• Fall 2005

• Corrosion Rate
Polarization Behavior
• Metallic surfaces can be polarized by the application of an external voltage or by
the spontaneous production of a voltage away from equilibrium. This deviation
from equilibrium potential is called polarization. The magnitude of polarization is
usually described as an overvoltage (h) which is a measure of polarization with
respect to the equilibrium potential (Eeq) of an electrode.
• This polarization is said to be either anodic, when the anodic processes on the
electrode are accelerated by changing the specimen potential in the positive
(noble) direction or cathodic when the cathodic processes are accelerated by
moving the potential in the negative (active) direction. There are three distinct
types of polarization in any electrochemical cell, the total polarization across an
electrochemical cell being the summation of the individual elements:
• E(applied) - Eeq = htotal = hact +hconc +iR   (see a typical fuel cell
polarization curve)
• where:
– hact is the activation overpotential, a complex function describing the charge transfer
kinetics of the electrochemical processes. hact is predominant at small polarization
currents or voltages.
– hconc is the concentration overpotential, a function describing the mass transport
limitations associated with electrochemical processes. hact is predominant at large
polarization currents or voltages.
– iR is often called the ohmic drop. iR follows Ohm's law and describes the polarization
that occurs when a current passes through an electrolyte or through any other
interface such as surface film, connectors ... The ohmic drop is the simplest of the
three polarization terms and can be evaluated either directly with a conductivity cell or
using conductance data.
Activation Overpotential
• Both the anodic and cathodic sides of a reaction can be studied individually
by using some well established electrochemical methods where the
response of a system to an applied polarization, current or voltage, is
studied. A general representation of the polarization of an electrode
supporting one redox system is given in the Butler-Volmer equation:
•

• where:
– i is the anodic or cathodic current;
– b = charge transfer barrier or symmetry coefficient for the anodic or cathodic
reaction. b values are typically close to 0.5;
– hact = Eapplied - Eeq, i.e. positive for anodic polarization and negative for
cathodic polarization;
– n = number of participating electrons;
– R = gas constant;
– T = absolute temperature;
– F = Faraday = 96485 C mol-1
• THERMODYNAMICS OF CORROSION
• As you learned in Chemistry there is a ree energy change with
reactions. This change in free energy must be negative for the
reaction to be spontaneous.
• There are two reactions involved in the corrosion process; the total
free energy change must be negative for corrosion to occur. These
reactions are an oxidation and a reduction.
• Oxidation occurs at the anode
• Mg = Mg+2 + 2e-
• Reduction occurs at the cathode
• 2H+ +2e- = H2
• For a total reaction:
• Mg +2H+ = Mg+2 +H2
• The Free energy can be calculated by:
 G=-nFE
• Where:
• n is the number of electons exchanged ( two in the above example)
• F is the Faraday Constant (96500 Coulombs/equivalent)
• E corresponds to the energy change in the reaction.
• Each reaction ( anodic and cathodic) has a half-cell potential associated
with it: given as- E*
• The sum of the anodic and cathodic half-cell potentials is the total potential:
given as- E*
• Further considering concentration effects of the hydrogen ion and reaction
species concentration yields the Nerst Equation

