CAGAYAN STATE UNIVERSITY

Carig Campus
College of Engineering

CHEMISTRY FOR ENGINEERS

CHEM111

UNIT V:
CORROSION CHEMISTRY
Learning Objectives:
At the end of this unit, the students will be able to:
1. Calculate for the rates of corrosion/plating; and
2. Determine ways to prevent or control corrosion.
CONTENTS:
V. Rate of Corrosion/Plating
VI. Corrosion Prevention and Control

V. RATE OF CORROSION/PLATING
Materials of all types may react with oxygen and other gases. These reactions can, like corrosion,
alter the composition, properties, or integrity of a material. For the oxidation reaction of the material,
M,
𝑛𝑀 + 𝑚𝑂2 → 𝑀𝑛 𝑂2𝑚
the Pilling-Bedworth (P-B) ratio is:
𝑜𝑥𝑖𝑑𝑒 𝑣𝑜𝑙𝑢𝑚𝑒 𝑝𝑒𝑟 𝑚𝑒𝑡𝑎𝑙 𝑎𝑡𝑜𝑚 (𝑀𝑊𝑜𝑥𝑖𝑑𝑒 )(𝜌𝑚𝑒𝑡𝑎𝑙 )
𝑃 − 𝐵 𝑟𝑎𝑡𝑖𝑜 = = 𝑬𝒒𝒏. (𝟓. 𝟓. 𝟏)
𝑚𝑒𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 𝑝𝑒𝑟 𝑚𝑒𝑡𝑎𝑙 𝑎𝑡𝑜𝑚 𝑛(𝑀𝑊𝑚𝑒𝑡𝑎𝑙 )(𝜌𝑜𝑥𝑖𝑑𝑒 )
where MW is the atomic or molecular weight, 𝜌 is the density, and n is the number of metal atoms in
the oxide.
If the Pilling-Bedworth ratio is less than one, the oxide occupies a smaller volume than the metal
from which it formed; the coating is therefore porous and non-protective and oxidation continues
rapidly—typical of metals such as magnesium. If the ratio is between one and two, the volumes of the
oxide and metal are similar and an adherent, non-porous, protective film forms—typical of aluminum
and titanium. If the ratio exceeds two, the oxide occupies a large volume and may flake from the
surface, exposing fresh metal that continues to oxidize— typical of iron.

Example 5.1
The density of aluminum is 2.70 g/cm3 and that of Al2O3 is about 4.00 g/cm3. (a) Describe the
characteristics of the aluminum-oxide film formed. (b) Compare it to the oxide film that forms
on tungsten. The density of tungsten is 19.254 g/cm3 and that of WO3 is 7.30 g/cm3.
Solution:
3
For the rxn 2𝐴𝑙 + 2 𝑂2 → 𝐴𝑙2 𝑂3 , the molecular weight of 𝐴𝑙2 𝑂3 is 101.96 g/mol and that of
aluminum is 26.981 g/mol.
3
For tungsten, the oxidation reaction is 𝑊 + 𝑂2 → 𝑊𝑂3 .The molecular weight of 𝑊𝑂3 is 231.85
2
g/mol and that of tungsten is 183.85 g/mol.

Module 22_Corrosion Chemistry (Part 2): Page 1 of 10

 𝑔 𝑔
(𝑀𝑊𝐴𝑙2 𝑂3 )(𝜌𝐴𝑙 ) (101.96 ⁄𝑚𝑜𝑙 ) (2.70 ⁄ 3 )
(𝑃 − 𝐵)𝐴𝑙 = = 𝑐𝑚 = 1.28
𝑛(𝑀𝑊𝐴𝑙 )(𝜌𝐴𝑙2 𝑂3 ) (2)(26.981 𝑔⁄ ) (4.00
𝑔
⁄ )
𝑚𝑜𝑙 𝑐𝑚3
𝑔 𝑔
(𝑀𝑊𝑊𝑂3 )(𝜌𝑊 ) (231.85 ⁄𝑚𝑜𝑙 ) (19.254 ⁄ 3 )
(𝑃 − 𝐵)𝑊 = = 𝑐𝑚 = 3.338
)(𝜌
𝑛(𝑀𝑊𝑊 𝑊𝑂3 ) (2)(183.85 ⁄ 𝑔 𝑔
𝑚𝑜𝑙 ) (7.30 ⁄𝑐𝑚3 )

(a) Since P-B ≅1 for aluminum, the Al2O3 film is nonporous and adherent, providing
protection to the underlying aluminum.
(b) Since P-B > 2 for tungsten, the WO3 should be non-adherent and non-protective.

