How it Works
The Evans diagram is a graphical representation of corrosion kinetics. It plots electrode potential (E) on the y-axis against the logarithm of current density (log i) on the x-axis. Two polarization lines are drawn: the anodic line (metal dissolution) and the cathodic line (oxygen reduction or hydrogen evolution). Where they intersect defines the corrosion potential E_corr and corrosion current density i_corr.
Butler-Volmer kinetics governs each electrode reaction. In the Tafel region (large overpotential), the exponential terms simplify to straight lines on a log scale with slopes βa (anodic) and βc (cathodic) in mV per decade of current.
Anodic Tafel: E = E_eq + βa · log(i/i₀)
Cathodic Tafel: E = E_eq − βc · log(i/i₀)
Stern-Geary: i_corr = B/Rp, B = (βa·βc)/(2.303·(βa+βc))
Frequently Asked Questions
What is the Evans diagram?
The Evans diagram plots electrode potential (E) vs. log of current density (log i). It shows anodic and cathodic polarization curves intersecting at the corrosion potential E_corr and corrosion current i_corr.
What are Tafel slopes?
Tafel slopes (βa for anodic, βc for cathodic) describe how the electrode potential changes with log current density in the Tafel region. Typical values are 60–120 mV/decade for many metal/electrolyte systems.
What is Butler-Volmer kinetics?
Butler-Volmer equation describes the relationship between electrode current and overpotential: i = i0[exp(αaFη/RT) − exp(−αcFη/RT)], where i0 is exchange current density, η is overpotential, and αa, αc are transfer coefficients.
How is corrosion rate determined from E_corr and i_corr?
The corrosion rate is proportional to i_corr determined at the intersection of anodic and cathodic Tafel lines. Using Faraday's law: CR = (i_corr × M)/(n × F × ρ), where M is molar mass, n is electrons, F is Faraday constant, ρ is density.
What is the exchange current density?
Exchange current density (i0) is the rate of anodic and cathodic reactions at equilibrium (zero net current). Higher i0 means faster electrode kinetics. It appears at the reversible potential of each half-reaction.
What is linear polarization resistance?
Near E_corr, current varies linearly with potential. The Stern-Geary equation relates polarization resistance Rp to corrosion current: i_corr = B/Rp, where B = (βa·βc)/(2.303·(βa+βc)).
Why do Tafel slopes vary between systems?
Tafel slopes reflect the reaction mechanism. For a simple 1-electron transfer, βa = RT/(αaF) ≈ 60 mV/decade at 25°C with α=0.5. Multi-step reactions, adsorption processes, and temperature all affect the observed slope.
What is passivation in corrosion?
Passivation occurs when an oxide film forms on the metal surface at high anodic potentials, drastically reducing the corrosion current. The anodic curve shows a peak (active peak) followed by a passive region with low, nearly constant current.
How does pH affect corrosion potential?
pH affects equilibrium potentials of both half-reactions via the Nernst equation. For hydrogen evolution: E = E0 − 0.0592·pH at 25°C. Higher pH generally shifts cathodic curve to more negative potentials, potentially lowering corrosion rate for some metals.
What is galvanic corrosion?
Galvanic corrosion occurs when two dissimilar metals are electrically connected in an electrolyte. The less noble metal (anode) corrodes preferentially. The mixed potential of the coupled system lies between the individual corrosion potentials of each metal.