THE ANODIC REACTION MECHANISM IN FUSED SILVER NITRATE.
Technical progress rept.,
NEW YORK UNIV N Y
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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 12O2. 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. AgAg are adopted, the two mechanisms are characterized by exchange current densities of 0.0024 ampsq. cm and 0.19 ampsq. 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 cmsec. Author