Module 1 - Notes
Module 1 - Notes
MODULE 1
Corrosion and Electrode system
Corrosion Chemistry: Introduction
The destruction/deterioration of metals/alloys by the surrounding environment through
chemical/electrochemical changes is known as corrosion.
• The process of corrosion is the transformation of pure metal into its undesired metallic ore state.
• Corrosion depends on the many factors such as Temperature, pH, concentration of the medium,
electrode potential of the metal and exposure area of the anode and cathode.
Examples
1. Rusting of iron-Reddish brown color: Fe2O3.3H2O
2. Green color scale on copper: CuCO3+Cu(OH)2
Types of corrosion
1. Dry or direct chemical corrosion: Corrosion is due to direct chemical reaction between metal and
gases such as HCl, H2S, SO2, Cl2, F2, NH3 etc. present in environment in the absence of moisture or
conducting medium.
2. Wet or electrochemical theory of corrosion: Metal undergoes corrosion in the presence of
moisture or conducting medium.
Anodic region-Oxidation
Cathodic region- Reduction
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Corrosion reactions
a) Anodic reaction- At the anodic area, oxidation take place, resulting in the corrosion of iron
1. Anode - M → Mn+ + ne-
Rust Formation
(i) In the presence of excess oxygen
Fe2+ + 2OH- → Fe(OH)2
2Fe(OH)2 + ½O2 + H2O →Fe2O3.3H2O (Reddish brown)
(ii) In the presence of limited oxygen
3Fe(OH)2 + ½O2 →Fe3O4.3H2O (Black colour)
Types of corrosion
According to electrochemical theory, corrosion occurs due to the formation of large number of galvanic
cells on thesurface of the metal. A galvanic cell is formed, when there is a difference in potential between
the regions across the metal surface. It can happen in different ways.
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When two metals Fe and Cu are in contact: Since iron has lower reduction potential compared to Cu,
iron undergoes corrosion and Cu is protected.
When two metals Zn and Fe are in contact: Since Zinc has lower reduction potential compared to Fe, Zn
undergoes corrosion and Fe is protected.
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More Aerated
Less Aerated
Reactions
Example
1. Windows rods inside the frame suffer corrosion but not the exposed region.
2. Paper pins inside the paper get corroded, and the exposed part is free from corrosion.
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Pitting Corrosion
Factors affecting rate of corrosion
The rate of corrosion depends on the following factors.
a) Nature of Metal:
1. In general the metals with lower electrode potential values are more reactive than the metal
with higher electrode potential values,
2. The more reactive metals are more susceptible for corrosion, thus the tendency of metal to
undergo corrosion decreases with increase in electrode potential. For example,
3. The active metals like k, Na, Mg, Zn etc, with low electrode potential values are highly
susceptible for corrosion.
4. The noble metal such as silver, gold, platinum etc, with higher electrode potential values is less
susceptible for corrosion. However, there are few exceptions for this general trend as some
metal show the property of passivity.
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b) Nature of Corrosion Product- The rate of corrosion depends on the nature of corrosion product
which is formed during corrosion. In the case of metal like iron, zinc and magnesium, the oxides
which are formed during corrosion are, highly porous, non-stoichiometric, highly soluble and good
ionic conductivities, As a result, corrosion is continued till the metal is completely destroyed. On
the other hand, in the case of metal like aluminium, titanium, chromium etc, the oxides formed are
non-porous, stoichiometric, and highly insoluble with low ionic and electronic conductivities. As a
result, the corrosion is stopped as soon as oxide film is formed.
c) Relative size of the anodic and cathodic areas: Smaller the anodic area and larger the cathodic
area, then more intense and faster will be the corrosion at anodic area. When cathodic area is large,
demand for electrons for reduction reaction is high. To meet this demand, oxidation reaction occurs
more intensely at anodic area.
Ex: In case of coating tin on iron, if some area is not covered, a small anodic area and large cathodic
area are formed. In this case rate of corrosion of iron becomes higher than that under normal
conditions.
On the other hand, if anodic area is large and cathodic area is small, then the rate of corrosion at anodic
area will be very low. In case of coating zinc on iron, if some areas are not covered, a small cathodic
and large anodic area is formed. In this case rate of corrosion of iron metal becomes lower.
d) pH of the medium: In general, lower the pH of corrosion medium, higher is the corrosion rate.
