Pourbaix Diagrams

:INTRODUCTION
For the behavior of metals in aqueous solutions, one of the most important
contributions to the corrosion literature has been the work of Pourbaix [1,2] and his
associates in the development of thermodynamic equilibrium diagrams (E vs. pH),
called Pourbaix diagrams. A vast amount of data may be presented simply and
concisely in Pourbaix diagrams. When the advantages and limitations of such
diagrams are understood, valuable inferences may be made regarding corrosion
phenomena. The selection of conditions for cathodic and anodic protection is
simplified. Candidates for consideration as inhibitor species may be selected with
greater efficiency. Critical corrosion experiments may be designed with equal
.efficiency

Pourbaix diagram of iron

Corrosion processes involve both chemical and electrochemical phenomena. In

1923, Evans [3] observed that, if two samples of iron connected by a galvanometer
are immersed in two solutions of potassium chloride, separated by a porous
membrane, and if a stream of air is bubbled through one of these solutions, an
electric current circulates between the aerated sample, which becomes the
cathode, and the nonaerated sample, which becomes the anode and corrodes. On
the other hand, if a sample of iron and a sample of another metal (copper, zinc, or
magnesium) are connected as above, a passage of electric current is also observed.
Under these circumstances, iron becomes the anode and corrodes when connected
to copper, whereas zinc or magnesium become the anode and corrode providing
protection to iron. Thus, it is necessary to consider not only chemical
thermodynamics, but also electrochemical thermodynamics when considering
.corrosion reactions
Chemical equilibria are defined as those that do not involve oxidation-reduction
processes, but do involve the law of mass action and the law of solubility product
(involving partial pressures or fugacities and concentrations or activities). By
contrast, electrochemical reactions are defined as those in which free electric
.charges, or electrons, participate

THERMODYNAMIC BACKGROUND
The procedure for calculating Pourbaix diagrams is straightforward and is amenable
to computer calculation. On the other hand, certain assumptions are made that
must be borne in mind when applying the information available from Pourbaix
diagrams in "real" situations. First is the assumption of equilibrium. Since Pourbaix
diagrams are equilibrium diagrams, they give no information on the kinetics of the
reactions considered. Kinetic information may be obtained experimentally by
methods described elsewhere [4]. It also is assumed that the reaction products are
known and that the free energy information of each solid and ionic species is
known for the conditions of temperature and pressure of interest. The pH of the
solution is assumed to be known and constant in the bulk as well as at the metal or
reaction-products surface. Temperature and pressure are considered to be
constant and are usually assumed to be 298 K (250C) and 1 atm, respectively.
Pourbaix diagrams may be calculated for other temperatures if thermodynamic
data are available or may be estimated [5]. Generally, the features of Pourbaix
diagrams are not significantly altered by increased pressures since thermodynamic
.properties are relatively insensitive to pressure (as compared with temperature)
The simple graphical methods described herein greatly facilitate the practical
consideration of the various equilibrium reactions involved. For chemical reactions,
it is convenient to make use of the Van't Hoff equation, which involves the
:equilibrium constant
AG0 = -RTInK = -2.303 x 1.987 x 298 log K
For electrochemical reactions, the procedures involve manipulation of the Nernst
equation, which can be written

:Where
Φ = reduction potential
Φo = Go /nF
Go= standard free energy change
f = Faraday's constant , n = Number of free electrons
,for the general reaction

-
rR + wH2O pP + hH+ + ne

Note that electrochemical reactions are written as oxidation reactions; that is,
electrons on the right. Taking
aH2o = 1
and
+
pH = -logaH
then

The standard free energy change, AG0 , for the reaction can be obtained readily
from tabulated thermodynamic data. Therefore, the first term to the right of the
equality sign in Eq. (2) is a constant. The second term also becomes a constant
when values of aP and aR are chosen in the normal manner. In constructing Pour-
baix diagrams, the concentration of the ionic species at the boundary between a
solid substance and a dissolved substance is usually taken as a very low value, such
as
M. The sum of the first two terms in Eq. (2) gives a constant equal to the value 10-6
of the potential, , at pH = O. The resulting expression is the equation of a straight
line of slope equal to the coefficient of the pH term, —0.0591 h/n, and intercept
. equal to Φ at pH =0
Pourbaix diagrams are constructed from the three, and only three, types of straight
line relationships, which result from the analysis of the possible chemical and
electrochemical equilibria in the system under consideration. Depending on the
reactants and products of the assumed reactions, these straight lines will be either
.horizontal, vertical, or sloping
A reaction involving a solid substance, a dissolved substance, and hydrogen ion )1
in water without free electrons gives a vertical straight line; that is,independent of potential
.(when n = O, the slope of the line equals ȹ)
A reaction involving a solid substance and a dissolved substance in water, plus free )2
electrons but without hydrogen ion gives a horizontal straight line; that is, independent of pH
.(when h = O, the slope = O)
A reaction involving a solid substance, a dissolved substance, free electrons, and )3
.hydrogen ion will give a straight line with a slope equal to — 0.059Ih/n
After plotting the straight lines on potential versus pH coordinates, the domain of the
thermodynamic stability for each individual species is determined by requiring that all
.equations involving that species be satisfied simultaneously

