Boron and lithium aqueous thermochemistry to model crud deposition in pressurized water reactors

Rizk, Jason Tyler; McMurray, Jacob W.; Wirth, Brian D.

doi:10.1016/j.jct.2024.107289

Boron and lithium aqueous thermochemistry to model crud deposition in pressurized water reactors

Journal Article · Tue Mar 26 04:00:00 EDT 2024 · Journal of Chemical Thermodynamics

DOI:https://doi.org/10.1016/j.jct.2024.107289· OSTI ID:2332799

^[1]; McMurray, Jacob W. ^[2]; Wirth, Brian D. ^[3]

Univ. of Tennessee, Knoxville, TN (United States); Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Univ. of Tennessee, Knoxville, TN (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Here, a comprehensive database of boron and lithium aqueous thermochemistry has been developed for use at elevated temperatures. The Helgeson-Kirkham-Flowers (HKF) formalism provides a framework to describe thermodynamic properties over a broad range of temperatures and pressures. Accuracy at high temperatures is vital to modeling nickel oxide and ferrite fuel deposits that occur in pressurized water nuclear reactors (PWRs). CALPHAD (CALculation of PHAse Diagrams) calculations are performed at PWR crud conditions to predict the stability regions of the solid lithium metaborate (LiBO₂) and lithium tetraborate (Li₂B₄O₇) precipitates. In addition, similar calculations are performed using sodium and potassium instead of lithium in order to assess the thermodynamics associated with preventing the formation of such precipitates. This database contributes to understanding of crud formation and composition and will aid in the prediction of phenomena such as Crud-Induced Power Shifts (CIPS).

View Accepted Manuscript (DOE)

Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE Office of Nuclear Energy (NE); USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: 89233218CNA000001

OSTI ID:: 2332799

Report Number(s):: LA-UR--24-22086

Journal Information:: Journal of Chemical Thermodynamics, Journal Name: Journal of Chemical Thermodynamics Vol. 195; ISSN 0021-9614

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (43)

