V Surender Rao
Articles written in Journal of Chemical Sciences
Volume 100 Issue 4 August 1988 pp 329-335 Physical and Theoretical
The stability constants of some tervalent lanthanide chelates of 1-(3-aryl-5-hydroxy 4-isoxazolylazo) 4-sulphonic acid (PHI-4S) and its substituents have been carried out by potentiometric and spectrophotometric methods. The results indicated the formation of 1:1 and 1:2 complexes with an order: Yb(III) > Y(III) > Gd(III) > Dy(III) > Tb(III) > Sm(III) > Nd(III) > Pr(III) > La(III). The stabilities increase with a decrease in the ionic or crystal radii [except a small break at Gd(III)], indicates the absence of extensive covalent bonding due to the non-availability of 4f-orbitals for bond formation. Structure-reactivity relationships of complex formation have been discussed by Hammett’s and Irving-Rossotti theories. Thermodynamic parameters have been discussed in terms of iso-equilibrium relationship.
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