ASSIGNMENT
Activation, Concentration, and Resistance (Ohmic) Polarization in Corrosion
Assignment question: Describe the concepts of activation polarization, concentration
polarization, and resistance (ohmic) polarization. Compare these three types of polarization in
terms of their mechanisms, controlling factors, and effects on the corrosion rate.
1. Introduction
Polarization is the change in electrode potential that occurs when a net current flows to or
from an electrode. An electrode carrying current is no longer at its equilibrium or reversible
potential. The potential shift produced by current always opposes the displacement from
equilibrium and therefore opposes further current flow. In a corrosion cell, this behavior
reduces the potential difference between the anodic and cathodic sites as current increases.
The corrosion potential is the mixed potential at which the total anodic current equals the
total cathodic current, and the corresponding current density is the corrosion current density,
i_corr. Since corrosion rate is proportional to i_corr through Faraday’s law, any form of
polarization that restricts anodic or cathodic current can directly reduce the corrosion rate.
The three principal contributions discussed in electrode kinetics are activation polarization,
concentration polarization, and resistance or ohmic polarization. They may act separately, but
in practical corrosion systems the measured potential change often contains contributions
from more than one type.
2. Activation Polarization
Activation polarization is caused by a slow electrochemical reaction at the electrode–solution
interface. Before electron transfer can occur, the reacting species must pass through an
activated state. The required activation energy makes the electrode reaction proceed at a finite
rate. Therefore, an additional potential, called activation overpotential, is needed to drive the
reaction at a specified current density.
A typical example is hydrogen evolution at a cathode. On a platinum surface, the reaction
may proceed through the adsorption of hydrogen followed by molecular hydrogen formation:
H⁺ + e⁻ → H_ads
2H_ads → H₂
The slower elementary step controls the overall rate and determines the magnitude of the
hydrogen overpotential. Activation polarization also occurs during oxygen evolution and
during the deposition or dissolution of metal ions. Its magnitude differs greatly among
electrode materials because surface catalytic activity and reaction mechanism differ from one
metal to another.
The activation overpotential is defined as the difference between the measured potential of
the current-carrying electrode and its reversible equilibrium potential:
η = φ_measured − φ_reversible
Within the Tafel region, activation polarization varies logarithmically with current density:
η = β log₁₀(i / i₀)
Here, β is the Tafel slope and i₀ is the exchange current density. The exchange current
density represents the equal forward and reverse reaction currents at equilibrium. A large i₀
indicates rapid charge-transfer kinetics; therefore, less activation overpotential is required to
produce a given current. Conversely, a small i₀ or a large Tafel slope produces greater
activation polarization.
The main controlling factors are electrode material, surface condition and catalytic activity,
temperature, current density, electrolyte composition, adsorbed species, and the nature of the
electrochemical reaction. A rough or catalytically active surface may reduce activation
polarization by increasing the effective reaction area or accelerating charge transfer.
Increasing temperature normally increases reaction rates and exchange current density,
thereby reducing activation polarization at a fixed current density.
Effect on corrosion rate: greater activation polarization reduces the anodic or cathodic current
that can flow at a given potential. Consequently, the intersection of the anodic and cathodic
polarization curves occurs at a smaller i_corr, and the corrosion rate decreases. For corrosion
controlled by hydrogen evolution, a metal with high hydrogen overpotential suppresses the
cathodic reaction and generally corrodes more slowly than a metal on which hydrogen
evolution is kinetically easy.
3. Concentration Polarization
Concentration polarization, also called diffusion overpotential, arises when the concentration
of an electroactive species at the electrode surface differs from its concentration in the bulk
solution. This difference develops when the electrochemical reaction consumes or produces
species faster than mass transport by diffusion, convection, and migration can restore the
surface concentration.
For example, when copper is deposited cathodically from a dilute CuSO₄ solution, Cu² ⁺ ions
are consumed at the electrode surface. The bulk-solution potential and the polarized surface
potential may be written as:
φ₁ = 0.337 + (0.0592 / 2) log₁₀(Cu²⁺)
φ₂ = 0.337 + (0.0592 / 2) log₁₀(Cu²⁺)ₛ
Because the surface activity (Cu²⁺)ₛ is lower than the bulk activity (Cu² ⁺), the cathode
potential becomes less noble, or more active. The resulting concentration polarization is:
φ₂ − φ₁ = −(0.0592 / 2) log₁₀[(Cu²⁺) / (Cu²⁺)ₛ]
As current density increases, the surface concentration becomes progressively smaller. When
the surface concentration approaches zero, the mass-transfer rate reaches its maximum and
the current approaches the limiting current density, i_L. The general cathodic concentration-
polarization relation is:
φ₂ − φ₁ = −(RT / nF) ln[i / (i_L − i)]
The limiting current density depends on diffusion and the thickness of the stagnant diffusion
layer:
i_L = (D n F c / δ) × 10⁻³
In this expression, D is the diffusion coefficient, n is the number of electrons transferred, F is
Faraday’s constant, c is the bulk concentration in mol/L, and δ is the diffusion-layer
thickness. For many ions in dilute solution at 25°C, the book gives the useful approximation:
i_L ≈ 0.02 n c
The controlling factors are bulk reactant concentration, diffusion coefficient, diffusion-layer
thickness, fluid velocity or stirring, temperature, electrode geometry, and the availability of
the reacting species. Stirring or flowing solution decreases δ, improves mass transfer,
increases i_L, and therefore decreases concentration polarization at a given current density. A
higher reactant concentration also raises i_L. In contrast, stagnant conditions, low
concentration, and thick diffusion layers increase concentration polarization.
