Journal article
Redox Potentials of Magnetite Suspensions under Reducing Conditions
Environmental science & technology, Vol.56(23), pp.17454-17461
12/06/2022
DOI: 10.1021/acs.est.2c05196
Appears in UI Libraries Support Open Access
Abstract
Predicting the redox behavior of magnetite in reducing soils and sediments is challenging because there is neither agreement among measured potentials nor consensus on which Fe(III) »| »Fe(II) equilibria are most relevant. Here, we measured open-circuit potentials of stoichiometric magnetite equilibrated over a range of solution conditions. Notably, electron transfer mediators were not necessary to reach equilibrium. For conditions where ferrous hydroxide precipitation was limited, Nernstian behavior was observed with an EH vs pH slope of -179 ± 4 mV and an EH vs Fe(II)aq slope of -54 ± 4 mV. Our estimated EHo of 857 ± 8 mV closely matches a maghemite|aqueous Fe(II) EHo of 855 mV, suggesting that it plays a dominant role in poising the solution potential and that it's theoretical Nernst equation of EH[mV] = 855 - 177 pH - 59 log [Fe2+] may be useful in predicting magnetite redox behavior under these conditions. At higher pH values and without added Fe(II), a distinct shift in potentials was observed, indicating that the dominant Fe(III)|Fe(II) couple(s) poising the potential changed. Our findings, coupled with previous Mössbauer spectroscopy and kinetic data, provide compelling evidence that the maghemite/Fe(II)aq couple accurately predicts the redox behavior of stoichiometric magnetite suspensions in the presence of aqueous Fe(II) between pH values of 6.5 and 8.5.
Details
- Title: Subtitle
- Redox Potentials of Magnetite Suspensions under Reducing Conditions
- Creators
- Thomas C. Robinson - University of IowaDrew E. Latta - University of IowaJohna Leddy - University of IowaMichelle M. Scherer - University of Iowa
- Resource Type
- Journal article
- Publication Details
- Environmental science & technology, Vol.56(23), pp.17454-17461
- DOI
- 10.1021/acs.est.2c05196
- ISSN
- 0013-936X
- eISSN
- 1520-5851
- Publisher
- American Chemical Society
- Grant note
- DOI: 10.13039/100006151, name: Basic Energy Sciences; DOI: 10.13039/100000082, name: Division of Graduate Education, award: 1633098; DOI: 10.13039/100000005, name: U.S. Department of Defense, award: ER20-1357
- Language
- English
- Electronic publication date
- 11/17/2022
- Date published
- 12/06/2022
- Academic Unit
- Civil and Environmental Engineering; IIHR--Hydroscience and Engineering; Chemistry
- Record Identifier
- 9984318254202771
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