Nitrogen oxidative activation in the radiolysis process of dioxide hydrocarbon composition, oxygen-nitrogen over 3-d transition metals

The radiochemical process of nitrogen fixation in carbon dioxide, oxygen-nitrogen composition in 3-d metal (iron, nickel) was studied. Bifunctional character of surface's role in the generation of radiolysis products was postulated: a) Chemisorption's of molecular ions (N2+, CO2+, O2+ ) on the surface of metal and their dissociative neutralization. b) Coordination of nitrogen and carbon oxide being generated in nitrosyl and carbonyl-nitrosyl complex of iron and nickel. Total yield of the products is over the rang 6,4†7,5, to explain radiolysis' what contribution of only neutral products is impossible. Evidently in the generation of final products, defined contribution brings in molecular ions N2+ (N+) and CO2+ . Interaction character of these ions with nickel proposes the formation of the relation between unpaired electrons N2+ and CO2+ with unfilled d-sub level of this metals with the nickel nitride generation [Ni-N=N+] and binding energy in ion diazotate decreases to twice. The yield of nitrogen dioxide on radiolysis of the air gave GNO2 =0,8±0,2 molecule/100eV which is proper to the date in the literature. Kinetic curve appears rapidly in the saturation. Air radiolysis over iron gave the following results: GNO2 = 2,75 ± 0,25, GN2O= 9,0 ± 1,0 molecule/100eV. Thus total yield of radiolysis products is Σ G = 10,5 ± 12,0 molecule/100eV. (author)