 showed higher alkaline earth metals loadings at acidic or neutral media. Monoethylsym-(n-octyldibenzo)-16-rown-5-oxymethylphosphonic acid _2 showed better selectivity and alkaline earth metals loading than did the analogous sym-(n-octyldibenzo)-16-crown-5-oxymethyldiphosphonic acid _6.