Corrosion
Corrosion is the process of disintegration or
deterioration of a metal by chemical or
electrochemical reaction with the environment.
Example: Rusting of iron and tarnishing of silver or
copper.
Based on mechanisms, corrosion can be explained
by two main theories:
1) Dry or chemical corrosion and 2) Wet or
electrochemical corrosion
Mechanism of Wet or Electrochemical corrosion
Electrochemical corrosion can occur when a conducting liquid is in contact with a
metal or when two dissimilar metals or alloys are partially immersed in a
conducting solution.
Hydrogen evolution corrosion in acid medium
This occurs when metals are in contact with acidic solution in the absence of
sufficient oxygen.
Oxidation takes place at the anodic area, resulting in the corrosion of the metal.
Fe → Fe2+ + 2e- (Oxidation) EO = - 0.44 V The Fe2+ ions so formed dissolves in the
solution.
Reduction occurs at the cathodic area. At the cathodic area, the dissolved
constituents in the conducting medium accept electrons to form ions like OH-, O2-
etc. The non-metallic ions so formed combine with the Fe2+ to form corrosion
product. The electrons released at the anode flow through the metal and get
consumed in the cathodic reaction, either for the evolution of hydrogen or for
the absorption of oxygen. 2H+ + 2e- → H2 (g) ; EO = 0 V
Net reaction : Fe + 2H+ → Fe2+ + H2; EOcell = 0 –(-0.44) = 0.44 V
Corrosion with evolution of H2 occurs, when the anodic area is very large and
cathodic area is small and it usually occurs in acidic environments.
Hydrogen evolution corrosion in alkaline medium
Hydrogen evolution corrosion does not take place
in the case of iron immersed in alkaline medium.
This is due to the fact that hydrogen electrode
potential in alkaline medium ( EO = - 0.828 V) is
lower than electrode potential of iron (EO = - 0.44
V). Whereas metals like aluminum can give
hydrogen evolution corrosion in alkaline medium.
Upon considering cell reactions:
Anode: Al → Al3+ + 3e-; EO = - 1.66 V
Cathode : 2H2O + 2 e- → H2+ 2OH-; EO = - 0.828 V
Therefore, corrosion cell potential is
EO cell = E cathode – E anode = - 0.828 – (-1.66) = 0.832 V
Oxygen absorption corrosion in acid medium
Rusting of iron is occur through this mechanism. In this initially a thin film of iron oxide is
formed on the surface of iron metal. Some cracks are developed on the iron oxide film. The
surface of the metal acts as the anodic area, whereas the interior of the metal behaves as
cathode.
At the anodic area, Fe dissolves as Fe2+ ions with the liberation of electrons.
Fe → Fe2+ + 2e- (Oxidation) EO = - 0.44 V
The electrons thus released from the anode move to the cathodic area through the metal.
These electrons are then taken up oxygen molecule to form OH- ions.
½ O2 + H2O + 2e- → 2OH-, EO = + 1.23 V
Corrosion cell potential EO cell = E cathode – E anode = 1.23 – (-0.44) = 1.67 V
The Fe2+ ions formed at the anodic area and the OH- ions formed at the cathodic area
combine to form Fe(OH)2 precipitate. Fe2+ formed further gets oxidized to Fe3+ as its
oxidation potential is more in acidic medium.
In the presence of excess of oxygen, Fe(OH)2 precipitate easily oxidises to get yellow rust
having the formula, Fe2O3.2H2O
2Fe(OH)2 + ½ O2 → Fe2O3.2H2O ; EO = + 0.77 V
If the amount of oxygen is limited, then the corrosion product is black rust (Hydrated
magnetite) 3Fe(OH)2 + ½ O2 → Fe3O4.3H2O
The rust formation leads to intense localized corrosion called pitting corrosion. This is due to
the formation of separate cathodic and anodic area. Thus the rate of corrosion of iron is
more in acid medium than in alkaline medium as Fe2+ gets oxidized to Fe 3+ in acidic
medium.
Oxygen absorption corrosion in alkaline medium
This occurs when metals are in contact with water
having dissolved oxygen in alkaline environment.
