THE SOLVATION FACTOR IN SPECIFICITY OF ION ADSORPTION AT ELECTRODES

被引:54
作者
CONWAY, BE
机构
[1] Chemistry Department, University of Ottawa, Ottawa, Ont. K1N 6N5
关键词
ION ADSORPTION; SOLUTION; DOUBLE-LAYER;
D O I
10.1016/0013-4686(95)00031-9
中图分类号
O646 [电化学、电解、磁化学];
学科分类号
081704 ;
摘要
The microscopic situations of ions, especially anions, adsorbed at metal/water and air/water interfaces are comparatively examined with regard to changes of ionic hydration that must be involved in so-called specific adsorption where short-range electronic chemisorptive interactions arise with the electrode-metal surface. Specific adsorption of non-hydrophobic ions takes place usually with significant charge-transfer related to the electrosorption valency. In order for such electronic effects to arise through metal/lone-pair electron interactions, it is necessary for accompanying changes of solvation energy and of related geometry of the inner-shell solvent coordination of the ions to take place so that lone-pair orbitals eg on anions, can have access to emergent surface orbitals of the metal electrode. Correspondingly, the ion solvation factor is demonstrated by consideration of ion adsorption at air-water interfaces where the ion/metal electronic interaction is absent. In relation to the solvation factors, individual hydrated-ion properties are plotted vs, ionic crystal radii and show that such properties are differently sensitive to radii of anions in comparison with those of cations.
引用
收藏
页码:1501 / 1512
页数:12
相关论文
共 37 条
  • [21] THEORY OF METAL-SURFACES - INDUCED SURFACE CHARGE AND IMAGE POTENTIAL
    LANG, ND
    KOHN, W
    [J]. PHYSICAL REVIEW B, 1973, 7 (08): : 3541 - 3550
  • [22] LORENZ W, 1977, J ELECTROANAL CHEM, V80, P1
  • [23] Lorenz W., 1961, Z PHYS CHEM, V218, P259
  • [24] The Surface Tension of Debye-Huckel Electrolytes
    Onsager, Lars
    Samaras, Nicholas N. T.
    [J]. JOURNAL OF CHEMICAL PHYSICS, 1934, 2 (08)
  • [25] Orgel LE, 1960, INTRO TRANSITION MET
  • [26] PAIK W, 1975, SURF SCI, V27, P491
  • [27] PARSONS R, 1969, J ELECTROANAL CHEM, V21, P35
  • [28] PARSONS R, 1981, COMPREHENSIVE TREATI, pCH1
  • [29] PARSONS R, 1954, MOD ASPECT ELECTROC, pCH2
  • [30] PARSONS R, 1964, J ELECTROANAL CHEM, V7, P136