Amphoteric poly(amido[ndash ]amine) polymers containing the ethylenediamine-N,N′-diaceticacid moiety Stability of copper(II) and calcium(II) chelates

Abstract

The thermodynamics of protonation and complexing ability with Cu^II and Ca^II ions of synthetic polyampholytes containing ethylenediamine-N,N′-diacetic acid residues is reported. The free and two cross-linked polymers, of poly(amido–amino) structure, have been studied in aqueous media (0.1 M NaCl and 25°C) mainly by potentiometry and solution calorimetry. Potentiometric and calorimetric titration curves have been fitted only with two basicity constants and two enthalpy changes, both relative to the protonation equilibria of the two amino nitrogens in each repeating unit. The first protonation step always revealed greater thermodynamic values owing to electrostatic and inductive effects.

The metal ion equilibrium constant revealed only a single complex species of M^IIL stoichiometry (where L^2- is the repeating unit of the polymer in the ionized form) with a considerably higher log β value for Cu^II. The CuL species was present over a wide range of acidity (pH 2–12), while CaL formed appreciably only above pH 5. The enthalpy change (-ΔH°) of the Cu^II complex species was also considerably greater than that of Ca^II, suggesting a strong chemical bond in the former case in which d orbitals are utilized. Both cross-linked polymers retained the same ability to form metal complexes in the same pH range.