(Exception: Metals like Al, Zn etc. undergo fast corrosion in media with high pH).Iron does not
undergo corrosion at pH greater than 10. This is due to the formation of protective coating of hydrous
oxides of iron. Between pH 10 and 3, the presence of oxygen is essential for corrosion. If the pH is
less than 3, severe corrosion occurs even in the absence of oxygen due to continuous evolution of
hydrogen gas.
e) Temperature: In general increase in temperature increase in corrosion rate. For many metals
the corrosion rate almost exponentially rises with increase in temperature. This is attributed to
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1. Increase in conductance of the medium- ions migrate fast at higher temperature.
2. Increase in the rate of chemical reaction
3. Increase in solubility of the corrosion products in the medium
4. Decrease in the polarization effects at the anode and cathode sites. However, if corrosion is due
to dissolved gases like O2, CO2 etc. The rate of corrosion decreases with an increase in
temperature as the solubility of these gases in the medium decreases.
Corrosion control
According to electrochemical theory, corrosion occurs due to the oxidation and reductions reactions at
the anodic and cathodic areas. These reactions occur simultaneously and are interdependent. So by
decreasing the rate of any of these reactions or by preventing any one reaction, the rate of corrosion can
be decreased. The methods used to control corrosion are:
1. Metal Coating
a) Anodic Metal Coating: Galvanisation
b) Cathodic Metal Coating: Tinning
2. Cathodic protection- Sacrificial Anode Method
3. Anodization
4. Corrosion inhibitors
1. Metal Coating
a) Anodic Metal Coating: Galvanisation: Anodic metal coatings are coatings which are anodic to
base metals. Example is Al, Zn etc. These metals are above the Fe in the galvanic series and undergo
corrosion thereby protecting Fe. A characteristics feature of anodic coating is that the base metal on
which the coating is done will not get corroded even if the coating peels off. This is due to formation of
large anodic area and small cathodic areas.
Example: Galvanisation: It is a process of coating Zn over the surface of iron. The method is
carried out by hot dipping process. It involves the following steps:
1. The iron sheet is washed with solvent to remove greasy & oily materials.
2. The iron sheet is washed with dil.H2SO4 to remove oxide film.
3. The sheet is then treated with a mixture of aqueous solution of zinc chloride and ammonium
chloride & dried
4. The dried sheet is dipped in molten zinc at 430 – 450 oC.
5. Excess Zn is removed by rolling, wiping or air blast.
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Galvanization process
Applications
1) Galvanized iron pipes are exclusively used for domestic purpose all over the world
2) Galvanized iron drum are used to preserve variety of chemicals, drugs & organic solvents.
3) Used in Roof sheets, fencing wires, barbed wire, buckets, pipes, etc.
In this the metal structure to be protected is connected to a more anodic metal like Mg, Zn and Al
which acts as anodic. In practice active metal Mg or Zn is connected to metal structure to be protected.
The more active metal Mg or Zn becomes anodic and corrodes but the metal structure becomes
cathodic is protected. Since the anode metal sacrifices to protect the metal structure the method is
known as sacrificial anode method.
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The metallic structure to be protected is connected to a more anodic metal using a metallic wire. The
more active metal gets corroded, while the parent structure is protected from the corrosion. The more
active metal so employed is called sacrificial anode. As the anodic metal sacrifices its life to protect
the base metal from corrosion is called sacrificial anodic protection. The commonly used sacrificial
anodes are Mg, Zn, Al etc this method is generally used for the protection of buried pipe lines ship
hulls, water tanks.
Impressed voltage method: In this method, current is applied from opposite direction to nullify the
corrosion current and convert the corroding metal from anode to cathode, usually; the impressed
current is derived from a direct current source with an insoluble anode (like graphite or platinum
Usually, a sufficient DC current is applied to an insoluble anode and buried pipe in the soil and
connected to the metallic structure to be protected (see the fig) to increase the electrical contact
between the anode and the soil, the anode is buried in a back fill such as gypsum under the earth. Thus
electrons are supplied from an external cell so that the object itself becomes cathodic and is not
oxidized. This type of cathodic protection has been applied to open water box cooler, water tanks,
ships etc.
