Three types of oxides may

form, depending on the

volume ratio between the
metal and the oxide:
a. Magnesium produces
a porous oxide film,
b. Aluminum forms a
protective, adherent,
nonporous oxide
film,
c. Iron forms an oxide
film that spills off the
surface and provides
poor protection.
2. Corrosion by gases
The gases such as SO2, CO2, H2S, Cl2, F2 etc., when come in direct
contact with metal surface corrosion occurs.
• The extent of corrosion depends on the chemical affinity
between the metal and the gas concerned.
• The prevention of metal corrosion can be known from the
nature of corrosion product.

Whether the layer of corrosion product is protecting or non-

protecting in nature.
• If the formed corrosion product is protecting (or) non porous metal is
prevented. Ex: AgCl layer on metallic silver by the action of Cl2 gas.
• If the formed corrosion product is non protecting (or) porous , the corrosion
of metals occurs non stop. Ex: H2S gas attacks on steel at high temperature
forming FeS , a corrosion product which is porous.
3. Liquid metal corrosion
The chemical action of the flowing liquid metal at high
temperature, on a solid metal or alloy produces liquid metal
corrosion.

There are two reasons for this corrosion –

• Dissolution of the solid metal by liquid metal

• Internal penetration of the liquid metal into the solid phase,

weakening the solid metal.

Example: liquid Na used as a coolant in a nuclear plants, these

causes cadmium corrosion.
Theories of corrosion
Pilling-Bedworth Ratio
The Pilling-Bedworth ratio (P-B ratio), in corrosion of metals, is
the ratio of the volume of the elementary cell of a metal oxide to
the volume of the elementary cell of the corresponding metal
(from which the oxide is created).

MOxide
VOxide ρOxide MOxide × ρMetal
𝐑 𝐏𝐁 = = =
VMetal M
𝑛 × Metal 𝑛 × MMetal × ρOxide
ρMetal

where,
RPB : is the Pilling-Bedworth ratio,
V : the molar volume
ρ : density,
M : the atomic or molecular mass,
n : number of atoms of metal per one molecule of the oxide
Pilling-Bedworth rule
The Pilling-Bedworth rule →
𝒗𝒐𝒍𝒖𝒎𝒆 𝒐𝒇 𝒎𝒆𝒕𝒂𝒍 𝒐𝒙𝒊𝒅𝒆
𝒔𝒑𝒆𝒄𝒊𝒇𝒊𝒄 𝒓𝒂𝒕𝒊𝒐 =
𝒗𝒐𝒍𝒖𝒎𝒆 𝒐𝒇 𝒎𝒆𝒕𝒂𝒍

Three types of oxides may form, depending on the volume ratio

between the metal and the oxide:
a. Magnesium produces a porous oxide film,
b. Aluminum forms a protective, adherent, nonporous oxide film,
and
c. Iron forms an oxide film that spills off the surface and provides
poor protection.
Pilling-Bedworth rule
The Pilling-Bedworth rule →
𝒗𝒐𝒍𝒖𝒎𝒆 𝒐𝒇 𝒎𝒆𝒕𝒂𝒍 𝒐𝒙𝒊𝒅𝒆
𝒔𝒑𝒆𝒄𝒊𝒇𝒊𝒄 𝒓𝒂𝒕𝒊𝒐 =
𝒗𝒐𝒍𝒖𝒎𝒆 𝒐𝒇 𝒎𝒆𝒕𝒂𝒍
Pilling-Bedworth Ratio
The Pilling-Bedworth ratio (P-B ratio), in corrosion of metals, is
the ratio of the volume of the elementary cell of a metal oxide to
the volume of the elementary cell of the corresponding metal
(from which the oxide is created).