Anode: Fe → Fe2+ + 2e-; EO = - 0.44 V
Cathode : O2 + 2 H2O + 4 e- → 4OH-; EO = + 0.40 V
Therefore, corrosion cell potential is
EO cell = E cathode – E anode = 0.40 – (-0.44) = 0.84 V
Here, Fe 2+ produced can not further oxidized to Fe 3+,
since oxygen electrode potential is less than
EO = + 0.77 V in alkaline medium. Here no insoluble
precipitate of Fe(OH)3 is produce, thus no intense
localized corrosion.
Galvanic series
Relative corrosion affinities of metals and alloys can be explained by
using a series called galvanic series. This series can be prepared by
studying the corrosion affinities of metals and alloys in unpolluted
sea water without their oxide films. A metal high in this series is
more anodic and undergoes corrosion faster than the metal below
it. The position of a metal in the form of an alloy is different from
that of the pure metal in this series.
Galvanic series is advantageous over electrochemical series in
corrosion chemistry. The electrochemical series gives useful
information regarding the reactivity of metals, but it does not
provide sufficient information in predicting the corrosion behavior.
In electrochemical series, the metal having lower reduction
potential are more anodic and undergo corrosion faster. However,
there are exceptions like Titanium and Aluminum.
Comparison of electrochemical series and galvanic series
Electrochemical Series Galvanic series
Eo is measured only for metals and Eo is measured only for metals and alloys.
non- metals.
Eo is measured by dipping pure Eo is measured by dipping metals and
metals in their 1M salt solution. alloys in unpolluted sea water.
SHE is used as the reference Calomel electrode is used as the reference
electrode. electrode.
Position of the metals is fixed.
Position of the metal and alloys may
It predicts the relative change.
displacement tendencies.
It predicts the corrosion tendencies.
Corrosion prevention methods
1) Cathodic protection
In this method, the metal to be protected is made as
cathode so that corrosion will not occur.
The following methods are employed for cathodic
protection.
a) Sacrificial anodic protection:
In this method, the metal to be protected is connected
by a wire to a more anodic or active metal. Then the
more active metal will undergo corrosion and the
cathode remains protected. Here the more active
anodic metal sacrifices for the protection of cathodic
metal and is called sacrificial anode. Metals commonly
used for this purpose are Mg, Zn, Al and their alloys.
b) Impressed current cathode protection:
In this method an impressed current is applied in opposite direction to
nullify the corrosion current. As a result corroding metal is converted
from anode to cathode. The impressed current required can be
obtained from a battery with an insoluble anode made of graphite or
high silica iron. This method is used for the protection of open water
box coolers, water tanks etc.
Electroplating
Copper Electroplating: Copper electroplating is a simple electrochemical process that
results in a thin copper coating on any conductive surface with the help of an
electrolyte bath. The article to be electroplated is first treated with organic
solvents to remove oil, grease, etc. Then, treated with dil. HCl to remove surface
scales. The cleaned article is made as the cathode and pure copper rod as anode.
Both the electrodes are dipped in copper sulphate solution in an electroplating
tank. Direct current is passed through the electrolyte, electrolysis occurs and
Cu2+ ions move towards the cathode and gets deposited there.
At cathode , Cu2+ + 2 e-Cu
At Anode, Cu Cu2+ + 2 e-
2) Electroless copper plating (Autocatalytic
plating)
It is the method of depositing copper from its salt solution on the
catalytically active surface of the metal to be plated using a suitable
reducing agent without using electrical energy.
The object to be plated is degreased using organic solvent and this followed
by acid treatment. In this method, article to be plated is immersed in a
plating bath containing CuSO4 (As a source of Cu), formaldehyde (Reducing
Agent), buffer solution of NaOH and Rochelle salt and a complexing
reagent. Air is bubbled slowly through the medium to control the
formation of cuprous oxide. Electroless plating of Cu takes place as
follows.
Oxidation (Anode)
2HCHO + 4OH- → H2 (Gas) + 2HCOO- + 2H2O +2e-; EO = + 0.056 V
Reduction (Cathode)
Cu2+ + 2e- → Cu ; EO = +0.34 V
Net reaction
2HCHO + 4OH- + Cu2+ → H2 (Gas) + 2HCOO- + 2H2O + Cu
Applications of electroless Cu plating
– Widely used for metalizing printed circuit boards.
