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Title: Thermodynamics of manganese oxides: Sodium, potassium, and calcium birnessite and cryptomelane

Abstract

Manganese oxides with layer and tunnel structures occur widely in nature and inspire technological applications. Having variable compositions, these structures often are found as small particles (nanophases). This study explores, using experimental thermochemistry, the role of composition, oxidation state, structure, and surface energy in the their thermodynamic stability. The measured surface energies of cryptomelane, sodium birnessite, potassium birnessite and calcium birnessite are all significantly lower than those of binary manganese oxides (Mn 3 O 4 , Mn 2 O 3 , and MnO 2 ), consistent with added stabilization of the layer and tunnel structures at the nanoscale. Surface energies generally decrease with decreasing average manganese oxidation state. A stabilizing enthalpy contribution arises from increasing counter-cation content. The formation of cryptomelane from birnessite in contact with aqueous solution is favored by the removal of ions from the layered phase. At large surface area, surface-energy differences make cryptomelane formation thermodynamically less favorable than birnessite formation. In contrast, at small to moderate surface areas, bulk thermodynamics and the energetics of the aqueous phase drive cryptomelane formation from birnessite, perhaps aided by oxidation-state differences. Transformation among birnessite phases of increasing surface area favors compositions with lower surface energy. These quantitative thermodynamic findings explainmore » and support qualitative observations of phase-transformation patterns gathered from natural and synthetic manganese oxides.« less

Authors:
;
Publication Date:
Research Org.:
Univ. of California, Davis, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1341471
Alternate Identifier(s):
OSTI ID: 1465689
Grant/Contract Number:  
FG02-97ER14749
Resource Type:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 114 Journal Issue: 7; Journal ID: ISSN 0027-8424
Publisher:
Proceedings of the National Academy of Sciences
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; manganese oxides; birnessite; cryptomelane; calorimetry; thermodynamics

Citation Formats

Birkner, Nancy, and Navrotsky, Alexandra. Thermodynamics of manganese oxides: Sodium, potassium, and calcium birnessite and cryptomelane. United States: N. p., 2017. Web. doi:10.1073/pnas.1620427114.
Birkner, Nancy, & Navrotsky, Alexandra. Thermodynamics of manganese oxides: Sodium, potassium, and calcium birnessite and cryptomelane. United States. doi:10.1073/pnas.1620427114.
Birkner, Nancy, and Navrotsky, Alexandra. Fri . "Thermodynamics of manganese oxides: Sodium, potassium, and calcium birnessite and cryptomelane". United States. doi:10.1073/pnas.1620427114.
@article{osti_1341471,
title = {Thermodynamics of manganese oxides: Sodium, potassium, and calcium birnessite and cryptomelane},
author = {Birkner, Nancy and Navrotsky, Alexandra},
abstractNote = {Manganese oxides with layer and tunnel structures occur widely in nature and inspire technological applications. Having variable compositions, these structures often are found as small particles (nanophases). This study explores, using experimental thermochemistry, the role of composition, oxidation state, structure, and surface energy in the their thermodynamic stability. The measured surface energies of cryptomelane, sodium birnessite, potassium birnessite and calcium birnessite are all significantly lower than those of binary manganese oxides (Mn 3 O 4 , Mn 2 O 3 , and MnO 2 ), consistent with added stabilization of the layer and tunnel structures at the nanoscale. Surface energies generally decrease with decreasing average manganese oxidation state. A stabilizing enthalpy contribution arises from increasing counter-cation content. The formation of cryptomelane from birnessite in contact with aqueous solution is favored by the removal of ions from the layered phase. At large surface area, surface-energy differences make cryptomelane formation thermodynamically less favorable than birnessite formation. In contrast, at small to moderate surface areas, bulk thermodynamics and the energetics of the aqueous phase drive cryptomelane formation from birnessite, perhaps aided by oxidation-state differences. Transformation among birnessite phases of increasing surface area favors compositions with lower surface energy. These quantitative thermodynamic findings explain and support qualitative observations of phase-transformation patterns gathered from natural and synthetic manganese oxides.},
doi = {10.1073/pnas.1620427114},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 7,
volume = 114,
place = {United States},
year = {2017},
month = {1}
}

Journal Article:
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DOI: 10.1073/pnas.1620427114

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