An analytical study of the neutralization process of solutions with high concentration of Fe(III) ions
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2017-01-01
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Abstract
With the means of software HSC Chemistry ver.7.1 modules: Equations Reaction and Eh-pH diagrams a thermodynamic assessment of the neutralization process of sulfuric acid solutions with high concentration of ferric ions (> 60 g l-1) with calcium carbonate and calcium hydroxide was carried out. Based on the calculated values of the energy of Gibbs and the equilibrium constants of the possible chemical interactions during the neutralization process with Ca(OH)2 and CaCO3 of a sulfuric acid solutions with a high concentration of ferric ions has been established that the neutralization process without participation of Fe3+ was thermodynamically more probable than in the presence of ferric ions. When Ca(OH)2 (hydrated lime) was used as neutralizer, the probability to obtain a precipitate of CaSO4*2H2O (gypsum) and FeO*OH (goethite) was the most thermodynamically probable, while using a neutralizer CaCO3 (limestone), the most probable was a precipitate of gypsum and Fe(OH)3. With increasing of the temperature from 25 to 60°C, the thermodynamic probability of goethite formation increases. Based on Eh-pH diagrams of the system H2SO4-CaCO3-Fe2(SO4)3-FeSO4-H2O it was established that in the pH range from -2 to 6 and temperature 25°C the most stable compound is calcium sulphate dehydrate. With the increase of temperature up to 60°C the most stable compound is anhydrite. The diagrams were built for molar concentrations of the elements in the solution (expressed as mol/kgH2O): 1,079 Fetotal, 0,622 S, 0,622 Ca and 0,622 C. The composition of the solution corresponds of the total iron and sulfuric acid concentrations and the quantity of CaCO3 necessary for neutralization of 100 % H2SO4. At the oxidation potential (Eh > 0.8 V) and high acidity of the solution (pH from -2 to 0.5), the areas of stability of iron ionic complex FeHSO4 2- and Fe3+ ion were found. In practice this means that the process of neutralization have to be carried out at a high oxidation potential and pH < 0.5 in order to avoid coprecipitation of iron sludge: Fe(OH)3 or FeO*OH.