Pourbaix Diagrams stability for a particular system, the classes of chemical

and electrochemical reactions of interest will be

The ability to predict, and ultimately control, elec- summarized. The four categories of reactions to be
trochemical reactions is a common goal for most presented are based on the two primary variables used
fundamental or applied process evaluations. Two to define the diagram: (i) the pH or H+ activity
basic approaches are used in such analyses; one is and (ii) electron transfer, e−, or potential. In turn,
thermodynamic while the other is related to the the reactions may be either homogeneous or
reaction kinetics. Although the approaches are in- heterogeneous. Examples of reactions include:
herently different, with one based on equilibrium (i) Reactions involving neither H+ nor electron
principles while the other is nonequilibrium or polar- transfer.
ization oriented, each is necessary for proper technical (a) Heterogeneous gas\solution reactions
understanding.
NH jH O(l) l NH OH(l)
The focus of this article will be on the use of the $(g) # %
thermodynamic approach to predict phase stability in
an electrochemically controlled system. Specifically, (b) Homogeneous reactions
the use of Pourbaix or potential–pH predominance
area diagrams will be described. Named after Marcel Cu#+jCl− l CuCl+
Pourbaix, the scientist who proposed this approach,
the thermodynamically stable regions in an electro- (ii) Reactions involving H+
chemical system are represented in graphical form. (a) Heterogeneous gas\solution reactions
The work began in the mid-1950s as a publication
CO (g)jH O(l) l HCO−(l)jH+(l)
by CEBELCOR, Lecons sur la Corrosion Electro- # # $
chemique. Most of the effort was directed toward using
the concepts to address the ubiquitous technical and (b) Homogeneous reactions
economic problems associated with the corrosion of
H PO (l) l H PO−(l)jH+(l)
metals. Ultimately this led to the publication of a text $ % # %
entitled Lectures on Electrochemical Corrosion, and
the internationally recognized Atlas of Electrochemical (c) Heterogeneous solid\solution reactions
Equilibria in Aqueous Solutions.
Mg#(l)+j2H O(l) l Mg(OH) (s)j2H+(l)
While much of the focus of the diagrams was related # #
to corrosion, their use was equally applicable in the
areas of electrolysis, batteries, geology, chemistry and (iii) Reactions involving electron transfer
hydrometallurgical leaching. Regardless of the area (a) Heterogeneous gas\solution reactions
being investigated, the concept was clearly directed at
2Cl−(l) l Cl (g)j2e−
providing a standard approach for the theoretical #
presentation of electrochemical equilibrium. There-
fore, it was the ability to incorporate both chemical (b) Homogeneous reactions
and electrochemical thermodynamics simultaneously
into a reasonably simple and straightforward diagram $+ l Ce%+je−
Ce(l) (l)
that provided the major appeal of the Pourbaix
diagram. A brief overview of Pourbaix diagrams is (c) Heterogeneous solid\solution reactions
presented here.
There have been a number of excellent reviews on Al(s) l Al$(l)+j3e−
the construction and use of the potential–pH diagrams
and innumerable articles have been published relating (iv) Reactions involving both H+ and electron
to their specific, wide-ranging applications in a variety transfer
of technical fields. For more detail and technical depth (a) Heterogeneous gas\solution reactions
on a particular topic, these sources should be con-
H (g) l 2H+(l)j2e−
sulted. The description provided here concentrates on #
the basic principles and computations used for the
diagrams, but there are also a number of computer- (b) Homogeneous reactions
based programs available that can be used for their
Mn#(l)+j4H O(l) l MnO−(l)j8H+(l)j5e−
construction. # %
(c) Heterogeneous solid\solution reactions
1. Classes of Reactions
Fe#(l)+j3H O(l) l Fe(OH) (s)j3H+(l)je−
Prior to combining all the possible thermodynamic # $
data and expressions used to identify the regions of In the Pourbaix Atlas, the equilibria for chemical

