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Gas-phase acid-base properties of melamine and cyanuric acid.
MedLine Citation:
PMID:  20621504     Owner:  NLM     Status:  PubMed-not-MEDLINE    
Abstract/OtherAbstract:
The thermochemical properties of melamine and cyanuric acid were characterized using mass spectrometry measurements along with computational studies. A triple-quadrupole mass spectrometer was employed with the application of the extended Cooks kinetic method. The proton affinity (PA), gas-phase basicity (GB), and protonation entropy (Δ(p)S) of melamine were determined to be 226.2 ± 2.0 kcal/mol, 218.4 ± 2.0 kcal/mol, and 26.2 ± 2.0 cal/mol K, respectively. The deprotonation enthalpy (Δ(acid)H), gas-phase acidity (Δ(acid)G), and deprotonation entropy (Δ(acid)S) of cyanuric acid were determined to be 330.7 ± 2.0 kcal/mol, 322.9 ± 2.0 kcal/mol, and 26.1 ± 2.0 cal/mol K, respectively. The geometries and energetics of melamine, cyanuric acid, and related ionic species were calculated at the B3LYP/6-31+G(d) level of theory. The computationally predicted proton affinity of melamine (225.9 kcal/mol) and gas-phase deprotonation enthalpy of cyanuric acid (328.4 kcal/mol) agree well with the experimental results. Melamine is best represented as the imide-like triazine-triamine form and the triazine nitrogen is more basic than the amino group nitrogen. Cyanuric acid is best represented as the keto-like tautomer and the N-H group is the most probable proton donor.
Authors:
Sumit Mukherjee; Jianhua Ren
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Publication Detail:
Type:  Journal Article     Date:  2010-06-11
Journal Detail:
Title:  Journal of the American Society for Mass Spectrometry     Volume:  21     ISSN:  1879-1123     ISO Abbreviation:  J. Am. Soc. Mass Spectrom.     Publication Date:  2010 Oct 
Date Detail:
Created Date:  2010-09-24     Completed Date:  2010-12-30     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  9010412     Medline TA:  J Am Soc Mass Spectrom     Country:  United States    
Other Details:
Languages:  eng     Pagination:  1720-9     Citation Subset:  -    
Copyright Information:
Copyright © 2010 American Society for Mass Spectrometry. Published by Elsevier Inc. All rights reserved.
Affiliation:
Department of Chemistry, University of the Pacific, Stockton, California 95211, USA.
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