Engineering Corrosion OH-4: University of Hafr Al Batin

ME 472 University of Hafr Al Batin
College of Engineering
Department of Mechanical Engineering
Engineering
Corrosion
OH-4
Course Instructor:
Dr. Tajammal Imran.
UHB Main Campus Room #2307,
tajammal@uhb.edu.sa
Engineering Corrosion
ME472
Kinetics of Corrosion
• The phenomena of polarization.
• Types and causes of polarization.
• Hydrogen over-voltage.
• Influence of polarization on corrosion rate.
Disclaimer: the contents of this lecture are referenced to various resources including textbook, internet resources and lectures.
The instructor claims no credit except the credit of the time and organization of the content.
Overview Kinetics of Corrosion
•What is corrosion kinetics?
•What is polarization or phenomena of
polarization?
•What are types and causes of polarization?
•What is Hydrogen over-voltage?
•How polarization influences corrosion rate?
02/08/2021 202ME472EngineeringCorrosion_Tajim_HO_4 3
What is Corrosion Kinetics?
• Corrosion studies can be carried-out by two methods
1. Thermodynamics
2. Electrode Kinetics (rate of reaction)
• Thermodynamics give the change in energy state;
➢Free Energy: Driving Force of a Chemical Reaction
• Also, thermodynamics predicts the directions of a reactions.
• By thermodynamic, rate of reaction can not be predicted.
• Corrosion kinetics refers to the controlled measurement of
the stability of chemical species present during corrosion
for various substrate materials.
What is Corrosion Kinetics?
• Corrosion kinetics study the • Corrosion rate is best expressed in
polarization (‫ )االستقطاب‬of reactants in terms of thickness or weight loss
terms of their cathodic and anodic where the surface of the metal
trends. corrodes uniformly across the area
• Passivity, inhibition and mass that has been exposed.
movement enabled characteristics of • It is found by:
corrosion are examined via corrosion R = d / t (µm/year)
kinetics
• Corrosion kinetics cannot be only In electrochemistry, polarization is a collective term for
used to determine the rate of certain mechanical side-effects (of an electrochemical
corrosion of a given metal surface process) by which isolating barriers develop at the
because corrosion depends on the interface between electrode and electrolyte. These side-
contribution of several external effects influence the reaction mechanisms, as well as the
chemical kinetics of corrosion and metal deposition.
factors other than polarization.
Electrode Kinetics
• Electrode kinetics is the study of reaction
• Important concepts of electrode
rates at the interface between an electrode
and a liquid. kinetics to understand the
corrosion are;
• Electrode reactions are assumed to induce
deviations from equilibrium due to the 1. Potential (also called the
passage of an electrical current through an mixed potential and the
electrochemical cell causing a change in rest potential )
the electrode potential. 2. Corrosion
• This electrochemical phenomenon is 3. Current density
referred to as polarization 4. Exchange current density ,
• The science of electrode kinetics has made and
possible many advances in the 5. Tafel slope
understanding of corrosion and the
practical
02/08/2021
measurement of corrosion rates.
202ME472EngineeringCorrosion_Tajim_HO_4 6
What is Polarization?
• Polarization is a term used for an electrochemical process in which isolating barriers
develop at the interface between electrode and electrolyte.
• Polarization can also be described as a kinetic deviation from equilibrium due to an
electric current passing through a galvanic cell.
• Polarization may occur at the cathode (cathodic polarization) or at the anode
(anodic polarization). Cathodic polarization is more common.
• For all metals and alloys in any aqueous environment, cathodic polarization always
reduces the corrosion rate.
• Cathodic protection refers to the application of a cathodic polarization to a corroding system.
• Polarization is sometimes also referred to as "overvoltage" or "overpotential".
• When electrode reactions take place, the potential will not be at equilibrium due
to current flow through an electrochemical cell thus causing a change in the
electrode potential. This electrochemical phenomenon is termed POLARIZATION.
Polarization?
• When there is no net current flows from an electrode, then this
electrode is at equilibrium state and its potential is the equilibrium
potential (Eo).
• When net current flows to, or from electrode surface, the potential
changes from Eo to Ei , the electrode is then said to be polarized
and the process is termed as polarization.
• Polarization is measured in volts as follows:
 = Ei - Eo
Where:
η = The overvoltage, and Ei = The polarization potential
Corrosion Rate (or corrosion current)
• Corrosion rate is the speed at which any metal in a specific environment
deteriorates.
• It also can be defined as the amount of corrosion loss per year in thickness.
• The speed or rate of deterioration depends on the environmental
conditions and, the type and condition of the metal under reference.
• Several pieces of data must be collected when calculating the corrosion rate
of any given metal.
• Required data includes:
• Weight lost (the decrease in weight of the metal during the period of reference).
• Density of the metal.
• Total surface area initially present.
• Length of time taken.
Corrosion Rate (corrosion current, or icorr)
• The rate of corrosion (or current density) is determined by • The action of these resistances may be expressed
the potential difference between the anode and the in a polarization diagram (Evans Diagram).
cathode and the resistance of the corrosion cell. • These diagrams plot potential difference versus
• The corrosion current is therefore: I = V/R current density (or log current).
• The slope of the curve represents the resistance.
