As part of a study of oxalic acid leaching to reduce the iron content of glass sand, photochemical reduction of trisoxalatoiron(III) species formed in the leachates and precipitation of the product as iron(II) oxalate dihydrate were examined as potential means of treating process liquors. Parametric studies showed that, under favourable conditions — including concentration (80–700 mg/l Fe, 1–2% w/v oxalic acid), quality and intensity of illumination (e.g., daylight of illumination > 2500 lux), temperature (ambient), mode and intensity of agitation (slow stirring), and pH (<2) — the primary reaction (reduction of iron(III) to iron(II) with evolution of carbon dioxide from oxalate) largely occurred within 1–2 h. Following an induction period of several h during which the solution became supersaturated with respect to iron(II) and oxalate, well-formed yellow 10–40 Am crystals of FeC 2O 4 · 2H 2O (matching those reported in the literature) were precipitated over about 24 h. An excess of oxalic acid was necessary to maximise the rate of photochemical reaction and minimise re-oxidation (which caused an increase in pH and led to the precipitation of hydrated iron(III) oxide). For both thermodynamic and kinetic reasons, the extent of reaction was normally restricted to about 80% of the theoretical maximum. Photodecomposition was shown to be a potential continuous hydrometallurgical process meriting more detailed evaluation. Because of its relatively high purity and good handling characteristics, the precipitated iron(II) oxalate dihydrate represented a useful potential feedstock for added-value products, e.g., speciality iron oxides.
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