:Example Problem
It is suggested that the reader construct the Pourbaix diagram for the Fe-H2O
system (considering the solid species Fe, Fe3O4, and Fe2O3) at 298 K and 1-atm
pressure. Plot the diagram on graph paper using pH ranging from -2 to +16 and the
electrode potential from -1.8 to +2.2 VSHE- .The equations for each coexistence
.already have been calculated and are listed in Table 1
It will be necessary to define what ionic activity will be considered to represent
"significant corrosion." The establishment of what is considered to be "corrosion"
evolves into a determination as to the amount of metal dissolution, which is
permissible "for all practical purposes." It often has been found convenient to
consider the solubility of 10-6 gram atoms of soluble ion per liter as representing
"no corrosion for all practical purposes." On Figure 1, this assumption is
.represented by the lines marked —6 (the logarithm of the activity)
The domain of the metal is found at the bottom of the diagram. For simplicity, it is
suggested that the equilibrium involving the metal and its least highly oxidized ionic
form is an easy equilibrium to start with. In this case, we are considering Eq. (23 *)
in Table 1 involving iron and ferrous ion. Inasmuch as no hydrogen ion is involved, it
is apparent that this equilibrium coexistence involves a family of horizontal lines on
potential versus pH coordinates the position of which depends on the assumed
value of thermodynamic activity chosen for the ferrous ion. If you choose 10 -6 for
the ionic activity, you will obtain only one line. The question arises as to whether
the domain of iron is above or below the line. Referring to the electrochemical
,equation
-
Fe → Fe2+ +2e
a "thought experiment" is helpful in answering this question. If electrons were
added, the reaction would be driven in the direction of iron; thus, the addition of
electrons (and hence, more negative potentials) favors iron rather than Fe 2+ .
Therefore, Fe is below the line and Fe2+ above the line. The next question is "How
far along the pH axis does the horizontal Fe/Fe2+ equilibrium coexistence extend?"
To the left, the boundary is usually chosen arbitrarily by selecting the range of pH of
interest. The limit for this line in the direction of higher pH depends on the activities
of the ionic species and the restrictions imposed by other equilibria e.g., line 13 in
.Fig. 1, which is the coexistence between iron and Fe3O4
-
3Fe + 4H2o → Fe3o4 +8H+ +8e
This is a logical choice for next consideration, since Fe 3O4 is the solid species that
involves oxide with the lowest level of oxidation of iron. Reaction (13) in Table 1
involves both electrons and hydrogen ion and will be a sloping line on the diagram.
Another thought experiment will reveal on which side of line 13 iron is stable and
on which side Fe3O4 is stable. Since this is a sloping line, there are two ways in
which this decision can be made. Adding electrons will favor Fe; hence, Fe will be
on the more negative side of the line (i.e., below the line). Addition of hydrogen ion
(lower pH) also stabilizes the species iron. Thus, iron should be to the left (or below)
the line and Fe3O4 to the right (or above). Simultaneous solution of the equations
for lines 23 and 13 will reveal the point of intersection, and consequently, the
.termination of dominance of the Fe/Fe2+ coexistence
A similar calculation for Reaction (26) in Table 1 between Fe 2+ and Fe3O4 yields
.another line with a slope different from Reaction (13)
-
3Fe2+ + 4H2o → Fe3o4 + 8H+ +2e
Adding either H+ or electrons to the right side pushes the reaction to the left to
restore equilibrium. This favors the species on the left (Fe2+). By using the same
procedures, it is observed that lines 23, 26, and 13 in Figure 1 intersect at an
.invariant point for a given activity of ferrous ion
Line 20, the equilibrium between Fe3+ and Fe2O3, represents a reaction in which
there is no electron transfer. Thus, by inspection of the equation, this coexistence
will appear as a vertical line on the Pourbaix diagram. The decision of which species
is on which side of the line can easily be made by assessing the effect of adding
hydrogen ions and observing that this addition favors Fe3+ . Thus, Fe3+ is on the low-
.pH side of the line