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k = constant depends on unit used, when K = 534 the mpy will be used. When K = 87.6, mm/yr
will be used.
W = Weight loss during testing
ρ = density of metal
A= area exposed for corrosion
t = duration of corrosion
Electrode system
Electrochemistry: It is a branch of chemistry which deals with the study of transformation of
chemicalenergy into electrical energy and vice versa”
Electrochemical cells: An electrochemical cell is a device which converts chemical energy into
electricalenergy or electrical energy into chemical energy”
Gibbs Free Energy (G): Gibbs energy is defined as maximum available energy in a system that can
beconverted into useful work.
G =H -TS
The thermodynamic free energy is the amount of work that a thermodynamic system can perform. The
free energy is the internal energy of a system minus the amount of energy that cannot be used to
perform work.
EMF of a cell Or Cell Potential : “Emf is the potential difference between the two electrodes of
a galvanic cell, which causes the flow of current from one electrode to other. It is also called as
cell potential or cell voltage. It is expressed in volts.
Mathematically,Ecell = Ecathode – Eanode
Ecell = Eright electrode – Eleft electrode
Types electrodes:
In Electrochemical work various type of electrodes are employed depending upon the purpose for
which they are used. Some of them are
1. Metal-Metal ion electrode: An electrode of this type consists of a metal dipped in a solution
containing its ions. Ex- Zn/Zn2+, Cu/Cu2+ etc.
The electrode rxn is, in general
Mn+ +ne- M
2. Metal-Metal insoluble salt electrode: These electrodes consist of a metal in contact with a
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sparingly soluble salt of the same metal dipped in a solution containing anion of the salt.
Example-Calomel (Hg|Hg2Cl2|Cl-), Silver- Silver salt electrode (Ag| AgCl |Cl-).
3. Gas electrode: Gas electrode consists of a gas bubbling about an inert metal wire, immersed in
solution containing ions to which the gas is reversible. The metal provides electrical contact
and facilitates the establishment of equilibrium between the gas and its ions.
Example-Hydrogen electrode (Pt|H2|H+), Chlorine electrode (Pt|Cl2|Cl-).
4. Oxidation-Reduction electrode: An oxidation-reduction electrode is a one in which the
electrode potential arises from the presence of oxidized and reduced forms of the same
substance in solution. The potential arises from the tendency of one form changes into the other
more stable form. The potential developed is picked up by an inert electrode like platinum.
Example-Pt|Fe2+, Fe3+, Pt|Ce3+, Ce4+
5. Amalgam electrode: It is an electrode which consists of a metal-amalgam dipped in a solution
containing its own metal ions. It is similar to Metal-Metal ion electrode.
Example-Pb-Hg|Pb2+, Zn-Hg|Zn2+
6. Ion selective electrode: it is an electrode, which consists of a membrane and in contact with a
solution, with which it can exchange ions.
Example- Glass electrode.
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Working:
The half-cell reaction of the glass electrode is represented as,
The glass electrode is constructed from a special soft glass of high electrical conductance. It consists of
a bulb that contains a solution of constant hydrogen ion concentration.
Usually, the solution contains 0.1 N hydrochloric acid (HCl) in which a silver/silver
chloride electrode is dipped. The blub is then placed in a solution of unknown pH.
The potential of the electrode is similar to that of a standard hydrogen electrode,
or,
Eglass = E0glass + 0.059 x log pH
Here E0glass is called asymmetric potential and the value is small. This type of potential is developed
across the membrane due to internal strain. It is the characteristic constant for each glass electrode.
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Applications
pH measurement by glass electrodes is used in many chemical and industrial analyses. The main
applications are
1. Control of industrial processes;
2. Analysis of foods and cosmetics;
3. Clinical analysis;
4. Environmental analysis;
5. Microelectrode measurements;
6. Measurement of soil pH level by glass electrode is an important process to observe soil acidity.
Reference electrode
“Reference electrode is an electrode whose potential is known and with reference to that, the electrode
potential of any electrode can be measured”. There are two types of reference electrodes. They are
primary and secondary reference electrodes. Primary Reference Electrode: It is an electrode, whose
potential is arbitrarily taken as zero at all temperatures. Eg- Standard Hydrogen Electrode (SHE)
Nernst equation for calomel electrode: Ecal = E0cal – 0.0591 log [Cl-] at 298 K
Hence, the electrode potential of Calomel electrode dependent on the concentration of chloride ions
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Concentration cells
The cells in which the EMF produced is due to the difference in the concentrations of the electrodes or
electrolytes.
