Adsorption of ions on zirconium oxide surfaces from aqueous solutions at high temperatures

D. A. Palmer; M. L. MacHesky; P. Bénézeth; D. J. Wesolowski; L. M. Anovitz; J. C. Deshon

doi:10.1007/s10953-009-9415-2

Adsorption of ions on zirconium oxide surfaces from aqueous solutions at high temperatures

D. A. Palmer, M. L. MacHesky, P. Bénézeth, D. J. Wesolowski, L. M. Anovitz, J. C. Deshon

Geochemistry & Interfacial Science

Research output: Contribution to journal › Article › peer-review

18 Scopus citations

Abstract

Surface titrations were carried out on suspensions of monoclinic ZrO ₂ from 25 to 290∈°C slightly above saturation vapor pressure at ionic strengths of 0.03, 0.1 and 1.0 mol · kg^-1(NaCl). A typical increase in surface charge was observed with increasing temperature. There was no correlation between the radius of the cations, Li⁺, Na⁺, K⁺ and (CH₃)₄N⁺, and the magnitude of their association with the surface. The combined results were treated with a 1-pK_a MUSIC model, which yielded association constants for the cations (and chloride ion at low pH) at each temperature. The pH of zero-point-charge, pH_zpc, decreased with increasing temperature as found for other metal oxides, reaching an apparent minimum value of 4.1 by 250∈°C. Batch experiments were performed to monitor the concentration of LiOH in solutions containing suspended ZrO₂ particles from 200 to 360∈°C. At 350 and 360∈°C, Li⁺ and OH^- ions were almost totally adsorbed when the pressure was lowered to near saturation vapor pressure. This reversible trend has implications not only to pressure-water reactor, PWR, operations, but is also of general scientific and other applied interest. Additional experiments probed the feasibility that boric acid/borate ions adsorb reversibly onto ZrO₂ surfaces at near-neutral pH conditions as indicated in earlier publications.

Original language	English
Pages (from-to)	907-924
Number of pages	18
Journal	Journal of Solution Chemistry
Volume	38
Issue number	7
DOIs	https://doi.org/10.1007/s10953-009-9415-2
State	Published - Jul 2009

Funding

Acknowledgements This work was sponsored by EPRI Inc., Palo Alto, CA, USA, under the guidance of the project managers, Jeff Deshon and Paul Frattini, and the results appear in an EPRI report entitled: Adsorption of Ions on Zirconium Oxide Surfaces from Aqueous Solutions at High Temperatures, Report Number 1007855 (2003). We would particularly like to thank the contribution of Ms. Yulia Zhgenti, who was a visiting IAPWS young scientist from the Moscow Power Engineering Institute, Technical University, Moscow, Russia.

Funders	Funder number
EPRI Inc.	1007855

Keywords

Adsorption
Batch experiments
Borate anions
High temperature
Lithium ions
MUSIC model
PWR applications
Potentiometry
Zirconium oxide

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abstract = "Surface titrations were carried out on suspensions of monoclinic ZrO 2 from 25 to 290∈°C slightly above saturation vapor pressure at ionic strengths of 0.03, 0.1 and 1.0 mol · kg-1(NaCl). A typical increase in surface charge was observed with increasing temperature. There was no correlation between the radius of the cations, Li+, Na+, K+ and (CH3)4N+, and the magnitude of their association with the surface. The combined results were treated with a 1-pKa MUSIC model, which yielded association constants for the cations (and chloride ion at low pH) at each temperature. The pH of zero-point-charge, pHzpc, decreased with increasing temperature as found for other metal oxides, reaching an apparent minimum value of 4.1 by 250∈°C. Batch experiments were performed to monitor the concentration of LiOH in solutions containing suspended ZrO2 particles from 200 to 360∈°C. At 350 and 360∈°C, Li+ and OH- ions were almost totally adsorbed when the pressure was lowered to near saturation vapor pressure. This reversible trend has implications not only to pressure-water reactor, PWR, operations, but is also of general scientific and other applied interest. Additional experiments probed the feasibility that boric acid/borate ions adsorb reversibly onto ZrO2 surfaces at near-neutral pH conditions as indicated in earlier publications.",

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AU - Bénézeth, P.

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AU - Anovitz, L. M.

AU - Deshon, J. C.

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N2 - Surface titrations were carried out on suspensions of monoclinic ZrO 2 from 25 to 290∈°C slightly above saturation vapor pressure at ionic strengths of 0.03, 0.1 and 1.0 mol · kg-1(NaCl). A typical increase in surface charge was observed with increasing temperature. There was no correlation between the radius of the cations, Li+, Na+, K+ and (CH3)4N+, and the magnitude of their association with the surface. The combined results were treated with a 1-pKa MUSIC model, which yielded association constants for the cations (and chloride ion at low pH) at each temperature. The pH of zero-point-charge, pHzpc, decreased with increasing temperature as found for other metal oxides, reaching an apparent minimum value of 4.1 by 250∈°C. Batch experiments were performed to monitor the concentration of LiOH in solutions containing suspended ZrO2 particles from 200 to 360∈°C. At 350 and 360∈°C, Li+ and OH- ions were almost totally adsorbed when the pressure was lowered to near saturation vapor pressure. This reversible trend has implications not only to pressure-water reactor, PWR, operations, but is also of general scientific and other applied interest. Additional experiments probed the feasibility that boric acid/borate ions adsorb reversibly onto ZrO2 surfaces at near-neutral pH conditions as indicated in earlier publications.

AB - Surface titrations were carried out on suspensions of monoclinic ZrO 2 from 25 to 290∈°C slightly above saturation vapor pressure at ionic strengths of 0.03, 0.1 and 1.0 mol · kg-1(NaCl). A typical increase in surface charge was observed with increasing temperature. There was no correlation between the radius of the cations, Li+, Na+, K+ and (CH3)4N+, and the magnitude of their association with the surface. The combined results were treated with a 1-pKa MUSIC model, which yielded association constants for the cations (and chloride ion at low pH) at each temperature. The pH of zero-point-charge, pHzpc, decreased with increasing temperature as found for other metal oxides, reaching an apparent minimum value of 4.1 by 250∈°C. Batch experiments were performed to monitor the concentration of LiOH in solutions containing suspended ZrO2 particles from 200 to 360∈°C. At 350 and 360∈°C, Li+ and OH- ions were almost totally adsorbed when the pressure was lowered to near saturation vapor pressure. This reversible trend has implications not only to pressure-water reactor, PWR, operations, but is also of general scientific and other applied interest. Additional experiments probed the feasibility that boric acid/borate ions adsorb reversibly onto ZrO2 surfaces at near-neutral pH conditions as indicated in earlier publications.

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Adsorption of ions on zirconium oxide surfaces from aqueous solutions at high temperatures

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