The aqueous ionic equilibrium and speciation of iron and nickel in sulphuric solutions

Abstract

This paper presents a theoretical investigation on the ionic equilibrium of Fe(III)-Ni(II)-H2SO4-H2O system. A non-ideal speciation model is developed to calculate the concentration distribution of iron and nickel species in a mixed ferric and nickel sulphate aqueous solution over the pH range from 0 to 4 and temperature from 25 to 100°C. A series of speciation diagrams for iron and nickel species is plotted with the effects of ionic strength and temperature on the equilibrium constants being taken into account. The ionic strength-dependent equilibrium constant is treated through a semi-empirical Vasil'eV equation, which is based on an extended Debye-Hückel theory. A Helgeson model is applied to extrapolate the equilibrium constant to elevated temperature. The ionic equilibrium reactions are described by a group of numerical equations containing the temperature and ionic strength-dependent equilibrium constants, which are solved by the Newton-Raphson method. The speciation model is also applied to estimate the hydrogen ion activities and corresponding pH values. The calculated pH values are in agreement with the experimentally measured pH, and are compared to literature data and pH values produced by the Visual MINTEQ® program (a computer code for the calculation of chemical equilibrium in natural aqueous system). This investigation provides a deep insight into the ionic equilibrium behavior of a mixed metal sulphate aqueous system which commonly occurs in hydrometallurgical processing.