The rate at which oxidation occurs depends on the access of oxygen to the metal atoms. A linear
rate of oxidation occurs when the oxide is porous (as in magnesium) and oxygen has continued access
to the metal surface: 𝑦 = 𝑘𝑡, where y is the thickness of the oxide, t is the time, and k is a constant
that depends on the metal and temperature.
A parabolic relationship is observed when diffusion of ions or electrons through a nonporous
oxide layer is the controlling factor. This relationship is observed in iron, copper, and nickel: 𝑦 =
√𝑘𝑡.
Finally, a logarithmic relationship is observed for the growth of thin-oxide films that are
particularly protective, as for aluminum and possibly chromium: 𝑦 = 𝑘 ln(𝑐𝑡 + 1), where k and c are
constants for a particular temperature, environment, and composition.
porous oxide: 𝑦 = 𝑘𝑡, 𝑬𝒒. (𝟓. 𝟓. 𝟐)
non-porous oxide: 𝑦 = √𝑘𝑡 𝑬𝒒. (𝟓. 𝟓. 𝟑)
thin protective oxide film: 𝑦 = 𝑘 ln(𝑐𝑡 + 1), 𝑬𝒒. (𝟓. 𝟓. 𝟒)

Example 5.2
At 1000°C, pure nickel follows a parabolic oxidation curve given by the constant k = 3.90x10-12
cm2/s in an oxygen-rich atmosphere. If this relationship is not affected by the thickness of the
oxide film, calculate the time required for a 0.10-cm nickel sheet to oxidize completely.
Solution:
Assuming that the sheet oxidizes from both sides at the same rate, you can imagine that the
sheet oxidizes towards the center of the sheet:

0.10 𝑐𝑚
→ = 0.05𝑐𝑚
2 𝑠𝑖𝑑𝑒𝑠
Considering the parabolic oxidation given:

𝑐𝑚2
𝑦 = √𝑘𝑡 = √(3.9 × 10−12 )(𝑡)
𝑠
Equating the given thickness with the equation:
𝑦 = √𝑘𝑡

𝑐𝑚2
0.05 𝑐𝑚 = √(3.9 × 10−12 )(𝑡)
𝑠

Module 22_Corrosion Chemistry (Part 2): Page 2 of 10

 𝑐𝑚2
(0.05 𝑐𝑚)2 = (3.9 × 10−12 )(𝑡)
𝑠
(0.05 𝑐𝑚)2
𝑡=
𝑐𝑚2
(3.9 × 10−12 𝑠 )
𝑡 = 6.4 × 108 𝑠 = 20.3 𝑦𝑒𝑎𝑟𝑠 ≈ 20 𝑦𝑒𝑎𝑟𝑠

Rate of Corrosion or Plating

The amount of metal plated on the cathode in electroplating, or removed from the anode by
corrosion, can be determined using Faraday’s equation,
𝐼𝑡𝑀
𝑤= 𝑬𝒒. 𝟓. 𝟓. 𝟓
𝑛𝐹
where w is the weight of metal plated or corroded (in g), I is the current (A), M is the atomic mass of
the metal, n is the charge of the metal ion, t is the time (s), and F is Faraday’s constant: 96,500
Cuolomb. This equation basically states that one-gram equivalent of a metal will be deposited by
96,500 C of charge.
Often the current is expressed in terms of current density, 𝑖=𝐼/𝐴, so Equation (5.5.5) becomes
𝑖𝐴 𝑡 𝑀
𝑤= 𝑬𝒒. 𝟓. 𝟓. 𝟓
𝑛𝐹
where the area A (cm2) is the surface area of the anode or cathode.
Example 5.3
An iron container 10cm x 10cm at its base is filled to a height of 20cm with a corrosive liquid.
A current is produced as a result of an electrolytic cell, and after four weeks, the container
has decreased in weight by 70 g. Calculate (a) the current and (b) the current density involved
in the corrosion of the iron.

Solution:
(a) The total exposure time from the given is:
𝑑𝑎𝑦𝑠 ℎ𝑟 𝑠
𝑡 = 4 𝑤𝑒𝑒𝑘𝑠 (7 ) (24 ) (3,600 ) = 2.42 × 106 𝑠
𝑤𝑒𝑒𝑘 𝑑𝑎𝑦 ℎ𝑟
From Faraday’s equation, using nFe = 2 and M W Fe = 55.847 g/mol,
𝐼𝑡𝑀 𝐼 (2.42 × 106 𝑠)(55.847 𝑔/𝑚𝑜𝑙)
𝑤= = 70 𝑔 =
𝑛𝐹 2 (96,500 𝐶)
𝐼 = 0.099 𝐴

