Eh-pH--1

Eh-pH Diagrams

I. Introduction
A. Nature of diagrams
1. Plot of Eh (the redox potential of a reaction) against pH
2. It is a predominance (phase) diagram showing, as a function of
these two parameters, the phases that are stable. For example,
with the S-H2O diagram
a) it shows that S is not stable at high pH and should only exist
in an acid medium
b) it shows that H2S appears only at low potential, i.e. reducing
conditions, and in acid media.
3. As we shall show this is in essence a free energy (actually
potential) vs pH diagram though done in terms of half reactions
4. These are equilibrium, or thermodynamic, diagrams

1.0
HSO4=

0.5
SO4=

So
Eh, Volts

0.0

H2S
-.5
HS-

0 7 14
pH

Eh-pH diagram for the S-H2O predominance diagram

 Eh-pH--2

B. History
1. Developed by Marcel Pourbaix in Belgium during the 1950s for
corrosion engineers
a) Pourbaix recognized that in atmospheric ambient situations
P and T were relatively constant
b) pH often the chief variable
c) oxidation state another variable
d) Zn is anodic to iron
e) Pourbaix developed Eh-pH diagrams for many metals
2. Geologists then recognized value of this in reconstructing
geochemistry of the earth
3. Not until the 1960s did hydrometallurgists really sieze on this
a) Previously this was taught (and still is) by metallurgists in
corrosion classes
b) Now we use this to show relative stability of Cu2S, CuS,
CuFeS2, Cu5FeS4, FeS2, etc.
4. A powerful hydrometallurgical tool
a) Often kinetics dominate low T reactions
b) Eh-pH shows possible phases
c) No use trying to get S at pH > 7
d) Hydrothermal decomposition of minerals of chief concern
5. We shall develop theory, construct diagrams from raw data and
learn how to use them.

II. Eh-pH Equilibria

A. Non-Redox
1. Dissociation of Fe2O3 in H2O
2. Most species are ionized and the dissociation of water in terms of
OH- and H+ is important

H2O H+ + OH-
 Eh-pH--3

Kw =
H OH H OH 10

14
at 25C
[H O]
2

Kw decreases as T increases = 0.96 X 10-14 at 60C

3. Consider dissociation of hematite in water

Fe2O3(c) + 3H2O(l) 2Fe+3(aq) + 6OH- (1)

a) But we derive this in terms of H+ so add to Equation (1) the
reverse of the water dissociation reaction

6OH- + 6H+ 6H2O

giving

Fe2O3(c) + 6H+ 2Fe+3(aq) + 6H2O (2)

4. In all Eh-pH relations we do a two step process:
a) Evaluate log K from the free energy of reaction
[Fe 3 ]2 [H 2 O]3 [Fe 3 ]2
K=
[Fe 2 O 3 ][H ]6 [H ]6
log K = 2log[Fe+3] 6 log[H+]
= 2log[Fe+3] + 6pH (3)
(because pH = -log[H+])
Equation (3) can be written in terms of pH
logK 2
pH = log[Fe 3 ]
6 6
or in terms of [Fe+3]
log[Fe+3] = 0.5 logK 3pH
b) Determine log K as a constant
To evaluate log K we must know some more information (like Go)
for the reaction because
GoR = - RT ln K
= -2.303RT log K

We must now determine what Go is for our reaction from the

thermodynamic data of each reactant and product for the reaction:
 Eh-pH--4

GoR = (Go)prod - (Go)reactants

where, subscript R = overall reaction
subscript prod = product components
subscript reactants = reactant components
v = stoichiometric amount
For instance for our reaction:

Fe2O3(c) + 6H+ 2Fe+3(aq) + 6H2O (2)

GoR = [2Gof(Fe+3) + 3Gof(H2O)] [Gof(Fe2O3) + 6Gof(H+)]

= 2Gof(Fe+3) + 3Gof(H2O) Gof(Fe2O3) - 6Gof(H+)

From Bard, Parsons and Jordan or Garrels and Christ or Pourbaix

we find out that:
Gof(Fe+3) = -2.53 kcal/mol
Gof(H2O) = -56.69 kcal/mol
Gof(Fe2O3) = -177.1 kcal/mol
Gof(H+) = 0.0 kcal/mol (free energy of an element in std. state)

