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pE pH Diagrams
Outline
Redox potential
-simple e-cell, Nernst, reactions
pE-pH diagrams
-fingerprinting with protons & electrons
1
Redox Potential: The Fundamentals
Redox potential expresses the tendency of an
environment to receive or supply electrons
the more positive the potential, the greater the species' affinity for electrons and
tendency to be reduced
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
3
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
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
Nernst Equation - 1
We know from a previous class:
{ products}x reduced species
G = G + RT ln
{reactants}y oxidized species
5
Nernst Equation - 2
Important points:
6
Redox Potential in Nature
A mixture of constituents, not really separate cells
General reaction:
[ reduced species ]
K= [ oxidized species ][ e ][ H + ]
7
Oxidized species + e- + H+ reduced species
[ reduced species ]
K = [ oxidized species ][ e ][ H + ]
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
8
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
1 1
O2 ( g ) + H + (aq ) + e H 2O(l )
4 2
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
9
Redox Reactions Have Characteristic pE Values
F
pE = EH
2.3RT
G
pE =
2.3nRT
10
Thus, if an environment is characterized by a
certain redox reaction, it has a characteristic pE
O2 + H+ + e- H2O
H2O + e- H2 + OH-
11
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.
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
12
pE-pH Diagrams - 3
Oxidizing limit of diagrams:
O2 + H+ + e- H2O
pE = 20.75 pH
13
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.
2
6. HSO 4 SO 4 + H+ logK = 2.0
K =
{ SO }{ H }
4
2 +
{ HSO } 4
{ HSO } 4
{
When SO4
2
}= { HSO }, 4
pH = 2.0
14
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
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
15
Free Energy and Electropotential
16
Types of metabolism
Light used
directly by
phototrophs
Hydrothermal
energy utilized
via heat-
catalyzed
production of
inorganics
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
CH4
17
Layered Microbial Mat Communities
18
Wisconsin & Australia
19
Tasmania, Australia
Canada, US sites
20
Hydrothermal vents
21
Lecture Summary
Redox reactions control organic-matter oxidation and element
cycling in aquatic ecosystems
22
SI
23
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.
24