1
Pourbaix Diagrams
element\water reactions are given. The presentation
for each element begins by listing the substances
considered and their chemical potential ( µ!) values
which are used in the calculations. Next, the reactions
and equilibrium expressions are listed. These
equations are the basis for establishing the various
domains that comprise the diagram, as described in a
subsequent section.
2. Generic Pourbaix Diagram
In the previous section the four classes of reactions,
and examples of each, were given. These reaction types
will have a characteristic shape, representing their
equilibria positions in the Pourbaix diagram. In
general, straight lines define the stability regions, but
the slope of the line changes depending on the type of
reaction and stoichiometry involved.
(i) Equilibrium equations dependent only on po-
tential or Eh are horizontal lines parallel to the pH axis.
(ii) Equilibrium equations dependent only on pH
are vertical lines parallel to the Eh axis.
(iii) Equilibrium equations dependent on both
potential and pH are sloped lines.
The generic reaction types representative of these
three possibilities are illustrated in Fig. 1. Activities
from 1 to 10−"' are also shown to indicate their effects
on the calculated values.
In a diagram, the following generalities usually
apply when analyzing changes occurring with either Eh
or pH. By the convention used:
(i) As the Eh or potential is moved in a more positive
direction:
(a) oxidation or electron loss is favored,
Figure 1
Schematic diagram showing the generic expressions in a Pourbaix diagram.
2
(b) metal dissolution is favored,
(c) higher oxidation state species become relatively
more stable.
Metals with more positive reversible equilibrium
potentials are said to be noble, for example, gold and
platinum.
(ii) As the Eh or potential is moved in a more
negative direction:
(a) reduction or electron gain is favored,
(b) Metal deposition is favored,
(c) Lower oxidation state species become relatively
more stable.
Metals with more negative reversible equilibrium
potentials are said to be actiŠe or base, for example
zinc, magnesium or sodium.
(iii) Moving in the direction of increased pH favors
oxide or hydroxide stability, while with decreasing pH
the uncomplexed metal ion is more stable.
The IUPAC convention for half-cell potentials, often
referred to as reduction potentials, is used in the
Pourbaix diagrams.
3. Diagram Convention
The Pourbaix diagram is constructed by combining
equilibrium expressions for the reactions of the species
being considered, consisting of conventional chemical
and electrochemical equations. The free energy cal-
culations are based on the chemical potentials of the
reactants and products using appropriate partial
pressure, concentrations or activity values in con-
junction with the proper stoichiometric coefficients.
 Pourbaix Diagrams

Each equation can then be expressed quantitatively in substituted, the expression converted to the log scale
terms of equilibrium constant expressions and stan- is:
dard potentials.
In order to insure that the presentation of data and 0.0592 a
the diagram format remained consistent, a convention Eeq l E !j log oxidized
was developed so the expressions would be properly n areduced
presented and balanced. The procedure developed by
Pourbaix is outlined below: and n is number of electrons transferred in the reaction.
(i) Choose the reaction of interest, in this case the
equilibrium expression between dichromate ion and
trivalent chromium ion.
4. Diagram for Water
Cr O#− l Cr$+ Using the general principles and conventions con-
# (
sidered previously, it is possible to construct regions
(ii) Balance the metal stoichiometrically for the water system, which is ultimately incorporated
into all the diagrams. The components of interest
Cr O#− l 2Cr$+ include H+, H , O and H O.
# ( The regions# of# stability
# defined are (i) oxygen
evolution and acid generation at more positive or
(iii) Balance the oxygen with H O
# oxidizing potentials, (ii) thermodynamically stable
H O at intermediate potentials, and (iii) hydrogen
Cr O#− l 2Cr$+j7H O #
liberation and hydroxide generation at more reducing
# ( #
potentials.
(iv) Balance the hydrogen with H+ The half-cell reaction and the expression for the
oxygen\water equilibrium is:
Cr O#−j14H+ l 2Cr$+j7H O
# ( # 2H O l O j4H+j4e−
# #
(v) Balance the charge with electrons, e−
and
Cr O#−j14H+j6e− l 2Cr$+j7H O
# ( # 0.0592 P [H+]%
Eeq l E !j log O#
Giving the final equation for inclusion in the diagram. n [H O]#
#
substituting in for the terms with n l 4, unit activity
for [H O] and an oxygen partial pressure of one with
3.1 Nernst Equation # 1.23 V, the expression becomes
an E ! l
Values for reversible electrode potentials are described
by use of the standard Nernst equation with reduction Eeq l 1.229k0.0592 pH
potentials as the required convention. It should be
remembered that for a reversible half-cell there is no For hydrogen evolution the reaction is
net reaction direction at equilibrium, thus the terms,
products and reactants have no real significance. Only H l 2H+j2e−
when a complete reaction is involved, such as by #
combining two half-cell reactions, is it possible to and
define a spontaneous direction.
For a metal in contact with its ions, M\Mn+, the
0.0592 [H+]#
equation relating potential and activities is: Eeq l E !j log
2 PH
#
M l Mn+jne− Eeq l 0.000k0.0592 pH
RT aMn+
Eeq l E !j ln when unit activity is assumed for hydrogen gas.
nF aM These two final expressions are referred to as lines b
and a respectively in Fig. 2, which shows the stable
Where Eeq is the equilibrium potential and E ! is the regions in the water system.
standard half-cell potential. When the gas constant R, As points of reference, these two lines are commonly
temperature T, and F the Faraday constant are shown on many Pourbaix diagrams, particularly those