Gof = 2 (-2.53) + 3 (-56.69) (-177.1) - 6(0)

= 1.97 kcal
But,
Gof = -2.303 RT log K

And, furthermore at room temperature and atmospheric pressures

Gof = -RT ln K
= -1363 ln K, at T = 25C (for Gof , R in cal)
= -1.363 ln K (in kcal)
So,
1.97 kcal
log K = = -1.44
1.363 kcal
 Eh-pH--5

But recall Equation (3) that:

log K = 2log[Fe+3] + 6pH = -1.44
or, solving for pH we get
pH = -0.24 1/3 log[Fe+3]
So essentially for any concentration of ferric in solution, we will
know the equilibrium pH involved.
B. Role of Oxidation-Reduction Potential (Eh)
1. For everything that is oxidized (raised oxidation state, lost
electrons) something must be equally reduced (lowered oxidation
state, gain of electrons).
2. Change of oxidation state

Fe+2(aq) + H+(aq) Fe+3(aq) + H2(g)

Iron is oxidized to a higher oxidation state, while hydrogen is
reduced to a lower oxidation state. (H+ ion is an oxidizing agent
because it oxidized ferrous to ferric; Fe+2 is a reducing agent
because it reduced the hydrogen ion to the gaseous state.)
a) The cell potential for this reaction can be measured as 0.771
volts when the hydrogen partial pressure is 1 atm, the pH is 0
and the total iron concentration in solution is 1M.
b) The overall reaction is actually made up of two half reactions:

Fe+2(aq) Fe+3(aq) + e- (4)

H+(aq) + e- H2(g) (5)

3. Free energy of reaction
a) Overall reaction:
GoR = [Gof(Fe+3) + Gof(H2)] [Gof(Fe+2) + Gof(H+)]
b) We can also do this for the individual half reactions, as well:
GoR(4) = [Gof(Fe+3) + Gof(e-)] [Gof(Fe+2)]
GoR(5) = [ Gof(H2)] [Gof(e-) + Gof(H+)]
c) The sum of the two individual equations equal the overall
reaction (note that the Gof(e-)s in both equations cancel)
 Eh-pH--6

4. Half cell reactions

a) We have two related problems:
i) we cannot measure the voltage of a half cell reaction but
only of the overall reaction. We dont know what the
voltage of either Equation (4) or (5) is.
ii) we do not know what the free energy of formation of the
two half cell reactions.
b) Nernst resolved this dilemma by selecting as a standard for all
electrode reactions the free energy of formation of H+; that is to
say, Gof(H+) = 0.00 kcal. With this accepted as true, and
knowing that the free energy for an element in its standard state
at 1 atm is 0, then:
GoR(5) = 0 - 0 - 0 = 0
Note: The free energy = 0 holds true for any number of electron
transferred between H+ and H2. In other words,

H+(aq) + e- H2(g) GoR = 0 kcal

2H+(aq) + 2e- H2(g) GoR = 0 kcal
4H+(aq) + 4e- 2 H2(g) GoR = 0 kcal

c) We do not know what Gof(e-) is, but we always assume in an

overall reaction, as long as there is an equal exchange of
electrons (which must happen, by definition of a redox reaction)
then we really dont need to know.
d) Therefore, general rules for our thermodynamic calculations:
Gof(e-) = 0
Gof(H+) = 0 (defined standard by Nernst)
Gof(element) = 0 (at 25C and 1 atm)
C. Voltage-Free energy relationships
1. Nernst (1864-1941) and Faraday (1791-1867), well-known
electrochemists, helped to define the field.
2. In his studies, Faraday designed experiments to measure the cell
potentials for any half cell. Remember, there really is no way to
 Eh-pH--7

measure only one half cell potential. To accomplish this, he made

a hydrogen/hydrogen ion electrode (shown below).

Pt wire
Glass
Tube 1 atm H2

Water
+
1MH
(pH = 0)

Standard hydrogen electrode (SHE)

2H (aq) + 2e = H2(g) G=0.0 kcal
+ -

3. Using this electrode he began measuring cell potentials for many

metal/metal ion half cells, as illustrated below with Cu/Cu+2.

