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Title: Chemical and Molecular Descriptors for the Reactivity of Amines with CO{sub 2}

Abstract

Amine-based solvents are likely to play an important role in CO{sub 2} capture applications in the future, and the identification of amines with superior performance will facilitate their use in CO{sub 2} capture. While some improvements in performance will be achieved through process modifications, modifying the CO{sub 2} capture performance of an amine also implies in part an ability to modify the reactions between the amine and CO{sub 2} through development of new functionalized amines. We present a computational study of trends in the reactions between CO{sub 2} and functionalized amines with a focus on identifying molecular descriptors that determine trends in reactivity. We examine the formation of bicarbonate and carbamate species on three classes of functionalized amines: alkylamines, alkanolamines, and fluorinated alkylamines including primary, secondary and tertiary amines in each class. These functional groups span electron-withdrawing to donating behavior, hydrogen-bonding, extent of functionalization, and proximity effects of the functional groups. Electron withdrawing groups tend to destabilize CO{sub 2} reaction products, whereas electron-donating groups tend to stabilize CO{sub 2} reaction products. Hydrogen bonding stabilizes CO{sub 2} reaction products. Electronic structure descriptors based on electronegativity were found to describe trends in the bicarbonate formation energy. A chemical correlation was observed betweenmore » the carbamate formation energy and the carbamic acid formation energy. The local softness on the reacting N in the amine was found to partially explain trends carbamic acid formation energy.« less

Authors:
;
Publication Date:
Research Org.:
National Energy Technology Lab. (NETL), Pittsburgh, PA, and Morgantown, WV (United States). In-house Research; National Energy Technology Lab. (NETL), Pittsburgh, PA, and Morgantown, WV (United States)
Sponsoring Org.:
USDOE Office of Fossil Energy (FE)
OSTI Identifier:
1127235
Report Number(s):
A-UNIV-PUB-006
Journal ID: ISSN 0888-5885
DOE Contract Number:  
DE-FE0004000
Resource Type:
Journal Article
Journal Name:
Industrial and Engineering Chemistry Research
Additional Journal Information:
Journal Volume: 51; Journal Issue: 42; Journal ID: ISSN 0888-5885
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 54 ENVIRONMENTAL SCIENCES; Carbon dioxide, CO{sub 2} capture, conceptual density functional theory, amine solvents

Citation Formats

Lee, Anita S., and Kitchin, John R. Chemical and Molecular Descriptors for the Reactivity of Amines with CO{sub 2}. United States: N. p., 2012. Web. doi:10.1021/ie301419q.
Lee, Anita S., & Kitchin, John R. Chemical and Molecular Descriptors for the Reactivity of Amines with CO{sub 2}. United States. doi:10.1021/ie301419q.
Lee, Anita S., and Kitchin, John R. Wed . "Chemical and Molecular Descriptors for the Reactivity of Amines with CO{sub 2}". United States. doi:10.1021/ie301419q. https://www.osti.gov/servlets/purl/1127235.
@article{osti_1127235,
title = {Chemical and Molecular Descriptors for the Reactivity of Amines with CO{sub 2}},
author = {Lee, Anita S. and Kitchin, John R.},
abstractNote = {Amine-based solvents are likely to play an important role in CO{sub 2} capture applications in the future, and the identification of amines with superior performance will facilitate their use in CO{sub 2} capture. While some improvements in performance will be achieved through process modifications, modifying the CO{sub 2} capture performance of an amine also implies in part an ability to modify the reactions between the amine and CO{sub 2} through development of new functionalized amines. We present a computational study of trends in the reactions between CO{sub 2} and functionalized amines with a focus on identifying molecular descriptors that determine trends in reactivity. We examine the formation of bicarbonate and carbamate species on three classes of functionalized amines: alkylamines, alkanolamines, and fluorinated alkylamines including primary, secondary and tertiary amines in each class. These functional groups span electron-withdrawing to donating behavior, hydrogen-bonding, extent of functionalization, and proximity effects of the functional groups. Electron withdrawing groups tend to destabilize CO{sub 2} reaction products, whereas electron-donating groups tend to stabilize CO{sub 2} reaction products. Hydrogen bonding stabilizes CO{sub 2} reaction products. Electronic structure descriptors based on electronegativity were found to describe trends in the bicarbonate formation energy. A chemical correlation was observed between the carbamate formation energy and the carbamic acid formation energy. The local softness on the reacting N in the amine was found to partially explain trends carbamic acid formation energy.},
doi = {10.1021/ie301419q},
journal = {Industrial and Engineering Chemistry Research},
issn = {0888-5885},
number = 42,
volume = 51,
place = {United States},
year = {2012},
month = {10}
}