• E=Eo-(RT)/(nF)*ln{[B]b [H2O]d}/{[A]a[H+]m}
•
Where:
• Eo is the defined value for the potential referenced to a standard*
• R is the gas constant
• T is temperature
• n and F are described above
• The terms of within the natural log are the concentrations of the products
over the reactants.
• That was certainly brief and very cursory but the important thing to take
away are the types of things that can play a role in the corrosion reactions.
Hopefully you have seen most of this in a freshman chemistry course.
• * The reference is the standard hydrogen electrode (SHE) which is
defined as Eo=0 Volts.
• Kinetics of Corrosion
• Thermodynamics are fundamental and show that corroison will occur in most
environments. It is also important to know how fast corrosion will occur.
• As shown in the thermodyanmics, the the reactions in the corrosive process produce
and consume electrons. Electron flow can be quantified as current; Faraday first
found the relationship between electrons exchanged and mass reacted:
• m=(Ita)/(nF)
• m= mass reacted
• I=Current
• t=time
• A=atomic weight
• n=nuber of equivalents
• F= Faraday's Constant (96500 Coulombs/equivalent)
• To find the corrosion rate (and equalize for area) divide through by time and Area
yielding:
• r=(ia)/nF
• r=corrosion rate
• i= current density
• Each reaction has a characteristic equilibrium current density this is termed io
• Electrochemical Polarization is a method used to better understand the corrosion
behavior of various materials by varying the potential above or below the equilibrium
potential (E). This polarization drives the reaction either in the noble ( anodic) or
active ( cathodic direction).
• While carrying the potential the current produced is recorded, as can be seen in the
equation above the higher the current density, the higher the corrosion rate.
• The curve above shows slightly different behavior. This is called passivity: an increased
corrosion resistance in oxidizing conditions due to a thin barrier film formed in these
conditions or at anodic potentials. Passivity can be seen by the lowering of the current
density as the potential is increased. A good example of this is stainless steel. The
reason that stainless steel does resist corrosion so well is that a thin chromium oxide film
naturally forms on the surface preventing an anodic reaction form occurring on the
surface of the steel. It is desirable to stay in the passive region ( above the critical point)
because of the reduced current density which correlates to a reduced dissolution rate.
The passive region shows a rather steady current density for a wide range of potential
values, until the passive film breaks down, causing an increase in the current density.
This is occurs at relatively high potential and is usually called trans-passive breakdown.
Summary of Electrochemical Theory

Electrochemical Reactions
• An electrochemical reaction is a reaction involving the transfer of
charge as a part of a chemical reaction. Typical electrochemical
reactions in corrosion are metal dissolution and oxygen reduction:
• In contrast a chemical reaction, such as the precipitation of a metal
hydroxide, does not involve a transfer of charge:

Faraday's Law
• Faraday's Law relates the amount of charge involved in an
electrochemical reaction with the number of moles of reactant
reacting and the number of electrons required for the reaction.
• In addition to Faradaic processes that obey Faraday's Law, non-
Faradaic processes may also occur. Typically these are processes
such as adsorption that do not involve a complete transfer of charge
from the solution to the metal.
Electrochemical Half Cells
• A half cell is an electrochemical reaction that results in a net surplus or deficit
of electrons, and it corresponds to the smallest complete reaction sequence
(while it may proceed as a sequence of simpler reactions, the intermediate
stages are not stable).

• Oxidation or anodic reactions are those that result in a surplus of electrons,

and for corrosion these typically correspond to the various metal dissolution
reactions, such as:
• Reduction or cathodic reactions result in the consumption of electrons, and for
corrosion these typically correspond to the oxygen reduction or hydrogen
evolution reactions:

• Note that the above reactions have been shown going in one direction only.
While the reverse reactions are perfectly possible, they reverse of an anodic
reaction is a cathodic reaction and vice versa.
Reversibility of Electrochemical Reactions
• A reaction is said to be reversible if it can proceed easily
in either direction as conditions change (typically as the
electrochemical potential is changed). There are several
aspects of reversibility.
• Chemical reversibility relates to the chemical feasibility of
the reaction, with a chemically irreversible reaction being
one in which the reverse reaction is prevented by the
occurrence of competing reactions,
• A thermodynamically reversible reaction is a chemically
reversible reaction for which the reaction will change
direction as a result of an infinitesimal change in
potential. 
• A practically reversible reaction is a thermodynamically
reversible reaction that occurs at a significant rate with
small overpotentials.
Electrochemical Equilibria
• Thermodynamically reversible reactions will adopt an equilibrium
potential which is described by the Nernst equation:

•  

• Example of an Electrochemical Equilibrium

• If we consider copper in equilibrium with copper ions in solution:

• Consequently the equilibrium potential will go up as the concentration of

copper ions in solution goes up
Reference Electrodes
• Reference electrodes are needed to convert from the charge
carriers in the metal (electrons) to the charge carriers in solution
(ions) in a reproducible fashion. They must be practically reversible.

• The Normal Hydrogen Electrode (NHE) is used as the (arbitrary)

standard. This consists of hydrogen at unit activity (i.e. solution in
equilibrium with hydrogen gas at 1 atmosphere) in equilibrium with
unit activity of hydrogen ions in solution (1.19 M HCl solution). The
equilibrium potential is detected with a platinum electrode that is
coated with platinum black (finely divided platinum) to enlarge the
effective surface area.

