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Title: Ion–ion interactions enhance aluminum solubility in alkaline suspensions of nano-gibbsite (α-Al(OH)3) with sodium nitrite/nitrate

Abstract

Despite widespread industrial importance, predicting metal solubilities in highly concentrated, multicomponent aqueous solutions is difficult due to poorly understood ion–ion and ion–solvent interactions. Aluminum hydroxide solid phase solubility in concentrated sodium hydroxide (NaOH) solutions is one such case, with major implications for ore refining, as well as processing of radioactive waste stored at U.S. Department of Energy legacy sites, such as the Hanford Site, Washington State. The solubility of gibbsite (α-Al(OH)3) is often not well predicted because other ions affect the activity of hydroxide (OH–) and aluminate (Al(OH)4–) anions. In the study reported herein, we systematically examined the influence of key anions, nitrite (NO2–) and nitrate (NO3–), as sodium salts on the solubility of α-Al(OH)3 in NaOH solutions taking care to establish equilibrium from both under- and oversaturation. Rapid equilibration was enabled by use of a highly pure and crystalline synthetic nano-gibbsite of well-defined particle size and shape. Measured dissolved aluminum concentrations were compared with those predicted by an α-Al(OH)3 solubility model derived for simple Al(OH)4–/OH– systems. Specific anion effects were expressed as an enhancement factor (Alenhc) conveying the excess of dissolved aluminum. At 45 °C, NaNO2 and NaNO3-containing systems exhibited Alenhc values of 2.70 and 1.88, respectively, indicating significantmore » enhancement. The solutions were examined by Raman and high-field 27Al NMR spectroscopy, indicating specific interactions including Al(OH)4––Na+ contact ion pairing and Al(OH)4––NO2–/NO3– ion–ion interactions. Dynamic evolution of the α-Al(OH)3 particles including growth and agglomeration was observed revealing the importance of dissolution/reprecipitation in establishing equilibrium. These studies indicate that incomplete ion hydration, as a result of the low water activity in these concentrated electrolytes, results in: (i) enhanced reactivity of the hydroxide ion with respect to α-Al(OH)3; (ii) increased concentrations of Al(OH)4– in solution; and (iii) stronger ion–ion interactions that act to stabilize the supersaturated solutions. This information on the mechanisms by which α-Al(OH)3 becomes supersaturated is essential for more energy-efficient aluminum processing technologies, including the treatment of millions of gallons of Al(OH)4–-rich high-level radioactive waste.« less

