Thursday, 29 September 2016

inorganic chemistry - Why can't I reproduce this photolytic reaction of ferrocyanide?


I was so intrigued by the reported observation that sunlight precipitates the iron from KX4Fe(CN)X6 (originally attributed to Matuschek, 1901) that I wanted to see it myself. I put a saturated aqueous solution, uncovered, in direct sunlight for four hours at mid-day. Absolutely nothing precipitated from the solution!


My understanding from the given reference is that in solution the KX4Fe(CN)X6 gives Fe(CN)X6X4 and then:


Fe(CN)X6X4+2HX2OFe(CN)X5+(HX2O)X3+HCN+OHX


The photolysis causes Fe(CN)X6X4hνFe(CN)X6X3+eX, so then we also have


Fe(CN)X6X3+2HX2OFe(CN)X5+(HX2O)X2+HCN+OHX


Is it correct to assume that if a Fe(CN)X6X4 anion absorbs a photon of adequate energy (in this case it appears to require λ<313nm) then with 100% probability the anion will photolyze the Fe bond?


And are there models that predict (at least order of magnitude) the absorption probability of a photon by an aqueous anion (being irradiated with a given spectral flux)?



Furthermore, what is the reaction that would precipitate iron in this case? When we bring the K back into the equations it looks like the HCN would react to produce KCN. I don't know what should happen to Fe(CN)X5.


In fact, after several days in open sunlight the solution is subjectively getting darker and I do see a small amount of red sediment at the bottom of the dish that appears to redissolve on swirling. Could be an iron oxide, but would also be consistent with KX3Fe(CN)X6. In either case I don't have any indication from the source what should happen to the (CN)X5 groups if iron is precipitating, or what else might take one of the K atoms from the initial compound.


(Ultimately I had hoped to quantify the rate of photolysis by weighing the precipitate.)




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