Hydrogen peroxide formation upon oxidation of oxalic acid in presence and absence of oxygen and of manganese(II)--III. Iron(III) and copper(II) as retarders.
The formation of considerable amounts of hydrogen peroxide upon the slow addition of various oxidizing agents to oxalic acid in dilute sulphuric acid in the presence of oxygen and Mn(II) is greatly retarded in the presence of Fe(III) or Cu(II). With hydrogen peroxide as oxidizing agent and a trace of Fe(II) there is considerable decomposition of peroxide, under a nitrogen atmosphere, after a few hours at 25 degrees in light (from a tungsten lamp), and less decomposition in the dark. This decomposition is decreased by Mn(II) and also when the original mixture contains Fe(III). With oxygen as the oxidizing agent Fe(II) is about 100 times as effective an inhibitor of peroxide formation as Fe(III). With all oxidizing agents used, Cu(II) is some 6-10 times more effective as a retarder than Fe(III). The inhibition is accounted for by the reaction Fe(III) [or Cu(II)] + CO(-)(2) --> Fe(II) [or Cu(I)] + CO(2).
Kolthoff
I M
IM
School of Chemistry, University of Minnesota, Minneapolis, MN 55455, USA.
Meehan
E J
EJ
Kimura
M
M