Nernst and Pourbaix
Nernst and Pourbaix
Nernst and Pourbaix
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Contents
Main pages
Aims
Before you start
Introduction
Background
The Nernst equation
Construction of a Pourbaix Diagram
Anatomy of a Pourbaix Diagram
Examples of a Pourbaix Diagram
Constructing a 3D Pourbaix Diagram
Summary
Questions
Going further
Additional pages
Aims
Introduce and explain the basic ideas of electrochemistry, including electrochemical potentials, half cell
reactions and equilibria.
Describe the mechanisms of aqueous corrosion
Derive the Nernst equation and show how it can be used to derive Pourbaix diagrams.
Explain the information contained in a Pourbaix diagram, and demonstrate how this can be used to
predict corrosion behaviour.
This TLP is largely self-explanatory, but a basic knowledge of logarithms and thermodynamics may be of some
help. A general introduction to relevant thermodynamics can be found here.
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Introduction
Corrosion is the wastage of material by the chemical action of its environment. It does not include
mechanisms such as erosion or wear, which are mechanical. Aqueous corrosion is the oxidation of a metal via
an electrochemical reaction within water and its dissolved compounds. Aqueous corrosion is dependent on the
presence of water to act as an ion conducting electrolyte.
An understanding of aqueous corrosion is essential for all industries. The lifetime and safety of chemical
plants, offshore platforms and ships are all dependent on controlling and predicting corrosion rates and
products.
This TLP introduces the concepts of electrochemical equilibrium reactions, electrode potentials, construction
of Pourbaix diagrams using the Nerst equation and their interpretation. A Pourbaix diagram is a plot of the
equilibrium potential of electrochemical reactions against pH. It shows how corrosion mechanisms can be
examined as a function of factors such as pH, temperature and the concentrations of reacting species.
Background
Electrode potentials
The electrode potential, E, of a metal refers to the potential difference measured (in volts) between a metal
electrode and a reference electrode.
Ee is the equilibrium potential (or reversible potential), which describes the equilibrium between two
different oxidation states of the same element, at whatever concentration (or pressure) they occur. Ee varies
with concentration, pressure and temperature. It describes the electrode potential when the components of
the reaction are in equilibrium. This does NOT mean that they are in equilibrium with the standard hydrogen
electrode. It means only that the reaction components are in equilibrium with each other. In the reaction
Az+ + ze- = A,
a concentration, CAz+, of AZ+ is in equilibrium with solid A. The reaction moves away from equilibrium only if
there is a source or sink for electrons. If this were the case, then the potential would move away from Ee.
E0, the standard equilibrium potential (or standard electrode potential), is defined as the equilibrium
potential of an electrode reaction when all components are in their standard states, measured against the
standard hydrogen electrode (SHE). It describes the equilibrium between two different oxidation states of the
same element. E0 is a constant for a given reaction, defined at 298 K. Values of E0 for various electrochemical
reactions can be found in data books.
At equilibrium, the chemical driving force for an electrochemical reaction, ;G is equal to the electrical driving
force, Ee. ;G corresponds to a charge, zF, taken through the potential, Ee. The measured potential for an
electrochemical reaction is therefore directly proportional to its free energy change.
;G = -zF Ee
where z is the number of moles of electrons exchanged in the reaction and F is Faraday’s constant, 96 485
coulombs per mole of electrons. Similarly, under standard conditions,
;G0 = -zF E0
Aqueous corrosion
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If oxidation does occur, the metal species is oxidised and loses electrons, forming metal cations; and a
corresponding reduction reaction that consumes electrons at the cathode
In aqueous corrosion water is the electrolyte, an ion-conducting medium. This means that the sites of
oxidation and reduction can be spatially separate. This is different from a gaseous environment, as a gas
cannot conduct ions.
A metal oxidising to produce metal ions may dissolve into the water, resulting in corrosion. This is different
from corrosion in a gas, where the oxidised metal stays where it is produced, as an oxide film on the metal.
A half-cell reaction is an electrochemical reaction that results in a net surplus or deficit of electrons. It is the
smallest complete reaction step from one species to another. Although this reaction may proceed as a
sequence of more simple reactions, these intermediate stages are not stable.
A half-cell reaction can either be a reduction, where electrons are gained, or an oxidation, where electrons
are lost.
Anions, such as O2-, are negatively charged ions, attracted to the anode.
Cations, such as Fe2+, are positively charged ions, attracted to the cathode.
