Corrosion Kinetics
Ch-3
Faradays Laws of Electrolysis and its
Application in Determining the
Corrosion Rate
The
classical
electrochemical
work
conducted by Michael Faraday in the
nineteenth century produced two laws
published in 1833 and 1834 named after
him.
The First Law:
The mass of primary products
formed at an electrode by
electrolysis
is
directly
proportional to the quantity of
electricity passed.
The Second Law:
The masses of different primary
products
formed
by
equal
amounts
of
electricity
are
proportional to the ratio of molar
mass to the number of electrons
involved
with
a
particular
reaction:
Combining the first law and the second law,
as in equation
Applications of Faradays Laws
in Determination of Corrosion
Rates of Metals and Alloys
Corrosion rate has dimensions of mass
reciprocal of time:
The rate of corrosion is proportional to the current passed
and to the molar mass.
The
above
equation
has
successfully used to
determine the rates of corrosion.
been
W=loss of weight of a meta
A very useful practical unit
for
representing
the
corrosion rate is milligrams
per decimeter square per
day
(mg.dm
.day1)
or
mdd. Other practical units
are
millimeter
per
year
(mmy1 ) and mils per year
orrosion Kinetics
Anodic and
Reactions
Cathodic
driving force is provided by the free energy of the
reaction (G).
EnergyDistance Profiles
Reversible Reactions
Reversibility and
Exchange Current
rreversible Process
This irreversibility can be brought
about by connecting the electrode
to an external source of current.
By connecting the electrode to the
positive pole of an external source
of current, the electrode is made
the anode, and similarly it can be
made a cathode by connecting to
the negative terminal.
Factors Affecting Exchange
Current Density
Forward reaction: As described above, only those atoms
which are energetically at unfavorable positions, such as
at grain boundaries, dislocations, half planes, are able to
detach themselves and participate in the reaction. Atoms
are more easily pulled from the kink sites than terrace
sites. The number of surface atoms available (Ns) in a
given area can be calculated.
Electrode composition: It depends upon the composition
of electrode (see Table 3.1). The exchange current
density
Pt is 103Large
A/cm2 surface
whereasareas
for mercury
it is
Surface for
Roughness:
provideHg
a high
13
2
10
A/cmcurrent.
in dilute acid.
exchange
Impurities: The exchange current density is reduced by
the presence of trace impurities, such as As, S and Sb
which are catalyst poisons
Reverse Reaction (Cathodic
Reaction)
Let us now consider the conditions under which a cation
would be transformed back to a metallic atom by the
reverse process. Energydistance profile for a reduction
reaction is shown in Fig. 3.5.
Activation
Polarization
Activation
polarization
is
the
potential difference beyond the value
of equilibrium needed to generate
currents depending on the energy
activation of a redox reaction. It is
the activation energy that is required
to have electrons transferred from
electrodes into analyte.
Activation polarization is also known
as electron transfer
Factors Affecting Activation
Polarization
Tafel
Equation
Where i0 is the exchange current density
B= Tafel slop
19
The Tafel equation is generally written as
20
Mixed Potential Theory and its
Application
21
22
23
Construction of a Polarization
Diagram
24
Evans Diagrams
25
26
Prediction of Corrosion Tendency on
the Basis of Mixed Potential Theory
27
28
29
Application of Mixed
Potential Theory
Effect of an Oxidizer
the effect of oxidizing metal ions
on the corrosion rate of a metal in
acid solutions, such as the effect of
Fe3+ ions on the corrosion of zinc in
hydrochloric acid.
30
Coupling of an Active Metal to a Noble
Metal
31
Effect of Galvanic
Coupling
basis of thermodynamics. Consider
coupling of zinc to gold and zinc to
platinum.
32
Effect of Area Ratio
Effect of Oxygen
and later oxygen is introduced into
the solution.
33
34
concentration polarization
concentration
polarization
is
the
polarization of an electrolytic cell resulting
from
changes
in
the
electrolyte
concentration due to the passage of current
through the electrode/solution interface.
Concentration polarization commonly occurs
during the cathodic processes, depending
on the reduction of dissolved oxygen, since
it is usually in low concentration
35
Effect of Various Factors on Concentration
Polarization
36
37
38
Resistance
Polarization
Polarization)
(Ohmic
39
40
Measurement of Corrosion
Corrosion Potential
and Corrosion Current
41
42
43
44
45
Kinetics of Passivity
46
47
Definition of Important Electrochemical
Parameters for ActivePassive Metals
48
49
50
