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CORROSION CHEMISTRY
LECTURE 3
Dr Willard Pinnock
CHEM 2601 (2013)
Recap of Lecture 2 (I)
Our view of rusting is that it is an electrochemical process
and so the corrosion cell is essentially
a short-circuited cell (on the same piece of iron or steel)
with the difference in dissolved O
2
concentration (in the electrolyte)
near the metal, determining the anode and cathode.
The Nernst equation gives the potential difference
between anode and cathode of the concentration cell.
Corrosion occurs essentially at the anode through loss
of metal ions while the cathode behaves as an inert
electrode.
One can use indicators to visualize anode and cathode in
corrosion on a single piece of metal Evans Water Drop
Experiment is one such demonstration.


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Recap of Lecture 2 (II)
Corrosion can also be driven by the potential that arises
when two metals are in physical contact with both being
also in touch with an electrolyte.
Again the Nernst Equation helps us to estimate the
potential of such cells with the help of tabulated reduction
potentials.
The equation also applies when the solution is an
electrolyte other than water as long as the potentials
(E
0
) used are appropriate to the electrolyte in question
like seawater, or acid environments.

Application of the Nernst Equation to these two types of
cells are explored in Tutorial 1
Rate of Corrosion
The potentials give some idea of the driving force for the
corrosion process and helps to identify anode and cathode in
various situations, but does not say much about the rate of
corrosion.

When the corrosion is uniform over a reasonable-sized area, the
rate of corrosion is usually expressed as the amount of metal
lost in mass per unit area per unit time. (g cm
-2
s
-1
)

The rate of loss of metal can be directly related to the rate of
charge exchange between the metal and the oxidizing species in
solution, expressed as the corrosion current, i
corr
, .

Common units i
corr
, are C cm
-2
s
-1
or A cm
-2
(since an A = C s
-1
)
or sometimes A cm
-2



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Rate of Corrosion
Rate of corrosion = (i
corr
/nF) M
Fe


where n is the number of electrons transferred in each reaction,
F is the Faraday constant (96485 C mol
-1
)
M
Fe
is the molar mass of iron/ g mol
-1
Note that the equation is essentially the definition of the term
rate of corrosion broken down into an expression in terms of
the corrosion current.
If this rate of corrosion is divided by the density of the metal, a
very useful corrosion rate, in cm s
-1
, results.
This is sometimes called the penetration depth expressed in mils, mm,
or cm per year.
1 mil is a thousandth of an inch (= 0.254 cm)
So: Rate of corrosion/ density = penetration depth
Rate of Corrosion
Remember that the corrosion cell is essentially a short-
circuited cell, so the current will be limited only by factors
affecting the rate of charge exchange at the electrode-
solution interfaces.
The corrosion current will therefore be dependent on factors
such as: temperature, concentration and mobility of ions in
solution, but most importantly on the nature of the metal-
solution interfaces at anode and cathode.
In a cell that is used to store and deliver electrical power,
the influence of effects at the metal-solution interfaces are
deliberately reduced by the use of a salt bridge.
Here we want them to be as effective as possible so the
corrosion current, i
corr
, is kept small.
We will investigate these factors in some depth after we
explore the practical implications of the magnitude of i
corr
.


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Corrosion Rate Calculation
Sample Problem:
Plain carbon-steel, immersed in seawater, has a uniform corrosion
rate expressed as a penetration depth of 0.125 mm per year.
Assuming that the density of steel is 7.87 g cm
-3
, and that steel has
a molar mass of 55.8 g mol
-1
, find the mass (in grams) of iron lost in
corrosion per cm per year, and the corrosion current in A cm
-2
.

Answer: 0.098 g cm
-2
year
-1
, i
corr
= 10.8 A cm
-2



Some idea of acceptable and unacceptable rates are
shown in the next slide.
Ranking of Corrosion Rates by NACE
Performance
Ranking
Corrosion
Rate in
mils*year
Corrosion Current Densities in A cm
-2

Aluminium Iron Lead
Outstanding 1 2.3 2.2 0.85
Excellent 1 - 5 2.3 12 2.2 11 0.8 4.3
Good 5 - 20 12 47 11 43 4.2 - 17
Fair 20 - 50 47 180 43 109 17 - 42
Poor 50 - 200 180 -470 109 430 42 - 170
Unacceptable 200 470 430 170
*1 mil = 0.0254 mm
Taken from Introduction to Corrosion Science by E. Mc Cafferty
(Springer)
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Measuring Corrosion Currents
It is really very useful to corrosion scientists to be able to measure
corrosion rates in various situations but it is difficult to measure
corrosion current directly .
This is because:
we cant readily separate cathode and anode electrically (since they are both on
the same piece of metal in most cases) and there is no net flow of charge to or
from the metal when the corrosion current flows.
This is true even when the electrodes are of two different metals in contact. If
they are separated in order to measure current, then the potential driving the
corrosion process is no longer operating.

We can measure the corrosion current indirectly however, by several
methods. The following are some of the most useful methods:
Weight loss method
Chemical analysis of corroding solutions
Thickness measurements
Electrical resistance measurements
Electrochemical polarization measurements
Measuring Corrosion Currents (I)
Weight Loss Method
Suitable when corrosion products are loose and do not adhere to
the metal.
Metal component is removed from the corroding environment and
cleaned (of corrosion products), dried and weighed at various
measured times.
In order to ensure accuracy, all the corrosion products (and only
corrosion products) should be removed from the component.
Weight loss per unit area of sample is plotted vs elapsed time and
the slope of that plot gives corrosion rate. From this the corrosion
current can be inferred.
The results of an experiment in which two types of steel were
exposed to the atmosphere (in an industrial environment) are
shown in the next slide.

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Measuring Corrosion Currents (II)
Note that the
corrosion rate
changes with time.

Note too that the
time scale of the
experiment is
several years, so it
is a demanding
experiment that
cannot be used to
give urgently
needed information.

Taken from:
Introduction to
Corrosion Science
by Mc Cafferty


Measuring Corrosion Currents (III)
Chemical Analysis of Solutions
Applicable when there is a constant volume of solution, or when the
investigator can isolate the corroding solution.
One must assume also that the time scale of measurements is
such that not much of the metal has precipitated as corrosion
product so the time scale is usually in hours or days.
Concentration of metal ions in the solution can be determined by
suitable means colorimetric or spectrophotometric for example.
Concentration vs elapsed time can be plotted as before and one
can determine corrosion rate and corrosion current from the slope,
with knowledge of the volume of solution involved.

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Measuring Corrosion Currents (IV)
Thickness Measurement Method
Suitable for measuring rates in situ in, for example, gas cylinders,
railroad hopper cars, storage tanks and pipelines.
X-ray or Ultra-sound can be used to measure thickness of walls.
Thickness of metal can be measured as a function of time and this
can be interpreted in terms of penetration depth which can then be
used with the density to infer corrosion currents.

Measuring Corrosion Currents (V)
Electrical Resistance Measurement Method
Suitable for use in wires or films whose resistance increases when
they are thinned by corrosion.
Resistance is given by R = l/A where is the resistivity of the
material.
If cross-sectional area A, decreases as a result of corrosion, resistance
increases and corrosion rates and currents may be inferred from the
density and dimensions of wire or film.
Comment on Methods so Far
Each of the methods described is useful in a very special situation,
and so they are not generally applicable to many practical corrosion
situations.
Also, in many situations of practical interest it can take years to obtain
reliable data.
Electrochemical methods (which we are about to discuss) offer the
advantages of: (i) being more generally applicable, and (ii) requiring
less time to obtain reliable data.