Kinetic Studies of the Induced Reduction of Tetranitromethane to Nitroform by Decomposition of Tris(oxalato)cobaltate(III) Ion

Abstract

Tris(oxalato)cobaltate(III) ion [Co(C₂O₄)₃]^3- decomposes thermally with the intramolecular electron-transfer reaction in acidic solutions of aqueous mixtures of ethanol, and produces the radical of C₂O₄- or CO₂- which is capable of inducing the reduction of tetranitromethane C(NO₂)₄ to trinitromethanide ion C(NO₂)₃- Both the rates of decomposition of tris (oxalato)cobaltate(M) ion and of formation of C(NO₂)₃- are accelerated with an increase in acidity and/or in an amount of ethanol in the binary solvent-systems. Kinetic studies are made under various conditions and the reaction mechanisms are discussed based on the empirical results obtained. All the experiments were carried out in a closed reaction-vessel to keep the concentration of tetranitromethane constant; because the concentration of tetranitromethane decreased by vaporization unless the vessel was covered.