• The resistance ‘R ’ of the cell may be as a result of electrical
resistance or electrode polarization.
• The greater the resistance the lower the corrosion current
and from Faraday’s law the lower the mass loss.
• A high resistance within the corrosion cell is beneficial for
control.
• This resistance may result from one or more of the
following factors:
1) Resistance of the electrical connection between anode and
cathode.
2) Resistance of the electrolyte.
3) High concentration of anode metal ions in solution.
4) Reactant build-up at the cathode.
5) Lack of reactants at the cathode.
Evans Diagram (polarization diagram)
• Based on EMF series and galvanic series, the common • Once the Zn is connected/immersed in hydrogen,
parameter for both series is potential (voltage). both experience activation polarization along
their lines.
• Current play a role too in corrosion but as in the form of • When the 2 lines meet, the corrosion potential
current density. (E_corr) & corrosion current density (i_corr) will
be known.
• Current Density is a measure of current per unit area.
• From here, the corrosion rate of zinc can be
• Evans (or polarization) diagram relate the corrosion rate estimated using current density value (i_corr).
(current density) to the potential.
• For Evans diagram, the y-axis remains as potential, but
the x-axis is now the current density in logarithmic scale.
• Typical Evans diagram for zinc in acid solution is shown.
• From the diagram,
• There are 4 slopes existed
• 2 comes from Zn & 2 comes from H2.
• The 2 slopes from each element corresponds to oxidation
(sloping up) reaction and reduction (sloping down) reaction. https://steemit.com/corrosion/@rahim.rahman/corrosion-evans-diagram
The Polarized Cell (CASE STUDY)
• After studying this topic you are required to write a summary of this topic and also write about your discoveries.
• Give description of the features, reactions that are taking place,
• What this diagram is about?
• How to use this diagram to explain the corrosion kinetics?
• Daniel cell
• Zinc in ZnSO4 solution
• Copper in CuSO4 solution
Expressions & Measures of Corrosion Rates
There are three main methods that are used to 3) Corrosion current density
express the corrosion rate: • Corrosion rate also can be expressed by corrosion current
1) Thickness reduction of the material per unit time density.
• Thickness reduction per unit time is the measure of most • The dissolution rate (the corrosion rate) is the amount of
practical significance and interest. metal ions removed from the metal per unit area and unit
• In the metric system this measure is usually expressed in time.
mm/year.
• In some literature one can still find the unit mils per year
• This transport of ions can be expressed as the electric
(mpy) = 1/1000 inches per year, possibly also inches per current Ia per area unit, that is;
year (ipy). Anodic current density ia = Corrosion current density icorr
2) Weight loss per unit area and unit time • If it is preferred to express the local corrosion current
• Weight loss per unit area and unit time was commonly density in the anodic area, then
used in earlier times, mainly because weight loss was
usually the directly determined quantity in corrosion icorr = ia = Ia /Aa
testing. where Aa is the anodic area.
• Here the test specimens were weighed before and after the
exposure to the corrosion medium. • However, usually the average corrosion current density
• On this basis one could calculate the thickness reduction as over the whole surface area A is given, i.e.
weight loss per unit area/density. icorr = ia = Ia /A
Polarization & a Polarized Cell
• Deviation of the potential from
its reversible value is referred
to as polarization.
• A cell or electrode is said to be
polarised when there is little
or no change in current with
larger changes in potential.
Types and Causes of Polarization
• There are three types of electrode polarization:
1. Activation Polarization
This is the energy required to overcome the exchange current density to allow the
electrode reaction to proceed
2. Concentration Polarization
This is the shift in potential due to concentration changes in the environment
adjacent to the electrode surface.
3. IR drop
This considers the electrolytic resistivity of an environment when the anodic and
cathodic elements of a corrosion reaction are separated by this environment while
still electrically coupled
1.Activation Polarization
• This is the energy required to overcome the exchange
current density to allow the electrode reaction to proceed
• All electrochemical reactions occur in a series of steps at the
interface between electrode and electrolyte.
• Activation polarization refers to the condition wherein the
reaction rate is determined by the slowest step.
• The term “activation” used because an activation energy
barrier is associated with this slowest, rate-limiting step.
• This polarization is caused by a slow electrode reaction.
• The reaction at the electrode requires activation energy in order to go.
• The most important is that of hydrogen ion reduction at the cathode reaction as:
• Stage (1) occurs rapidly, whereas stage (2) is generally the slower and rate-controlling step.
• The activation overpotential, and hence the activation energy varies exponentially with the rate of
charge transfer per unit area of electrode surface, as defined by the well-known Tafel equation:
• Tafel equation for cathode process
• Tafel equation for anode process
• The Tafel constant (β) varies with the nature of the electrode process and with the nature
of the solution.
• Thus (ηA) will be linearly related to (log i) at overpotential greater than 0.05 V and the
position of the curve will be dependent on the equilibrium exchange current density (io),
the transfer coefficient (α) and the number of electrons (z) involved in one act of the rate
