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Title: The Reactivity of the Nitrate Radical ( NO 3) in Aqueous and Organic Solutions

In this study, rate constants for the ( NO 3) radical reaction with alcohols, alkanes, alkenes and several aromatic compounds were measured in aqueous and tert-butanol solution for comparison to aqueous and acetonitrile values from the literature. The measured trends provide insight into the reactions of the NO 3 radical in various media. The reaction with alcohols primarily consists of hydrogen-atom abstraction from the alpha-hydroxy position, and is faster in solvents of lower polarity where the diffusivity of the radical is greater. Alkenes react faster than alkanes, and their rate constants are also faster in non-polar solution. The situation is reversed for nitrate radical reaction with the aromatic compounds, where the rate constants in tert-butanol are slower. This is attributed to the need to solvate the NO 3 - anion and corresponding tropylium cation produced by the NO 3 radical electron transfer reaction. Finally, a linear correlation was found between measured rate constants in water and acetonitrile, which can be used to estimate aqueous nitrate radical rate constants for compounds having low water solubility.
Authors:
 [1] ;  [1] ;  [1] ;  [2]
  1. California State University at Long Beach, CA (United States). Department of Chemistry and Biochemistry
  2. Idaho National Lab. (INL), Idaho Falls, ID (United States). Aqueous Separations and Radiochemistry Department
Publication Date:
Report Number(s):
INL/JOU-17-41197-Rev000
Journal ID: ISSN 0538-8066
Grant/Contract Number:
AC07-05ID14517; NE0008406
Type:
Accepted Manuscript
Journal Name:
International Journal of Chemical Kinetics
Additional Journal Information:
Journal Volume: 49; Journal Issue: 9; Journal ID: ISSN 0538-8066
Publisher:
Wiley
Research Org:
Idaho National Lab. (INL), Idaho Falls, ID (United States)
Sponsoring Org:
USDOE Office of Nuclear Energy (NE); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; nitrate radical; kinetics; organic phase chemistry; solvent extraction; atmospheric chemistry
OSTI Identifier:
1465944