Corrosion and Electrode System

Gradual deterioration or loss metal at its surface by chemical or electrochemical reaction

between the metal and the surrounding environment is called as corrosion.
Example: i) rusting of iron.
ii) Formation of green layer on copper metal.

Depending on the type of the environment to which the metal is exposed, corrosion is classified
into
1) Dry corrosion: it occurs due to attack of metal by dry chemicals.
Example: corrosion of sodium by direct attack of O2
2) Wet corrosion: it occurs due to electrochemical reaction of metals with air (O2) and
moisture (H2O) present in the atmosphere.
Example: rusting of iron

Electrochemical theory of corrosion

• When a metal is exposed to atmosphere (air and aqueous media), a large
numbers of galvanic cells are formed on the surface of the metal i.e a large
number of anodic and cathodic areas are formed.
• At anode oxidation occurs with the liberation of electrons that moves over the
surface of metal and species in contact with cathode undergoes reduction.
• The anodic part of the metal undergo oxidation and suffers from corrosion,
cathodic part undergo reduction and protected from corrosion.
Example: rusting of iron
• The following reactions takes place during corrosion
➢ Reaction at anodic region,
Fe ⎯⎯→ Fe2+ + 2e−
➢ The reaction at cathode (reduction reaction) depends on the nature of the
environment:
If the medium is acidic,
❖ In the absence of dissolved oxygen: 2H+ + 2e− → H2
❖ In the presence of dissolved oxygen: 2H+ + 1/2O2 + 2e− → H2O
If the medium is alkaline/neutral
❖ In the presence of dissolved oxygen: 2H2O + 2e− → 2OH− + H2
❖ In the absence of dissolved oxygen: H2O + 1/2O2 + 2e−→ 2OH−

Overall reaction: The metal ions (Fe2+) liberated at anode and anions (OH-)
formed at cathode diffuse towards each other through the conducting medium
and form a corrosion product somewhere between the anode and cathode as
2Fe2+ + 4OH- 2Fe(OH)2
In presence of oxygen
2Fe (OH)2 + ½O2 Fe2O3.2H2O (brown rust)
Factors affecting the rate of corrosion:

1. nature of metal:
a. Electrode potential of metal : Lower the electrode potential higher is its
tendency to undergo oxidation and hence higher is the tendency to undergo
corrosion.
• When two dissimilar metal are in contact with each other, one with lower
potential becomes anode and other with higher potential becomes cathode
• The rate of corrosion depends on the difference in potential between anodic
and cathodic area, higher the difference in potential, higher the rate of corrosion
of anodic metal.
Eg: Potential difference between iron and copper is 0.78V which is
more than b/w iron and tin (0.3V), therefore iron corrodes faster which is in
contact with copper.
b. Relative surface area of anodic to cathodic areas: If the metal has
smaller the anodic area and larger the cathodic area then more intense and
faster corrosion takes place at the anodic area. When cathodic area is large,
demand for electrons for reduction will be high.
• Smaller the cathodic and larger the anodic area the rate of corrosion will be
slow

c. Nature of corrosion product: If the corrosion product is non-

stoichiometric highly ionic, porous, conducting and unstable then, the rate of
corrosion increase. On the other hand, if corrosion product is stoichiometric,
less ionic, nonporous, non-conducting, stoichiometric and stable then the
corrosion product deposited on the metal surface prevents further corrosion.

2. nature of the environment:

a. pH of the medium: the rate of corrosion increases with decrease in pH.
In acidic medium
b. Temperature: The rate of corrosion is directly proportional to temperature
i.e., rise in temperature, increases the rate of corrosion
c. Conductance of the medium: The rate of corrosion is directly proportional
to conductance,
as the conductance increases, rate of corrosion also increases.

Types of corrosion
Corrosion can be classified into two types

Differential metal corrosion (Galvanic corrosion)

When two dissimilar metals are in contact with each other, the metal with
lower electrode potential becomes anodic and undergoes corrosion. Whereas,
the metal with higher potential becomes cathodic and remains unaffected. This
kind of corrosion is called differential metal corrosion.
Example: standard electrode potential of iron (-0.44V) is less than that of
copper (0.34V).
Therefore iron becomes anodic and undergoes corrosion whereas copper
becomes cathodic and remains unaffected.
 Differential aeration corrosion
1. When a metal is exposed to different concentration of air (O2), part of the
metal exposed to lower concentration of O2 becomes anodic and undergoes
corrosion.
2. Other part of the metal exposed to higher concentration of O2 becomes
cathodic and protected from the corrosion.
3. The difference in O2 concentration produces a potential difference and
causes corrosion. This type of corrosion is called differential aeration
corrosion.
Example: Iron rod partially immersed in NaCl solution. Part of the metal
immersed in solution is exposed to lower concentration of oxygen becomes anodic
area and undergoes corrosion. Whereas, part of the metal outside water is exposed
to more oxygen becomes cathodic and remains unaffected.

