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ELECTROCHEMICAL KINETICS OF

CORROSION-UNIT-4
CHE-545-172
DR IME B.OBOT

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POLARIZATION
 The concept of corrosion tendency is based on thermodynamics —
the equilibrium between metals and their environments
 In practice, however, we are concerned primarily with rates of
corrosion — that is, with kinetics.
 Some metals with pronounced tendency to react (e.g., aluminum)
nevertheless react so slowly that they meet the requirements of a
structural metal and may actually be more resistant in some media
than other metals that have inherently less tendency to react.
 The considerations of equilibria are irrelevant to the study of
corrosion. Instead, a fundamental approach to nonequilibrium states,
along with calculation of corrosion rates, begins with the primary
consideration that equilibrium has been disturbed.
 In general, therefore, we must know the equilibrium state of the
system before we can appreciate the various factors that control the
rate at which the system tends toward equilibrium, that is, the rate of
corrosion.
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POLARIZATION
 An electrode is not at equilibrium when a net current flows to or
from its surface.
 The measured potential of such an electrode is altered to an
extent that depends on the magnitude of the external current and
its direction.
 The direction of potential change always opposes the shift from
equilibrium and, hence, opposes the flow of current, whether the
current is impressed externally or is of galvanic origin.
 When current flows in a galvanic cell, for example, the anode is
always more cathodic in potential and the cathode always
becomes more anodic with the difference of potential between
the anode and cathode becoming smaller as current is increased.
 The potential change caused by net current to or from an
electrode, measured in volts, is called polarization.
 Electrode kinetics is the study of reaction rates at the interface
between an electrode and a liquid. 3
THE POLARIZED CELL
 Consider a cell made up of zinc in ZnSO4
solution and copper in CuSO4 solution
(the Daniell cell), the electrodes of which
are connected to a variable resistance R ,
voltmeter V , and ammeter A.
 The potential difference (emf) of zinc and
copper electrodes of the cell without
current flow is about 1 V.
 If a small current is allowed to flow
through the external resistance, the
measured potential difference falls below
1 V because both electrodes polarize.
 The voltage continues to fall as the
current increases.
 On complete short - circuiting (very small Polarized copper – zinc cell.
external resistance), maximum current
flows and the potential difference of
copper and zinc electrodes becomes
almost zero.
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THE POLARIZED DIAGRAM
 The effect of net current flow on voltage of the Daniell cell can be
represented by plotting a polarization diagram — that is, a graph
showing potential, φ, of copper and zinc electrodes.
 The thermodynamic potentials (no current flow through the cell) are
given by φZn and φCu .
 The zinc electrode polarizes along curve abc , and the copper
electrode polarizes along curve def .
 At a value of current through the ammeter equal to I1 , the
polarization of zinc in volts is given by the difference between the
actual potential of zinc at b and the thermodynamic value a or φZn .
 Similarly, the polarization of copper is given by the difference of
potential e – d .
 The potential difference of the polarized electrodes, b – e , is equal to
the current I1 multiplied by the total resistance of both the external
metallic resistance R m and the internal electrolytic resistance, R e , in
series, or I1 ( R e + R m ).
 On short - circuiting, the current becomes maximum, I max . Then R
Polarization diagram for
m can be neglected, and the potential difference of both electrodes
decreases to a minimum equal to I max Re . copper – zinc cell.
 The maximum current is equivalent to (65.38/2) Imax /F grams zinc
corroding per second-where I max is in amperes, F is equal to 96,500
C/eq, and 65.38/2 is the equivalent weight of zinc.

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THE POLARIZED DIAGRAM
 The cathodic reaction corresponds to the identical
chemical equivalents of copper depositing per second
on the cathode.
 The corrosion rate of zinc can exceed the indicated
equivalent corrosion rate, I max , only if a method is
introduced for reducing the polarization of zinc or
copper, or both, thereby reducing the slopes of abc or
def , causing an approach to intersection at a larger
value of I.
 Similarly, any factor tending to increase polarization
will decrease current through the cell and decrease
the corresponding corrosion rate of zinc.
 Obviously, the polarization curves can never actually
intersect, although they can approach each other very
closely if anodes and cathodes are closely spaced in
media of moderate to good conductivity.
 There will always be a finite potential difference
accompanying an observed flow of current.

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THE POLARIZED DIAGRAM AND
CORROSION CELL
 Electrolytic cells that account for the corrosion of metals are analogous
to the short - circuited cell.

 The measured potential of a corroding metal, the mixed potential of


both polarized anodes and cathodes, is also referred to as the corrosion
potential, φcorr .