Reduction reactions occur at the cathode and involve the consumption of electrons. In corrosion these
normally correspond to reduction of oxygen or evolution of hydrogen, such as:
2H+ + 2e- = H2
Oxidation reactions occur at the anode and involve the production of electrons. For the corrosion of metals,
these reactions normally correspond to the various metal dissolution or oxide formation reactions, such as:
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Fe = Fe2+ + 2e-
Fe2+ = Fe3+ + e-
In addition to causing corrosion, oxidation may result in the formation of a passive oxide. The passive oxide
produced may protect the metal beneath from further corrosion –significantly slowing further corrosion. An
example of such passivation is that of aluminium in water, where aluminium is oxidised to from a layer of
Al2O3 that protects the metal beneath from further oxidation.
Reference electrodes
Since only differences in potential can be measured, a benchmark electrode is required, against which all
other electrode potentials can be compared. The particular reference electrode used must be stated as part
of the units.
2H+ + 2e- = H2
is defined as having an electrode potential, EH+/H2 of zero volts, when all reactants and products are in the
standard state. The standard chemical potential of H+ at 1 molar (M) concentration is by definition equal to
zero.
The standard state is defined as 298 K, 1 bar pressure for gases and a concentration 1 molar (1 mol dm-3) for
ions in aqueous solution.
As a direct result of this, the standard hydrogen electrode (SHE) is commonly used as a reference electrode.
When coupled with an electrode, the potential difference measured is the electrode potential of that
electrode, as the SHE establishes by definition the zero point on the electrochemical scale.
The standard hydrogen electrode consists of a platinum electrode suspended in a sulphuric acid solution with a
one molar concentration of H+. Purified hydrogen is bubbled through to equilibrate the 2H+ + 2e- =
H2 electrode reaction.
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The diagram above shows how the standard potential, E0 of nickel can be determined. The nickel electrode
contains Ni2+ ions in equilibrium with nickel metal.
The hydrogen electrode is linked via a salt bridge to the deaerated solution in which the nickel electrode is
immersed. This permits charge transfer and potential measurement but not mass transfer of the acid solution
in the electrode.
When Ee or E0 are measured relative to the SHE (or some other reference electrode), a voltmeter is used. The
voltmeter is required to have a high impedance to resist any current flowing between the electrode and the
SHE. If a current were allowed to flow, the electrodes would become polarised and would no longer be at
equilibrium.
In practice, it is often difficult or impossible to determine experimentally the standard electrode potential for
electrochemical systems. Many systems lie outside the water stability zone or are passive. For example, zinc
will immediately begin to oxidise when immersed in water.
It is very simple to determine accurately the standard equilibrium potential from the equation linking
chemical driving force with the electrical driving force,
;G0 = -zF E0
To obtain a standard equilibrium potential, E0, for an electrochemical reaction, all that is required is to look
up relevant values of standard chemical potential.
If a metal surface is immersed in an electrolyte such as water, metal ions tend to be lost from the metal into
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the electrolyte, leaving electrons behind on the metal. This will continue to occur until the metal reaches its
equilibrium potential and the system comes to equilibrium, with a certain concentration of dissolved ions. The
metal is at its equilibrium potential, Ee. If the electrolyte were to be continuously replaced (by water flowing
in through a pipe for example), more and more metal ions would be lost, resulting in continuous corrosion of
the metal.
A cathodic reaction may occur that uses up the electrons lost by the metal species. In the reaction,
2H+ + 2e- = H2
if the hydrogen gas evolved is lost from the system, the reaction is prevented from reaching equilibrium.
The cathodic reaction acts as a sink for electrons liberated in the oxidation reaction of the metal. As a result
of this, the metal will not reach its equilibrium potential. The metal oxidation reaction is therefore not in
equilibrium and carries a net reaction. The difference between the potential, E, of the metal and its
equilibrium potential, Ee is called the overpotential and is given the symbol η.
η = E − Ee
As corrosion occurs, the mass of metal is reduced due to the conversion of atoms to ions, which are
subsequently lost. The sites of oxidation (the anode) and reduction (the cathode) can both be situated on the
same piece of metal – there is no need for an external electrode to be present for the process to occur.
The aim of this procedure is to balance electrochemical equations in terms of electronic charge and moles of
components, given the main reaction product and reactant.
By convention, electrochemical reactions are written as the REDUCTION of the species concerned, proceeding
to the right. The species with the lower oxidation state is written on the right hand side.
1. Write down the main reaction components, with the reduced form (the form with the lowest valency) on
the right.
2. Add stoichiometric numbers to balance the number of metal atoms. (Don’t worry about charge or oxygen
being balanced at this point).
