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Title: Mechanochemical Synthesis, Accelerated Aging, and Thermodynamic Stability of the Organic Mineral Paceite and Its Cadmium Analogue

Abstract

We demonstrate the use of ball milling mechanochemistry for rapid, simple, and materials-efficient synthesis of the organic mineral paceite CaCu(OAc) 4·6H 2O (where OAc is the acetate ion), composed of coordination polymer chains containing alternating Ca 2+ and Cu 2+ ions, as well as its cadmium-based analogue CaCd(OAc) 4·6H 2O. While the synthesis of paceite in aqueous solutions requires a high excess of the copper precursor, mechanochemistry permits the use of stoichiometric amounts of reagents, as well as the use of poorly soluble and readily accessible calcium carbonate or hydroxide reactants. As established by thermochemical measurements, enthalpies of formation of both synthetic paceite and its cadmium analogue relevant to the mechanochemical reactions are highly exothermic. Reactions can also be conducted using accelerated aging, a synthetic technique that mimics geological processes of mineral weathering. Accelerated aging reactivity involving copper(II) acetate monohydrate (hoganite) and calcium carbonate (calcite) provides a potential explanation of how complex organic minerals like paceite could form in a geological environment.

Authors:
 [1];  [1];  [2]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]
  1. McGill Univ., Montreal, QC (Canada). Dept. of Chemistry
  2. Univ. of California, Davis, CA (United States). Peter A. Rock Thermochemistry Lab. NEAT ORU
Publication Date:
Research Org.:
Univ. of California, Davis, CA (United States); McGill Univ., Montreal, QC (Canada)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); Natural Sciences and Engineering Research Council of Canada (NSERC)
OSTI Identifier:
1501726
Alternate Identifier(s):
OSTI ID: 1508786
Grant/Contract Number:  
SC0016573; RGPIN-2017-06467; SMFSU 507347-17
Resource Type:
Published Article
Journal Name:
ACS Omega
Additional Journal Information:
Journal Volume: 4; Journal Issue: 3; Journal ID: ISSN 2470-1343
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 58 GEOSCIENCES; crystal structure; molecular structure

Citation Formats

Li, Shaodi, Huskić, Igor, Novendra, Novendra, Titi, Hatem M., Navrotsky, Alexandra, and Friščić, Tomislav. Mechanochemical Synthesis, Accelerated Aging, and Thermodynamic Stability of the Organic Mineral Paceite and Its Cadmium Analogue. United States: N. p., 2019. Web. doi:10.1021/acsomega.9b00295.
Li, Shaodi, Huskić, Igor, Novendra, Novendra, Titi, Hatem M., Navrotsky, Alexandra, & Friščić, Tomislav. Mechanochemical Synthesis, Accelerated Aging, and Thermodynamic Stability of the Organic Mineral Paceite and Its Cadmium Analogue. United States. doi:10.1021/acsomega.9b00295.
Li, Shaodi, Huskić, Igor, Novendra, Novendra, Titi, Hatem M., Navrotsky, Alexandra, and Friščić, Tomislav. Tue . "Mechanochemical Synthesis, Accelerated Aging, and Thermodynamic Stability of the Organic Mineral Paceite and Its Cadmium Analogue". United States. doi:10.1021/acsomega.9b00295.
@article{osti_1501726,
title = {Mechanochemical Synthesis, Accelerated Aging, and Thermodynamic Stability of the Organic Mineral Paceite and Its Cadmium Analogue},
author = {Li, Shaodi and Huskić, Igor and Novendra, Novendra and Titi, Hatem M. and Navrotsky, Alexandra and Friščić, Tomislav},
abstractNote = {We demonstrate the use of ball milling mechanochemistry for rapid, simple, and materials-efficient synthesis of the organic mineral paceite CaCu(OAc)4·6H2O (where OAc– is the acetate ion), composed of coordination polymer chains containing alternating Ca2+ and Cu2+ ions, as well as its cadmium-based analogue CaCd(OAc)4·6H2O. While the synthesis of paceite in aqueous solutions requires a high excess of the copper precursor, mechanochemistry permits the use of stoichiometric amounts of reagents, as well as the use of poorly soluble and readily accessible calcium carbonate or hydroxide reactants. As established by thermochemical measurements, enthalpies of formation of both synthetic paceite and its cadmium analogue relevant to the mechanochemical reactions are highly exothermic. Reactions can also be conducted using accelerated aging, a synthetic technique that mimics geological processes of mineral weathering. Accelerated aging reactivity involving copper(II) acetate monohydrate (hoganite) and calcium carbonate (calcite) provides a potential explanation of how complex organic minerals like paceite could form in a geological environment.},
doi = {10.1021/acsomega.9b00295},
journal = {ACS Omega},
number = 3,
volume = 4,
place = {United States},
year = {2019},
month = {3}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1021/acsomega.9b00295

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