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Nitrate/nitrite chemistry in NaNO/sub 3/-KNO/sub 3/ melts

Journal Article · · Inorg. Chem.; (United States)
DOI:https://doi.org/10.1021/ic00147a004· OSTI ID:5694504

By chemical analysis of samples taken under carefully controlled conditions, we have been able to show that the only reaction of any consequence that takes place in the equimolar binary NaNO/sub 3/-KNO/sub 3/ system over the temperature range 500-600/sup 0/C is represented by NO/sub 3//sup -/ ..-->..reverse arrow NO/sub 2//sup -/ + 1/2O/sub 2/. Over this temperature range there is no evidence of the formation of any anionic oxygen species such as oxide, peroxide, or superoxide at concentrations greater than 10/sup -5/ mol/kg. Equilibrium constants for the above reaction have been determined over the temperature range 500-600/sup 0/C. The standard free energy for this reaction (..delta..G/sup 0/ (kcal/mol) = 23000 + 20.6T) has been derived from the experimental data and is in good agreement with similar results for the single salts. A study of the kinetics of the oxidation of nitrite showed the rate of that reaction to be overall second order, first order with respect to both nitrite and oxygen. The rate constants have been measured from 400 to 500/sup 0/C, and from their temperature dependence the activation energy for the oxidation of nitrite was calculated: 26.4 kcal/mol.

Research Organization:
Sandia National Lab., Livermore, CA
DOE Contract Number:
AC04-76DP00789
OSTI ID:
5694504
Journal Information:
Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 22:5; ISSN INOCA
Country of Publication:
United States
Language:
English