『Abstract
The kinetics of Fe(II) oxygenation in aqueous solutions over
the pH range 6.0-8.0 have been revisited in terms of kinetic modeling
approach, rate constant estimation and the importance of various
oxidation pathways. Despite the experimental agreement with earlier
studies, previous oxidation models (which describe the oxidation
of micromolar Fe(II)) have failed to provide an adequate description
of Fe(II) oxidation at nanomolar concentrations. This failure
could be due to the difficulties in reliably estimating values
for the number of kinetic and stability constants involved but
is more likely associated with the fact that several reaction
pathways that could become important at low Fe(II) concentrations
have not been included in the previous models. A condition-specific
model has been developed which uses a single Fe(II) entity as
a representative of all Fe(II) species to overcome the difficulty
of dealing with the large number of unknown kinetic constants.
By incorporation of various reaction pathways, the model is shown
to be capable of adequately describing the oxidation of Fe(II)
over a range of pH and initial Fe(II) concentrations. While the
oxidation of Fe(II) by oxygen and super oxide is critically important
at any pH and initial Fe(II) concentration considered, oxidation
of Fe(II) by hydrogen peroxide only becomes critical at high pH
and high Fe(II) concentrations or in the later stage of the oxidation
process. Back reduction of Fe(III) by superoxide is important
at low initial Fe(II) concentrations and high pH. Precipitation
of Fe(III) on the other hand exerts a marked effect in the overall
oxidation of Fe(II), particularly at high pH. Disproportionation
of superoxide has minimal effect on the overall oxidation of Fe(II),
despite the rapidity of this process at low pH.』
1. Introduction
2. Experimental
2.1. Reagents
2.2. Experimental procedure
2.3. Modelling method
2.4. Speciation model
3. Results and discussion
3.1. Oxidation of Fe(II) at nanomolar concentrations
3.2. Testing of the previous Fe(II) oxidation models
3.3. Modeling the kinetics of Fe)II) oxidation using the FeL
modelling approach
3.3.1. Assignment of kinetic constants
3.3.2. Model fitting
3.4. Estimation of intrinsic rate constants for oxygenation of
particular Fe(II) species
3.5. Relative importance of various reactions in the Fe(II) oxidation
model
3.5.1. Oxygenation of Fe(II) (reaction 1)
3.5.2. Oxidation of Fe(II) by O2.-
(reaction 2)
3.5.3. Disproportionation of superoxide
3.5.4. Oxidation of Fe(II) by H2O2
3.5.5. Back reduction of Fe(III) by superoxide
3.5.6. Precipitation of Fe(III)
3.5.7. Combination of reaction 1 and 2 in the overall oxidation
of Fe(II)
3.6. Limitations of the study
4. Conclusion and implications
Acknowledgments
References