Voltameter

Cu Current Direction
1 atm H2

or

1M H+ Soln.
1 M Cu+2 Soln
Salt Bridge

Cu+2 + 2e- = Cuo 2H+ + 2e- = H2(g)

4. Using the potentiometer (voltameter) he could measure the cell

potentials of the metal/ion half-cell with the hydrogen electrode at
zero current. In the example provided, he measured a potential of
0.34 V. But what direction did the potential go; what direction did
the current want to flow? Were the electrons going from left-to-
 Eh-pH--8

right, or from right-to-left? Were the cations of the salt bridge

moving from right-to-left or left-to-right to complete the circuit?
5. In other words, which reaction is correct?

Cu+2 + H2(g) Cu+ 2H+

Cu+ 2H+ Cu+2 + H2(g)
Would copper rather plate or be corroded?
6. NOTE: Trying to determine the direction of the potential is
exactly like the examples of determining direction of equilibrium
reactions.
7. He had to determine it by observing the metal/ion electrodes. As
the measurement was being taken, the Nernst observed that the
mass of the Cu metal was increasing; in other words, the copper
electrode was the place where Cu+2 reacts to make Cu. That is,

Cu+2 + 2e- Cu.

In order for this to occur, the hydrogen electrode must be the site of
the reaction that provides the electrons for the deposition, or

H2(g) 2e- + 2H+

8. Another way to look at this, the copper electrode is more positive
(more attractive to electrons than the hydrogen electrode)
9. The overall equation becomes:

Cu+2 + H2(g) Cu+ 2H+

10. The potential for this reaction was 0.34 with the electrons flowing
towards the copper electrode. Through lots of experiments, he was
able to determine the relationship of free energy with potential.
11. Nernst recognized the similarities between potential and free
energy. He derived the following equation to relate them:

G = -nE, where, G = free energy (kcal/mol)

n = stoichiometric amounts of electrons
transferred
= Faradays constant (23.06 kcal/molV)
E = electromotive potential (V)
 Eh-pH--9

G = -nE, where, G = standard free energy (kcal/mol)

n = stoichiometric amounts of electrons
transferred
= Faradays constant (23.06 kcal/molV)
E = standard electromotive potential (V)

12. This allows us to better predict effective red-ox reactions for any
half cells. Also, it shows that E for the hydrogen electrode is 0.00V
(the standard by which all other half-cells are made); this is
significant, because it shows that for all Eocell measured for cells
connected to hydrogen electrode is the Eo for the half-cell itself
(Eo for Cu+2/Cuo is +0.34 V)
13. Faraday (and others throughout history) completed an entire
series of possible half-cell electrodes. A few are listed below:
Half-cell Reaction E, Volts

Au+3 + 3e- Auo +1.42

Cu +2
+ 2e Cu
- o
+0.34
2H + 2e H2(g)
+ -
0.00
Pb +2
+ 2e Pb
- o
-0.16
Ni +2
+ 2e Ni
- o
-0.23
Co+2 + 2e- Coo -0.28
Fe +2
+ 2e Fe
- o
-0.41
Zn + 2e Zn
+2 - o
-0.76
This is known as the Standard Electromotive Potential series and is
only valid under standard conditions--25C, 1M [Me+n], 1 atm Pg.
NOTE: The sign of the E tells the direction of e- flow w.r.t. SHE.
14. Cell potentials:
When two half cells are combined, we can use the above tables
to predict which will be reductions, and which will be oxidations
using the following equation.
Eocell = Eored -Eooxid
 Eh-pH--10

If Eocell > 0, then Gocell <0 (spontaneous as written)