ChemInform Abstract: Conductivity Measurements of Dilute Aqueous LiOH, NaOH, and KOH Solutions to High Temperatures and Pressures Using a Flow‐Through Cell. Ho, Patience C.; Palmer, Donald A.; Wood, Robert H. ChemInform, Vol. 32, Issue 8 https://doi.org/10.1002/chin.200108008	journal	February 2001
Volumes and heat capacities of H3BO3(aq) at temperatures from 298.15 K to 705 K and at pressures to 35 MPa Hnedkovsky, L. The Journal of Chemical Thermodynamics, Vol. 27, Issue 7 https://doi.org/10.1006/jcht.1995.0083	journal	July 1995
Aqueous solutions of the mono- and di-hydrogenphosphate salts of sodium and potassium at elevated temperatures. Isopiestic results Holmes, H. F.; Simonson, J. M.; Mesmer, R. E. The Journal of Chemical Thermodynamics, Vol. 32, Issue 1 https://doi.org/10.1006/jcht.1999.0571	journal	January 2000
Aqueous solutions of lithium hydroxide at various temperatures: Conductivity and activity coefficients Corti, Horacio; Crovetto, Rosa; Fern�ndez-Prini, Roberto Journal of Solution Chemistry, Vol. 8, Issue 12 https://doi.org/10.1007/BF00644886	journal	December 1979
Phosphoric acid dissociation equilibria in aqueous solutions to 300°C Mesmer, R. E.; Baes, C. F. Journal of Solution Chemistry, Vol. 3, Issue 4 https://doi.org/10.1007/BF00648228	journal	April 1974
Measurement of pH in subcritical and supercritical aqueous systems Macdonald, Digby D.; Hettiarachchi, Samson; Song, Herking Journal of Solution Chemistry, Vol. 21, Issue 8 https://doi.org/10.1007/BF00651512	journal	August 1992
Structure of Aqueous Lithium Tetraborate Solution Zhou, Yongquan; Xu, Sha; Fang, Yan Journal of Cluster Science, Vol. 27, Issue 4 https://doi.org/10.1007/s10876-015-0948-9	journal	March 2016
D2O Isotope Effects on the Ionization of β-Naphthol and Boric Acid at Temperatures from 225 to 300 °C using UV-Visible Spectroscopy Bulemela, E.; Tremaine, Peter R. Journal of Solution Chemistry, Vol. 38, Issue 7 https://doi.org/10.1007/s10953-009-9411-6	journal	May 2009
Raman-Spectroscopic Measurements of the First Dissociation Constant of Aqueous Phosphoric Acid Solution from 5 to 301 °C Rudolph, Wolfram W. Journal of Solution Chemistry, Vol. 41, Issue 4 https://doi.org/10.1007/s10953-012-9825-4	journal	April 2012
Complexation of Nickel Ions by Boric Acid or (Poly)borates Graff, Anais; Barrez, Etienne; Baranek, Philippe Journal of Solution Chemistry, Vol. 46, Issue 1 https://doi.org/10.1007/s10953-016-0555-x	journal	December 2016
Experimental determination of the stability constants of NaSO4− and NaB (OH)40 in hydrothermal solutions using a new high-temperature sodium-selective glass electrode — Implications for boron isotopic fractionation Pokrovski, Gleb S.; Schott, Jacques; Sergeyev, Alexandre S. Chemical Geology, Vol. 124, Issue 3-4 https://doi.org/10.1016/0009-2541(95)00057-S	journal	August 1995
Calculation of the thermodynamic and transport properties of aqueous species at high pressures and temperatures: Correlation algorithms for ionic species and equation of state predictions to 5 kb and 1000°C Shock, Everett L.; Helgeson, Harold C. Geochimica et Cosmochimica Acta, Vol. 52, Issue 8 https://doi.org/10.1016/0016-7037(88)90181-0	journal	August 1988
Calculation of the thermodynamic and transport properties of aqueous species at high pressures and temperatures: Standard partial molal properties of inorganic neutral species Shock, Everett L.; Helgeson, Harold C.; Sverjensky, Dimitri A. Geochimica et Cosmochimica Acta, Vol. 53, Issue 9 https://doi.org/10.1016/0016-7037(89)90341-4	journal	September 1989
Raman spectra of polyborate ions in aqueous solution Hirao, Toshiyuki; Kotaka, Masahiro; Kakihana, Hidetake Journal of Inorganic and Nuclear Chemistry, Vol. 41, Issue 8 https://doi.org/10.1016/0022-1902(79)80490-X	journal	January 1979
SUPCRT92: A software package for calculating the standard molal thermodynamic properties of minerals, gases, aqueous species, and reactions from 1 to 5000 bar and 0 to 1000°C Johnson, James W.; Oelkers, Eric H.; Helgeson, Harold C. Computers & Geosciences, Vol. 18, Issue 7 https://doi.org/10.1016/0098-3004(92)90029-Q	journal	August 1992