(b) The total surface area of iron in contact with the corrosive liquid and the current
density are:
𝑠𝑢𝑟𝑓𝑎𝑐𝑒 𝑎𝑟𝑒𝑎 = 4𝐴𝑠𝑖𝑑𝑒𝑠 + 𝐴𝑏𝑜𝑡𝑡𝑜𝑚
= 4[(10)(20)] + (10)(10) 𝑐𝑚2
= 900 𝑐𝑚2

𝐼 0.099 𝐴
𝑖= = = 1.1 × 10−4 𝐴/𝑐𝑚2
𝐴 900 𝑐𝑚2

Module 22_Corrosion Chemistry (Part 2): Page 3 of 10

Example 5.4
Suppose that in a corrosion cell composed of copper and zinc, the current density at the copper
cathode is 0.05 A/cm2. The area of the copper electrode is 100 cm2 while that of the zinc
electrode is 120 cm2. Calculate (a) the corrosion current, (b) the current density at the zinc
anode, and (c) the zinc loss per hour.
Solution:
(a) The corrosion current is
𝐴
𝐼 = 𝑖𝐶𝑢 𝐴𝐶𝑢 = (0.05 2 ) (100 𝑐𝑚2 ) = 5 𝐴
𝑐𝑚

(b) The current in the cell is the same everywhere. Thus,

𝐼 = 𝑖𝑍𝑛 𝐴𝑍𝑛 = 5 𝐴 = 𝑖𝑍𝑛 (120 𝑐𝑚2 )
5𝐴 𝐴
𝑖𝑍𝑛 = 2
= 0.04
120 𝑐𝑚 𝑐𝑚2

(c) The atomic mass of zinc is 65.38 g/mol. From Faraday’s equation:
𝐼 𝑡 𝑀 (5 𝐴)(3600 𝑠/ℎ)(65.38 𝑔/𝑚𝑜𝑙) 𝑔
𝑤𝑍𝑛 𝑙𝑜𝑠𝑠 = = = 6.1 ≈ 6 𝑔/ℎ
𝑛𝐹 2 (96,500 𝐶) ℎ

Example 5.5
Consider a copper-zinc corrosion couple. If the current density at the copper cathode is 0.050
A/cm2, calculate the weight loss of zinc per hour if (a) the copper cathode area is 100 cm2 and
the zinc anode area is 1.0 cm2 and (b) the copper cathode area is 1.0 cm2 and the zinc anode
area is 100 cm2.

Solution:
(a) For the small zinc anode area,
𝐴
𝐼 = 𝑖𝐶𝑢 𝐴𝐶𝑢 = (0.050 ) (100 𝑐𝑚2 ) = 5.0 𝐴
𝑐𝑚2
𝐼 𝑡 𝑀 (5.0 𝐴)(3600 𝑠/ℎ)(65.38 𝑔/𝑚𝑜𝑙) 𝑔
𝑤𝑍𝑛 𝑙𝑜𝑠𝑠 = = = 6.1 ≈ 6 𝑔/ℎ
𝑛𝐹 2 (96,500 𝐶) ℎ
(b) For the large zinc anode area,
𝐴
𝐼 = 𝑖𝐶𝑢 𝐴𝐶𝑢 = (0.050 2 ) (1.0 𝑐𝑚2 ) = 0.050 𝐴
𝑐𝑚
𝐼 𝑡 𝑀 (0.050 𝐴)(3600 𝑠/ℎ)(65.38 𝑔/𝑚𝑜𝑙) 𝑔
𝑤𝑍𝑛 𝑙𝑜𝑠𝑠 = = = 6.1 ≈ 0.061 𝑔/ℎ
𝑛𝐹 2 (96,500 𝐶) ℎ

The rate of corrosion of the zinc is reduced significantly when the zinc anode is much larger
than the cathode.
Example 5.6
Design a process to electroplate a 0.10 cm-thick layer of copper onto a 1.00cm x 1.00cm
cathode surface. Copper density = 8.93 g/cm3.

Solution:
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑐𝑜𝑝𝑝𝑒𝑟 = (1.00 𝑐𝑚2 )(0.10 𝑐𝑚) = 0.10 𝑐𝑚3
𝑔
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑐𝑜𝑝𝑝𝑒𝑟 = (8.93 3 ) (0.10 𝑐𝑚3 )(0.10 𝑐𝑚) = 0.893𝑔
𝑐𝑚

Module 22_Corrosion Chemistry (Part 2): Page 4 of 10

 From Faraday’s equation, where MWCu = 63.54 g/mol and n = 2:
𝑤𝑛𝐹 (0.893𝑔)(2)(96,500 𝐶)
𝐼𝑡 = = = 2,712 𝐴 ∙ 𝑠
𝑀 63.54 𝑔/𝑚𝑜𝑙

