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Redox and

pE pH Diagrams

OCN 623 Chemical Oceanography

Reading: Libes, Chapter 7

Outline

Redox potential
-simple e-cell, Nernst, reactions

pE-pH diagrams
-fingerprinting with protons & electrons

Electropotential & free energy


-quantifying electron transfer

The leap to metabolism(s)

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Redox Potential: The Fundamentals
Redox potential expresses the tendency of an
environment to receive or supply electrons

An oxic environment has high redox potential because


O2 is available as an electron acceptor

For example, Fe oxidizes to rust in the presence of O2


because the iron shares its electrons with the O2:

4Fe + 3O2 2Fe2O3

In contrast, an anoxic environment has low redox


potential because of the absence of O2

the more positive the potential, the greater the species' affinity for electrons and
tendency to be reduced

A Simple Electrochemical Cell


FeCl2 at different Fe oxidation
Voltmeter states in the two sides

Agar, KCl Wire with inert Pt at ends --


Salt bridge
e- voltmeter between electrodes
e -

Electrons flow along wire, and


Cl- diffuses through salt
bridge to balance charge
Pt Pt
Cl-
Cl- Cl- Fe3+ Voltmeter measures electron
Fe2+
Cl- Cl- flow
Fe2+ - e- = Fe3+ Fe + e- = Fe2+
3+

Charge remains neutral

2
Container on right side is more
oxidizing and draws electrons
from left side
Voltmeter
Electron flow and Cl- diffusion
continue until an equilibrium is
Agar, KCl established steady voltage
e-
Salt bridge
measured on voltmeter
e-
If container on right also
contains O2, Fe3+ will
precipitate and greater voltage
Pt Pt is measured
Cl-
Cl- Cl- Fe3+ 4Fe3+ + 3O2 + 12e-
Fe2+
Cl- Cl- 2Fe2O3 (s)
Fe2+ - e- = Fe3+ Fe3+ + e- = Fe2+
The voltage is characteristic for
any set of chemical conditions

Electrochemical Cells - 1
Consider the following simple electrochemical cell
operating at 25C:

ions

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Electrochemical Cells - 2
We arbitrarily assign a potential of 0 to
the reaction in the left cell:
2H+(aq) + 2e- H2(g) E= 0.000 V

Then the potential for the reaction in


the right cell is:
Cu2+(aq) + 2e- Cu0(s) E= 0.337 V
(always write as a reduction)

The standard potentials for all redox reactions are similarly


determined against the standard hydrogen electrode:

Electrochemical Cells - 3

= E = EH

4
Electrochemical Cells - 4
An electrochemical cell is capable of doing work by
driving electrons across a potential difference.
This can be measured as a change in free energy:
G = -nFE
where
n = number of moles of electrons (equivalents) involved in
the reaction
F = Faraday constant = 23.1 kcal V-1 equiv-1
E = the cell potential (V) at standard state

For the general case: G = -nFE

Nernst Equation - 1
We know from a previous class:
{ products}x reduced species
G = G + RT ln
{reactants}y oxidized species

Sustituting G = -nFE, we get the Nernst Equation:


RT { products}x
E = E ln
nF {reactants} y
Or:
y
RT {reactants}
E = E + ln
nF { products}x
At 298K:
y
0.0592 {reactants}
E = E + log
n { products}x

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Nernst Equation - 2
Important points:

Geochemists usually use the symbol EH instead of E


(indicating the hydrogen scale is being used).

The Nernst Equation relates the EH of a cell to the


standard EH and to the activities of reactants and
products.

When at standard state (all activities = 1), EH = E

We can use EH as an indicator of the state of natural


waters:

Example #1: Use Eh values to


Calculate Vanadium Speciation
V 3+ + e V 2 +
What species of V dominates in seawater?
0.059! V 3+
Eh = Eh + log 2+
1 V
1. Assume measured Eh = 0.729 V
2. From Table 7.1: Eh= -0.26 V 3+
0.729 = 0.26 + 0.059 log 2+
V
3. Plug into equation:
V 3+
0.989 = 0.059 log 2+
V
3+
V
V3+ dominates 16.8 = log 2+
V
V 3+ 16
2+ = 6x10
V

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Redox Potential in Nature
A mixture of constituents, not really separate cells

We insert an inert Pt electrode into an environment and


measure the voltage relative to a standard electrode
[Std. electrode = H2 gas above solution of known pH (theoretical, not
practical). More practical electrodes are calibrated using this H2
electrode.]