If Eocell < 0, then Gocell >0 (not spontaneous as written)
Eg. The Cu electrode reaction was a reduction (more attractive to
electrons) then the H electrode (less attractive to electrons). So by
looking at the table, the Eocell = 0.34V, because 0.34-0 =0.34. So
assuming the Cu electrode was the reduction worked!
15. Sign conventions of the E series:
Note that the Emf series in the table above shows all of the
reactions written as reduction reactions. If we write the reactions
backwards (that is, as oxidations) all of the signs would be
reversed. This simple fact, can create HUGE confusion. So two
sign conventions were adopted.
a) American Convention(convention of most American
electrochemists)
i) All reactions are written as oxidations, and assigned
the measured potential voltage. (Keep SHE as 0.00 V

potential); Meo Me+n + ne-

ii) Standard notation for half-cells - Meo/Me+n
b) European Convention(convention of most metallurgists)
i) All reactions are written as reductions, and assigned
the measured potential voltage. (Keep SHE as 0.00 V

potential) Meo Me+n + ne-

ii) Standard notation for half-cells - Me+n/Meo
c) International Union of Pure and Applied Chemists (IUPAC) has
adopted the European convention; therefore, we will too!
d) MAKE SURE YOU ARE CONSISTENT. IF THE TABLE YOU
USE IS IN AMERICAN CONVENTION, MENTALLY REWRITE
IT AS THE EUROPEAN CONVENTION (i.e., look to see if the
equations are reductions, and, if not, rewrite them.) Luckily for
 Eh-pH--11

us, IUPAC has made sure most texts are written in this
convention.
16. Nernst Equation-
Allows us to calculate potentials of systems not under standard
conditions.
From Thermodynamics:
G = Go + RT ln K
K = ratio of prod activities to reactant activities.

But recall that G = -nE, and Go = -nEo

-nE = -nE o + RT ln K
RT
E Eo lnK
nF
2.303RT
E Eo logK
nF

At 25C, knowing R = 1.987cal/mol, and = 23,060 cal/gV,

then we can write it as follows:
0.0591
E Eo log K (6)
n
17. Rules about K to keep in mind:

Generally speaking, for the reaction: aA + bB cC +dD

(activities)
products
[C]c [D]d
K all

(activities)
all

reactants [A]a [B]b

a) Assume the activity = concentration

(that is, assume the activity coefficients are unity)
b) Activity of solids = 1
c) Activity of water is 1
For example, the Cu electrode example with a solution of 0.1 M Cu +2:

Cu+2 + 2e- Cuo Eo = 0.34

[Cu o ] 1
K 2
10
[Cu ] (0.1)
 Eh-pH--12

0.059
E 0.34 log(10) 0.31 volts
2
III. Eh-pH Relations
A. Consider all possible half-reactions
B. Balancing equationsion electron method (this method works even if
no electron transfer occurs.)
1. Write the skeletal partial equation for the half-reaction and balance
them for the main element that is involved in the oxidation. (Write
both reactions if an overall equilibrium is required):

e.g.- Cr2O7-2 2Cr+3

2Cl- Cl2(g)
2. Add H2O and H+ as needed to balance the oxygens in the half
reactions:

e.g.- 14H+ + Cr2O7-2 2Cr+3 + 7H2O

2Cl- Cl2(g)
3. Balance the partial equations electrically:

e.g.- 14H+ + Cr2O7-2 2Cr+3 + 7H2O 2Cl- Cl2(g)

(+14 2 = 12) (2(+3) + 0 = 6) (-2) (0)
To balance the equations: add 6e- to the left add 2e- on the right
6e- + 14H+ + Cr2O7-2 2Cr+3 + 7H2O
2Cl- Cl2 + 2e-

4. If your dealing with only one skeletal equation, then this is it. If you
are looking for a balanced equilibrium reaction, we need to multiply
each equation by the least common factor to get an equal amount
of electrons on opposite sides of each equation.

1{6e- + 14H+ + Cr2O7-2 2Cr+3 + 7H2O}

3{2Cl- Cl2 + 2e-}

6e- + 14H+ + Cr2O7-2 2Cr+3 + 7H2O

6Cl- 3Cl2 + 6e-
 Eh-pH--13

5. Add them up and subtract like species (electrons, water, H+, etc.)
from both sides.

6e- + 14H+ + Cr2O7-2 + 6Cl- 2Cr+3 + 7H2O + 3Cl2 + 6e-

14H+ + Cr2O7-2 + 6Cl- 2Cr+3 + 7H2O + 3Cl2

C. Generalized Equations
1. Chemical Equations (without electron transfer)
Like Equation (2) from earlier
For instance for our reaction:

Fe2O3(c) + 6H+ 2Fe+3(aq) + 6H2O (2)

Gof = 1.97 kcal

log K = -1.44 (at 25oC)
But,
[Fe 3 ]2
K
[H ]6
So,
log K = -1.44 = 2log[Fe+3] 6log[H+]
-1.44 = 2log[Fe+3] + 6pH
If we are given a concentration of the ions, we can deduce
the equilibrium pH

2. Reduction-oxidation Reactions
a) Half-cell reactions (as Equation (4) written as a reduction!)

Fe+3 + e- Fe+2 Eo = 0.77 V

For this equation, luckily, we already know the Eo. If we dont, we
can calculate it from thermodynamics. Once we have it, we can go
to the Nernst Equation:
[Fe 2 ]
E = 0.77 (0.059/1)log
[Fe 3 ]
If we know the concentrations of ferric and ferrous ions in solution,
we can readily calculate the potential of the solution.
 Eh-pH--14

b) Complex redox reactions involving oxides/water

e.g. Formation of Hg(OH)2(s) from elemental Hg(l) (passivation)

Hg(OH)2 Hgo(l)
Balancing gives us:

2H+ + Hg(OH)2 + 2e- Hgo + 2H2O

(Written as a reduction!!)
From Bard, Parson, and Jordan we can determine that the
GoR = -47.68 kcal
Eo = -47.68/(23.06)(2) = 1.034 V
Now with Nernst
1
E = 1.034 0.059/2log
[H ] 2
E = 1.034 0.059pH
D. Applications and Diagram Construction
1. Natural SystemsWater Stability
a. Three electrodes (half-reactions) of importance occur in water:

i) Hydrogen electrode: 2H+ + 2e- H2(g); Eo = 0.00 V

ii) Oxygen electrode: 4e- + O2 + 2H2O4OH-; Eo = 0.40 V

iii) Water electrode: 4e- + O2 + 4H+2H2O; Eo = 1.228 V

b. Water will chemically breakdown into hydrogen and oxygen. So
lets use equations i) and iii) above to determine under what pH
and Eh conditions water is stable.

2H+ + 2e- H2(g) Eo = 0.00 V (i)

PH 2
K=
[H ] 2

log K = 2pH log PH2

If the partial pressure of H2 is 1 atm

E = 0.00 0.059 pH
 Eh-pH--15

4e- + O2 + 4H+2H2O Eo = 1.228 V (iii)

1
K= 4
[H ] PO 2

log K = 4pH - log PO2

If we assume the partial pressure of O2 is 1atm

Eh = 1.228 0.059pH
2. Plot Eh vs. pH for both equations:

2.0

1.0
O2

H2 O
Eh, volts

0.0

H+
3.
-1.0
H2

0 7 14
pH

Essentially it shows the equilibrium lines between O2 and H2O and

H+ and H2. Above the lines, the most oxidized species will prevail.
 Eh-pH--16

E. General Rules about Eh-pH diagrams

1. The diagrams can be broken into four main areas:
a. high oxidation-low pH
b. low oxidation(reducing)-low pH
c. high oxidation-high pH a c

d. low oxidation(reducing)-high pH 0

b d
7

2. For a given Eh (holding Eh constant, and varying pH) the following

observations can be made:
a. The number of Hs attached decreases with increasing pH
So, H2S HS- S=
H2SO4 HSO4- SO4=
H2SeO4 HSeO4- SeO4=
As, pH 0 7 14
b. Likewise, the relative atom % O increases (Increased # of
OHs)
So, Hg+2 HgOH+ Hg(OH)2 HHgO2- HgO2-2
[at.%O] 0% 33% 40% 50% 67%
As, pH 0 14

3. For a given pH (holding pH constant, and varying Eh) the following

observations can be made:
a. The oxidation state of all oxidizable atoms increases as Eh
+6
+2V H2SO4 Me
+4
Me
+3
o
Me
Eh S Me
+2

+
Me
o
-2V H2S Me
 Eh-pH--17

4.

5.
6.