Effect on corrosion rate: concentration polarization limits the maximum rate of a mass-
transfer-controlled cathodic or anodic process. As the current approaches i_L, a very large
potential change is needed for only a small additional increase in current. Therefore, the
corrosion current cannot exceed the mass-transfer limit imposed by the controlling reaction.
However, agitation may increase corrosion when it removes concentration polarization and
supplies depolarizer, such as dissolved oxygen, more rapidly to the surface. At an anode,
accumulation of dissolved metal ions can produce concentration polarization in the noble
direction and also oppose further anodic dissolution.
4. Resistance (Ohmic) Polarization
Resistance polarization, commonly called ohmic polarization or IR drop, is the potential loss
caused by electrical resistance in the current path. The resistance may be located in the
electrolyte between the working electrode and the reference-electrode tip, in a corrosion-
product film on the metal surface, or in both. This potential drop does not arise from slow
charge transfer or mass transfer; it follows directly from Ohm’s law.
For an electrolyte path of length l, cross-sectional area S, and specific conductivity κ, the
resistance is:
R = l / (κS)
Therefore, the ohmic potential drop is:
Δφ_ohmic = IR = i l / κ
Here, I is total current and i is current density. The IR drop increases with current density,
path length, electrode spacing, and film resistance, but decreases with electrolyte conductivity
and exposed area. It is most important in poorly conducting solutions, narrow or long current
paths, and systems covered by resistive oxide or corrosion-product films. Placing a Luggin
capillary close to the working electrode minimizes uncompensated solution resistance during
measurement.
The ohmic contribution disappears essentially immediately when the current is interrupted
and is not significantly reduced by stirring. Because it consumes part of the available cell
voltage, high solution or film resistance lowers the effective driving potential, corrosion
current, and corrosion rate. It must be separated from true electrode polarization to avoid
incorrect interpretation of reaction kinetics.
5. Comparison of the Three Types of Polarization
Basis of comparison Activation polarization Concentration polarization Resistance (ohmic) polarization
Basic mechanism Slow electron-transfer or interfacial Depletion or accumulation of Potential loss caused by electrical
reaction requiring activation energy. reacting species at the electrode resistance in the electrolyte, surface
surface because mass transport film, or current path.
cannot keep pace with reaction.
Rate-controlling step Charge-transfer kinetics or a slow Diffusion, convection, or other mass Ionic/electronic conduction through
elementary surface-reaction step. transport of the electroactive species. a resistive medium.
Principal relation η = β log₁₀(i / i₀) φ₂ − φ₁ = −(RT / nF) ln[i / (i_L − i)] Δφ_ohmic = IR = i l / κ
Important controlling factors Electrode material, catalytic activity, Bulk concentration c, diffusion Conductivity κ, path length l,
surface condition, temperature, coefficient D, diffusion-layer electrode spacing, area S, current
current density, electrolyte species, thickness δ, stirring or flow, density, temperature, and resistive-
i₀, and Tafel slope β. temperature, and electrode geometry. film thickness.
Stirring and current interruption Stirring has little direct effect. After Stirring strongly reduces it by Stirring has little effect. It disappears
interruption, the activation decreasing δ. After interruption, it essentially instantaneously when
component decays as the interface decays as the surface concentration current becomes zero.
returns toward equilibrium. gradient relaxes.
Effect on corrosion rate Greater activation polarization Limits the supply or removal of Reduces the effective driving
restricts anodic or cathodic kinetics, species and caps the reaction at i_L. voltage and therefore lowers
lowers i_corr, and reduces corrosion Removing it by agitation can corrosion current; may also distort
rate. increase corrosion when the process measured polarization data if
is mass-transfer controlled. uncompensated.
6. Overall Interpretation and Conclusion
All three forms of polarization oppose current flow, but they originate from different physical
processes. Activation polarization is a kinetic limitation at the electrode interface;
concentration polarization is a mass-transfer limitation in the electrolyte near the electrode;
and resistance polarization is an electrical potential loss in the conducting path. Their
diagnostic responses are also different: concentration polarization is strongly reduced by
stirring, activation polarization is governed mainly by interfacial reaction kinetics, and IR
drop vanishes immediately when current is interrupted.
The corrosion rate is controlled by the combined anodic and cathodic polarization behavior.
Increasing any polarization contribution generally reduces the corrosion current density and
therefore reduces the corrosion rate. Nevertheless, the practical effect depends on which
reaction controls the corrosion process. For example, stirring can raise corrosion rate by
reducing oxygen concentration polarization, whereas a high hydrogen activation
overpotential can protect a metal by slowing the cathodic hydrogen-evolution reaction.
Accurate corrosion analysis must therefore identify the dominant mechanism and separate
true electrode polarization from uncompensated IR drop.
Reference
Revie, R. W., and Uhlig, H. H. Corrosion and Corrosion Control. Chapter 5: “Kinetics:
Polarization and Corrosion Rates,” pp. 53–64. John Wiley & Sons, 2008.