Oxidation of hydroxylamine by nitrous and nitric acid

Journal Article · Tue Jun 01 04:00:00 UTC 1982 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic00136a066· OSTI ID:6596021

Bennett, M R; Brown, G M; Maya, L; Posey, F A

The kinetics of the reaction of hydroxylamine with nitrous acid and with nitric acid were studied in an acidic nitrate medium. The mechanism of the reaction with nitrous acid in an acidic perchlorate medium, proposed by previous workers, is O-nitrosation of the hydroxylammonium ion; our data are consistent with this mechanism at an ionic strength of 2 M. The data at higher ionic strength (3 and 4 M), when compared to an extended treatment of the proposed mechanism, indicate either a deviation from this mechanism at high acid concentration or a change in one of the principal species in solution. Raman and UV spectroscopies were unable to verify a change in the species. In the reaction of hydroxylamine with nitric acid, we identified HNO/sub 2/, N/sub 2/O, and N/sub 2/ as products. This reaction is autocatalytic in HNO/sub 2/, and the distribution of products is dependent on the initial concentration of HNO/sub 2/, NH/sub 3/OH/sup +/, and HNO/sub 3/. The product N/sub 2/O derives from the nitrosation of NH/sub 3/OH/sup +/. HNO/sub 2/ with hyponitrous acid, which is an intermediate in the nitrosation of NH/sub 3/OH/sup +/. A kinetic model is partially successful in rationalizing the distribution of products.

• Research Organization: Oak Ridge National Lab., TN
• DOE Contract Number: W-7405-ENG-26
• OSTI ID: 6596021
• Journal Information: Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 21:6; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201 -- Chemical & Physicochemical Properties
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
AMINES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
DATA
EXPERIMENTAL DATA
HYDROGEN COMPOUNDS
HYDROXYLAMINE
INFORMATION
INORGANIC ACIDS
KINETICS
MEDIUM TEMPERATURE
NITRIC ACID
NITROUS ACID
NUMERICAL DATA
ORGANIC COMPOUNDS
OXIDATION
QUANTITY RATIO
REACTION KINETICS
TIME DEPENDENCE
YIELDS