 The value, Imax , is known as the corrosion current, Icorr.

 By Faraday’s law, the corrosion rate of anodic areas on a metal surface is


proportional to Icorr , and hence the corrosion rate per unit area can
always be expressed as a current density.

 We can calculate the corrosion rate of a metal if data are available for
the corrosion potential and for the polarization behavior and
thermodynamic potential of either anode or cathode.

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MEASUREMENT OF POLARIZATION
 A typical cell that is commonly used in
corrosion studies to measure polarization,
in which the working electrode (the
electrode being studied), two (for
uniformity of current flow) counter
electrodes, gas inlet and outlet, Luggin
capillary, and thermometer.
 The Luggin capillary can disturb the
distribution of the current applied to
electrode.
 In addition, particularly in low conductivity
solutions, the distance of the tip of the
Luggin capillary from the electrode can
have a significant effect on IR drop that
arises because of the current flow through
the electrolyte.
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Calculation of IR Drop in an Electrolyte
 The resistance of an electrolyte solution measuring l cm long
and S cm2 in cross section is equal to l / κ S ohms, where κ is
the specific conductivity.
 Hence, the IR drop in volts equals il / κ , where i is the
current density.
 For seawater, κ = 0.05 Ω− 1 cm− 1 ; therefore, a current density
of 1 × 10− 5 A/cm 2 (0.1 A/m 2 )(the magnitude of current
density that might be applied for cathodically protecting
steel) produces an IR drop correction for a 1 - cm separation
of probe from cathode equal to (1 × 10 − 5 V)/0.05 = 0.2 mV.
This value is negligible in establishing the critical minimum
current density for adequate cathodic protection.
 In some soft waters, however, where κ may be 10 − 5 Ω − 1 cm−
1 , the corresponding IR drop equals 1 V/cm.

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TYPE OF ELECTROCHEMICAL
POLARIZATION
 Activation Polarization: Caused by slow electrode reaction.
 Concentration polarization: Caused by concentration
changes in reactants or products near an electrode surface.
 Ohmic Polarization: Caused by IR drops in solution or across
surface films such as oxides or salts.
 The degree of polarization is defined as overvoltage (or
overpotentials) η, given by:
η = E-Eo, where E is the electrode potentials for some
conditions of current flow and Eo is the electrode potentials for
zero current flows(also called open-circuit potentials, corrosion
potentials or rest potentials). Note: Eo shouldn’t be confused
with the standard electrode potentials E or ϕo which plays a
prominent role in thermodynamics 10
ANODIC AND CATHODIC POLARIZATION
 Either an anode or a
cathode can be polarized.
 Anodic polarization is the
displacement of the
electrode potentials in the
positive direction so that
the electrode acts more
anodic.
 Cathodic polarization is the
displacement of the
electrode potentials in the
negative direction so that
the electrode acts more
cathodic.

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VISUALIZATION OF CATHODIC
POLARIZATION

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VISUALIZATION OF ANODIC
POLARIZATION

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OHMIC POLARIZATION
 Ohmic polarization within a
solution is due to the
inability to place the
reference electrode directly
at the metal surface under
investigation.
 The use of Luggin-Haber
capillary minimizes the
error due to IR drops.
 IR drops is negligible for
high conductivity solutions
but affect low conductivity
solutions.
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HYDROGEN OVERPOTENTIAL
 The polarization term that controls the corrosion rate of many metals in
deaerated water and in nonoxidizing acids is hydrogen overpotential.
 Hydrogen overpotential is the difference of potential between a cathode at
which hydrogen is being evolved, φ measured , and a hydrogen electrode at
equilibrium in the same solution: H2 overpotential = φmeasured − (−0.059pH).
 Hydrogen overpotential includes only the activation polarization term
corresponding to the reaction 2H+ + 2 e − → H2 .
 Absolute values of hydrogen overpotential for a given metal decreases with:
(1)-Increasing temperature ( i0 increases). For metals that corrode by hydrogen
evolution, decreasing hydrogen overpotential is one factor accounting for increase of
corrosion as the temperature is raised.
(2) Roughening of the surface. A sandblasted surface has a lower hydrogen
overpotential than a polished surface.
(3) Decreasing current density- according to Tafel Equation η = βlog i/Io, (the term β
is equal to 2.3 RT/αF). where α is a constant and the other terms have their usual
significance. The term α is approximately 2 for platinum and palladium and is
approximately 0.4 – 0.6 for Fe, Ni, Cu, Hg, and several other metals.
 Note Reduction of water as the controlling reaction applies generally to metals in
alkaline solutions at high and low current densities.