Inorganic species in geologic fluids: Correlations among standard molal thermodynamic properties of aqueous ions and hydroxide complexes Shock, Everett L.; Sassani, David C.; Willis, Marc Geochimica et Cosmochimica Acta, Vol. 61, Issue 5 https://doi.org/10.1016/S0016-7037(96)00339-0	journal	March 1997
Computation of dielectric constants of solvent mixtures and electrolyte solutions Wang, Peiming; Anderko, Andrzej Fluid Phase Equilibria, Vol. 186, Issue 1-2 https://doi.org/10.1016/S0378-3812(01)00507-6	journal	August 2001
A speciation-based model for mixed-solvent electrolyte systems Wang, Peiming; Anderko, Andrzej; Young, Robert D. Fluid Phase Equilibria, Vol. 203, Issue 1-2 https://doi.org/10.1016/S0378-3812(02)00178-4	journal	December 2002
FactSage thermochemical software and databases, 2010–2016 Bale, C. W.; Bélisle, E.; Chartrand, P. Calphad, Vol. 54 https://doi.org/10.1016/j.calphad.2016.05.002	journal	September 2016
Ionization of boric acid in water from 298K to 623K by AC conductivity and Raman spectroscopy Arcis, H.; Ferguson, J. P.; Applegarth, L. M. S. G. A. The Journal of Chemical Thermodynamics, Vol. 106 https://doi.org/10.1016/j.jct.2016.11.007	journal	March 2017
A model of chemistry and thermal hydraulics in PWR fuel crud deposits Henshaw, Jim; McGurk, John C.; Sims, Howard E. Journal of Nuclear Materials, Vol. 353, Issue 1-2 https://doi.org/10.1016/j.jnucmat.2005.01.028	journal	July 2006
Application of the Specific Ion Interaction Theory (SIT) for the ionic products of aqueous electrolyte solutions of very high concentrations Sipos, Pál Journal of Molecular Liquids, Vol. 143, Issue 1 https://doi.org/10.1016/j.molliq.2008.04.003	journal	September 2008
Polyborates in aqueous borate solution: A Raman and DFT theory investigation Zhou, Yongquan; Fang, Chunhui; Fang, Yan Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Vol. 83, Issue 1 https://doi.org/10.1016/j.saa.2011.07.081	journal	December 2011
Ion-Pair Formation Constants of Lithium Borate and Lithium Hydroxide under Pressurized Water Nuclear Reactor Coolant Conditions Ferguson, J. P.; Arcis, H.; Zimmerman, G. H. Industrial & Engineering Chemistry Research, Vol. 56, Issue 28 https://doi.org/10.1021/acs.iecr.7b01015	journal	July 2017
Raman Spectroscopic and ab Initio Investigation of Aqueous Boric Acid, Borate, and Polyborate Speciation from 25 to 80 °C Applegarth, Lucas M. S. G. A.; Pye, Cory C.; Cox, Jenny S. Industrial & Engineering Chemistry Research, Vol. 56, Issue 47 https://doi.org/10.1021/acs.iecr.7b03316	journal	November 2017
Thermodynamics of Polyborates under Hydrothermal Conditions: Formation Constants and Limiting Conductivities of Triborate and Diborate Ferguson, Jane P.; Arcis, Hugues; Tremaine, Peter R. Journal of Chemical & Engineering Data, Vol. 64, Issue 10 https://doi.org/10.1021/acs.jced.9b00496	journal	September 2019
Triborate Formation Constants and Polyborate Speciation under Hydrothermal Conditions by Raman Spectroscopy using a Titanium/Sapphire Flow Cell Sasidharanpillai, Swaroop; Arcis, Hugues; Trevani, Liliana The Journal of Physical Chemistry B, Vol. 123, Issue 24 https://doi.org/10.1021/acs.jpcb.9b03062	journal	June 2019
Concentrated Solutions of Strong Electrolytes. Scatchard, George. Chemical Reviews, Vol. 19, Issue 3 https://doi.org/10.1021/cr60064a008	journal	December 1936
Acidity measurements at elevated temperatures. VI. Boric acid equilibriums Mesmer, R. E.; Baes, C. F.; Sweeton, F. H. Inorganic Chemistry, Vol. 11, Issue 3 https://doi.org/10.1021/ic50109a023	journal	March 1972
Identification of polyborate and fluoropolyborate ions in solution by Raman spectroscopy Maya, L. Inorganic Chemistry, Vol. 15, Issue 9 https://doi.org/10.1021/ic50163a036	journal	September 1976
The Effect of Sodium Chloride upon the Ionization of Boric Acid at Various Temperatures ¹ Owen, Benton Brooks; King, Edward J. Journal of the American Chemical Society, Vol. 65, Issue 8 https://doi.org/10.1021/ja01248a046	journal	August 1943