It is suggested that the equilibrium coexistences be taken one at a time progressing from the
elemental state through the various oxidized states, to establish the limits of each of the lines.
It usually becomes complicated to draw all the lines and to remove those lines and portions of
.lines that are redundant or improper
When the diagram is complete, it is possible to test the predictions of the Pourbaix diagram
you have just drawn. Table 2 reports a number of experiments conducted by Pourbaix in
which iron electrodes were immersed in various solutions. The pH and the electrode potential
were measured in each case, and the specimens were allowed to stand in beakers containing
each of the indicated chemical environments. Now plot on the diagram the data from the
experiments numbered 1-25 in Table 2. For convenience, the sample numbers should be
written beside each data point. This will make it possible to compare the experimental results
of Pourbaix with the predictions based on the Pourbaix diagram. Remember, the term
"immunity" is reserved for noncorrosion and represents the case in which corrosion cannot
occur for thermodynamic reasons. The term "corrosion" is reserved for areas of the diagram
where an ionic species is the stable species thermodynamically. "Passivation" describes the
portion of the diagram where a solid reaction product is formed. Presumably, if the solid
reaction product is protective, corrosion will stop. Thus, the term "passivation" might be said
to apply to a region in the diagram where (thermodynamically) corrosion is possible, but it
does not occur, because of the formation of a barrier coating. The diagram is not sufficient to
decide whether a solid reaction product is also protective. This information can only be gained
by performing an experiment. Comparison between the data points on your diagram with the
information contained in Table 2 should reveal that in each case shown, the Pourbaix diagram
would have predicted correctly whether or not corrosion would occur merely by knowing the
.electrode potential and the pH of the solution
:APPLICATIONS OF POURBAIX DIAGRAMS
It is possible to predict conditions under which corrosion, noncorrosion, and
passivation are possible. It is also possible to make a number of other useful
predictions. For example, the electrode potential for cathodic protection is
represented by the equilibrium coexistence line between ferrous ion and iron in
Figure 1. The domain of potential and pH in which anodic protection may be
considered is represented by the passive region (either Fe3O4 or Fe2O3), but care
.should be exercised to avoid the domains where Fe2+ , Fe3+ , or HFeO2" are stable
If the electrode potential falls in a corrosion regime (e.g., in the region where
ferrous ion is stable) it is possible to stop corrosion either by adding an oxidant that
would bring the electrode potential into the region of stability for Fe2O3 by raising
the electrode potential, or by changing the pH in the alkaline direction so as to
move horizontally into the passive region, or by cathodic protection that has the
effect of lowering the potential into the immunity region. It should be emphasized
that the predictions made by using the Pourbaix diagram should be tested prior to
actual use, since the formation of a reaction- product film does not necessarily
mean that this film is protective. In addition, cathodic protection may result in
hydrogen evolution at the cathode, which could have an adverse effect on
protective coatings or might under some circumstances induce hydrogen
.embrittlement of certain metals
It is also possible to predict the types of ions that have promise as oxidizing
corrosion inhibitors. Superposition of the chromium-water diagram over the iron-
water diagram, for example, shows that the region of stability for Cr 2O3 coincides
.with a portion of the iron diagram wherein ferrous ion is the stable species
Consequently, in the absence of an inhibitor, corrosion of iron would be anticipated
in this domain of potential and pH. The effect of adding chromates is to provide a
means of forming a protective Cr2O3 film that inhibits corrosion. Figure 2 suggests
the influence of various oxidizing inhibitors on the corrosion of iron [I]. These
.predictions should be tested before actual use
:REFERENCES
M. Pourbaix, Atlas of Electrochemical Equilibria in Aqueous Solutions, National .1
Association of Corrosion Engineers (NACE), Houston, TX, and Centre Beige d'Etude
.de Ia Corrosion (CEBELCOR), Brussels, 1974
.M. Pourbaix, Lectures on Electrochemical Corrosion, Plenum, New York, 1973 .2
.U. R. Evans, J. Inst. Metals 30, 263, 267 (1923) .3
E. D. Verink and M. Pourbaix, Corrosion 27(12), 495 (1971). 5. C. M. Criss and J. .4
W. Cobble, J. Am. Chem. Soc. 86, 5394 (1964)