The reaction between NaN, and I, in aqueous solution with liberation of N, is induced by both Na,S,O, and Na,S,O,, and studies of both processes have been made over fairly wide ranges of conditions. The induction by Na,S,O, which yields H,SO, and N, is slow, and kinetic measurements have been made by determining the rates of consumption of iodine and of production of N,. The effect of [I-] on both rates is characterized by a pronounced minimum in the region of [I-] = 0*01-0'02. The results are accounted for in terms of a chain mechanism, involving the intermediates S,O,Iand S,O,N; (or S,O;), with different primary steps in the regions of low [I-] and high [I-]. The latter correspond t o the first steps in reactions which have been found t o take place in absence of N;, viz. the reaction between S, O; -and I, in presence of very low [I-] and the reaction between S,O;-and I-. The former of these has been studied kinetically but as yet no mechanism is proposed for it. The products of reaction in S205---I,-N~ systems include S,O;-, H2S04 and N,. The reactions are too fast to follow by ordinary kinetic methods and experimental work has been limited t o investigation of the over-all stoichiometry and of the relation between I, consumed to Na,S,O, consumed under a variety of conditions. A possible chain mechanism for the reaction is suggested. Based on this work an experimental method was evolved by means of which the rate of the direct reaction between Na,S,O, and I, could be measured in mixtures containing excess I,, and a reaction mechanism derived from these data is proposed for the I,-S,O;reaction. The mechanism suggested is