3. Balance the number of oxygen atoms by adding H2O to the appropriate side.
4. Balance the number of hydrogen atoms by adding hydrogen ions (H+) to the appropriate side.
5. Balance the residual charge by adding electrons (e-) to the appropriate side.
Now each side of the equation has the same number of atoms of each element and the same overall charge.
Find the electrochemical reaction for an equilibrium between Cr2O3 and CrO42-
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Check: Each side of the equation has: Two Cr, eight O, ten H and zero residual charge – so it is balanced.
Example 1
Example 2
Example 3
The Nernst equation links the equilibrium potential of an electrode, Ee, to its standard potential, E0, and the
concentrations or pressures of the reacting components at a given temperature. It describes the value of Ee
for a given reaction as a function of the concentrations (or pressures) of all participating chemical species.
In its most fundamental forms, the Nernst equation for an electrode is written as:
or
The notation [reduced] represents the product of the concentrations (or pressures where gases are involved)
of all the species that appear on the reduced side of the electrode reaction, raised to the power of their
stoichiometric coefficients. The notation [oxidised] represents the same for the oxidised side of the electrode
reaction.
Explanation of Activity
Example 1
water is the reduced species and the oxygen gas is the oxidised species. By convention, electrochemical
half-equations are written as
Taking into account the stoichiometric coefficients of the species, the log term of the Nernst equation for this
reaction appears as
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Some of the species that take part in electrode reactions are pure solid compounds. The standard state for
these compounds is unit mole fraction, and as they are pure, and are in their standard states. In dilute
aqueous solutions, water has an overwhelming concentration, so it may be considered pure. The standard
state for a gas is taken as 1 atm (or 1 bar) and the standard state for solutes (such as ions) is taken as 1 mol
dm-3. The log term of the Nernst equation can now be reduced to
At 298.15 K (25 °C), the numeric values of the constants can be combined to give a simpler form of the
Nernst equation for an electrode under standard conditions:
This equation can be applied both to the potentials of individual electrodes and the potential differences
across a pair of half-cells. However, it is generally more convenient to apply the Nernst equation to one
electrode at a time.
A Pourbaix diagram plots the equilibrium potential (Ee) between a metal and its various oxidised species as a
function of pH.
M = Mz+ + ze-
depend on various factors, including the potential, E, pH and the concentration of the oxidised species, Mz+.
The Pourbaix diagram can be thought of as analogous to a phase diagram of an alloy, which plots the lines of
equilibrium between different phases as temperature and composition are varied.
To plot a Pourbaix diagram the relevant Nernst equations are used. As the Nernst equation is derived entirely
from thermodynamics, the Pourbaix diagram can be used to determine which species is thermodynamically
stable at a given E and pH. It gives no information about the kinetics of the corrosion process.
The following animation illustrates how a Pourbaix diagram is constructed from first principles, using the
example of Zinc.
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Note: This animation requires Adobe Flash Player 8 and later, which can be downloaded here.
The Pourbaix diagram provides much information on the behaviour of a system as the pH and potential vary.
The following animation explains how a Pourbaix diagram is built up from fundamentals.
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Gold’s Pourbaix diagram explains why it is the most immune substance known. It is immune in all regions in
which cathodic reactions can take place. So gold never* corrodes in an aqueous environment.
Immunity of aluminium only occurs at lower potentials. Therefore, unless under conditions that cause it to
passivate, it is much more susceptible to corrosion than gold or zinc.
* provided that the water is pure; that no ion complexes are present to provide a cathodic half cell reaction
that occurs at a potential higher than +1.5 V(SHE).
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A Pourbaix Diagram does not have to be limited to two dimensions. Three (or higher) dimension diagrams can
be constructed by varying other parameters such as concentration or temperature.
Note: This animation requires Adobe Flash Player 8 and later, which can be downloaded here.
Summary
In this package:
Please follow this link if you would like to provide a short review for this TLP
Questions
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Quick questions
You should be able to answer these questions without too much difficulty after studying this TLP. If not, then
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6.
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Going further
Books
Websites
Kinetics of Aqueous Corrosion TLP - introduces the mechanism of aqueous corrosion and the associated
kinetics (DoITPoMS).
It is often impractical to use the standard hydrogen electrode owing to the clumsy nature of using hydrogen
gas. In practice, a range of alternative, secondary electrodes are used.
