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

Abstract

Despite its widespread importance, predicting metal solubilities in highly concentrated multicomponent aqueous solutions is often difficult due to the poorly understood balance of ion-ion and ion-solvent interactions. Aluminum solubility in concentrated sodium hydroxide solutions is one such case, with major consequences in ore refining as well as processing of legacy radioactive waste stored at U.S. Department of Energy sites such Hanford. In particular, the solubility of gibbsite (a-Al(OH)3) is often not well predicted because other ions interact with and affect the activity coefficients of the OH- and Al(OH)4- in a manner that has not yet been carefully scrutinized. In the present study we systematically examine the influence of key anions, NO2- and NO3- on the solubility of a-Al(OH)3 in NaOH solutions across a range of temperatures, taking care to establish equilibrium values by approaching from both under- and oversaturation. Rapid equilibration was enabled by use of a nano-sized, highly pure, and crystalline synthetic a-Al(OH)3 phase of well-defined particle size and shape. Measured dissolved aluminum concentrations were compared with those predicted by the Misra equation, and specific anion effects were expressed as an enhancement factor, Alenhc, conveying the multiplicity of excess soluble aluminum. For NaNO2 and NaNO3-containing systems, respective Alenhc valuesmore » for NaNO2 or NaNO3 containing systems were 2.25 and 1.56 at 27°C, 2.44 and 1.69 at 45°C, and 3.28 and 2.17 at 80°C, consistently indicating significant enhancements and a larger effect from NO2-, likely due to stronger nature of anion-anion interactions with the aluminate anion, Al(OH)4-. Terminal solids characterization suggested a dynamic evolution of the a-Al(OH)3, including particle coarsening and agglomeration, revealing the likely importance of dissolution/reprecipitation in establishing equilibrium.« less

Authors:
ORCiD logo [1];  [1]; ORCiD logo [2];  [3]; ORCiD logo [1];  [4]; ORCiD logo [1];  [1];  [1];  [1]; ORCiD logo [1];  [1];  [1]
  1. BATTELLE (PACIFIC NW LAB)
  2. TRADEWIND SERVICES LLC
  3. WASHINGTON RIVER PROTECTION SOLUTIONS
  4. OAK RIDGE NATIONAL LAB
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1605423
Alternate Identifier(s):
OSTI ID: 1579759
Report Number(s):
[PNNL-SA-142835]
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]
Country of Publication:
United States
Language:
English

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 (a-Al(OH)3) with sodium nitrite/nitrate. United States: N. p., 2020. Web. doi:10.1039/C9CP05856G.
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 (a-Al(OH)3) with sodium nitrite/nitrate. United States. doi:10.1039/C9CP05856G.
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 (a-Al(OH)3) with sodium nitrite/nitrate". United States. doi:10.1039/C9CP05856G.
@article{osti_1605423,
title = {Ion-ion interactions enhance aluminum solubility in alkaline suspensions of nano-gibbsite (a-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 its widespread importance, predicting metal solubilities in highly concentrated multicomponent aqueous solutions is often difficult due to the poorly understood balance of ion-ion and ion-solvent interactions. Aluminum solubility in concentrated sodium hydroxide solutions is one such case, with major consequences in ore refining as well as processing of legacy radioactive waste stored at U.S. Department of Energy sites such Hanford. In particular, the solubility of gibbsite (a-Al(OH)3) is often not well predicted because other ions interact with and affect the activity coefficients of the OH- and Al(OH)4- in a manner that has not yet been carefully scrutinized. In the present study we systematically examine the influence of key anions, NO2- and NO3- on the solubility of a-Al(OH)3 in NaOH solutions across a range of temperatures, taking care to establish equilibrium values by approaching from both under- and oversaturation. Rapid equilibration was enabled by use of a nano-sized, highly pure, and crystalline synthetic a-Al(OH)3 phase of well-defined particle size and shape. Measured dissolved aluminum concentrations were compared with those predicted by the Misra equation, and specific anion effects were expressed as an enhancement factor, Alenhc, conveying the multiplicity of excess soluble aluminum. For NaNO2 and NaNO3-containing systems, respective Alenhc values for NaNO2 or NaNO3 containing systems were 2.25 and 1.56 at 27°C, 2.44 and 1.69 at 45°C, and 3.28 and 2.17 at 80°C, consistently indicating significant enhancements and a larger effect from NO2-, likely due to stronger nature of anion-anion interactions with the aluminate anion, Al(OH)4-. Terminal solids characterization suggested a dynamic evolution of the a-Al(OH)3, including particle coarsening and agglomeration, revealing the likely importance of dissolution/reprecipitation in establishing equilibrium.},
doi = {10.1039/C9CP05856G},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = [8],
volume = [22],
place = {United States},
year = {2020},
month = {2}
}

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