Department of Mechanical Engineering

Chittagong University of Engineering and Technology

Basic Principle of Corrosion

 During metallic corrosion, the rate of oxidation equals to the rate of reduction (In terms of
electron production and consumption)

Zn Zn2+ + 2e- (Oxidation or Anodic reaction)

2H+ + 2e- H2 (Reduction or Cathodic reaction)

Four necessary conditions for corrosion to take place

 Anodic reaction
 Cathodic reaction
 Metallic contact between anodic and cathodic sites
 Presence of an electrolyte

MSc/PhD # ME 6351 Principles of Corrosion Page # 1

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Half Cell reaction: Each half-cell is the portion of an electrochemical cell in which a half-
reaction takes place and consist of Anodic and Cathodic reactions

Oxidation & Reduction

1. What species is being oxidized (or, what is the reducing agent)? What species is being reduced
(or, what is the oxidizing agent)?
2. What species result from the oxidation and reduction?
3. Does the reaction occur in acidic or basic solution?

MSc/PhD # ME 6351 Principles of Corrosion Page # 2

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Anodic or Oxidation reaction

 Electrons as products - leads to loss of metal
Various reactions showing oxidation
Fe(s) → Fe2+(aq) + 2e-
Al(s) → Al3+(aq) + 3e-
2Cu(s) + H2O(l) → Cu2O(s) + 2H+(aq) + 2e-

Points to remember ϴ
1) A given species oxidizes its oxidation number increases M(s) → M2+(aq) + 2e-
2) There are losses of electrons at the anodic site (electrons are produced by the reaction)

 The following are also anodic reactions but they are not corrosion reactions since there is no
loss of metals: conversion of (s) to (aq)
Fe(CN)6-4(aq) → Fe(CN)6-3(aq) + e-
Cr+3(aq) + 4H2O → CrO4-2(aq) + 8H+(aq) + 3e-

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 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Cathodic or Reduction Reaction

 Electrons as reactants: Accumulation of materials

Various reactions showing Reductions

Fe2+(aq) + 2e- → Fe(s)
Al3+(aq) + 3e- → Al(s)
Cu2O(s) + 2H+(aq) + 2e- → 2Cu(s) + H2O(l)

Hydrogen reactions in different solutions

 Acid solutions: 2H+(aq) + 2e- → H2(g)
 Neutral or basic solutions: O2(g) + 2H2O + 4e- → 4OH-(aq)
.

Points to remember (ϴ)

1) A given species undergoes reduction there is decrease in oxidation number
2) There is a gain of electrons at the cathodic site (electrons are consumed)

MSc/PhD # ME 6351 Principles of Corrosion Page # 4

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology
Coupled electrochemical reactions

 During corrosion of a surface, anodic and cathodic reactions take place simultaneously at
different places

 Surface inhomogeneities: higher energy atoms pass into solution (s) → (aq)

 Over time, anodic and cathodic sites interchange leading to uniform corrosion

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 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Electrochemical cell: A system consisting of electrodes that dip into an electrolyte and in which
a chemical reaction either uses or generates an electric current.

1) Voltaic or Galvanic cell: An electro-chemical cell in which a spontaneous reaction generates

an electric current.

2) Electrolytic cell: An electrochemical cell in which an electric current drives an otherwise

nonspontaneous reaction.

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 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Notion for Voltaic cell: The anode or oxidation half-cell is always written on the left and the cathode

or reduction half-cell is written on the right. The two electrodes are electrically connected by
means of a salt bridge denoted by two vertical bars.

MSc/PhD # ME 6351 Principles of Corrosion Page # 7

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Practice Problem: Write the cell reaction for the following voltaic cell.

Solution: The half-cell reactions are

The cell reaction is

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 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

The standard cell potential (Ecell): The emf of a voltaic cell operating under standard-state
conditions (Solute concentrations are each 1 M, gas pressures are each 1 atm and the temperature
has a specified value - usually 25oC).

Cell Potential: The maximum potential difference between the electrodes of a voltaic cell is
referred to as the cell potential or electromotive force (emf) of the cell or Ecell. The maximum
electrical work of a voltaic cell for molar amounts of reactants

Limitations of EMF Series [12]

1) Emf series do not represent real situation – in reality the metals ions do not have unit activity
2) The position of the metal in emf series may change because of the complex formation
3) Alloys are not included in this series
4) Activation – passivation condition is not reflected
5) Emf series has only limited usefulness in predicting anodic behavior of a metal with another
metal.

MSc/PhD # ME 6351 Principles of Corrosion Page # 9

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Practice Problem: The cell potential of a particular voltaic cell with the cell reaction is 0.650 V.
Calculate the maximum electrical work of this cell when 0.500g H2 is consumed.

Practice Problem: Order the following oxidizing agents by increasing strength under standard-state
conditions: Cl2(g), H2O2 (aq), Fe3+(aq).

Solution:

MSc/PhD # ME 6351 Principles of Corrosion Page # 10

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Three types of cell important to corrosion

Dissimilar Electrode Cells: The cell generated from different metals or phases of the same
metal. Examples the dry cell , a metal containing electrically conducting impurities on the
surface as a separate phase, a copper pipe connected to an iron pipe, and a bronze propeller in
contact with the steel hull of a ship.

Concentration Cells: These are cells with two identical electrodes, each in contact with a
solution of different composition.
a) Salt concentration cell
b) Differential aeration cell

Differential Temperature Cells: Components of these cells are electrodes of the same metal,
each of which is at a different temperature, immersed in an electrolyte of the same initial
composition. These cells are found in heat exchangers, boilers, immersion heaters, and similar
equipment.

