Ligand number, adsorption

The determination of the ligand number (27) for adsorption reactions has been discussed by Hohl and Stumm (22). The following example illustrates the relationship between the net proton release and ligand number. 

Since these two possibilities were mentioned 21), it has become apparent that 7r-allylic complexes of transition elements usually occupy two ligancy positions. In particular, this is true in tris(7r-allyl)chromiura (III) 72). Thus, TT-allyl bonding to surface Cr3+ would seem to require the coordination number of Cr3+(cus) to be 4 or for some structural rearrangement to occur in the vicinity of Cr +(cus) analogous to ligand substitution adsorption (Section V,E). At the present time, it seems best to assume that a [Pg.76]

Thus in Fig. 5.22 the first outgassing at 25°C will have removed physisorbed water only, so that curve (1) is the isotherm of physical adsorption on the fully hydroxylated material. The 300°C outgassing, on the other hand, will have removed all the ligand water and the majority of the hydroxyl groups when isotherm (4) is determined, therefore, the Ti ions will chemisorb ligand water at low relative pressure, but the number of hydroxyl groups reformed will be very small. 

For undersaturated ([M] < Km) systems with relatively fast internalisation kinetics (kmt > k, ), the uptake of trace metals may be limited by their adsorption. Because the transfer of metal across the biological membrane is often quite slow, adsorption limitation would be predicted to occur for strong surface ligands (small values of k ) with a corresponding value of Km (cf. equations (35) and (36)) that imposes an upper limit on the ambient concentration of the metal that can be present in order to avoid saturation of the surface ligands. More importantly, as pointed out by Hudson and Morel [7], this condition also imposes a lower limit on the carrier concentration. Since the complexation rate is proportional to the metal concentration and the total number of carriers, for very low ambient metal concentrations, a large number of carriers are required if cellular requirements are to be satisfied. 

Instead of electrostatic (or physical) adsorption, metal uptake onto oxides might be considered chemical in nature. In chemical mechanisms, the metal precursor is envisioned to react with the oxide surface, involving as surface-ligand exchange [13,14] in which OH groups from the surface replace ligands in the adsorbing metal complex. In this section it will be shown that a relatively simple electrostatic interpretation of the adsorption of a number of catalyst precursors is the most reasonable one for a number of noble metal/oxide systems. 

By convention, the number of solvent molecules shed by the peptide on adsorption to the nonpolar RPC ligands has been represented by either Z, where... 

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