There are two types of concentration cells.
i) Electrode concentration cells: A cell is formed by combination of same electrodes of different
concentrations dipped in same electrolyte solutions is called electrode concentration cell.
For example: Pt, H2 (1atm) ǀ H+(1M)ǀǀ H+(1M)ǀ H2(2 atm),Pt
ii) Electrolyte concentration cells: A cell is formed by combination of same electrodes dipped in
same electrolyte solutions of different concentration is called electrolyte concentration cell.
For example: Cu(s) / Cu2+ (C1) // Cu2+ (C2) / Cu(s) Where C2 > C1
EMF of a concentration cell: Consider a concentration cell
M / Mn+ (C1) // Mn+ (C2) / M Where C2 > C1
Anode Cathode
E cell = E Cathode – E anode
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0.0591 [C 2]
Ecell = log
n C1
This is the expression of Nernst equation for concentration cell at 25 C.
Numerical Problems:
1. A concentration cell was constructed by immersing two silver electrodes in 0.05 M and 1M of
AgNO3 solution. Write the cell representation and calculate the Ecell at 298K.
Solution: AgǀAgNO3 (0.05M)ǀǀAgNO3 (1M)ǀAg
0.0591 𝐶2
Eg= 𝑛 log𝐶1
0.0591 1
= log0.05 = 0.0768 V
1
2. Represent the cell formed by coupling two Cu-electrode immerses in CuSO4 solution
concentration of Cu2+ ions in one electrode system and 100 times more concentrated than other.
Calculate the Ecell at 298K
Solution : CuǀCu2+ (1M)ǀǀCu2+ (100M)ǀCu
0.0591 𝐶2
Eg= log
𝑛 𝐶1
0.0591 100
= log = 0.0591 V
2 1
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Corrosion Penetration Rate (CPR)
The Corrosion penetration rate is the speed at which any metal or alloy deteriorates in a specific
corrosive environment through chemical or electrochemical reactions. It is also defined as the
amount of weight loss per year in the thickness of metal or alloy due to corrosion. The
Corrosion penetration rate also referred as corrosion rate.
1. Nature of metal.
2. Nature of corrosive environment/medium.
3. Nature corrosion product.
4. Speed at which corrosion spreads in the inner portion of metal.
The CPR is conveniently expressed in terms of either mils (0.001 inch) per year (mpy) or
millimeters per year (mmpy). K=534 for CPR in mpy when surface area of test specimen is in
inch2 and K=87.6 for CPR in mmpy when surface area of test specimen is in cm2
Given;
K = 87.6
W (wt loss) = 40 g = 40 x 1000 mg
ρ = 7.8 g/ cm3 = 7.8 g/ cm3
A = 1m x 3m = 3m2 = 3x100 x 100 cm2
T = 6 months = 6 x 30 x 24 hrs
We have
K .W
CPR =
. A.t
87.6 x 40 x1000
CPR =
7.8 x3 x100 x100 x6 x30 x 24
Given;
K = 534
W (wt loss) = 40 g = 40 x 1000 mg
ρ = 7.8 g/ cm3 = 7.8 g/ cm3
A = 1m x 3m = 3m2 = 3 x 1550 inch2
T = 6 months = 6 x 30 x 24 hrs
We have
K .W
CPR =
. A.t
534 x 40 x1000
CPR =
7.8 x3 x100 x100 x6 x30 x 24
2 Calculate the CPR in both mpy and mmpy for a thick steel sheet of area 100 inch2
which experiences a weight loss of 485g after one year. (Density of steel=7.9g/cm3).
Given;
K = 87.6
W (wt loss) = 485 g = 485 x 1000 mg
ρ = 7.9 g/ cm3 = 7.9 g/ cm3
A = 100 inch2 = 100 x 6.45 cm2
t = 1 year = 365 x 24 hrs
We have
K .W
CPR =
. A.t
534 x 485 x1000
CPR =
7.9 x100 x365 x 24