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 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Relative severity of corrosion rates:

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 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Faraday’s Law:

Faraday’s Law states that the current is proportional to the reaction rate and expressed by the
∆
equation = e. I,
∆

where ∆m is the mass of the substance produced or consumed the reaction in the time ∆t and e is the
electrochemical equivalent of the substance.

For Metals, e = MX/ nXF, where MX is the atomic mass and nX is the valency of metal X
Faradays law can also be written
W=ZIT
∆𝑮 = −𝒏𝑬𝑭
Where ∆𝐺 is the free energy change of the corrosion process, F is the charge transported by one mole
of electrons =96494 Colombs /mole, E is the measured potential (Volts) and n is the number of
electrons transferred

Units for corrosion rates

-Corrosion current: µA/cm2, mA/cm2, A/m2; - Weight loss: g/cm2-dia, mg/cm2-dia (mdd); -
Penetration rate: pol/ano (ipy), pol/mês, mil/ano (mpy).

MSc/PhD # ME 6351 Principles of Corrosion Page # 13

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Exercises:

1) Plain carbon steel immersed in seawater has a uniform corrosion rate expressed as a
penetration rate of 5.0 mpy (mils per year, where 1 mil = 0.001 in.). The density of iron is 7.87
g/cm3. The atomic weight of iron is 55.8 g/mol.
a) Calculate the weight loss after 1 year.
b) Calculate the corresponding current density in µA/cm2 assuming the corrosion current is
given by: Fe(s) → Fe2+(aq) + 2e-

2) Calculate the half - cell potential of the hydrogen electrode in a solution of pH = 7 and
partial pressure of H 2 = 0.5 atm at 40 ° C.

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 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Properties of solutions
1) Hydrogen potential (pH):
pH = -log[H+]
[H+] = H+ concentration in solution (mol/l);
2) Ionization constant (Kw):
In an aqueous solution: Kw = [H+][OH-] = 1.0 x 10-14

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 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

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 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Figure: All relations relating to Free energy [11]

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 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Summarizing various relationship among K, ∆Go and Eocell [11]

The thermodynamic equilibrium constant (K): The equilibrium constant in which the
concentrations of gases are expressed in partial pressures in atmospheres, whereas the
concentrations of solutes in liquid solutions are expressed in molarities.
K is defined in terms of activities which are dimension-less quantities numerically equal to
effective concentrations and pressures
For reaction involving only solutes in liquid solution, K is identical to Kc; for reactions
involving only gases, K equals Kp.
.
The equations learned so far
∆Go = - nFEocell and ∆Go = - RT lnK
nFEocell = RT lnK
𝑹𝑻
Eocell = lnK
𝒏𝑭

MSc/PhD # ME 6351 Principles of Corrosion Page # 18

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Electrodes normally used in Corrosion Measurement

1) Natural Hydrogen Electrode (NHE)

2) Copper- Copper Sulphate (Cu- CuSO4) Electrode
3) Saturate Calomel Electrode (SCE)
4) Platinum (Pt) Electrode

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 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Figure 6: Conversion chart among electrodes [5]

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 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Galvanic series: Galvanic series is an arrangement of both metals and alloys according to
their actual measured potential in particular environment [12]. Rapid prediction of the
corrosion resistance of dissimilar metals [4].

Difference between Galvanic Series and Electrochemical Series [4]

1. Electrochemical Series is an absolute quantitative series listing data to be used in precise
calculations, galvanic series is a relative qualitative series.
2. Electrochemical series list the data for metallic elements, Galvanic Series contains both
pure metals and alloys

Practice problems: Using Galvanic series find out the more corrosive combinations among
metals: Ag - Pb and Zn-Cu.

MSc/PhD # ME 6351 Principles of Corrosion Page # 21

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Practice Problem: What is the cell potential of the following voltaic cell at 25oC? The standard cell potential
of this cell is 1.10 V.

Solution:
The reaction for this cell

MSc/PhD # ME 6351 Principles of Corrosion Page # 22

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Determination of pH using the cell potential

Practice Problem: What is the concentration of the solution or pH of the solution?

MSc/PhD # ME 6351 Principles of Corrosion Page # 23

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Practice Problem: What is the cell potential of the following voltaic cell at 25oC? The standard cell
potential of this cell is 1.10 V.

Solution:
The reaction for this cell

MSc/PhD # ME 6351 Principles of Corrosion Page # 24

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Direction of spontaneity:

Practice Problem: Consider the reaction

Does the reaction go spontaneously in the direction indicated under standard conditions?

Solution:

The stronger oxidizing agent is the one involved in the half-reaction with the more positive standard
electrode potential, so Fe3+ is the stronger oxidizing agent. The reaction is nonspontaneous as
written.

MSc/PhD # ME 6351 Principles of Corrosion Page # 25

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Practice Problem: Calculate the standard cell potential of the following voltaic cell at 25oC
using standard electrode potentials for the following reaction.

What is the cell reaction?

Solution: Method I

The half-cell reaction and standard potentials

Reverse the 1st half cell reaction to show oxidation or to make anodic reaction

Finally,

MSc/PhD # ME 6351 Principles of Corrosion Page # 26

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Alternative method:

The cell potential formula

Practice problem: Using standard electrode potentials, calculate the standard free-energy change
at 25oC for the reaction.

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 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

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 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

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 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

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 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

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