Example: when O2 is present, electrons migrate to the Pt


electrode:

O2 + 4e- + 4H+ 2H2O

The electrons are generated at the H2 electrode:

2H2 4H+ + 4e-

Voltage between electrodes measures the redox potential

Redox Potential of a Reaction

General reaction:

Oxidized species + e- + H+ reduced species

Redox is expressed in units of pe, analogous to pH:

pe = - log [e-] (or Eh = 2.3 RT pE/F)

where [e-] is the electron concentration or activity

pe is derived from the equilibrium constant (K) for an


oxidation-reduction reaction at equilibrium:

[ reduced species ]
K= [ oxidized species ][ e ][ H + ]

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Oxidized species + e- + H+ reduced species

[ reduced species ]
K = [ oxidized species ][ e ][ H + ]

log K = log [red ] log [ox] log [e ] log [ H + ]


log K = pred + pox + pe + pH

If we assume [oxidized] = [reduced] = 1 (i.e., at standard state),


then:
log K = pe + pH

log K = pe + pH
The Nernst Equation can be used to relate this equation to
measured Pt-electrode voltage (Eh, Eh , EH):

F
pe pE = Eh or Eh = 2.3 RT pE/F
2.3RT
where:
Eh = measured redox potential as voltage
R = the Universal Gas Constant (= 8.31 J K-1 mol-1)
T = temperature in degrees Kelvin
F = Faraday Constant (= 23.1 kcal V-1 equiv-1)
2.3 = conversion from natural to base-10 logarithms

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Example #2: Calculation of pE
Assume:
pE in a given environment is controlled by this reaction:
Fe3+ + e- Fe2+ 1 oxid
pE = pE ! + log
(n = 1) n reduc

{Fe3+} = 10-5
log(K )
{Fe2+} = 10-3 Table 7.1 pE ! = = 13.0
n

10 5
pE = 13 .0 + log 3 = 11.0
10

{ e }= 10
11

Example #3: Effect of Atmospheric O2


Assume: Natural water at pH 7.5 in equilibrium with atmosphere
PO2 = 0.21 atm { O2 } = 0.21

1 1
O2 ( g ) + H + (aq ) + e H 2O(l )
4 2

pE ! = 20.75 (Table 7.3, Libes)

pE = pE + ! 1 {O }4 {H + }
log 2 {H } = 10
+ 7.5
1
n {H 2O}2 1

pE = 13.08 { }
e = 10 13.08

Conclusion: This environment has lower electron activity than


Example #2, and is thus more oxidizing

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Redox Reactions Have Characteristic pE Values
F
pE = EH
2.3RT

G
pE =
2.3nRT

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Thus, if an environment is characterized by a
certain redox reaction, it has a characteristic pE

O2 + H+ + e- H2O

H2O + e- H2 + OH-

Garrels & Christ (1965)

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pE-pH Diagrams - 1
pE-pH stability field diagrams show in a comprehensive
way how protons (pH) and electrons (pE)
simultaneously shift equilibria of reactions under various
conditions.
These diagrams also indicate which species predominate
under any given condition of pE and pH.

Two equations are used to produce the diagrams:


o
1
pE = pE + log
{oxid }
n {reduc}r
1
pE = log K
n

pE-pH Diagrams - 2
Oxidizing limit of diagrams: O2 + H+ + e- H2O
1
pE = +20.75 (Table 7.3) 1
pE = pE + log
{O2 } 4 H+ { }
n=1 1
n {H 2O} 2
pH = -log{H+}
Set limit: {O2} = 1 pE = 20.75 pH

Reducing limit of diagrams: H2O + e- H2 + OH-


OH- + H+ H2O
H + + e- H2
pE = 0.0 (Table 7.3) 1
pE = pE + log
{ }
H+
n=1 1
n {H 2 } 2
pH = -log{H+}
Set limit: {H2} = 1 pE = pH

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pE-pH Diagrams - 3
Oxidizing limit of diagrams:
O2 + H+ + e- H2O
pE = 20.75 pH

Reducing limit of diagrams:


H + + e- H2
pE = pH

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pE-pH Diagrams - 4

Phase-boundary lines on a
pE-pH diagram indicate stability
field boundaries defined as
lines where activities of both
adjacent dominant species are
equal.
Lines are defined by reactions
between adjacent dominant
species
Reactions must have known
log K or pE values.

