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Title: A Thermodynamic Model for ZrO 2(am) Solubility at 25 °C in the Ca 2+–Na +–H +–Cl -–OH -–H 2O System: A Critical Review

Abstract

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 ZrO 2(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 ZrOH 3+, Zr(OH) 2+ 2, Zr(OH) 4(aq), Zr(OH) 5 -, and Zr(OH)more » 6 2-, and the solubility product for ZrO 2(am) which are consistent with the Hf system, 2) report a revised value for the formation of Ca 3Zr(OH) 6 4+, 3) show that several hypothetical polynuclear species (Zr 3(OH) 9 3+, Zr 4(OH) 15 +, and Zr 4(OH) 16(aq)) proposed in previous reviews are not needed, and 4) show that polynuclear species (Zr 3(OH) 4 8+ and Zr 4(OH) 8 8+) 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 CaCl 2, and 23.5 mol·kg -1 in NaOH.« less

Authors:
ORCiD logo; ; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1490216
Report Number(s):
PNNL-SA-133220
Journal ID: ISSN 0095-9782
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Journal of Solution Chemistry
Additional Journal Information:
Journal Volume: 47; Journal Issue: 5; Journal ID: ISSN 0095-9782
Publisher:
Springer
Country of Publication:
United States
Language:
English
Subject:
solubility, ZrO2(am), solubility product, thermodynamic data, zirconium

Citation Formats

Rai, Dhanpat, Kitamura, Akira, Altmaier, Marcus, Rosso, Kevin M., Sasaki, Takayuki, and Kobayashi, Taishi. A Thermodynamic Model for ZrO2(am) Solubility at 25 °C in the Ca2+–Na+–H+–Cl-–OH-–H2O System: A Critical Review. United States: N. p., 2018. Web. doi:10.1007/s10953-018-0766-4.
Rai, Dhanpat, Kitamura, Akira, Altmaier, Marcus, Rosso, Kevin M., Sasaki, Takayuki, & Kobayashi, Taishi. A Thermodynamic Model for ZrO2(am) Solubility at 25 °C in the Ca2+–Na+–H+–Cl-–OH-–H2O System: A Critical Review. United States. doi:10.1007/s10953-018-0766-4.
Rai, Dhanpat, Kitamura, Akira, Altmaier, Marcus, Rosso, Kevin M., Sasaki, Takayuki, and Kobayashi, Taishi. Tue . "A Thermodynamic Model for ZrO2(am) Solubility at 25 °C in the Ca2+–Na+–H+–Cl-–OH-–H2O System: A Critical Review". United States. doi:10.1007/s10953-018-0766-4.
@article{osti_1490216,
title = {A Thermodynamic Model for ZrO2(am) Solubility at 25 °C in the Ca2+–Na+–H+–Cl-–OH-–H2O System: A Critical Review},
author = {Rai, Dhanpat and Kitamura, Akira and Altmaier, Marcus and Rosso, Kevin M. and Sasaki, Takayuki and Kobayashi, Taishi},
abstractNote = {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.},
doi = {10.1007/s10953-018-0766-4},
journal = {Journal of Solution Chemistry},
issn = {0095-9782},
number = 5,
volume = 47,
place = {United States},
year = {2018},
month = {5}
}