Radiation chemical formation of Turnbull blue from Fe(III)-oxalate

Complete text of publication follows. The radiation chemical analogue of the photochemical disproportionation reaction K3[Fe(III)(oxalate)3] into Fe(II)2+ and CO2 was investigated through the formation and precipitation of Turnbull blue, K[Fe(II)Fe(III)(CN)6] by pulse radiolysis. Beyond the establishment of the qualitative analogy between the effects of fast electrons and visible light, the phenomenological kinetics of the process was established. After a fast first order process (time scale of the order of 1 ms) a slower first order reaction takes place (time scale of the order of several seconds) whereas the transformation is concluded by a slow autocatalytic step. The possible mechanism is discussed with a view also to photochemical observations