skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: A Thermodynamic Model for ZrO2(am) Solubility at 25 °C in the Ca2+–Na+–H+–Cl-–OH-–H2O System: A Critical Review

Journal Article · · Journal of Solution Chemistry
ORCiD logo; ; ; ; ;

Zirconium is an important element in the nuclear fuel cycle. Thermodynamic data and models to reliably predict Zr-OH system behavior in various conditions including high ionic strengths are required and currently are unavailable. Most available experimental data are rather old, obtained using inadequate methodologies, and provide equilibrium constant values that differ by many orders of magnitude. Previous reviews have recommended values based on available data. These reviews used all of the available data, including poor quality data, in a global fit to determine these values. This has resulted in recommended thermodynamic models with a large number of polynuclear species and a number of mononuclear species with values of thermodynamic constants for the solubility product of ZrO2(am) and Zr-OH hydrolysis constants that are many orders of magnitude different than those for the reliable analogous Hf reactions. In this critical review, we have evaluated the quality of the available data, selected only those data that are of high quality, and reinterpreted all of the high quality data using SIT and Pitzer models for applications to high ionic strength solutions. Herein for 25°C we 1) present formation constant values for ZrOH3+, Zr(OH)2+2, Zr(OH)4(aq), Zr(OH)5-, and Zr(OH)62-, and the solubility product for ZrO2(am) which are consistent with the Hf system, 2) report a revised value for the formation of Ca3Zr(OH)64+, 3) show that several hypothetical polynuclear species (Zr3(OH)93+, Zr4(OH)15+, and Zr4(OH)16(aq)) proposed in previous reviews are not needed, and 4) show that polynuclear species (Zr3(OH)48+ and Zr4(OH)88+) are not important in a very extensive H+ concentration range (0.1 to 10-15.4 mol·kg-1). Our review has also resulted in SIT and Pitzer ion-interaction parameters applicable to as high ionic strength solutions as 5.6 mol·kg-1 in NaCl, 2.11 mol·kg-1 in CaCl2, and 23.5 mol·kg-1 in NaOH.

Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Organization:
USDOE
DOE Contract Number:
AC05-76RL01830
OSTI ID:
1490216
Report Number(s):
PNNL-SA-133220
Journal Information:
Journal of Solution Chemistry, Vol. 47, Issue 5; ISSN 0095-9782
Publisher:
Springer
Country of Publication:
United States
Language:
English

References (30)

Hydrolysis of Metal Ions book March 2016
PuPO4(cr, hyd.) Solubility Product and Pu3+ Complexes with Phosphate and Ethylenediaminetetraacetic Acid journal June 2010
Limits of the Natural Environment in Terms of pH and Oxidation-Reduction Potentials journal May 1960
Thorium(IV) hydrous oxide solubility journal December 1987
Studies on the Hydrolytic Behavior of Zirconium(IV) journal January 2004
Uranium(IV) hydrolysis constants and solubility product of UO2.cntdot.xH2O(am) journal January 1990
Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides journal September 1976
Hydrolysis Constant and Coordination Geometry of Zirconium(IV) journal August 2008
Electrometric Titrations of Zirconium and Hafnium Solutions 1 journal August 1950
Combined LIBD and XAFS investigation of the formation and structure of Zr(IV) colloids journal July 2005
Solubility of Zr(IV), Th(IV) and Pu(IV) hydrous oxides in CaCl2 solutions and the formation of ternary Ca-M(IV)-OH complexes journal January 2008
Thermodynamic Model for ThO2(am) Solubility in Alkaline Silica Solutions journal October 2008
Refinement of the crystal structure of zirconyl chloride octahydrate journal November 1968
Chromium(III) Hydroxide Solubility in the Aqueous K+-H+-OH−-CO2-HCO 3 − -CO 3 2− -H2O System: A Thermodynamic Model journal September 2007
Stability of some inorganic and organic complex compounds of zirconium and hafnium journal June 1964
Molecular orbital theory of the properties of inorganic and organometallic compounds. 6. Extended basis sets for second-row transition metals journal September 1987
The Hydrolysis of Zr(4+) and Hf(4+). journal January 1973
Thermodynamic Model for SnO2(cr) and SnO2(am) Solubility in the Aqueous Na+–H+–OH−–Cl−–H2O System journal July 2011
Self-consistent molecular orbital methods. 21. Small split-valence basis sets for first-row elements journal January 1980
Solubility measurement of zirconium(IV) hydrous oxide journal January 2006
The prediction of mineral solubilities in natural waters: The Na-K-Mg-Ca-H-Cl-SO4-OH-HCO3-CO3-CO2-H2O system to high ionic strengths at 25°C journal April 1984
A new mixing of Hartree–Fock and local density‐functional theories journal January 1993
Precipitation and Hydrolysis of Metallic Ions. II. Studies on the Solubility of Zirconium Hydroxide in Dilute Solutions and in 1 M NaClO4. journal January 1966
Properties of Plutonium(IV) Polymer of Environmental Importance journal July 1981
Environmental Mobility of Pu(IV) in the Presence of Ethylenediaminetetraacetic Acid: Myth or Reality? journal May 2008
NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations journal September 2010
The Aqueous Chemistry of Zirconium journal September 1949
On the Hydrolysis of Tetravalent Metal Ions journal January 2000
Solubility of Zirconium(IV) Hydrous Oxides journal January 2007
The Hydrolytic Polymerization of Zirconium in Perchloric Acid Solutions 1 journal November 1956

Similar Records

Thermodynamic Model for BiPO 4(cr) and Bi(OH)3(am) Solubility in the Aqueous Na+–H+–H2PO- 4 –HPO 2- 4 –PO 3- 4 –OH- –Cl- –H2O System
Journal Article · Sat Jul 10 00:00:00 EDT 2010 · Journal of Solution Chemistry · OSTI ID:1490216
+1 more
Solubility of U(VI) in chloride solutions. III. The stable oxides/hydroxides in MgCl2 systems: Pitzer activity model for the system UO22+–Na+–K+–Mg2+–H+–OH––Cl––H2O(l)
Journal Article · Wed Oct 24 00:00:00 EDT 2018 · Journal of Chemical Thermodynamics · OSTI ID:1490216
+3 more
Experimental Determination of Solubilities of Brucite [Mg(OH)2(cr)] in Na2SO4 Solutions with Borate to High Ionic Strengths: Interactions of MgB(OH)4+ with Na2SO4
Journal Article · Wed Apr 18 00:00:00 EDT 2018 · Journal of Solution Chemistry · OSTI ID:1490216

Related Subjects

solubility
ZrO2(am)
solubility product
thermodynamic data
zirconium