3
Pourbaix Diagrams

Figure 2
Pourbaix diagram for water.

relating to metal corrosion in an aqueous system. In
the region above b, water can be electrolytically
decomposed to form oxygen gas and H+ as an anodic
reaction, while hydrogen gas can be evolved cathod-
ically below a. The area between the two then
represents the region of stability for water.
teraction. This would be plotted as a horizontal line on
the diagram. Such an equilibrium reaction is readily
depicted by the Nernst equation, which for aluminum
is
Al l Al$+j3e−

giving the expression

5. Equilibrium Calculation Examples
RT [Al$+]
A basic qualitative description of the Pourbaix dia- E l E !j ln
gram and the types of equilibrium expressions used to nF [Al]
define the various stability regions has been given. The
procedures and conventions used to quantify a specific where E is the equilibrium potential for the couple
system will now be presented. As with any ther- Al$+\Al, E ! is the standard potential and [Al$+] is the
modynamic calculation, the accuracy and precision activity of the aluminum ion.
obtained will depend entirely on the ability to identify The value of E ! may be taken from existing tabular
the correct phases involved. The second critical item is data or calculated. Using the following convention
to insure that the free energy or chemical potential and the standard free energy values for the oxidized
data are available and correct. and reduced components and the proper n value and
The aluminum–water system will be used as an stoichiometry, the E ! computation becomes
example for constructing Pourbaix diagrams. The
thermodynamic data are from the CRC Handbook of ∆G ! µ!oxidizedkµ!reduced
Chemistry and Physics. The initial information re- E! l l
nF nF
quired is the solid and dissolved substances to be
considered and the µ! values for each. Other data may µ!Al$+kµ!Al k115 918k0
also be given, such as the crystal system for the E! l l lk1.676 V
different species. Table 1 shows a typical compilation 3F 3i23 060
of the data used in constructing the diagram.
The final expression for the Al$+\Al equilibrium in the
form of the Nernst equation is
5.1 Electron Transfer Dependent Reactions
EAl$+/Al lk1.676j0.0197 log [Al$+]
Two of the principal regions of importance are defined
by the metal and its ions, independent of pH in- In many cases, values for the metal ion activity will be

4
 Pourbaix Diagrams

Table 1
Substances considered.
Oxidation number Substance considered µ! (cal.) Name
Solid substance j3 Al 0 Aluminum
j3 2oAl(OH) q (a) k384 530 Hydrargillite
j3 2oAl(OH)$q (b) k382 400 Bayerite
j3 2oAlOOHq$ (c) k378 310 Boehmite
j3 Al O (d) k378 179 Corundum
j3 # $
Al(OH) (e) k274 402 Aluminum hydroxide
$
Dissolved substance j3 Al$+ k115 918 Aluminic ion
j3 AlO − k198 590 Aluminate ion
0 H O# k56 668 Water
k1 OH# − k37 572 Hydroxy ion
j1 H+ 0 Hydrogen ion

selected, usually 1, 10−#, 10−% and 10−', and the substituting into the previous expression gives:
resulting horizontal lines will be shown on the plot for
reference. For example, with standard conditions of [Al(OH) ][H+]$
unit activity there would be one horizontal line, 11 520 lk2.303RT log $
[Al$+][H O]$
parallel to the pH axis, initiating at k1.667 V. Another #
line might be drawn for an Al$+ activity of 10−%, which k11 520 [Al(OH) ][H+]$
would have an equilibrium potential of l log $
1364 [Al$+][H O]$
#
EAl$+/Al lk1.676j0.0197 log (10−%) lk1.755 V
and assuming the activities of H O and Al(OH) are
unity, # $
Thus, the four-fold change in activity would cause a
decrease in potential of about 80 millivolts. In practical k8.446 l 3 log [H+]klog [Al$+]
terms this shows that aluminum would be more prone
to oxidize, or corrode, when the ionic concentration in or log [Al$+] l 8.446k3 pH
contact with the metal was decreased.
which is drawn as a vertical line on the diagram and by
substituting in the conditions, such as the Al$+ con-
centration, the pH for precipitation of the hydroxide
5.2 pH Dependent Reactions can be predicted. If the activity of Al$+ is unity then the
A second class of reactions involves only H+, or pH, critical pH is about 2.82, shown as the vertical line on
and no electron transfer. An example is the pre- the diagram.
cipitation of a hydrated oxide from an aqueous
solution containing Al$+.
5.3 Electron Transfer and pH Dependent Reactions
Al$+j3H O l Al(OH) j3H+
# $ The Pourbaix diagrams also contain reactions in-
volving both electron transfer and pH dependence.
The standard free energy for this reaction can be The equilibrium between metallic aluminum and its
calculated using hydroxide is an example.
∆G ! lkRT ln K Alj3H O l Al(OH) j3H+j3e−
# $
where K is given by ∆G! lk274 402j3i0k(0j3i(k56 668))
lk274 402j170 004 lk104 398
[Al(OH) ][H+]$
Kl $ k104 398
[Al$+][H O]$ E! l lk1.509 V
# 3i23 060
The G! for the reaction is calculated from the chemical then
potential values.
E lk1.509k0.0592 pH
∆G! l µAl(OH)
! j3µ!H+k( µ!Al$+j3µ!H O)
$ # The final diagram for the Al–H O system is given
lk274 402j3i0k(k115 918j3i(k56 668))
in Fig. 3 and contains the three# equilibrium lines
l 11 520 illustrated in the previous example calculations.