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POLARIZATION DIAGRAMS OF CORRODING METALS
 Polarization diagrams of corroding metals, sometimes called Evans diagrams, are
graphs of potential versus log current or log current density.
 They were originally developed by U. R. Evans at the University of Cambridge in
England, who recognized the usefulness of such diagrams for predicting corrosion
behavior.
 To establish a polarization diagram, the usual electrodes that are employed, in
addition to the electrode being studied (the “ working ” electrode), are the
reference electrode and the inert counter (or auxiliary) electrode that is usually
made of platinum.
 A design of a 1 - liter electrochemical cell is mostly used in many corrosion
laboratories. A gas bubbler in used for atmospheric control — for example, to
deaerate the solution or to saturate the solution with a specific gas.
 The measurements are usually made using a potentiostat — an instrument that
automatically maintains the desired potential between the working and
reference electrodes by passing the appropriate current between the working
and counter electrodes.
 The current between working and counter electrodes is controlled, and the
potential of the working electrode with respect to the reference electrode is
measured.
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POLARIZATION DIAGRAMS OF CORRODING METALS
 In experimentally establishing a polarization diagram,
the first measurement is usually that of the corrosion
potential, φcorr , when the applied current, Iappl , is
zero.
 The working electrode is then polarized either
anodically or cathodically to establish one of the
dashed lines.
 The polarization procedure is then repeated, but with
Iappl reversed, to obtain the second dashed line.
 Using Potentiostat, polarization may be carried out
either in potential steps (i.e., potentiostatically) or
continuously (i.e., potentiodynamically).
 In this system, the oxidation reaction may be the
dissolution of metal, M → M z+ + ze − , and the
reduction reaction may be symbolized as Rn+ + ne − →
R.
 In an aerated neutral or basic aqueous solution, the
reduction reaction could be O2 + 2H2O + 4 e − → 4OH−
, whereas in a deaerated acid, the reduction reaction
could be 2H+ + 2 e − → H2 .

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INFLUENCE OF POLARIZATION ON CORROSION RATE
• When polarization occurs mostly at
the anodes, the corrosion reaction is
said to be anodically controlled.
• Under anodic control, the corrosion
potential is close to the
thermodynamic potential of the
cathode.
• Examples are magnesium exposed to
natural waters and iron immersed in
a chromate solution.
• When polarization occurs mostly at
the cathode, the corrosion rate is
said to be cathodically controlled.
• The corrosion potential is then near
the thermodynamic anode potential.
• Examples are zinc corroding in
sulfuric acid and iron exposed to
natural waters.

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INFLUENCE OF POLARIZATION ON CORROSION RATE
• Resistance control occurs when
the electrolyte resistance is so
high that the resultant current is
not sufficient to appreciably
polarize anodes or cathodes.
• An example occurs with a porous
insulating coating covering a
metal surface.
• The corrosion current is then
controlled by the IR drop
through the electrolyte in pores
of the coating.
• It is common for polarization to
occur in some degree at both
anodes and cathodes.
• This situation is described as
mixed control.

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CALCULATION OF CORROSION RATES FROM
POLARIZATION DATA
• The corrosion current can be calculated from the corrosion
potential and the thermodynamic potential if the equation
expressing polarization of the anode or cathode is known, and if
the anode – cathode area ratio can be estimated.
• For corrosion of active metals in deaerated acids, for example, the
surface of the metal is probably covered largely with adsorbed H
atoms and can be assumed, therefore, to be mostly cathode.
• The thermodynamic potential is − 0.059 pH, and if icorr is
sufficiently larger than i0 for H + + e − → 1/ 2H2, the Tafel equation
expresses cathodic polarization behavior is:

• From which icorr and the equivalent corrosion rate can be


calculated.

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CALCULATION OF CORROSION RATES FROM
POLARIZATION DATA
• Stern showed that calculated corrosion Comparison of Calculated and Observed Corrosion Currents for Pure
rates for iron and employing empirical Iron in Various Deaerated Acids
values for β and i0 , were in excellent
agreement with observed rates.

• Stern and Geary derived the very important


and useful equation, now known as the
Stern – Geary equation.

• Where βc and βa refer to Tafel constants for


the cathodic and anodic reactions,
respectively, and Iappl / Δφ is the
polarization slope (the reciprocal of the
polarization resistance, R = Δ φ / I appl ) in
the region near the corrosion potential, for
which the change of potential, Δφ, with Iappl
is essentially linear.

• If corrosion is controlled by concentration


polarization at the cathode, as when oxygen
depolarization is controlling, then we
have:βa is between 0.06 and 0.12 V.

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