Lecture 9: Electrode Kinetics: Mechanism and Corrosion, Ionic Mass Transport

Reaction Mechanism
The overall reaction is composed of several elementary reactions in series. For
electrochemical reactions, an elementary reaction usually involves transfer of a single
electron. Several possible reaction mechanisms can be postulated to explain an overall
reaction. The most probable mechanism will be the one that is consistent with the
experimental observations.

The reaction order for an electrochemical reaction is defined in terms of current density
as follows:

a
C
i
j
C P T
A
, , ,
ln
ln


a is the order with respect to the species A.

One of the elementary reactions (in a sequence of elementary reactions) is typically the
rate controlling step. A Tafel-type equation can be written for this step if an electron
transfer is involved. The nature of the curve will vary depending upon which step is rate
controlling. The validity of the postulated mechanism (and the rate controlling step) can
be tested from the experimentally obtained overpotential vs. current density curves.

Corrosion: Kinetics and Evans Diagram
Metallic surface in aqueous environment can corrode through anodic oxidation, with
cathodic reaction (hydrogen evolution or oxygen reduction) taking place on the same
surface in the region adjacent to anodic reaction site. Current flows through electrolyte
next to the sites and the circuit is completed through the transfer of electrons in the metal.
Evans diagram is obtained by plotting the Tafel approximation of polarization curves
(potential vs. current density) for both the cathodic and anodic reactions on one graph.
Corrosion potential (E
corr
) and corrosion current density (i
corr
) are obtained from the
intersection of the two curves. Cathodic protection involves introduction of another metal
in the system that is polarized at lower potentials. On Evans diagram, this translates into
another anodic polarization line closer to the current density axis (has lower potential)
than the original metal. The intersection of this line with the cathodic polarization line
yields the new E
corr
and i
corr
. At this new potential the original metal undergoes cathodic
rather than anodic reaction and does not corrode (cathodic protection). If the corrosion
potential is not lowered enough to prevent anodic oxidation of the original metal, the
lowering of the potential greatly reduces the current density and hence rate of corrosion
of the original metal. Corrosion potential and current density can be calculated using
equations 5.102 and 5.104 respectively (Prentice text) when the transfer coefficients are
equal to 0.5 or equations 5.101 and 5.103 in more general case. Cathodic protection may
be obtained by imposing a potential (which is different from E
corr
) on the system, and in
that case the current density can be obtained by a form of the Stern-Geary relation shown
below.
) (
corr
cr ax
corr
E
RT
F
RT
F
i i

Ionic Mass Transport
Concentration gradient, potential gradient and convection contribute to the flux of an
ionic species in an electrochemical system. The current density i is related to the flux N
of the charged species (i = F z
i
N
i
, z being the charge on the species).