Authors:
ORCiD logo [1];  [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [1]; ORCiD logo [4]; ORCiD logo [1];  [1];  [1];  [1]; ORCiD logo [1];  [1]; ORCiD logo [1]
+ Show Author Affiliations
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  2. Trade Wind Services, LLC, Richland, WA (United States)
  3. Washington River Protection Solutions, LLC, Richland, WA (United States)
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Interfacial Dynamics in Radioactive Environments and Materials (IDREAM); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Washington River Protection Solutions; USDOE Office of Science (SC), Biological and Environmental Research (BER)
OSTI Identifier:
1605423
Alternate Identifier(s):
OSTI ID: 1579759
Report Number(s):
PNNL-SA-142835
Journal ID: ISSN 1463-9076; PPCPFQ
Grant/Contract Number:  
AC05-76RL01830
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP
Additional Journal Information:
Journal Volume: 22; Journal Issue: 8; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Dembowski, Mateusz, Snyder, Michelle MV, Delegard, Calvin H., Reynolds, Jacob G., Graham, Trenton R., Wang, Hsiu-Wen, Leavy, Ian I., Baum, Steven R., Qafoku, Odeta, Fountain, Matthew S., Rosso, Kevin M., Clark, Sue B., and Pearce, Carolyn I. Ion–ion interactions enhance aluminum solubility in alkaline suspensions of nano-gibbsite (α-Al(OH)3) with sodium nitrite/nitrate. United States: N. p., 2019. Web. doi:10.1039/C9CP05856G.
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Dembowski, Mateusz, Snyder, Michelle MV, Delegard, Calvin H., Reynolds, Jacob G., Graham, Trenton R., Wang, Hsiu-Wen, Leavy, Ian I., Baum, Steven R., Qafoku, Odeta, Fountain, Matthew S., Rosso, Kevin M., Clark, Sue B., & Pearce, Carolyn I. Ion–ion interactions enhance aluminum solubility in alkaline suspensions of nano-gibbsite (α-Al(OH)3) with sodium nitrite/nitrate. United States. https://doi.org/10.1039/C9CP05856G
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Dembowski, Mateusz, Snyder, Michelle MV, Delegard, Calvin H., Reynolds, Jacob G., Graham, Trenton R., Wang, Hsiu-Wen, Leavy, Ian I., Baum, Steven R., Qafoku, Odeta, Fountain, Matthew S., Rosso, Kevin M., Clark, Sue B., and Pearce, Carolyn I. Fri . "Ion–ion interactions enhance aluminum solubility in alkaline suspensions of nano-gibbsite (α-Al(OH)3) with sodium nitrite/nitrate". United States. https://doi.org/10.1039/C9CP05856G. https://www.osti.gov/servlets/purl/1605423.
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@article{osti_1605423,
title = {Ion–ion interactions enhance aluminum solubility in alkaline suspensions of nano-gibbsite (α-Al(OH)3) with sodium nitrite/nitrate},
author = {Dembowski, Mateusz and Snyder, Michelle MV and Delegard, Calvin H. and Reynolds, Jacob G. and Graham, Trenton R. and Wang, Hsiu-Wen and Leavy, Ian I. and Baum, Steven R. and Qafoku, Odeta and Fountain, Matthew S. and Rosso, Kevin M. and Clark, Sue B. and Pearce, Carolyn I.},
abstractNote = {Despite widespread industrial importance, predicting metal solubilities in highly concentrated, multicomponent aqueous solutions is difficult due to poorly understood ion–ion and ion–solvent interactions. Aluminum hydroxide solid phase solubility in concentrated sodium hydroxide (NaOH) solutions is one such case, with major implications for ore refining, as well as processing of radioactive waste stored at U.S. Department of Energy legacy sites, such as the Hanford Site, Washington State. The solubility of gibbsite (α-Al(OH)3) is often not well predicted because other ions affect the activity of hydroxide (OH–) and aluminate (Al(OH)4–) anions. In the study reported herein, we systematically examined the influence of key anions, nitrite (NO2–) and nitrate (NO3–), as sodium salts on the solubility of α-Al(OH)3 in NaOH solutions taking care to establish equilibrium from both under- and oversaturation. Rapid equilibration was enabled by use of a highly pure and crystalline synthetic nano-gibbsite of well-defined particle size and shape. Measured dissolved aluminum concentrations were compared with those predicted by an α-Al(OH)3 solubility model derived for simple Al(OH)4–/OH– systems. Specific anion effects were expressed as an enhancement factor (Alenhc) conveying the excess of dissolved aluminum. At 45 °C, NaNO2 and NaNO3-containing systems exhibited Alenhc values of 2.70 and 1.88, respectively, indicating significant enhancement. The solutions were examined by Raman and high-field 27Al NMR spectroscopy, indicating specific interactions including Al(OH)4––Na+ contact ion pairing and Al(OH)4––NO2–/NO3– ion–ion interactions. Dynamic evolution of the α-Al(OH)3 particles including growth and agglomeration was observed revealing the importance of dissolution/reprecipitation in establishing equilibrium. These studies indicate that incomplete ion hydration, as a result of the low water activity in these concentrated electrolytes, results in: (i) enhanced reactivity of the hydroxide ion with respect to α-Al(OH)3; (ii) increased concentrations of Al(OH)4– in solution; and (iii) stronger ion–ion interactions that act to stabilize the supersaturated solutions. This information on the mechanisms by which α-Al(OH)3 becomes supersaturated is essential for more energy-efficient aluminum processing technologies, including the treatment of millions of gallons of Al(OH)4–-rich high-level radioactive waste.},
doi = {10.1039/C9CP05856G},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = 8,
volume = 22,
place = {United States},
year = {Fri Dec 13 00:00:00 EST 2019},
month = {Fri Dec 13 00:00:00 EST 2019}
}
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https://doi.org/10.1039/C9CP05856G
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