Corrosion kinetics

Flavio Deflorian
University of Trento Italy

1st training school – mcBEEs network, Delft 15-20 July 2018

 Corrosion Cycle

cations e-
ia im
Anodic process

Solution current Ia = Iel = Ic = Im = icorr Metal current

transport transport

Cathodic process
ic
iel
 Corrosion dissipation

electrolyte
Electrical work (potential
difference)
MN
-Eeq = e* where e* is dissipate
energy

Potential differences between different pints EMQ, EQP, EPP’, EP’W’, EW’W, EWY, EYN
EP’W’ = EMN Equilibrium potential
EMQ e EYN ohmic drop
EQP e EYW anodic and cathodic overpotential
EPP’ (EWW’) ohmic drop in PP’ and polarisation concentration
 EMN = 0 - short-circuit

EMN = EMQ + EQP + EPP’+ EP’W’ – EWW’ - EYW + EYN = 0

EP’W’ = EeqMN e –EeqMN = e*

Total dissipation e* = (EMQ + EYN) + (EQP - EYW) + (EPP’ – EWW’)

Ohmic drop in metallic conductors →

negligible

Solution energy dissipation, ohmic drop

and concentration polarisation
Electrodes dissipation
EQP Overpotential anodic ηa and
- EWY = EYW Overpotential cathodic ηc
Charge transfer at the interface
 Overpotential

ηact charge transfer overpotential

ηconc mass transport limitation overpotential
iR ohmic drop
 Normal metal: overpotential η less than 10mV
Low melting point metals Sn, Pb, Al, Zn, Mg
Inert metals: overpotential η more than 100mV
High melting point metals Fe, Co, Ni, Cr, Ti
Intermediate metals: η
Cu, Au, Ag

Normal metals: linearity between overpotential and current I/S (S = area)

Inert or intermediate metals:

a and b constants; Tafel law

With the exception of normal metals, the values of ηM are different from 0 even for low current values: it is
necessary an activation energy
Hydrogen evolution

2H+ + 2e- → H2 (g)

Butler Volmer equations
 Current versus overpotential
polarization plot of the ferric/ferrous
ion reaction on palladium showing
both the anodic and cathodic branches
of the resultant current behavior
Fe3+ + e- ↔ Fe2+

ηreaction is cathodic (negative)

bc Tafel coefficient (slope of the curve η

log|i|
ηreaction is anodic(positive)
Tafel law

Tafel slopes as a function of the

exchange currents ia e ic in the
electrodes
far from equilibrium 50mV
 Concentration overpotential

Oxigen reduction cathodic reaction

O2 + 2H2O + 4e- → 4OH-

 Concentration overpotential

Solubility of Oxygen in Air-Saturated Water

 Without electrical filed: migration
term negligible

Diffusion control– O flux : first Fick’s

law

Approximation of diffusion coefficient

A= cost, μ solution viscosity
 Concentration a a function of the distance

Nerst diffusion layer

Effect of stirring of solution (O2 reduction reaction*)
Diffusion control

O2 + 2H2O + 4e- → 4OH-

 Ohmic drop

As a function of the environment (conductivity)

Evans diagrams

pH = 0
deaerated
 pH = 5
dearated

The shift of the Ecorr to a more negative value of −0.368 V vs SHE should be
noted.
Concentration Controlled Processes

pH = 5
Aerated stagnant
pH = 5
aerated
stirred
Zinc in H2SO4 Lead immersed in H2SO4
Iron exposed to natural Magnesium exposed to
waters natural waters
Iron immersed in a chromate
solution

Porous insulating covering a

metal surface
 Further reading
• Fundamentals of Electrochemical Corrosion
Eugene Stansbury, Robert Angus Buchanan ASM International, 2000
• Corrosion Engineering Principles and Solved Problems
Branko N. Popov, Elsevier 2015
• Corrosion for Science and Engineering
K. R. Trethewey, J. Chamberlain, Addison Wesley Pub. Company 1995
• Electrochemistry and Corrosion Science
Nestor Perez, Springer, 2018
• Corrosion and Corrosion Control: An Introduction to Corrosion Science and
Engineering
A.W. Revie, Wiley-Interscience; 4 ed, 2010