THE MECHANISM OF DIRECTIONAL OXIDATION OF HYDRAZINE BY SILVER COORDINATION-COMPOUNDS

The reactions of different Ag complexes with hydrazine have been studi ed and it has been shown that a trace amount of Cu-II ion can increase the rate, greatly raising the percentage of N-2 formed by the four-el ectron oxidation of hydrazine (Reaction 4). In the absence of the Cu-I I ion, the percentage of N-2 formed is linearly related to log beta(2) of the Ag complex. In the presence of the Cu-II ion, the percentage o f N-2 formed by the one-electron oxidation of hydrazine is likewise li nearly related to 1/log beta(2): 4Ag(+)(AgL(2)(q+/-)) + N2H4 <-> 4Ag N-2 + 4H(+)(+ 8L([q+/-(-1)]/2)) (4) Ag+(AgL(2)(q+/-)) + N2H4 <-> Ag 1/2N(2) + NH3 + H+(+ 2L([q+/-(-1)]/2)) (5) A mechanism is proposed in which the first oxidation product is a hydrazyl radical, which furthe r oxidizes or dimerizes. When a catalytic quantity of Cu-II ion was ad ded to the system, Reaction 4 is accelerated and Reaction 5 inhibited.