N-(2-Hydroxyethyl)iminodiacetic
acid (HEIDA-H2) is one of the major chelating agents present
in the mixed
nuclear waste of the Hanford site. The complexation of thorium with
HEIDA-H2 in aqueous medium was investigated to understand
the capability of HEIDA-H2 to affect the migration of actinides
from the waste storage sites. The present studies aimed at determining
the thermodynamic parameters of Th(IV)–HEIDA complexes to know
the speciation, stability (log K) and strength of
bond formations (enthalpy and entropy changes) by potentiometric and
calorimetric titrations, respectively. Thorium forms ML, ML2 and ML3 complexes with HEIDA. The obtained log K values 11.25 ± 0.10, 9.24 ± 0.10, and 8.1 ±
0.10, are higher than the complexes of thorium with monodenatate ligands
(simple carboxylates), bidentate ligands (aminomonocarboxylates, dicarboxylates),
and heterodicarboxylates. The very high entropy values of the Th(IV)–HEIDA
complexes in comparison to the Th(IV) complexes with structurally
similar ligands reflects the stronger complexation of Th with HEIDA
over others. HEIDA acts as a tridentate ligand forming two five-membered
chelates through the two carboxylate oxygens and the nitrogen with
thorium, while the hydroxyethl group was found to enhance the stabilization
by indirect participation. Density functional theory was used to optimize
the geometries and to determine the thermodynamic parameters, bond
distances and partial charges on individual atoms for the experimentally
predicted complexes. The theoretical predictions are found to be in
agreement with the experimental observations.