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A Pitzer Model for Lead Oxide Solubilities in the Presence of Borate to High Ionic Strength

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Abstract

In this study, a hydrolysis model for lead, applicable to high ionic strength, is developed based on lead oxide solubilities as a function of ionic strength. Solubility measurements on lead oxide, α-PbO (tetragonal, red), mineral name litharge, as a function of ionic strength were conducted in NaClO4 solutions up to I = 0.45 mol·kg−1, in NaCl solutions up to I = 5.0 mol·kg−1, and in Na2SO4 solutions up to I = 5.4 mol·kg−1, at room temperature (22.5 ± 0.5 °C). The lead hydroxyl species considered in this work include the following,

$$ {\text{PbO}}\left( {\text{cr}} \right) \, + {\text{ 2H}}^{ + } \rightleftharpoons {\text{Pb}}^{ 2+ } + {\text{ H}}_{ 2} {\text{O}}\left( {\text{l}} \right) $$
(1)
$$ {\text{Pb}}^{ 2+ } + {\text{ H}}_{ 2} {\text{O}}\left( {\text{l}} \right) \rightleftharpoons {\text{PbOH}}^{ + } + {\text{ H}}^{ + } $$
(2)
$$ {\text{Pb}}^{ 2+ } + {\text{ 2H}}_{ 2} {\text{O}}\left( {\text{l}} \right) \rightleftharpoons {\text{Pb}}\left( {\text{OH}} \right)_{ 2} \left( {\text{aq}} \right) \, + {\text{ 2H}}^{ + } $$
(3)
$$ {\text{Pb}}^{ 2+ } + {\text{ 3H}}_{ 2} {\text{O}}\left( {\text{l}} \right) \rightleftharpoons {\text{Pb(OH}})_{3}^{ - } + 3{\text{H}}^{ + } $$
(4)

The equilibrium constants for Reactions (1) and (2) were taken from literature. The equilibrium constants in base 10 logarithmic units for Reactions (3) and (4) are determined in this study as − 17.05 ± 0.10 (2σ) and − 27.99 ± 0.15 (2σ), respectively, with a set of Pitzer parameters describing the interactions with Na+, Cl−, and \( {\text{SO}}_{4}^{2 - } .\) In combination with the parameters from literature including those that have already been published by our group, the solution chemistry of lead in a number of media including NaCl, MgCl2, NaHCO3, Na2CO3, Na2SO4, NaClO4, and their mixtures, can be accurately described in a wide range of ionic strengths.

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Acknowledgements

Sandia National Laboratories is a multimission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International, Inc., for the U.S. Department of Energy’s National Nuclear Security Administration under Contract DE-NA-0003525. This research is funded by WIPP programs administered by the Office of Environmental Management (EM) of the U.S Department of Energy, SAND2017-7184 J. The laboratory assistance from Diana Goulding, Brittany Hoard, Chase Kicker, Danelle Morrill, Rachael Roselle, Mathew Stroble, William Sullvan, Kira Vicent, and Yoni Xiong is gratefully acknowledged. Two journal reviewers are thanked for their insightful reviews, which improved our presentation. Journal editor Dr. Luigi Paduano is thanked for his time and editorial efforts.

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  1. Carlsbad Programs Group, Sandia National Laboratories (SNL), 4100 National Parks Highway, Carlsbad, NM, 88220, USA

    Yongliang Xiong, Leslie Kirkes, Terry Westfall, Jandi Knox, Cassandra Marrs & Heather Burton

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Xiong, Y., Kirkes, L., Westfall, T. et al. A Pitzer Model for Lead Oxide Solubilities in the Presence of Borate to High Ionic Strength. J Solution Chem 47, 1905–1925 (2018). https://doi.org/10.1007/s10953-018-0835-8

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