Reduction of nitric oxide by hydroxylamine. 1. Kinetics and mechanism
The reaction of nitric oxide with hydroxylamine conforms to the rate law -dP/sub NO//dt = k/sub 2/(NH/sub 2/O/sup -/)P/sub NO/ in the pH range 7.29-13.14, confirming the rate-determining abstraction of an N-bound H atom by NO. Measured kinetic quantities: k/sub 2/ = 6.68 x 10/sup -3/ M/sup -1/ s/sup -1/ at 25/sup 0/C; ..delta.. H double dagger = 29.6 kJ mol/sup -1/; ..delta.. S double dagger = -189 J K/sup -1/ mol/sup -1/. Thermodynamic values have been obtained for the pK/sub a/ of NH/sub 2/OH at several temperatures; ..delta.. H of dissociation = 55.29 kJ mol/sup -1/. The presence of trace amounts of O/sub 2/ in the NO-NH/sub 2/OH reaction system catalyzes the reaction and leads to a reduced molar product ratio n/sub N/sub 2/O/, effects that are ascribed at least in part to reactive N/sub 2/O/sub 3/. The difference in reactivity between the NO/sup -/ intermediate formed in this reaction and that produced in trioxodinitrate decomposition is discussed.
- Research Organization:
- State Univ. of New York, Stony Brook
- OSTI ID:
- 5456712
- Journal Information:
- Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 25:11; ISSN INOCA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
AMINES
CATALYSIS
CATALYTIC EFFECTS
CHALCOGENIDES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
DATA
ELEMENTS
EXPERIMENTAL DATA
HYDROGEN COMPOUNDS
HYDROXIDES
INFORMATION
KINETICS
NITRIC OXIDE
NITROGEN COMPOUNDS
NITROGEN OXIDES
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
OXIDES
OXYGEN
OXYGEN COMPOUNDS
PH VALUE
PHYSICAL PROPERTIES
REACTION INTERMEDIATES
REACTION KINETICS
REDUCTION
TEMPERATURE DEPENDENCE
THERMODYNAMIC PROPERTIES
THERMODYNAMICS