Construction of pE-pH Diagram - 1


Acid-base reactions with no pE dependency

2
6. HSO 4 SO 4 + H+ logK = 2.0

K =
{ SO }{ H }
4
2 +

{ HSO } 4

log K = 2.0 = log


{ SO } pH 4
2

{ HSO } 4

{
When SO4
2
}= { HSO }, 4

pH = 2.0

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Construction of pE-pH Diagram - 2
Redox reactions of dissolved species
2
5. SO 4 + 9H + + 8e HS + 4H 2 O log K = 34.0

1
pE = pE + log
SO4! H+ { 2
}{ } 9

8 HS {H 2O}
4
{ } =1

1 34
pE ! = log K =
n 8

pE =
34 1
+ log
SO4 { 2
} 9
pH
8 8 HS { } 8

34 9
When SO4{ 2
} = { HS },
pE =
8
pH
8

Construction of pE-pH Diagram - 3


Redox reactions of dissolved and solid species

2
1. SO 4 + 8H + + 6e S(s ) + 4H 2 O log K = 36.2

pE =
36.2
+
1
log
SO4 H+ { 2
}{ } 8

6 6 { S(s )}{ H 2O }4 =1

36.2 1 8
pE =
6
+ log SO4
6
2
{
pH
6
}

8
When SO4 { 2
} = 10 2
, pE = 5.70
6
pH

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Free Energy and Electropotential

Talked about electropotential (aka emf, Eh)


driving force for e- transfer
How does this relate to driving force for any
reaction defined by Gr ??
Gr = - nE
Where n is the # of e-s in the rxn, is Faradays
constant (23.06 cal V-1), and E is electropotential (V)
pe for an electron transfer between a redox
couple analogous to pK between conjugate acid-
base pair

The higher the energy yield, the greater the benefit to


organisms that harvest the energy
In general:

There is a temporal and spatial sequence of energy


harvest during organic matter oxidation

Sequence is from the use of high-yield electron


acceptors to the use of low-yield electron acceptors

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Types of metabolism
Light used
directly by
phototrophs

Hydrothermal
energy utilized
via heat-
catalyzed
production of
inorganics

Nealson and Rye 2004

Marine Sediment Depth Profiles


0 Concentration (not to scale)
0 O2

G NO3-
Reaction Eh (V)
Reduction of O2
O2 + 4H + +4e- --> 2H2O +0.812 -29.9
Reduction of NO3- Mn2+
2NO3- + 6H+ + 6e- --> N2 + 3H2O +0.747 -28.4
Reduction of Mn4+ SO42-
Depth

MnO2 + 4H+ + 2e- --> Mn2+ +2H2O +0.526 -23.3


Reduction of Fe3+
Fe(OH)3 + 3H+ + e- --> Fe2+ +3H2O -0.047 -10.1
Reduction of SO42-
SO42- + 10H+ + 8e- --> H2S + 4H2O -0.221 -5.9
Reduction of CO2
CO2 + 8H+ + 8e- --> CH4 + 2H2O -0.244 -5.6

CH4

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Layered Microbial Mat Communities

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Wisconsin & Australia

Hamelin Bay, Australia

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Tasmania, Australia
Canada, US sites

Rio Tinto, Spain Czech Republic

Banded iron formation

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Hydrothermal vents

The bottom line


Oxic-anoxic transitions

There is a principle difference between gradients of


compounds used for biomass synthesis and those
needed for energy conservation, such as oxygen.

Nutrient limitation leads to a decrease of metabolic


activity, but absence of an energy substrate causes a
shift in the composition of a microbial community,
or forces an organism to switch to a different type of
metabolism.

Brune et al. 2000

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Lecture Summary
Redox reactions control organic-matter oxidation and element
cycling in aquatic ecosystems

Eh pH diagrams can be used to describe the thermo-dynamic


stability of chemical species under different biogeochemical
conditions

Biogeochemical reactions are mediated by the activity of


microbes, and follow a sequence of high-to-low energy yield
that is thermodynamically controlled

Example organic matter oxidation:

O2 reduction (closely followed by NO3- reduction) is the


highest- yield redox reaction

CO2 reduction to CH4 is the lowest-yield redox reaction

ps - some cautions on convention

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SI

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Redox Equations Worth Knowing - SI
G = nFE
0.0592 oxid a
E = E! + log b
n reduc
1 oxid a
Equations are
pE = pE ! + log b written as
n reduc
REDUCTIONS
F
pE = Eh
2.3RT
1 Note: These equations
pE ! = log K will be provided on
n
exams, if necessary, but
G MGG students will be
pE =
2.3nRT expected to know them
during PQE, Comps,
etc.

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