Inner-sphere complex adsorption selectivity

Depending on the difference in adsorption energies (see Section 5.4) dinitrosyl complexes are formed either concomitantly or subsequently with the mononitrosyl complexes. Those processes have been widely investigated for selected TMIs and can be followed easily by IR technique [57], The appearance of a characteristic doublet due to the collective antisymmetric and symmetric vibrations of the M(NO)2 moiety growing at the expanse of the NO valence band is usually taken as a confirmation of the dinitrosyl formation. As discussed below in more detail, they play important role in the inner-sphere route of the N—N bond making (see Section 6.2.1). 

Mineral or particle surfaces are enriched with As due to several processes that are collectively referred to as sorption (Parks, 1990), but the chemical properties of surface-associated As have been difficult to study directly. Outer-sphere, or physisorption, describes weak, long range, attractive forces between the surface and sorbing As inner-sphere, or chemisorption, refers to the formation of chemical bonds between the surface and adsorbing As. Stronger adsorption is expected by the formation of a bidentate (two bond) adsorbed complex rather than a monodentate (1 bond) complex. Selective chemical extraction methods have been useful for empirical determination of the dominant chemical/mineralogical compartments retaining As in aquifer... 

The concept of inner-sphere surface complexation as the basis for relative metal adsorption selectivity in soils was introduced in W. R. Heald, M. H. Frere, and C. T. deWit, Ion adsorption on charged surfaces. Soil Sci. Soc. Am. J. 28 622 (1964). Further quantitative development of this concept was given in... 

The goal in applying any SCM is to develop a self-consistent methodology for parameter estimation such that a set of standard parameters to describe surface acidity, site density, and the charge/potential relationships for different minerals can be developed and can be used in conjunction with spectroscopic data to guide the selection of appropriate adsorption reactions for the formation of metal ion surface complexes (i.e., inner vs. outer sphere, mono vs. hidentate, mononuclear vs. 

---