THE ANODIC REACTION MECHANISM IN FUSED SILVER NITRATE.
Abstract
The oxidation of the nitrate ion at a Pt anode in molten AgNO3 was studied by steady state and fast sweep voltammetry. Two mechanisms are found, both leading to NO2 + 1/2O2. The first is susceptible to transport control and has an N-alpha value of 1.17 at 238C. It is postulated that this mechanism involves the preliminary dissociation of the nitrate ion to form NO2(+) + O2(=), the latter (possibly bound as orthonitrate) being the electroactive species. The second mechanism is not subject to transport control and has an N-alpha value of 0.90. This is thought to involve the formation of NO3 radical followed by its decomposition to form the products. If the E sub o values of 0.357V and 1.25V (vs. Ag/Ag(+)) are adopted, the two mechanisms are characterized by exchange current densities of 0.0024 amp/sq. cm and 0.19 amp/sq. cm, respectively. The corresponding values calculated for k sub o, the heterogeneous rate constant, are 1.3 x 10 to the -7th power and 1.1 x 10 to the-7th power cm/sec. (Author)
Document Details
- Document Type
- Technical Report
- Publication Date
- Feb 16, 1965
- Accession Number
- AD0611848
Entities
People
- Benson R. Sundheim
- Nirmal Gupta
Organizations
- New York University