5
Pourbaix Diagrams

Figure 3
Pourbaix diagram of Al–H O system at 25 mC.
#

Figure 4
Pourbaix diagram of Al–H O system at 25 mC showing regions of immunity, passivation, and corrosion.
#

6. Theoretical Corrosion Domains it is thermodynamically stable in its reduced state.

When a metal is corroding the most stable form is a
Another generalized way to present metal corrosion
simple or complex ion dissolved in the aqueous media.
using the diagrams is to divide them into regions of
Passivity is more loosely defined, but refers to a
immunity, corrosion and passivity, as shown in Fig. 4.
condition where a condensed oxide or hydroxide phase
While these classifications are somewhat arbitrary,
is stable. The true level of corrosion resistance in
such plots do provide an immediate overview of metal
regions indicated as passive may vary substantially
reactivity in the chosen system.
depending on other factors such as morphology,
The metal is immune when conditions are such that
hydration, density and film thickness.

6
 Pourbaix Diagrams

Figure 5
Pourbaix diagram of Cu–H O–Cl− at 25 mC with [Cu#+] l 8i10−# mol L−" and [Cl−] l 200 mg L−".
#
7. Miscellaneous Diagram Features getics, such as overpotential, that might be required
for the reactions to proceed. This is particularly true
Once the concept of representing thermodynamic
when gas evolution, such as hydrogen or oxygen, is
stability for a simple system, such as metal–water, has
evolved. The equilibrium lines a and b given on the
been established, other additions to the diagram are
water diagram could be shifted substantially de-
possible. In the previous examples, no anion was
pending upon the electrode materials upon which the
listed, and in many applications the formation of other
reactions are occurring, and while the Pourbaix
stable complex ionic or solid species is of practical
diagrams may be used to infer trends in kinetic
importance. It is common in analyzing phenomena in
behavior, caution must be exercised when attempting
leaching, electrodeposition or geology to incorporate
to use the plots in a polarized system.
species such as chlorine, sulfur or carbonate into the
Overall, Pourbaix diagrams provide a very practical,
calculations. For the example shown in Fig. 5, chlorine
yet fundamental, approach to the presentation of
has been added to the Cu–H O system. Note that both
complex ions and condensed# phases are now present,
thermodynamic stability of a wide range of elec-
trochemical systems.
in addition to those with oxygen as the main com-
ponent. Another area of interest is alloy behavior, in
which more than one metal is involved. The cal-
culations become slightly more involved, but the same Bibliography
procedures presented previously are used to construct
the diagrams and the two metal systems are super- ASM Metals Handbook 1987 Vol. 13, Corrosion, ASM Inter-
national, Metals Park, OH
imposed into a single diagram. CRC Handbook of Chemistry and Physics 2000, CRC Press,
There are some fundamental limitations to consider Boca Raton, FL
when using the diagrams that deserve mention. As Pourbaix M 1995 Lectures on Electrochemical Corrosion. NACE
always, thermodynamic analyses do not take into International, Houston, TX
account kinetics or reaction rates. The diagrams depict Pourbaix M 1974 Atlas of Electrochemical Equilibria in Aqueous
stable phase regions, but only when the system is at Solutions. NACE Cebelcor, Houston, TX
equilibrium. It does not in any way infer how long it
took to reach equilibrium or any other system ener- T. J. O’Keefe and P. Yu

7
Pourbaix Diagrams

Copyright ' 2001 Elsevier Science Ltd.

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Encyclopedia of Materials : Science and Technology
ISBN: 0-08-0431526
pp. 7774–7781