Potential-pH Diagrams

and Its Applications

B Y:
KASU MALLA THAKURI
076BCH020
Potential-pH Diagrams
Pourbaix diagrams, also known as potential-pH diagrams, are named after their creator, Pourbaix, a Belgian
electrochemist and corrosion scientist, who introduced them in 1963. A crucial milestone in electrochemical
corrosion science was the creation of these diagrams, which illustrate thermodynamic conditions relative to
electrode potential (E) and hydrogen ion concentration (pH). They depict a metal's stability in relation to both
potential and pH values. They are analogues to phase equilibrium diagrams, where the stability of various phases is
shown as a function of temperature and percentage composition of the metal. At a particular temperature and
composition a stable phase can be easily determined. Similarly, at a particular combination of pH and potential, a
stable phase can be determined from the Pourbaix diagram. The diagrams identify conditions under which
(a) the metal is stable and will not corrode,
(b) soluble reaction products are formed and corrosion will occur, and
(c) insoluble reaction products are formed and passivity will occur.
The diagrams are derived from thermodynamic computations rather than being derived experimentally through
corrosion assessments. They are primarily computed for pure metals in distilled water at 25°C (75°F). However,
efforts have expanded to incorporate additional ionic species and varying temperatures, broadening their
applicability and accuracy.
Potential-pH Diagram of Water
Figure shows the potential-pH diagram for water with no metal involved. The horizontal axis
identifies the pH of the solution. The solutions range from acid conditions at the left (pH 0 to 7)
to alkaline solutions at the right (pH 7 to 14). In the middle of the diagram are relatively neutral
solutions (pH 5 to 9). The vertical axis is used to plot the oxidizing power (electrode potential) of
the solution. These values range from strongly reducing solutions with large negative potentials,
for example, –1.2 V-SHE, to strongly oxidizing solutions with large positive potentials, for
example, +1.2 V-SHE. The two diagonal lines, identified as (a) and (b), define the region of
stability of water as a function of potential and pH. For any value of potential and pH above line
(b), water is thermodynamically unstable with respect to the evolution of oxygen. At any
conditions of potential and pH below line (a), water is thermodynamically unstable with respect
to the generation of hydrogen gas. For potential and pH conditions between lines (a) and (b),
water is thermodynamically stable.
Line (a) represents the equilibrium for the reaction of hydrogen
ions to evolve hydrogen gas:

Using the Nernst equation, the equation for this line is as follows:
E = 0.00 – 0.059 pH
The potential at pH 0 is 0.0, and the potential decreases by 0.059
V for each unit increase of pH. At any potential and pH below this
line, the hydrogen ion in water will react with electrons to evolve
hydrogen gas. Line (b) represents the equilibrium of oxygen plus
hydrogen ions and electrons to form water:
+4+4
Based on the Nernst equation, the equation for this equilibrium is
as follows: E = 1.229 – 0.059 pH The potential is +1.229 V-SHE at
pH 0 and decreases by 0.059 V for every unit increase in pH.
Above line (b) the oxidized species are stable, and water under
those conditions reacts spontaneously to produce oxygen and
hydrogen ions
Potential-pH Diagram of Iron
The potential-pH diagram for iron is shown in Figure . The diagram serves as a graphical
representation of the immune, passive, and corrosion regions for iron based on potential and
pH. It delineates four distinct areas. The lowermost segment indicates immunity, where iron
remains stable without corrosion across the entire pH spectrum, spanning from acidic to alkaline
conditions. In both narrow, cross-hatched zones, iron undergoes corrosion. The left segment,
characterized by oxidizing and acidic conditions, as well as the small area on the far right,
marked by reducing and highly alkaline conditions, witness iron corrosion, forming soluble
products. The shaded portion denotes passivity, where iron reacts under oxidizing circumstances
in neutral to alkaline solutions, forming insoluble products that inhibit further corrosion through
a protective film. An underlying assumption of the diagram is that any insoluble product confers
protection, though this isn't always the case. For instance, while titanium's insoluble product
yields a stable passive film, iron's often porous insoluble products fail to protect in many
environments.
Contd..
Iron, being relatively active, corrodes under various conditions, including reducing, moderately
oxidizing, and strongly oxidizing states in strong acids. In weak acids, it corrodes under reducing
and moderately oxidizing conditions; however, it can become passive under highly oxidizing
conditions. In neutral to mildly alkaline conditions, iron remains corrosion-free due to immunity
under strongly reducing circumstances or passivity under more oxidizing conditions. In strong
alkaline environments, iron generally resists corrosion, except for a small range of potentials and
pHs where a soluble, alkaline corrosion product forms.The thermodynamically stable species in
the immune region is metallic iron. The thermodynamically stable species in the acid corrosion
regions are ferrous ions (Fe2+) and ferric ions (Fe3+). Both ferric and ferrous ions are soluble. The
thermodynamically stable species for the alkaline corrosion region is hypoferrite ion (HFeO2–). In
the passive range, the insoluble corrosion products that are thermodynamically stable are oxides
or hydroxides of iron, for example Fe3O4 and Fe2O3.
Potential-pH Diagram of Zinc
The potential-pH diagrams for iron and zinc are shown in
Figure 3.Zinc, being more reactive than iron, displays an
immune region at substantially lower potential and pH
levels. Under acidic conditions, spanning from reducing to
highly oxidizing, as well as in strongly acidic to neutral
environments, zinc experiences active corrosion. Moreover,
it undergoes attack and forms soluble corrosion byproducts
in strongly alkaline environments. However, zinc shows
resistance to corrosion in mildly alkaline conditions due to
the formation of passive films, aligning with its observed
corrosion behavior. Consequently, zinc is commonly utilized
for sacrificial cathodic protection of iron and for exposed
surfaces in atmospheric corrosion, where it develops a
protective passive film. However, it is not suitable for
structural applications in strongly acidic or strongly alkaline
conditions.
Potential-pH Diagram of Lead
The figure shows that the equilibrium potential for the
reaction

for a concentration of to be negative with respect to

the equilibrium potential for the hydrogen-reduction
reaction at a pH less than about 5. This implies a
tendency on the part of lead to corrode in an aerated
aqueous environment. In actual fact, however, the rate
of corrosion is so negligible that lead is often used in
pipes for carrying water. Thermodynamics, therefore,
defines a necessary, vital precondition for corrosion; it
determines the direction in which an overall corrosion
reaction will tend. But the determination of the rate and
control of a corroding system can emerge only by a study
of the electrodics of corrosion.
Applications
1. Material Selection
These diagrams assist engineers in selecting materials suitable for specific applications based on
their corrosion resistance properties. By evaluating the susceptibility of various metals to
corrosion in different environments, engineers can choose materials that offer adequate
protection against degradation
2. Corrosion Prediction
Engineers can use potential-pH diagrams to predict the corrosion behavior of metals under
different pH, temperature, and potential conditions. This predictive capability enables the
implementation of proactive corrosion management strategies, such as applying protective
coatings or employing corrosion inhibitors
Contd..
3. Failure Analysis
In cases of corrosion-related failures, potential-pH diagrams help investigators analyze root
causes. By comparing actual operating conditions with predicted corrosion behavior from the
diagrams, engineers can identify factors contributing to the failure and implement corrective
measures to prevent recurrence.

4. Alloy Design
Potential-pH diagrams are valuable tools in designing corrosion-resistant alloys. Engineers utilize
these diagrams to optimize alloy compositions and microstructures, enhancing their
performance in aggressive environments. This application is particularly relevant in industries
such as aerospace, marine, and chemical processing.
Thank You!!