Example: 1 Water line corrosion

1) It is observed in steel or iron water tank partially filled with water. Part of the
tank just below water level is exposed to lower concentration of O2 becomes
anodic and undergoes corrosion.
2) Part of the tank above the water line which is exposed to higher concentration
of O2 becomes cathodic and protected from the corrosion.
3) More corrosion is observed just below the water line; hence this type is
called water line corrosion.

Reactions:
𝐴𝑡 𝐴𝑛𝑜𝑑𝑒: 𝐹𝑒 → 𝐹𝑒2+ + 2𝑒-
𝐴𝑡 𝐶𝑎𝑡ℎ𝑜𝑑𝑒 ∶ 𝐻2𝑂 + 1/2 𝑂2 + 2𝑒 − → 2𝑂𝐻−
𝐹𝑒2+ + 2𝑂𝐻− → 𝐹𝑒(𝑂𝐻)2
2𝐹𝑒(𝑂𝐻)2 + 1/2 𝑂2 → 𝐹𝑒2𝑂3. 2𝐻2𝑂

Example: 2 pitting corrosion

1) Pitting corrosion is observed when dust particles get deposited over the metal surface.
2) The portion of the metal covered by dust which is less aerated becomes
anodic and suffers from corrosion.
3) Thus, metal is lost below the surface of dust particle forming a deep and narrow pit.
4) The adjacent area of the metal which is exposed to higher concentration
 of O2 becomes cathodic and protected from corrosion.

𝐴𝑡 𝐴𝑛𝑜𝑑𝑒: 𝐹𝑒 → 𝐹𝑒2+ + 2𝑒-

𝐴𝑡 𝐶𝑎𝑡ℎ𝑜𝑑𝑒 ∶ 𝐻2𝑂 + 1/2 𝑂2 + 2𝑒 − → 2𝑂𝐻−
𝐹𝑒2+ + 2𝑂𝐻− → 𝐹𝑒(𝑂𝐻)2 ,
2𝐹𝑒(𝑂𝐻)2 + 1/2 𝑂2 → 𝐹𝑒2𝑂3. 2𝐻2𝑂

Corrosion Control:
The following methods are commonly used to control corrosions
1. Protective coatings
a. Metal coatings
• Anodic metal coatings
• Cathodic metal coatings
b. Surface conversion coatings
• Anodizing
2. Cathodic protection

❖ Protective coatings: corrosion can be prevented by isolating metal from the

surrounding environment by coating a protective layer over the surface of the
metal.
❖ Metal coatings: In this case corrosion of the base metal can be prevented by
coating a layer of another metal over it
❖ Anodic metal coating: It is the coating of a layer of metal which is anodic to base
metal
Eg: Coating of Zn or Mg or Cd metal on iron
❖ Cathodic metal coating: It is the coating of a layer of metal which is anodic to
base metal
Eg: Coating of Sn or Ni metal on iron
❖ Surface conversion coating: in this method, outer surface of the base metal is
converted into a protective coating through appropriate modification
❖ Cathodic protection: The process of protecting a metal against corrosion by
making the entire metal cathodic by providing electrons from the external source is
called cathodic proctection

Galvanization
Coating a layer of zinc on iron or steel by hot dipping process is called galvanizing.
It is carried out as follows,
 • Iron sheet is passed through organic solvent to remove oil or grease present in it
• Then it is washed with dil H2SO4 to remove any rust present on the surface
• Then it is treated with a mixture of aq solution of ZnCl2 and NH4Cl which acts as flux and
then dried.
• Finally dipped in molten zinc at 450oC
• Excess zinc present in the iron is removed by passing through rollers

Anodizing
Anodizing is the process of oxidation of outer layer of metal to its metal oxide
by electrolysis. Oxide layer formed over the metal itself acts as protective layer.
Anode : Aluminium
Cathode : Steel or Copper
Electrolyte : 5-10% chromic acid
Temperature : 30-40 °C
Applied potential : 0-40V
Aluminum is cleaned, degreased and polished and then taken as anode and copper
or steel is taken as cathode. The electrodes are immersed in an electrolyte
consisting of 5-10% chromic acid. The temperature is maintained at 30-40 °C.
Potential of 0-40 V is applied which oxidizes outer layer of Al to Al2O3 and that
get deposited over the metal. The reactions involved are as follows

At anode: 2Al + 3H2O Al2O3 + 6H+ + 6e-

At cathode: 6H+ + 6e- 3H2
Overall reaction: 2Al + 3H2O Al2O3 + 3H2

Sacrificial anodic protection:

1) The metal to be protected is connected to a more active (anodic) metal using a metallic
wire.
2) The more active metal becomes anodic area and the metal to be protected becomes
cathodic area
3) The more active metal so employed is called sacrificial anode.
4) Anodic metal undergoes oxidation and provides electron to the specimen and the entire
specimen becomes cathodic and hence protected from the corrosion
5) The sacrificial anodes to be replaced by fresh ones as and when it is required.
6) Commonly used sacrificial anodes are: Mg, Zn, Al etc.
Example: steel pipe is protected by connecting it to a block of Zn. In such cases
steel acts as a cathode and is unaffected or protected from corrosion and Zn act as
anode and undergoes sacrificial corrosion.
 Corrosion Penetration Rate (CPR)
The corrosion penetration rate (CPR) is defined as “the speed at which any metal in a specific
environment deteriorates due to chemical reactions when it is exposed to a corrosive
environment”

To calculate CPR in a metal, a known weight of metal is taken. It is allowed to corrode in a

specific environment for a specific period of time, then the surface is thoroughly cleaned to
remove the corrosion product.
From the weight loss of the metal, corrosion penetration rate (CPR) can be calculated using the
following equation.
𝑘×𝑊
corrosion penetration rate (CPR) = 𝑇 × 𝐷 × 𝐴
where k = constant
W = total weight lost
T = time taken for the loss of metal
A = the surface area of the exposed metal
D = the metal density in g/cm³

• CPR can be calculated in terms of mils per year or in mm per year, 1mil=0.001inch.
• To calculate CPR in terms of mil per year, the value of k is taken as 534, W in mg, D in
g/cm3, A in inch2 and T in hours.
• To calculate CPR in terms of mm (millimeter) per year, the value of k is taken as 87.6,
W in mg, D in g/cm3, A in cm2 and T in hours.
• If CRP is less than 20m/year or 0.5 mm/year, it is acceptable for most of the application.
Electrode system

Electrolytic concentration cells:

It is a galvanic cell in which metal and electrolyte are same in both the half cells but only the
concentration of the electrolyte is different.
Example:
Consider two metal electrodes that in contact with the electrolyte solution of different
concentrations (C1 and C2) connected through voltmeter. The electrolytes are connected through
salt bridge.
Metal immersed in the dilute solution will have lower potential and is taken as anode, whereas
Metal immersed in the concentrated solution will have higher potential and is taken as cathode

It is represented as : M │ Mn+(C1) ││ Mn+(C2) │M

Metal immersed in dilute solution acts as anode, where oxidation occurs
M Mn+(C1) + ne-
Metal immersed in concentrated solution acts as cathode, where reduction occurs
Mn+(C2) + ne- M

Net cell reaction: Mn+(C2) Mn+(C1)

As both half cells are made of same electrode, E0cell is zero.

Hence, Nernst equation foe electrolytic concentration cell is
2.303𝑅𝑇 [𝑀𝑛+ 𝑎𝑡 𝑐𝑎𝑡ℎ𝑜𝑑𝑒]
E cell = E0cell + log
𝑛𝐹 [𝑀𝑛+ 𝑎𝑡 𝑎𝑛𝑜𝑑𝑒]

For concentration cell, E0cell = 0

2.303𝑅𝑇 [𝑀𝑛+ 𝑎𝑡 𝑐𝑎𝑡ℎ𝑜𝑑𝑒]

E cell = log
𝑛𝐹 [𝑀𝑛+ 𝑎𝑡 𝑎𝑛𝑜𝑑𝑒]

2.303𝑅𝑇 𝐶2
E cell = log
𝑛𝐹 𝐶1

0.0591 𝐶2
E cell = log at 298K
𝑛 𝐶1

• E cell is positive and the reaction is spontaneous only when C2 > C1

 Analytical Techniques

Conductometric Titration The electrochemical method of analysis used for the

determination of the electrical conductance of an electrolyte solution by means of
a conductometer.

Principle: the principle underlying in conductometric titration is the replacement

of ions of particular conductance by the ions of another conductance.

According to ohm’s law the current flowing through the conductor is directly
proportional to voltage and inversely proportional to the resistance.
I= or E=IR
The resistance of the any conductor is directly proportional to the length,
inversely proportional to the area of cross section of the conductor
Therefore R = S (l/a)
where S is specific resistance
Therefore C = 1/R =1/S (a/l)
 K(a/l), K = specific conductance & a/l = cell constant

Specific conductance (K): It is defined as the conductance of the solution

present between two parallel electrodes of 1cm2 area of cross section and 1cm
apart.

Instrumentation:
It consists of two platinum electrodes each of unit area of cross section placed at unit
distance apart. The electrodes are dipped in the electrolytic solution taken in a
beaker. It is connected to a conductometer to measure the conductance. The
conductance is measured after the addition of the titrant at interval of 0.5 ml.