determining step.
• This is the shift in potential due to
concentration changes in the environment
adjacent to the electrode surface.
• Concentration polarization in the environment
adjacent to the surface is caused by
concentration changes as illustrated in Fig.
• When a chemical species (O2) participating in a
corrosion process is in short supply, the mass
transport of that species to the corroding
surface can become rate controlling.
• Mass transport to a surface is governed by three
forces, that is, diffusion, migration, and
convection.
• Concentration polarization is obtained when the rate of an electrode
reaction is dependent on mass transfer, i.e. the rate at which the reactant
is transported to the surface of the electrode and the rate at which the
product is transported away from the electrode.
• For concentration polarization reaction current is given by Fick’s law:
3. IR Drop
• The resistance polarization is the ohmic potential drop through a portion of the electrolyte
surrounding the electrode, through a metal reaction product film on the surface or both.
• An ohmic potential drop always occurs between the working electrode and the capillary
tip of reference electrode.
• The ohmic (i.e., solution) IR drop is given by:
IR soln. = i  l =i l / k
Where: ρ = The specific resistance (i.e. resistivity) (Ω.cm),
k = The conductivity (Ω-1.cm-1) or(S.cm-1);
S = Siemens,
l = The solution gap between the capillary tip and the working electrode(cm).
• Resistance polarization is important only at high current densities or in high resistance
electrolyte solution.
Over-Potential & Over-Voltage
• The deviation from equilibrium causes an electrical
potential difference between the polarized and the
equilibrium (unpolarized) electrode potential known
as overpotential.
• Overpotential is defined as the polarization (potential
change) of an equilibrium electrode that results from
current flow across the electrode – solution interface.
• Overpotential, η , is the difference between the
measured potential and the thermodynamic, or • Overvoltage, ε , is the difference
reversible potential; that is, between the measured potential and the
η = φmeasured − φ reversible corrosion (or mixed) potential; that is,
• Overvoltage is defined as polarization (potential • ε = φmeasured − φ corrosion
change) of a corroding electrode caused by flow of an
applied current.
Overpotential and Electrochemical Cell
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, Ei , and a hydrogen electrode at equilibrium in the same
solution; that is,
• Hydrogen overpotential is measured in the same way as polarization is measured.
Hydrogen OverPotential
• The absolute values of hydrogen overpotential for a given metal
decrease with:
• 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.
• Roughening of the surface.
• A sandblasted surface has a lower hydrogen overpotential than a polished
surface. Greater area and improved catalytic activity of a rough surface
account for the observed effect.
• Decreasing current density.
Influence of Polarization on Corrosion Rate
• Both resistance of the electrolyte and polarization of
the electrodes limit the magnitude of current
produced by a galvanic cell.
• For local - action cells, on the surface of a metal, the
electrodes are near each other and hence anodic
polarization becomes more important factor of polarization.
1) Anodically controlled
• 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.
• A practical example is impure lead immersed in sulfuric acid,
where a lead sulfate film covers the anodic areas and
exposes cathodic impurities, such as copper.
2) Cathodically controlled
• 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.
3) Resistance controlled
• It 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.
4) Mixed controlled
• It is common for polarization to occur in some degree at
both anodes and cathodes. This situation is described as
mixed control
• The extent of polarization depends not only on the nature
of the metal and electrolyte, but also on the actual
exposed area of the electrode
• If the anodic area of a corroding metal is very small, caused by
porous surface films, there may be considerable anodic
polarization accompanying corrosion, even though measurements
show that unit area of the bare anode polarizes only slightly at a
given current density.
• Consequently, the anode – cathode area ratio is also an important
factor in determining the corrosion rate.
• If current density is plotted instead of total corrosion
current, corresponding polarization curves are shown in
bottom figure.
Calculation of Corrosion Rates from Polarization Data
Corrosion rates (or current) can be
calculated from the • Tafel equation expresses cathodic
1. Corrosion potential polarization behavior as
2. Thermodynamic potential
• If the equation expressing polarization of
the anode or cathode is known, • The thermodynamic potential is − 0.059 pH
• If the anode – cathode area ratio can be • icorr and the equivalent corrosion rate can
estimated be calculated
• For corrosion of active metals in deaerated
acids, the surface of the metal can be
assumed to be mostly cathode because it is
probably covered largely with adsorbed H
atoms.
Typical Calculated Corrosion Rates Values for Iron
Example to find Corrosion Rate from Polarization Data
• Rate of Oxidation Computation: Zinc experiences corrosion in an acid solution
according to the reaction
Zn + 2H+ → Zn2+ + H2
The rates of both oxidation and reduction half-reactions are controlled by activation polarization.
1. Compute the rate of oxidation of Zn in (mol/cm2 –s) given the following
activation polarization data:
For Zn For Hydrogen
𝐄(Zn/Zn𝟐+ ) = −0.763 V E 𝐇 + /H𝟐 = 0V
𝐢𝐨 = 10−𝟕 A/cm𝟐 i𝐨 = 10−10A/cm𝟐
𝛃 = +0.09 β = −0.08
2. Compute the value of the corrosion potential