Volume of the elementary cell of a metal oxide

𝐏 − 𝐁 𝐫𝐚𝐭𝐢𝐨 =
Volume of the elementary cell of the metal

On the basis of the P-B ratio, it can be judged if the metal is likely
to passivate in dry air by creation of a protective oxide layer.
Pilling-Bedworth Ratio
On the basis of measurements, the following connection can be shown:

VOxide MOxide × ρMetal

𝐑 𝐏𝐁 = =
VMetal n × MMetal × ρOxide

𝐑 𝐏𝐁 < 𝟏: the oxide coating layer is too thin, likely broken and
provides no protective effect (for example magnesium)
𝐑 𝐏𝐁 > 𝟏: the oxide coating provides protective effect

However, the exceptions to the above P-B ratio rules are numerous. Many of
the exceptions can be attributed to the mechanism of the oxide growth: the
underlying assumption in the P-B ratio is that oxygen needs to diffuse through
the oxide layer to the metal surface; in reality, it is often the metal ion that
diffuses to the air-oxide interface.
Calculation of Pilling-Bedworth Ratio

VOxide MOxide × ρMetal

𝐑 𝐏𝐁 = =
VMetal n × MMetal × ρOxide

Oxide Oxide Density Atomic Metal Molecular P-B Ratio

(g/cc) weight of Density Weight of
Metal (g/cc) Oxide

MgO 3.65 24.3 1.74 40.3 0.79

CaO 3.40 40.08 1.55 56.1 0.04

Al2O3 3.70 27.00 2.70 102.0 1.37

Calculation of Pilling-Bedworth Ratio

VOxide MOxide × ρMetal

𝐑 𝐏𝐁 = =
VMetal n × MMetal × ρOxide

Oxide Oxide Atomic Metal Molecular P-B Ratio

Density Weight of Density Weight of
(g/cc) Metal (g/cc) Oxide
Cr2O3 5.22 52 7.19 152.0 ?

Na2O 2.27 23 0.97 62.0 ?

NiO 6.67 58.69 8.91 74.7 ?

K2O 2.13 39.09 0.86 94.2 ?

Calculation of Pilling-Bedworth Ratio

VOxide MOxide × ρMetal

𝐑 𝐏𝐁 = =
VMetal n × MMetal × ρOxide

Oxide Oxide Atomic Metal Molecular P-B Ratio

Density Weight of Density Weight of
(g/cc) Metal (g/cc) Oxide
Cr2O3 5.22 52 7.19 152.0 2.01

Na2O 2.27 23 0.97 62.0 0.57

NiO 6.67 58.69 8.91 74.7 1.70

K2O 2.13 39.09 0.86 94.2 0.48

Mechanism of wet corrosion

1. The formation of anodic and cathodic areas or parts in contact

with each other.

2. Presence of a conducting medium.

3. Corrosions of anodic areas only.

4. Formation of corrosion product somewhere between anodic

and cathodic areas.
 Electrochemical corrosion
The metal surface undergoes an electrochemical reaction with the
moisture and oxygen in the atmosphere. This theory is known as
electrochemical theory of corrosion.
Mechanism :
• Anodic reaction : Oxidation of metal (corrosion)
• Cathodic reaction : Consumption of electrons

Corrosion always occurs at the anode

 1) Mechanism of wet corrosion

Wet corrosion takes place by the following two ways based on the
nature of medium:
1) Anodic reaction: Fe (s) → Fe2+ (aq) + 2e-
2) Cathodic reaction: a) Evolution of H2 (acidic medium) in absence of
oxygen
2 H+ (aq) + 2e- → H2

Displacement of hydrogen ions from the acidic solution by metal ions)

 b) Absorption of O2 : Neutral medium
Cathode: ½ O2(g) + H2O (aq) +2 e- → 2OH-

If the solution is aerated and almost neutral, O2 is reduced in presence of water

to OH-
c. If the solution is deaerated and almost neutral, H2 is liberated along
with OH-

Cathode: H2O (aq) +2 e- → H2 + 2OH-

Final Step
Salt speeds up the process

Water
Fe2+ Rust

e-
Iron Dissolves-
Fe → Fe+2
Fe2+ + 4 OH- 2Fe(OH)2
2Fe(OH)2 + ½ O2 + (x-2) H2O Fe2O3. xH2O
If limited oxygen is supplied, black rust is formed as follows

3Fe(OH)2 + ½ O2 -----------Fe3O4. 3H2O

Black Rust
Theories of corrosion
Dry or chemical corrosion:
• This occurs at dry
conditions
• Corrosion is uniform
• It is a slow process
• It involves direct chemical
attack
• Explained by absorption
mechanism
Wet or electrochemical corrosion:
• This occurs at wet conditions
(electrolytic medium)
• Corrosion Is not uniform
• It is a rapid process
• It involves formation of
electrochemical cells
• Explained by mechanism of
electrochemical reactions