Oxidation of hydrazine by nitric acid

Journal Article · Wed Dec 18 04:00:00 EST 1985 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic00220a011· OSTI ID:5975735

Karraker, D G

Hydrazine is oxidized by hot nitric acid in a first-order reaction to produce N/sub 2/, N/sub 2/O, HN/sub 3/, and NH/sub 4//sup +/. The rate law for the reaction is -d ln (N/sub 2/H/sub 4/)/dt = k(NO/sub 3//sup -/)(H/sup +/)/sup 2/ where k = 5.8 x 10/sup -5/ M/sup -3/ min/sup -1/ at 100/sup 0/C in 5.44 M HNO/sub 3/ and ..mu.. = 6. The data are consistent with a reaction mechanism that involves HN/sub 3/, HNO/sub 2/, and the N/sub 2/H/sub 2/, and the N/sub 2/H/sub 2/ free radical as intermediates and N/sub 2/, N/sub 2/O, and NH/sub 4//sup +/ as products. The Arrhenius equation constants over the temperature range 70-100/sup 0/C were A = 1.2 x 10/sup 11/ M/sup -3/ min/sup -1/ and E = 26 kcal/mol. The reaction is catalyzed by Fe/sup 3 +/, and the rate data are correlated by the semiempirical expression ln((N/sub 2/H/sub 4/)/(N/sub 2/H/sub 4/)/sub 0/) = -(a'(Fe/sup 3 +/) + b'(Fe/sup 2 +/))(H/sup +/)t where a' = 0.114 M/sup -2/ min/sup -1/ and b' = 0.065 M/sup -2/ min/sup 71/. A reaction mechanism is proposed for the ferric-catalyzed reaction whose major reactions involve the reduction of Fe/sup 3 +/ to Fe/sup 2 +/ by hydrazine and the oxidation of Fe/sup 2 +/ to Fe/sup 3 +/ by nitric acid. 21 references, 12 figures, 6 tables.

• Research Organization: E.I. du Pont de Nemours and Co., Aiken, SC
• DOE Contract Number: AC09-76SR00001
• OSTI ID: 5975735
• Journal Information: Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 24:26; ISSN INOCA
• Country of Publication: United States
• Language: English

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AMMONIUM COMPOUNDS
ARRHENIUS EQUATION
CATALYSIS
CATALYSTS
CATALYTIC EFFECTS
CHALCOGENIDES
CHEMICAL REACTION KINETICS
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
DATA
ELEMENTS
EQUATIONS
EXPERIMENTAL DATA
HYDRAZINE
HYDROGEN COMPOUNDS
INFORMATION
INORGANIC ACIDS
IRON
KINETICS
MEDIUM TEMPERATURE
METALS
NITRIC ACID
NITROGEN
NITROGEN COMPOUNDS
NITROGEN OXIDES
NITROUS OXIDE
NONMETALS
NUMERICAL DATA
OXIDATION
OXIDES
OXYGEN COMPOUNDS
PREDICTION EQUATIONS
RADICALS
REACTION INTERMEDIATES
REACTION KINETICS
TEMPERATURE DEPENDENCE
TRANSITION ELEMENTS
YIELDS