Solubility of Lithium Monoborate in High-Temperature Water Byers, W. A.; Lindsay Jr., W. T.; Kunig, R. H. Journal of Solution Chemistry, Vol. 29, Issue 6, p. 541-559 https://doi.org/10.1023/A:1005194129783	journal	June 2000
The IAPWS Formulation 1995 for the Thermodynamic Properties of Ordinary Water Substance for General and Scientific Use Wagner, W.; Pruß, A. Journal of Physical and Chemical Reference Data, Vol. 31, Issue 2 https://doi.org/10.1063/1.1461829	journal	June 2002
The Ionization Constant of Water over Wide Ranges of Temperature and Density Bandura, Andrei V.; Lvov, Serguei N. Journal of Physical and Chemical Reference Data, Vol. 35, Issue 1 https://doi.org/10.1063/1.1928231	journal	March 2006
Ion product of water substance, 0–1000 °C, 1–10,000 bars New International Formulation and its background Marshall, William L.; Franck, E. U. Journal of Physical and Chemical Reference Data, Vol. 10, Issue 2 https://doi.org/10.1063/1.555643	journal	April 1981
Thermodynamic Assessment of the Lithium‐Borate System Yu, Hao; Jin, Zhanpeng; Chen, Qing Journal of the American Ceramic Society, Vol. 83, Issue 12 https://doi.org/10.1111/j.1151-2916.2000.tb01686.x	journal	December 2000
Thermodynamic modeling of boric acid and selected metal borate systems Wang, Peiming; Kosinski, Jerzy J.; Lencka, Malgorzata M. Pure and Applied Chemistry, Vol. 85, Issue 11 https://doi.org/10.1351/pac-con-12-07-09	journal	January 2013
MULTEQ: Equilibrium of an electrolytic solution with vapor-liquid partitioning and precipitation: Volume 1: User's manual, Revision 1 Alexander, J. H.; Luu, L. https://doi.org/10.2172/6012064	report	May 1989
Theoretical prediction of the thermodynamic behavior of aqueous electrolytes by high pressures and temperatures; IV, Calculation of activity coefficients, osmotic coefficients, and apparent molal and standard and relative partial molal properties to 600 degrees C and 5kb Helgeson, H. C.; Kirkham, D. H.; Flowers, G. C. American Journal of Science, Vol. 281, Issue 10 https://doi.org/10.2475/ajs.281.10.1249	journal	December 1981
Calculation of the thermodynamic and transport properties of aqueous species at high pressures and temperatures; revised equations of state for the standard partial molal properties of ions and electrolytes Tanger, J. C.; Helgeson, H. C. American Journal of Science, Vol. 288, Issue 1 https://doi.org/10.2475/ajs.288.1.19	journal	January 1988
Critical phenomena in hydrothermal systems; state, thermodynamic, electrostatic, and transport properties of H 2 O in the critical region Johnson, J. W.; Norton, D. American Journal of Science, Vol. 291, Issue 6 https://doi.org/10.2475/ajs.291.6.541	journal	June 1991
An Introduction to the Calphad Method and the Compound Energy Formalism (Cef) Cacciamani, Gabriele Tecnologia em Metalurgia Materiais e Mineração, Vol. 13, Issue 1 https://doi.org/10.4322/2176-1523.1048	journal	January 2016
Ionization constant of boric acid and the pH of certain borax-chloride buffer solutions from 0 degrees to 60 degrees C Manov, G. G.; DeLollis, N. J.; Acree, S. F. Journal of Research of the National Bureau of Standards, Vol. 33, Issue 4 https://doi.org/10.6028/jres.033.013	journal	October 1944

Similar Records

Experimental Investigation on the Effects of Coolant Concentration on Sub-Cooled Boiling and Crud Deposition on Reactor Cladding at Prototypical PWR Operating Conditions

Technical Report · Fri Oct 20 00:00:00 EDT 2006 · OSTI ID:894209

Implementation of equilibrium aqueous speciation and solubility (EQ3 type) calculations into Cantera for electrolyte solutions.

Technical Report · Mon Jun 01 00:00:00 EDT 2009 · OSTI ID:970260

The Hydrothermal Chemistry of Gold, Arsenic, Antimony, Mercury and Silver

Technical Report · Sat Mar 22 23:00:00 EST 2003 · OSTI ID:840338

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
CALPHAD
Helgeson-Kirkham-Flowers
Pitzer
aqueous
boric acid
crud

Boron and lithium aqueous thermochemistry to model crud deposition in pressurized water reactors

Citation Formats

References (43)

Similar Records

Related Subjects