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