The potentials of these electrodes are precisely known with respect to the SHE, so a measured potential can
be easily converted to an equivalent one relative to the SHE. Three of the most common secondary electrodes
are:
The reaction is based on the reaction between this elemental mercury (Hg) and mercury(I) chloride (Hg2Cl2,
"calomel").
A one molar solution of potassium chloride in water forms the aqueous phase in contact with the mercury and
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In cell notation the electrode is written as: Cl- (saturated) | Hg2Cl2(s) | Hg(l) | Pt
The measured potential, E, of the SCE is +0.241 V (SHE) for a saturated chloride ion solution at 298 K.
This is based on the reaction is between the silver metal (Ag) and silver(I) chloride (AgCl). The half-cell
reaction is
AgCl + e- = Ag + Cl-
Changing the electrolyte concentration with this electrode changes the equilibrium electrode potential, so
fixed values of chloride concentration are required.
The copper-copper(II) sulphate electrode is based on the redox reaction between copper metal and its salt -
copper(II) sulphate.
The corresponding equation can be presented as follows:
Cu2+ + 2e- = Cu
The Nernst equation below shows the dependence of the potential of the copper-copper(II) sulphate electrode
on the concentration copper-ions:
The equilibrium potential of a copper-copper sulphate electrode is -0.318 V with respect to the standard
hydrogen electrode for a saturation concentration of copper ions at 298 K.
Example 1
Zn(OH) 4 2– Zn
Zn(OH) 4 2– Zn
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Zn(OH) 4 2– Zn + 4 H2O
Zn(OH) 4 2– + 4 H+ Zn + 4 H2O
Zn(OH) 4 2– + 4 H+ + 2 e- Zn + 4 H2O
Check: Each side of the equation has: One Zn, four O, four H and zero residual charge – so it is balanced.
Example 2
Find the electrochemical reaction for an equilibrium between NO3- and NO.
NO3- NO
NO3- NO
NO3- NO + 2 H2O
NO3- + 4 H + NO + 2 H2O
Check: Each side of the equation has: One N, three O, four H and zero residual charge – so it is balanced.
Example 3
Find the electrochemical reaction for an equilibrium between MnO4- and MnO2
MnO4- MnO2
2. Balance Mn atoms
MnO4- MnO2
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Check: Each side of the equation has: One Mn, four O, four H and zero residual charge – so it is balanced.
Activity
When the concentration of a species is high or a complex is involved, concentration should be replaced by the
term, activity. The system can be more or less active than its concentration suggests.
The left hand reaction represents the equilibrium between atoms of A on a metal surface and Az+ ions in
solution. The term ‘equilibrium’ refers to the fact that the rate of reaction in one direction equals the rate of
the reverse reaction.
For the above reaction, the free energy change, ;G, is given by
where XA is the mole fraction of A in the metal and CA is the concentration of Az+ in solution. When the
metal, A, is pure, XA = 1. Also, the standard states X0A and C0Az+ can be omitted, as the standard state for the
metal phase is unit mole fraction, and for the dissolved ions is 1 mol dm-3. Thus, the free energy change can
be expressed as
(1)
At equilibrium, the chemical driving force, ;G is always equal to the electrical driving force, Ee. As discussed
previously, this can be expressed as
;G0 = -zF Ee
where z is the number of moles of electrons exchanged in the reaction and F is Faraday’s constant, 96 485
coulombs per mole of electrons. Under standard conditions,
.;G0 = -zF E0
;G0 = -RT ln K
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However, only the standard equilibrium potential, E 0, is related directly to K. The non-standard potential, Ee
is not.
Equation (1) can now be expressed in terms of electrode potential by substituting for ΔG and .;G0
It is conventional to work in decadic logs rather than natural logs, since this is arithmetically more convenient
and the pH scale is expressed in the decadic form: ln X = 2.303 log X so the equation may be written as:
Note that for this simple reaction, the Nernst equation shows that the equilibrium potential, Ee is
independent of the pH of the solution. Many half-cell reactions contain H+ ions and their Nernst equations
therefore depend on the pH.
The notation [reduced] represents the product of the concentrations (or pressures where gases are involved)
of all of the species that appear on the reduced side of the electrode reaction, raised to the power of their
stoichiometric coefficients. The notation [oxidised] represents the same for the oxidised side of the electrode
reaction.
Solutions in which components, such as Cl- ions, can complex with the metal ions require a different
treatment.
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Additional support for the development of this TLP came from the Worshipful Company of Armourers and
Brasiers'
© University of Cambridge
DoITPoMS, Department of Materials Science and Metallurgy, University of Cambridge
Information provided by doitpoms@msm.cam.ac.uk.
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