Strong acid v/s strong base (HCl v/s NaOH)

•
• When strong acid like HCl is titrated against a strong base such as NaOH,
the conductance firstdecreases due to replacement of fast moving 𝐻+ ions by
slow moving Na+ ions
• HCl + NaOH → NaCl + H2 O
• After the neutralization point, there will be rapid increase in conductivity
with further addition of NaOH because of continuous addition of fast moving
OH- ions.
• A plot of conductance against the volume of base added is shown in the
figure.
• The point of intersection of two curves gives the neutralizationpoint.

Weak acid v/s Strong base (CH3COOH v/s NaOH)

• When weak acid like CH3COOH titrated against a strong base such as
NaOH, the conductance of the acid will be initially low since acetic acid is a
weak electrolyte.
• CH3 COOH + NaOH → CH3COONa + H2O
• When NaOH is added to the acid, the sodium acetate salt (strong electrolyte)
is formed which is highly ionized and the conductance increases.
• After the neutralization point, there will be rapid increase in conductivity with further
addition of NaOH because of continuous addition of fast moving OH- ions
• A plot of conductance against the volume of base added is shown in the figure
• The point ofintersection of two curves gives the neutralization point.

Mixture of strong acid and weak acid v/s strong base (HCl & CH3COOH v/s NaOH)

• When acid mixture containing HCl & CH3COOH titrated against a

strong base such as NaOH,
• the conductance firstdecreases due to replacement of fast moving 𝐻+ ions
by slow moving Na+ ions
• HCl + NaOH → NaCl + H2 O
• The weak acid does not get neutralized initially because in the presence of
excess of H+ ions, the ionization of the weak acid is suppressed
• After the first neutralization of HCl, neutralization of acetic acid starts and
conductance increases due to the formation of strong electrolyte.
• CH3 COOH + NaOH → CH3COONa + H2O
• After the neutralization point, there will be rapid increase in conductivity with further
addition of NaOH because of continuous addition of fast moving OH- ions
• A plot of conductance against the volume of base added is shown in the figure
• The point ofintersection of two curves gives the neutralization point.
.

Potentiometric Titration
Principle: Redox titrations can be carried out potentiometrically using platinum and calomel
electrode combination.
For the reaction; Reduced form Oxidised form + n electrons
The potential is given by Nernst equation
0.0591 𝑜𝑥𝑖𝑑𝑖𝑠𝑒𝑑 𝑓𝑟𝑜𝑚
E = Eo + 𝑛 log 𝑟𝑒𝑑𝑢𝑐𝑒𝑑 𝑓𝑜𝑟𝑚

Where, E0 is the standard electrode potential of the system. The potential of the system is
controlled by the ratio of concentration of the oxidized to that of the reduced species. A plot
of change in potential against volume is characterized by a sudden change of potential at the
equivalent point. At the end point, potential is determined by large jump in the potential value.
Hence there is large increase in potential at the end point.

Instrumentation:
A potentiometer consists of a indicator electrode (e.g.: Platinum) and an saturated reference
electrode (E.g.: Calomel electrode), stirrer & potentiometer to measure the potential values.
Potential of the solution can be measured by combining reference electrode and indicator
electrode. The electrode which responds to the change in the concentration of the ion in the
solution is called indicator electrode & reference electrode is one whose potential is constant. A
known volume of the analyte is taken in beaker and its potential is measured. The titrant is added
in increments of 0.5ml and potential is measured each time. Near the equivalence point there is a
sharp increase in the potential. The end point is determined by plotting change in potential against
volume of the titrant.

Applications
• It is used to find the end point of redox, precipitation and acid –base titration
• It is also used when suitable indicators are not available.
 For example: estimation of iron in FAS potentiometrically
Procedure: Pipette out 25cm3 of FAS solution into a 50 cm3 beaker. Add one test tube
full of dil H2SO4. Immerse Pt. & calomel electrodes into the solution, & connect the
electrodes to a potentiometer. Fill the burette with K2Cr2O7 solution. Add K2Cr2O7
solution from the burette with increment of 0.5cm3, stir well and measure the potential
after each addition. Continue the titration till the potential indicates a rapid jump with a
drop of titrant. Plot the graph of ∆E/ ∆V v/s vol. of K2Cr2O7.

(𝑁×𝑉)𝐾2 𝐶𝑟2 𝑂7 0.5×𝑣 𝑓𝑟𝑜𝑚 𝑡ℎ𝑒 𝑔𝑟𝑎𝑝ℎ

Calculations: normality of FAS = =
𝑉𝐹𝐴𝑆 25

weight of Ferrous per liter: normality × equivalent weight of ferrous ion