– Used for plating on non-conductors.
– It is also used for making decorative plating on plastics.
Advantages
– This method produces even coatings.
– It does not use electrical power.
– This coating is having improved hardness, strength,
ductility and resistance to corrosion.
Disadvantages
– The reducing agent, formaldehyde is a human health
hazard.
– The instability of the electroless copper bath creates
difficulties in process control.
MODULE 1
[Link] the procedure for copper electroplating of an iron nail.
[Link] the EMF of the cell at 250C Al/Al3+(0.1M)//Sn4+(0.1M)/Sn2+(0.01M) is E0Al/Al3+= -
1.66V and E0Sn4+/Sn2+=0.15V.
[Link] full charging of Li-ion cell is not allowed?
[Link] is a galvanic series? How is the galvanic series advantageous over the electrochemical
series in corrosion chemistry?
[Link] the equilibrium constant for the following reaction at 250C:- Fe(s) + Cu2+ (aq) = Fe 2+
(aq) + Cu (s) Given E0 = Fe2+/Fe= -0.44 V, E0 = Cu2+/Cu = 0.34 V6. How Helmholtz's electric
double layer is formed?
[Link] any three advantages of electroless plating over electroplating.
[Link] the sacrificial anodic method for the prevention of corrosion.
[Link] galvanic and electrochemical series.
10. Explain the principle of electroless plating of corrosion.
[Link] do you mean by a reference electrode? Mention any two examples.
[Link] between reversible and irreversible cells with examples.
[Link] Iron does not corrode in alkaline oxygen deficient condition?
[Link] any three applications of electrochemical series.
[Link] the procedure of electroless plating of copper.
[Link] is calomel electrode? Explain its working and write the electrode reaction when it acts as
anode and a cathode
[Link] is the orgin of single electrode potential
[Link] any 4 application of Nernst equation
[Link] are reference electrodes?Give examples for primary reference and secondary reference
electrodes and give their electrode reaction
[Link] the relation between emf and pH of glass electrode calomel [Link] emf versus
pH graph
[Link] will you determine the standard electrode potential of Fe/Fe2+ electrode using calomel
electrode? Write the cell reaction and cell representation
[Link] the construction and working of Hydrogen-oxygen fuel cell which uses acid electrolyte in it.
32. Give the importance of automatic circuit breakers in Li-ion battery specifying the anode reaction during
charging.
33. Discuss the oxygen absorption electrochemical mechanism for the corrosion of iron. (6)
34. Write a note on Helmholtz electrical double layer and single electrode
potential
35. Explain the construction and working of Lithium-ion cell.
36. Discuss any three applications of electrochemical series.
[Link] the construction and working of glass electrode used for pH
measurement.
[Link] is Calomel electrode? How does the single electrode potential of
calomel electrode vary with concentration of Cl- ?
39. Explain various types of cathodic protection.
40. Explain the principle and procedure of electroless copper plating.
41. Derive the Nernst equation for the cell EMF of Daniel cell.
[Link] the procedure of electroplating of copper.
43. Discuss the design of glass electrode and explain how a glass electrode can be employed in the
measurement of pH of a solution
[Link] sacrificial anodic protection can be used for prevention of corrosion
[Link] are reference electrodes? Give examples for primary and secondary reference electrodes and draw
their electrode diagram
[Link] is electrochemical corrosion. Explain with an example
47Write the anode , cathode reactions and calculate the standard emf of the cell formed by silver and
aluminium [Link] that E0 Ag+/Ag=.8 V. E0 Al3+/Al= -1.66V
48. Consider the following half cell reactions:
Fe3++1e- Fe2+ , E0Fe3+/Fe2+ = +0.77
Al3++3e- Al , E0Al3+/Al = -1.66V
In a galvanic cell, the concentration of Fe3+ is 0.10 M, the concentration of Fe2+ is 0.01 M and the
concentration of Al3+ is 0.50M. Write the overall cell reaction and calculate the emf of cell at 250C