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The Role of One- and Two-Electron Transfer Reactions in Forming Thermodynamically Unstable Intermediates as Barriers in Multi-Electron Redox Reactions

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Abstract

In the aquatic geochemical literature, a redox half-reaction is normally written for a multi-electron process (n > 2); e.g., sulfide oxidation to sulfate. When coupling two multi-electron half-reactions, thermodynamic calculations indicate possible reactivity, and the coupled half-reactions are considered favorable even when there is a known barrier to reactivity. Thermodynamic calculations should be done for one or two-electron transfer steps and then compared with known reactivity to determine the rate controlling step in a reaction pathway. Here, thermodynamic calculations are presented for selected reactions for compounds of C, O, N, S, Fe, Mn and Cu. Calculations predict reactivity barriers and agree with one previous analysis showing the first step in reducing O2 to O2 − with Fe2+ and Mn2+ is rate limiting. Similar problems occur for the first electron transfer step in these metals reducing NO3 −, but if reactive oxygen species form or if two-electron transfer steps with O atom transfer occur, reactivity becomes favorable. H2S and NH4 + oxidation in a one-electron transfer step by O2 is also not favorable unless activation of oxygen can occur. H2S oxidation by Cu2+, Fe(III) and Mn(III, IV) phases in two-electron transfer steps is favorable but not in one-electron steps indicating that (nano)particles with bands of orbitals are needed to accept two electrons from H2S. NH4 + oxidation by Fe(III) and Mn(III, IV) phases is generally not favorable for both one- and two-electron transfer steps, but their reaction with hydroxylamine and hydrazine to form N2O and N2, respectively, is favorable. The anammox reaction using hydroxylamine via nitrite reduction is the most favorable for NH4 + oxidation. Other chemical processes including photosynthesis and chemosynthesis are considered for these element–element transformations.

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Acknowledgments

This work was supported by grants from the U.S. National Science Foundation (DEB-0516121; OCE-00963635; OCE-0732439; MCB-0919682), from the U.S. National Oceanic and Atmospheric Administration Sea Grant program (NA09OAR4170070) and from a subcontract to the University of Delaware from the NASA Astrobiology grant to University of California, Berkeley NASA (NCC2-1056 and NAG2-1523). I thank two anonymous reviewers for their constructive comments. The statements, findings, conclusions, and recommendations are those of the author and do not necessarily reflect the views of the granting agencies. The author also wishes to express his gratitude and appreciation to Frank Millero for his encouragement and friendship.

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  1. School of Marine Science and Policy, College of Earth, Ocean and Environment, University of Delaware, Lewes, DE, 19958, USA

    George W. Luther III

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Luther, G.W. The Role of One- and Two-Electron Transfer Reactions in Forming Thermodynamically Unstable Intermediates as Barriers in Multi-Electron Redox Reactions. Aquat Geochem 16, 395–420 (2010). https://doi.org/10.1007/s10498-009-9082-3

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