Differences between Light-Platinum Group Metals (L-PGMs) and Heavy- PGMs in General Chemical Properties

In hydrometallurgical processes of PGMs separation and refining, differences between 1-PGMs (Ru;Rh;Pd) and h-PGMs(Os;Ir;Pt) in thermodynamics and kinetics have been observed. The successful practice in the separation and refining of PGMs in China, is mainly based on the following two kinetically extraction sequences of: (1) for the extraction of PGMs complexes in different configurations with coordination mechanism (AuCI,) -> (MCl6)2-> (MCl4 )2-> (MCI6) 3- , and the substitution rate for h-PGMs complexes with higher effective nuclear charge Z' is much more slow than that of I-PGMs. and (2) for the extraction of PGMs in different configurations with oxonium (or ion -exchange) mechanism (AuCl4)-> (MCl4)2--> (MCl6)2-> (MCl6)3- and the extraction of h-PGMs complexes with low surface charge density is more fast than that of I-PGMs complexes. In view of atomic structure theory, the similarity of atomic radii and chemical properties and difficult separation of PGMs resulted from the Lanthanide Contruction between 5th period (1-PGMs) and 6th period (h-PGMs). The differences between h-PGMs and 1-PGMs are due to the loss shielding of 4f subshells on 5d electrons for h-PGMs with higher nuclear number, which makes h-PGMs have a higher Z' (effective nuclear charge) and strong attraction for outer space electrons. As a result, h-PGMs metals and complexes are thermodynamically more stable and kinetically more inert than the corresponding 1-PGMs. The differences between h-PGMs and 1 -PGMs in aspects of elements properties, complexes, hydration, substitution and redox reactions , are discussed.