• The NHE is inconvenient for general-purpose use, and a range of

secondary reference electrodes have been developed (Table 1).
 Table 1 Practical Reference Electrodes

Common Name Electrode V vs NHE

Hg/Hg2Cl2/sat.
SCE +0.241
KCl
Hg/Hg2Cl2/1M
Calomel +0.280
KCl
Mercurous Hg/Hg2SO4/sat.
+0.640
sulphate K2SO4
Hg/Hg2SO4/0.5
+0.680
M H2SO4
Mercurous Hg/HgO/1M
+0.098
oxide NaOH
Ag/AgCl/sat.
Silver chloride +0.197
KCl
Copper sulphate Cu/sat. CuSO4 +0.316
Zinc/Seawater Zn/seawater -0.8

Note that zinc in seawater is a useful practical reference electrode, although it has
no theoretical basis for the reference potential.
Electrochemical Kinetics
• The Electrochemical Double Layer
• There is a tendency for charged species to be attracted
to or repelled from the metal-solution interface. This
gives rise to a separation of charge, and the layer of
solution with different composition from the bulk solution
is known as the electrochemical double layer. There are
a number of theoretical descriptions of the structure of
this layer, including the Helmholtz model, the Gouy­
Chapman model and the Gouy­Chapman­Stern model.
•  
• As a result of the variation of the charge separation with
the applied potential, the electrochemical double layer
has an apparent capacitance (known as the double layer
capacitance).
Kinetics of a Single Electrochemical Reaction
Activation control
An activation controlled reaction is one for which the rate of reaction is controlled
solely by the rate of the electrochemical charge transfer process, which is in turn
an activation-controlled process. This gives rise to kinetics that are described by
the Butler­Volmer equation:

While the Butler-Volmer equation is valid over the full potential range, we
can obtain simpler approximate solutions over more restricted ranges of
potential:
Large overpotentials - the Tafel equations are obtained (only applicable
for irreversible reactions):
 or, in terms of the anodic and cathodic Tafel slopes, ba and bc,

(note that bc above is taken to be positive, as this is commonly assumed;

however, bc is strictly negative, and the divisor in the Stern-Geary equation
should be 2.303(ba - bc) RCT
Mass transport control
This implies fast kinetics, hence the surface reaction is
reversible and the potential is given by the Nernst equation
applied to the surface concentrations:
The Kinetics of Multiple Reactions
When multiple reactions are possible, the resultant kinetics are described by the
mixed potential theory. This simply says that the total current in an external
circuit is the sum of all of the currents due to the individual reactions (with
anodic currents being positive and cathodic current negative). In free corrosion
conditions this implies that the sum of the negative currents is equal to the sum
of the positive currents. When there are only two reactions of any significance
(one anodic and one cathodic), the theory is analogous to that for a single
reaction.
The behaviour can be summarized diagrammatically with the Evans and E-log |
i | diagrams.
The mixed potential theory leads to the concepts of the corrosion potential,
Ecorr, and the corrosion current density, icorr. Ecorr is simply that potential at
which the sum of the anodic and cathodic currents is zero, and it is therefore
that potential that the specimen will adopt in free corrosion. icorr is, in some
ways, a more important parameter, as it describes the rates of the anodic and
cathodic reactions. Providing all of the anodic reactions lead to the
oxidation of metal, then icorr is the corrosion rate of the metal (with the
current being related to the rate of loss of metal through Faraday's Law).
The Rate Determining Step
• Real electrochemical reactions tend to occur as a sequence of very
simple steps. For example, even a very simple reaction such as
hydrogen evolution occurs as two steps, with two alternatives for the
second step:

• The rate of the overall reaction is controlled by the rate of the

slowest reaction, and this is known as the rate controlling step. This
may be an electrochemical reaction (such as Step 1 above) or a
chemical reaction (such as Step 2a). Different rate controlling steps
will typically give a different Tafel slope for the reaction and a
different reaction order (dependence on concentration of reactants).
Electrochemical measurements may be used to help to determine
the reaction mechanism and the rate-controlling step.