Studies on the Hydrolytic Behavior of Zirconium
Journal article, 2004
The stability constants of zirconium(IV) hydrolysis species have been measured at
15, 25, and 35°C [in 1.0 mol-dm-3 (H,Na)ClO4] using both potentiometry and solvent
extraction. In addition, the solubility of [Zr(OH)4(am)] has been investigated in a 1 moldm
-3 (Na,H)(ClO4,OH) medium at 25°C over a wide range of -log [H+] (0-15). The results indicate the presence of the monomeric species Zr(OH)3+, Zr(OH)2+2, Zr(OH)+3,
and Zr(OH)04(aq) as well as the polymeric species Zr4(OH)8+8 and Zr2(OH)2+6. The solvent
extraction measurements required the use of acetylacetone. As such, the stability constants of zirconium(IV) with acetylacetone were also measured using solvent extraction.
All stability constants were found to be linear functions of the reciprocal of
temperature (in kelvin) indicating that ΔHo and ΔSo are both independent of temperature
(over the temperature range examined in the study). The results of the solubility
experiments have shown four distinctly different solubility regions. In strongly acidic
solutions, the solubility is controlled by the formation of polynuclear hydrolysis species
in solution whereas in less acidic solution the formation of mononuclear hydrolysis
species becomes dominant. The largest portion of the solubility curve is controlled
by equilibrium with aqueous Zr(OH)04(aq) where the solubility is independent of the
proton concentration. In alkaline solutions, the solubility increases due to formation
of the zirconate ion. The middle region was used to determine the solubility constant
(log ∗Ks10) of Zr(OH)4(s). From the data in the alkaline region, a value of the stability
of the zirconate ion has been determined. This is the first time that the possible evidence
for the zirconate ion has been identified in aqueous solution that has previously been
found only in the solid phase.
hydrolysis
thermodynamics
temperature
solvent extraction
Zirconium
potentiometry
solubility