Solution of the Example to find Corrosion Rate from Polarization Data
1. Compute the rate of oxidation of Zn from the given activation polarization data:
Step 1: To compute the rate of oxidation for Zn, it is first necessary to establish relationships in the form of Tafel equation for
the potential of both oxidation and reduction reactions.
Step 2: Next, these two expressions are set equal, and then we solve for the value of “i” that is the corrosion current density, iC.
Step 3: Finally ,the corrosion rate may be calculated using Equation (1). The two potential expressions are follows:
For hydrogen reduction  i 

E H = E (H + /H ) + β H log 
 i oH 
2
And for Zn oxidation  i 

E Zn = E (Zn/Zn2 + ) + β Zn log 
 i oZn 
Now setting E H = E Zn leads to
 i   i 
E (H + /H ) + β H log  = E (Zn/Zn2+ ) + β Zn log 
2
 i oH   i oZn 
1
log iC = E H+ /H2 − E Zn/Zn2+ − βH log ioH + βZn log ioZn
βZn − βH
1
= 0 − −0.763 − −0.08 log 10−10 + 0.09 log 10−7
0.09− −0.08
= −3.924
Or
io
And from eq.(1) rred = roxid =
nF
2. Now it becomes necessary to compute the value of the corrosion potential EC. This is
possible by using either of the above equations for EH or EZn and substituting for “i” the
value determined above for iC. Thus using the EH expression yields
iC
EC = E H+ /H2 + βH log
ioH
1.19 × 10−4 A/cm2

