The binding capacity of three aminopolycarboxylates
[nitrilotriacetic
acid (NTA), ethylene-glycol-bis(2-aminoethyl ether)-
N,N,N′,N′-tetraacetic
acid (EGTA), and diethylenetriamine-
N,N,N′,N″,N″-pentaacetic
acid (DTPA)] and two aminopolyphosphonates {(1-hydroxyethane-1,1-diyl)bis(phosphonic
acid) (HEDP) and [[(phosphonomethyl)imino]bis[2,1-ethanediylnitrilobis(methylene)]]
tetrakis-phosphonic acid (DTPP)} toward palladium(II) ion was studied
by potentiometric and spectrophotometric titrations at different temperatures
(283.15 ≤ T/K ≤ 318.15) and ionic strengths
(0.1 ≤ I/mol·dm–3 ≤
1.0) in NaClO4. The hydrolysis of Pd2+ and the
protonation of ligands were always taken into account in the speciation
models of Pd2+/L systems investigated. Equilibrium reaching
experiments were performed to check and confirm the reaching of the
equilibrium state. Owing to the high stability of the PdL species
(K > 1020), for EGTA, HEDP, and DTPP
it
was determined using exchange measurements with auxiliary ligands,
such as iodide (I–) and ammonia (NH3).
For the other ligands the stability of the PdL species was reported
in the literature. The general speciation scheme consisted of mononuclear
differently protonated species with general formula PdHiL and only in the case of the NTA ligand the formation of the PdL2 species was found. The stability of the PdL species is high:
as an example we have log K
ML = 17.82,
22.60, 36.31, 23.49, and 27.27 for NTA, EGTA, DTPA, HEDP, and DTPP,
respectively. Among the ligands, DTPA shows the highest formation
constants and sequestering ability, evaluated using the pL0.5 parameter, as well. The complex formation reaction is always exothermic
and in general the entropic contribution to the stability is dominant.
Some empirical relationships were found to model the dependence of
the formation constants on the number of protons and of the sequestering
ability on pH.