『Abstract
Analytical methods used for determining dissolved Fe(II) often
yield inaccurate results in the presence of high Fe(III) concentrations.
Accurate analysis of Fe(II) in solution when it is less than 1%
of the total dissolved Fe concentration (FeT)
is sometimes required in both geochemical and environmental studies.
For example, such analysis is imperative for obtaining the ratio
Fe(II)/Fe(III) in rocks, soils and sediments, for determining
the kinetic constants of Fe(II) oxidation in chemical or biochemical
systems operating at low pH, and is also important in environmental
engineering projects, e.g. for proper control of the regeneration
step (oxidation of Fe(II) into Fe(III)) applied in ferric-based
gas desulphurization processes. In this work a method capable
of yielding accurate Fe(II) concentrations at Fe(II) to FeT ratios as low as 0.05% is presented. The method
is based on a pretreatment procedure designed to separate Fe(II)
species from Fe(III) species in solution without changing the
original Fe(II) concentration. Once separated, a modified phenanthroline
method is used to determine the Fe(II) concentration, in the virtual
absence of Fe(III) species. The pretreatment procedure consists
of pH elevation to pH 4.2-4.65 using NaHCO3
under N2(g) environment, followed by filtration
of the solid ferric oxides formed, and subsequent acidification
of the Fe(II)-containing filtrate. Accuracy of Fe(II) analyses
obtained for samples (Fe(II)/FeT ratios between
2% and 0.05%) to which the described pretreatment was applied
was>95%. Elevating pH to above 4.65 during pretreatment was shown
to result in a higher error in Fe(II) determination, likely resulting
from adsorption of Fe(II) species and their removal from solution
with the ferric oxide precipitate.』
1. Introduction
2. Proposed pretreatment procedure
3. Materials and methods
3.1. Analyses
3.2. Reagents
3.3. Pretreatment procedure
3.4. Experimental
3.4.1. Preliminary experiment
3.4.2. Suggested procedure verification experiments
4. Results
4.1. Determining the minimal pH required for efficient Fe(III)
precipitation in the pretreatment procedure
4.2. Determining the Fe(II) impurity concentration in the Fe2(SO4)3
background solution
4.3. Applying the suggested method (pretreatment + analysis by
the modified phenanthroline method) to samples with different
Fe(II):FeT ratios at various pH values during
pretreatment
5. Discussion
6. Conclusions
Acknowledgements
References