EVSC 590 Oxidation -Reduction (Redox)

Soil Microbiology: An Exploratory Approach Chapter 2 and 13 Pages 17-18 and 163-165

Redox Reactions

An Oxidation-Reduction (redox) reaction is a chemical reaction in which electrons are transferred completely from one species to another.

Redox Reactions

The chemical species which loses electrons

in this transfer process is called oxidized

whereas the one receiving electrons is

called reduced.

Redox Reactions

Oxidation is the loss of electrons and Reduction is the gain of electrons. All chemical elements can accept or donate electrons under appropriate conditions.

Redox Reactions

Oxidation and Reduction always occur together because a substance can only donate electrons if another substance can accept it.

Redox Reactions

The chemical conditions of soils and nature limit the number of elements involved in natural electron exchange.
Many inorganic chemical reactions and virtually all biological reactions of C, N, and S are oxidation-reduction (redox) reactions

Redox Potentials

The redox reaction below has two half cells H2 + 1/2O2 H0 Eq. 1 an oxidation H2 2H+ + 2eEq. 2 and a reduction 1/2 O2 + 2H+ +2e- H 0 Eq. 3
2 2

Redox Potentials

The tendency of reactions to occur is based on the relative tendencies of reactions 2 and 3 to proceed in the directions indicated.
This tendency is determined by the electromotive force or potential(E) of the reaction.

Redox Potentials
The electromotive force for a half reaction is determined by measuring the electric potential generated relative to a reference electrode(normally a hydrogen electrode). By convention, the H electrode is assigned a half reaction potential (Eh) of 0.00v under standard state conditions, i.e. H+ (1M) + e- 1/2H2 (1atm) Eho=0.00V

Redox Potentials

The Eho is corrected to pH 7 and designated Eho to reflect metabolic activity at neutral conditions.

To facilitate comparisons, half reactions are written as reductions and the sign of the corresponding electrical potential is adjusted accordingly.

Redox Couples

In redox couples oxidized form is always placed on the left. e.g. 2H +/H2 or O2/ H2O H+ and O2 are the oxidized forms

Redox Couples

When constructing complete oxidation reduction reactions from constituent half reactions, the reduced substance of a redox couple whose reduction potential is the more negative donates electron to the oxidized substance whose potential is more positive.

Redox Potentials

The standardized values are referred to as reduction potentials , for example, 2H+ + 2e- H2 Eo= -0.42V Eq.4 1/2 O2 + 2H++ 2e- H 0 Eo=+0.82V Eq.5
2

Since Eq 4 is more negative than Eq 5, Eq 5 has a greater tendency to proceed as written.

FREE ENERGY

For the reaction; H2 +1/2 O2 H 0

2

Eo = +0.82 (-0.42) = +1.2 Go = -(2) (23.1) (1.24) = -239 KJ mol-1 of H20 produced

FREE ENERGY

One very useful measure of metabolic reaction is the free energy change also known as the Gibbs free energy. Gro is the intrinsic energy contained in a given substance.

FREE ENERGY

For a reaction X Y, the free energy change DGo is the difference between the free energy of the product Y and the reactant X DGo = Gy -Gx

FREE ENERGY

Negative DG = Exergonic, Positive Zero DG = Endogonic, DG = Equlibrium

FREE ENERGY

DGo for redox reaction can be calculated using the following equation. DGo = -nFDEo

N = # of electrons transferred F = Faradays constant (96.5KJV-1 mol-1) = 23.1 V-1 mol-1

FREE ENERGY

DEo= difference in reduction potentials for the two half reactions comprising the combined reaction. For the reaction; H2 + 1/2 O2 H20 DEo = +0.82 (-0.42) = +1.2 DGo = -(2) (23.1) (1.24) = -239 KJ mol-1 of H20 produced

FREE ENERGY

For the reaction

Ox + mH+ + ne Red DGr = DGro + RTln(Red)/(Ox)(H+)m

DGro = -nFEo

DGr = -nFE

Nerst Equation

Nernst Equation relates activities of to Eh -nFE = -nFEo + RT ln(Red)/(Ox)(H+)m Eh= Eho- RT/nFln(red)/(Ox) - mRT/nF lnH+

Reduces to Eh = 2.303RT/F x pe

Concept of pe

Just as pH is based on moles L-1, redox potential can also be expressed in terms of pe (-log of electron activity) which is compatible with units of moles per liter. In this way, electrons can be treated as other reactants and products so that both can be expressed by a single equilibrium constant.

Concept of pe

pe = -log (e-) It measures the relative tendency of a solution to accept electrons.

Reducing solutions have low pe and tend to donate electrons to species placed in the solution.

Concept of pe

Oxidizing solutions have high pe and tend to accept electrons from species placed in the solution.

Large values of pe favor the existence of electron- poor (i.e) oxidized species just as large values of pH favor the existence of proton poor species (i.e bases)

Concept of pe

Small values of pe favor electron- rich, or reduced, species, just as small values of pH favor proton rich species, acids.

Concept of pe

Unlike pH, however, pe can take on negative values. The largest pe value is +13.0 and the smallest is near -6.0.

pe vs Eh

Eh (millivolts) = 59.2pe Eh (Volts) = 0.059 pe e.g. For (CO2/ CH2O), -0.43V pe = 0.059 x 0. 43 =

Table 1. Redox Pairs Arranged in Order from the Strongest Reductants to the Strongest Oxidantsa (Paul and Clark, 1989).

Redox Pair
CO2/CH2O SO42-/H2S NO3-/N2 MnO2/Mn2+ NO3-/N2 Fe3+/Fe2+ 1/2 O2/H2O

pe
-7.3 -3.7 7.11 8.1 12.4 12.9 13.9

Eh (volts)
-0.43 -0.22 0.42 0.48 0.74 0.76 0.82

Concept of pe
In soils the pe range can be divided into 3 parts that corresponds to: 1) oxic soils (pe > + 7 at pH 7)

2) Sub oxic soils (2 < pe < + 7 pe at pH 7)

3) Anoxic soils

( pe < + 2 at pH 7)

pe + pH
Most soil systems consist of aqueous environments in which the dissociation of water into H2(g) or O2(g) imposes redox limit on soils On the reduced side the redox limit is given by the reaction;

H+ + e-

1/2 H2 g Rxn.1

pe + pH
H+ + e 1/2 H2 g K = (H2)g1/2/(H+) (e-) , K = 1, thus log K = 0 or log K = 1/2 log H2 (g) - log (H+) - log(e-) At H2 =1 atm, pe + pH = O

This represents the most reduced equilibrium conditions in natural aqueous environments.

pe + pH
On the oxidized side the redox limit is given by the reaction H+ + e- + 1/4 O2(g) = 1/2 H2O Rxn.2 K =1/2 H2O /(H+)(e-)(O2)1/4 =1020.78. Log K =Log (H+) -log(e-) 1/4 log O2(g) = 20.78 pe + pH = 20.78 + 1/4 O2(g)

pe + pH

Thus when O2 is 1 atm, pe + pH = 20.78. This represents the most oxidized equilibrium conditions in natural aqueous environments

pe + pH
When the redox limits of natural aqueous environments defined by reactions 1 and 2 are plotted we get a graph which is known as a pE-pH diagram, and shows the domain of electron and proton activity that has been observed in soil environment worldwide. Both pe and pH are needed to specify the redox status of aqueous systems.

Redox in soils
1)

This pe range can be divided into 3 parts that corresponds to: Oxic soils (pE > + 7 ) at pH 7

2) Sub-oxic soils (2 < pE < + 7 ) at pH 7

3) Anoxic soils

(pE < + 2 ) at pH 7