I.

Oxidation-Reduction Reactions
A. Definitions Oxidation is the removal of electrons from an atom of an element, often by oxygen; this causes an increase in valence. Reduction is the addition of electrons, decreasing valence. All redox reactions involve the transfer of electrons.

Many elements occur in multiple valence states in the earth. Major elements include H, O, C, S, N (all important volatile components of fluids), Fe and Mn. Minor elements include U, Cr, As, Mo, Cu, Hg and others. Can write redox reactions in terms of oxygen transfer: Eq. I-1 Eq. I-2 Fe2O3 2 Fe3O4 + O2 3 Fe2O3 + 2H+ + 2e- 2 Fe3O4 + H2O Or in terms of electron transfer: The two methods are thermodynamically equivalent, but the latter is closer to reality for aqueous solutions. In Eq. I-2 H2O is the source of O2. Thus, oxidation generally releases protons, while reduction consumes them. As a result, the pH of a fluid is intimately related to the oxidation state as measured by Eh or pe. B. Electromotive Series Some elements are more readily oxidized than others. The oxidation potential is a measure of how much energy is needed to remove an electron from an element in a given valence state. The electromotive series ranks the elements and their ions in terms of their strengths as reducing agents. C. Redox Equilibria and Electrochemical Cells

Complete redox reactions represent the sum of two half-reactions, an oxidation reaction and a reduction reaction. All electrons produced by an oxidation must be consumed by a corresponding reduction - there are no free electrons in solution. Oxidation: Reduction: Redox (sum) H2(g) H+ + eFe3+ + e- Fe2+ Fe3+ + H2(g) H+ + Fe2+ E = 0 E = + 0.77V E = + 0.77V

E is the standard electromotive force (emf), the potential difference in volts between expressed in volts relative to the SHE: the Standard Hydrogen Electrode, represented by the oxidation reaction above, and is also referred to as Eh. Species with positive standard

electrode potentials such as Fe3+ act as electron acceptors in the standard state (concentration of 1m for aqueous species, partial pressure of 1 atm. for gases). D. Thermodynamics A fundamental thermodynamic relationship discovered by Michael Faraday is: Eq. I-3 G = -nFE where n: # of electrons transferred in the reaction F: Faradays constant = 96,489 coulombs/mole = 96.5 kJ/Volt mole E: electromotive force in volts This equation is equivalent to the statement: charge * potential = work. F represents the quantity of electricity that will produce a chemical change involving one equivalent (mole), i.e., the total charge of one mole of electrons. Another fundamental thermodynamic relationship is: Eq. I-4 Gr = Gr + RTlnKeq Notes: 1. At equilibrium, Gr = 0, and lnKeq = -Gr/RT 2. If all species in their standard states, activities = 1, RTlnKeq = 0, and Gr = Gr. Substituting Eq. I-3 into Eq. I-4 and dividing by nF, we obtain the Nernst Equation: Eq. I-5 For T=298K, this reduces to: Eq. I-6 Eh = E + 0.059/n log Keq Analogous to Eh (E) is pe, the activity of electrons, = -log ae-. The two have a linear relationship according to: Eq. I-7 D. pe = (F/2.303RT )Eh; at 25C Eh = 0.059pe Balancing Half Reactions
Eh = E o RT RT 1 ln K eq = E o + ln nF K eq nF

1. Write reaction with oxidized form on left and reduced form on right. 2. Balance all elements but H and O. 3. Balance O by adding H2O. 4. Balance H by adding H+. 5. Balance charge by adding e-s to left side (i.e., write reaction as a reduction). Half reactions include e-s; a full redox reaction is obtained by adding together complementary oxidation and reduction reactions, which always occur together because e-s dont usually float around in solution.

Example half reactions: Fe2O3 - Fe2+: HS- - SO42-: Mn2O3 - MnCO3: Fe2O3 + 2e- + 6H+ 2Fe2+ + 3 H2O SO42- + 8e- + 9H+ HS- + 4 H2O Mn2O3 + 2e- + 2H+ + 2CO2 2MnCO3 + H2O

E. Types of Redox Equilibria 1. Two aqueous species (speciation): Fe2+ - Fe3+ 2. Solid - aqueous specie (solubility): Fe2O3 Fe2+ 3. Solid-solid (solid buffers): Fe2O3 - Fe3O4 (Hematite-Magnetite) F. Eh-pH and pe-pH Diagrams Redox equilibria generally involve the transfer not only of electrons but also of + H , and therefore are pH dependent. The stabilities of aqueous species and of minerals containing multivalent elements are generally described by constructing Eh-pH or pe-pH diagrams, which are special types of activity-activity diagrams. 1. Stability Limits of Water Written in terms of half-reactions. Dont need to add SHE reaction to make complete redox reaction because the Eh is generated entirely by the half-reactions describing the decomposition of water. a) Upper Stability Limit (oxidizing, high Eh) H2O decomposes to form O2: H2O(l) = 2 H+ + O2 + 2 eEh = E 0 + 0.059 0.059 1/ 2 log K eq = 1.23 + log [O2 ] H + n 2 Eh = 1.23 + 0.01479 log[O2 ] 0.059 pH

[ ])
2

This equation relates Eh and pH of an environment to its fO2. b) Lower Stability Limit (reducing, low Eh)

H2O decomposes to form H2, i.e., [H2] = PH2 = 1 atm (and [O2 = 10-83.1 atm.) H2 = 2 H+ + 2 e-, E0 = 0 volts

0.059 H+ Eh = E + log ; if [H 2 ] = 1 atm., [H 2 ] 2

0

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Eh = 0 +

0.059 2 log H + = 0.059 pH 2

c) Solubility of hematite (Fe2O3)

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Fe in natural waters is predominantly in the form of Fe2+; Fe compounds are generally more soluble at low Eh and pH. Write solubility as an oxidation half-reaction: 2 Fe2+ + 3 H2O = Fe2O3 + 6 H+ + 2 eG r0 = 30.16 kcal , E 0 = + 0.65 V

Eh = 0.65 0.177 pH 0.059 log Fe 2 +

6 0.059 H+ log Eh = 0.65 + Fe 2 + 2 2

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