= 0 + −0.08 V log
10−10 A/cm2
= − 0.486 V
• Let us compare the example problem with

the problem that is represented graphically.
• Let us analyze the same problem that is
solved graphically in the voltage-versus
logarithm current density plot as given in the
figure.
• It is worth noting on the graph that the values
are of iC = 1.19  10−4 and EC = -0.486 V
• These we have obtained by the analytical
treatment and are agreeing with those values
occurring at the intersection of the two-line
segments on the graph.
Tafel Equation
• The Tafel equation is an equation • An electrochemical reaction occurs in
in electrochemical kinetics relating two half reactions on
the rate of separate electrodes.
an electrochemical reaction to • Tafel equation is applied to each
the overpotential electrode separately. On a single
• It describes how the electrical current electrode the Tafel equation can be
through an electrode depends on the stated as:
voltage difference between the
electrode and the bulk electrolyte for
• The plus sign under the exponent refers to an anodic
a simple, unimolecular redox reaction, and a minus sign to a cathodic reaction
reaction. •  : overpotential
• A : "Tafel slope", V
• i : current density, A/m2
• i0 : "exchange current density", A/m2
Exchange Current Density
• The exchange current density, i0 is defined as the current
flowing in both directions per unit area when an electrode
reaction is at equilibrium (and, hence, at its equilibrium
potential).
• Exchange current density is a parameter used in the Tafel equation,
Butler–Volmer equation and other electrochemical kinetics expressions.
• The Tafel equation describes the dependence of current for an
electrolytic process to overpotential.
• By plotting electrode potential versus reaction rate as shown in figure, It
is possible to establish a point corresponding to the platinum-hydrogen
electrode.
• This point represents the particular exchange reaction rate of electrode
Figure: Hydrogen-Hydrogen ion on Platinum.
expressed in terms of moles reacting per square centimeter per second ,
at no net reaction and at zero overpotential;
oxidation rate = reduction rate = exchange reaction rate 𝑖𝑜
𝑟𝑜𝑥𝑖𝑑 = 𝑟𝑟𝑒𝑑 = . . . . . . . . . (1)
• Exchange reaction rate can be expressed in terms of current density, and 𝑛𝐹
current density can be directly derived from Faraday's law:
Homework - 3
• What is a difference between Tafel plot and Evans Diagram?
• Quiz # 2 and 3 ?????????
Summary and Conclusions
• What is Corrosion Kinetics?
• How to calculate rate of a reaction?
• What is Tafel plot and Evans Diagram?
• How to study a polarized cell?
• What is Polarization and different types of Polarization
• What is exchange current density?
• What is Tafel equation?
Spontaneous and non-Spontaneous reactions
• For spontaneous reactions , the systems must decrease their Free-energy

and move to a lower energy state, e.g. Corrosion is a spontaneous reaction.
• For non-spontaneous reactions energy must be added to the system in order
to facilitate the reaction.
Fe → Fe2O3 spontaneous ( - ∆G )
Fe ← Fe2O3 non-spontaneous ( + ∆G )

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ME 472 University of Hafr Al Batin

• Tafel equation for anode process

• Hydrogen overpotential is measured in the same way as polarization is measured.

2. Compute the value of the corrosion potential

For hydrogen reduction  i 

And for Zn oxidation  i 

1.19 × 10−4 A/cm2

• Let us compare the example problem with

• Quiz # 2 and 3 ?????????

• For spontaneous reactions , the systems must decrease their Free-energy

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