Partition coefficients and equilibrium constants of crown ethers between water and organic solvents determined by proton nuclear magnetic resonance

被引:10
作者
Cheng, HW [1 ]
Rustenholtz, A [1 ]
Porter, RA [1 ]
Ye, XR [1 ]
Wai, CM [1 ]
机构
[1] Univ Idaho, Dept Chem, Moscow, ID 83844 USA
关键词
D O I
10.1021/je034195c
中图分类号
O414.1 [热力学];
学科分类号
摘要
The extraction of water by several crown ethers into chloroform + carbon tetrachloride mixtures has been investigated using a proton NMR technique. The equilibrium is well described by formation of a 1:1 water-crown complex in rapid exchange with uncomplexed ligand and water. The fraction (k) of crown ether complexed with water increases with crown cavity size, varying from (15 +/- 1)% for 12-crown-4 to (97 +/- 5)% for 18-crown-6. Addition of carbon tetrachloride to chloroform lowers the k value for all crown ethers in equilibrium with water, and the value is close to zero in pure CCl4. The partition coefficient follows the opposite trend: the amount of crown ether in the organic phase increases with the percentage of CCl4 in this phase. The chemical shifts of free and complexed water also vary with solvent composition. Interaction of water with crown ether depends on solvation environment and may play a significant role in liquid-liquid extraction of metal ions using macrocyclic polyethers as extractants.
引用
收藏
页码:594 / 598
页数:5
相关论文
共 24 条
[1]   Solvent extraction of alkaline-earth ions by dicarboxylated calix[4]arenes [J].
Barakat, N ;
Burgard, M ;
Asfari, Z ;
Vicens, J ;
Montavon, G ;
Duplatre, G .
POLYHEDRON, 1998, 17 (20) :3649-3656
[2]  
BENESI HA, 1969, J AM CHEM SOC, V91, P2703
[3]   HYDRATION OF 18-CROWN-6 IN CARBON-TETRACHLORIDE - INFRARED SPECTRAL EVIDENCE FOR AN EQUILIBRIUM BETWEEN MONODENTATE AND BIDENTATE FORMS OF BOUND WATER IN THE 1-1 CROWN WATER ADDUCT [J].
BRYAN, SA ;
WILLIS, RR ;
MOYER, BA .
JOURNAL OF PHYSICAL CHEMISTRY, 1990, 94 (13) :5230-5233
[4]  
de Jong F., 1976, TETRAHEDRON LETT, V17, P1371
[5]  
deNamor AFD, 1997, J CHEM SOC FARADAY T, V93, P3955
[6]   THEORY OF MEASUREMENT OF WEAK MOLECULAR COMPLEXES .I. GENERAL CONSIDERATIONS [J].
DERANLEAU, DA .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1969, 91 (15) :4044-+
[7]   Extraction of cesium from acidic nitrate media using macrocyclic polyethers: The role of organic phase water [J].
Dietz, ML ;
Horwitz, EP ;
Rhoads, S ;
Bartsch, RA ;
Krzykawski, J .
SOLVENT EXTRACTION AND ION EXCHANGE, 1996, 14 (01) :1-12
[8]   Ligand reorganization energies as a basis for the design of synergistic metal ion extraction systems [J].
Dietz, ML ;
Bond, AH ;
Hay, BP ;
Chiarizia, R ;
Huber, VJ ;
Herlinger, AW .
CHEMICAL COMMUNICATIONS, 1999, (13) :1177-1178
[9]   SALT COMPLEXES OF CYCLIC POLYETHERS - DISTRIBUTION EQUILIBRIA [J].
FRENSDORFF, HK .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1971, 93 (19) :4684-+
[10]  
GOLOVKOVA P, 1984, THEOR EXP CHEM, V20, P219