In this paper, new information on physical and chemical properties of the widely used nanostructured Halloysite mineral are reported. Given that the Halloysite has a tubular structure formed by a variable number of wrapped layers containing Si-OH and Al-OH groups, their proton binding affinity was measured at different ionic strengths and ionic media by means of potentiometric measurements in heterogeneous phase. One protonation constant for the Si-OH groups and two for the Al-OH groups were determined. The protonation constant values increase with increasing of the ionic strength in all the ionic media. This suggests that the presence of a background electrolyte stabilizes the protonated species through the formation of weak complexes between ions of the supporting electrolytes and the protonated species. Ten weak species were determined with different stoichiometry. It was shown that the interactions do not depend on the nature of the supporting electrolytes but on the charge. The surface charge of Halloysite was estimated by ζ potential measurements as a function of pH, and the values obtained are consistent with the nanotubes ionization predicted by using the protonation constants for the Si-OH and Al-OH groups. The total solubility of the Halloysite nanotubes, was also determined in NaCl aqueous solution. These measurements showed that the solubility slightly increases with increasing ionic strength and contact time between Halloysite and NaCl solution. Goodness-of-fit (GOF) criteria were used to test the application of these models with good results. The obtained results confirm that the behavior of Halloysite in water is strictly correlated to the experimental conditions of the aqueous suspension (e.g., pH, ionic strength, and ionic media). The thermodynamic data here reported are of main importance in the several applications where is exploited the charge separation between the inner and outer surfaces of this nanotubular material
Quantitative parameters for the interactions between phytate (Phy) and Al(3+), Fe(3+), and Cr(3+) were determined potentiometrically in NaNO(3) aqueous solutions at I = 0.10 mol L(-1) and T = 298.15 K. Different complex species were found in a wide pH range. The various species are partially protonated, depending on the pH in which they are formed, and are indicated with the general formula MH(q)Phy (with 0 ≤ q ≤ 6). In all cases, the stability of the FeH(q)Phy species is several log K units higher than that of the analogous AlH(q)Phy and CrH(q)Phy species. For example, for the MH(2)Phy species, the stability trend is log K(2) = 15.81, 20.61, and 16.70 for Al(3+), Fe(3+), and Cr(3+), respectively. The sequestering ability of phytate toward the considered metal cations was evaluated by calculating the pL(0.5) values (i.e., the total ligand concentration necessary to bind 50% of the cation present in trace in solution) at different pH values. In general, phytate results in a quite good sequestering agent toward all three cations in the whole investigated pH range, but the order of pL(0.5) depends on it. For example, at pH 5.0 it is pL(0.5) = 5.33, 5.44, and 5.75 for Fe(3+), Cr(3+), and Al(3+), respectively (Fe(3+) < Cr(3+) < Al(3+)); at pH 7.4 it is pL(0.5) = 9.94, 9.23, and 8.71 (Al(3+) < Cr(3+) < Fe(3+)), whereas at pH 9.0 it is pL(0.5) = 10.42, 10.87, and 8.34 (Al(3+) < Fe(3+) < Cr(3+)). All of the pL(0.5) values, and therefore the sequestering ability, regularly increase with increasing pH, and the dependence of pL(0.5) on pH was modeled using some empirical equations.
The formation constants of various M/Phy systems (M = Cu2+, Zn2+, Pb2+, Ni2+; Phy = Phytate) were determined in NaNO3 solutions at 0.1 ≤ I/mol·L−1 ≤ 1.0 and T = 298.15 K, by potentiometry and voltammetry. The formation constants of the Cu/Phy and Zn/Phy species, already determined, were reanalyzed together with new voltammetric and potentiometric experiments at low concentrations. A new potentiometric and voltammetric study was carried out on the Ni/Phy and Pb/Phy systems. For all of the investigated systems, the dependence on ionic strength was modeled by the Debye−Hückel and the specific interaction theory (SIT) approaches. The sequestering ability of phytate was evaluated toward the considered cations by calculating the pL50 values (i.e., the total ligand concentration necessary to bind 50 % of the cation present in trace) at different ionic strengths and pH. A complete set of “suggested” formation constants was provided. A comparison between the formation constants obtained for the Zn/Phy, Cu/Phy, and Pb/Phy systems reveals that the interactions of phytate with Zn2+, Cu2+, and Pb2+ are quite similar, while the Ni/Phy species showed a weaker complexation. For example, for the MH3Phy species, log K 3 = 7.81, 7.51, 7.10, and 5.97 for Zn2+, Cu2+, Pb2+, and Ni2+, respectively. The same trend is observed concerning the pL50. Their dependence on pH and ionic strength was modeled by two empirical equations.
A study on chemical equilibria of different Hg2+−organic ligand systems is reported to establish the sequestration power of N/O donor groups versus metal. Ligand classes considered are: O-donors (succinate, 1,2,3,4-butanetetracarboxylate, 1,2,3,4,5,6-benzenehexacarboxylate, polymethacrylate, and polyacrylates); N-donors (ethylenediamine, diethylenetriamine, spermidine, triethylentetramine, tetraethylenpentamine, poly(allylamine), and poly(ethylenimine)); and amino acids (glycine, histidine, and aspartic acid). Equilibria were studied potentiometrically in NaNO3 at I = 0.1 mol·L−1 and t = 25 °C. For some systems, the dependence on ionic strength in the range (0 ≤ I ≤ 1) mol·L−1 (NaNO3) and the overall enthalpy changes, by calorimetric measurements, were also determined. The sequestering ability of ligands toward Hg2+ was evaluated, defining the amount of ligand necessary to sequester 50 % of the total metal cation concentration, pL50. The dependence on temperature and on ionic strength of pL50 was determined. General trends for the formation parameters for Hg2+−O-donor and −N-donor species depending on the binding sites were found. The free energy of binding for both unprotonated and monoprotonated species of carboxylates (ΔG b = −21.7 ± 3 kJ·mol−1) and for unprotonated species of amines (ΔG b = −35.4 ± 5 kJ·mol−1) was estimated.
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