Therefore, we might use several different combinations of current and time (provided that
the final 𝐼𝑡 value is equal to 2,712 A-s) to produce the copper plate:
current time
0.1 A 27,124 s (or 7.5h)
1.0 A 2,712 s (or 45.2 min)
10.0 A 271.2 s (or 4.5 min)
100.0 A 27.1 s

Our choice of the exact combination of current and time might be made on the basis of
the rate of production and quality of the plated copper. Low currents require very long plating
times while high currents may reduce plating efficiencies. Currents such as 10 A or 100 A are
too high—they can initiate other side reactions that are not desired. The deposit may also not
be uniform and smooth. Additional background or experimentation may be needed to obtain
the most economical and efficient plating process. A current of ~1A and a time of ~45 minutes
are not uncommon in electroplating operations.

.
VI. CORROSION PREVENTION AND CONTROL
A. DESIGN
A material’s geometrical form is an important factor in design – particularly with regard to
assembly shape (joints, flanges, crevices, deposits, and liquid containment and entrapment). The
objective here is to minimize or avoid factors that worsen corrosion.
1) Avoid sharp bends and sharp corners: Impingement takes place in sharp bends in flowing
systems. Fluid movement need not be excessive to damage a material so avoid sharp
bends/corners as much as possible.
2) Avoid galvanic coupling: If two metals have to be coupled, (a) Use insulation between them
or (b) Select the metals which are close to one another in the electrochemical series so that
the potential difference between them is smaller/negligible (and hence, will induce less
corrosion.)
3) Fluid system: Design components so that fluid systems are closed, rather than open, so that
stagnation of fluid due to improper drainage structures, nondraining/dead ends, poorly
located components, and poor assembly or maintenance practices can be avoided.
4) Avoid crevices: Avoid crevices between assembled or joined materials by using fillers or by
employing joining techniques such as welding.
5) Avoid having a small anodic area and large cathodic area. It is desirable to limit cathodic
reaction, thus limiting electron acceptance from the anode and slowing down corrosion. (see
Example 5.5.)
6) Improved wall thickness: Wall thickness of the component should be double the theoretical
thickness that would give the desired functional lifespan of the component.

Module 22_Corrosion Chemistry (Part 2): Page 5 of 10

 7) Careful fabrication and inspection should eliminate or reduce poor profiles (e.g., welds,
rivets, bolts), rubbing surfaces (e.g., wear, fretting), and galvanic effects due to the assembly
of incompatible components.

B. MATERIALS SELECTION AND TREATMENT

Elements of material selection includes the review of operating conditions as well as equipment
design. Materials consideration include the complexity associated with material requirements (field
chemistry, mechanical engineering, metallurgy), cost considerations, material properties
considerations (density, modulus of elasticity, tensile strength, thermal conductivity), and processing
and fabrication considerations.
The resistance of a metallic material can be improved by changing its composition either by
refining, decreasing the concentration of impurities, or alloying, addition of metal or non-metal to
improve the properties. Corrosion can be prevented or minimized by selecting appropriate materials
and heat treatments. We can improve corrosion resistance with a homogenization heat treatment
which affects crystals of the components at grain boundaries. When dissimilar metals are to be used,
select combinations of metals as close together as possible in the galvanic series suitable for the
particular application or service environment.

C. ENVIRONMENT AND OPERATING VARIABLES

One factor that is occasionally overlooked is the surrounding environment. Exposure to winds and
airborne particulates can lead to the deterioration of structures. Designs that leave structures
exposed to the elements should be carefully reviewed because atmospheric corrosion is significantly
affected by temperature, relative humidity, rainfall, and pollutants. Also important are the season
and location of on-site fabrication, assembly, and painting. Codes of practice must be adapted to
the location and the season.
(a) Removal of corrosive constituents: Moisture can be removed by dehumidification by using
silica gel, 𝐴𝑙2 𝑂3 , etc.; 𝑂2 can be removed by deaeration thru proper temperature control and
mechanical agitation or using oxygen scavengers or salts by filtration.
(b) Change in operating variables: (i) lowering of temperature decreases corrosion rate
considerably in most of the cases, and (ii) the effect of pH on the rate of corrosion can be
judged by using the Pourbaix diagram which gives an idea about the pH range in which the
metal undergoes the least corrosion.
(c) Cleaning and preventive maintenance: Corrosion is a surface phenomenon, and the effects of
poorly prepared surfaces, rough textures, and complex shapes and profiles can be expected
to be harmful. Regular cleaning involving mechanical methods is commonly employed. Filters
can also be employed to remove materials that can deposit on the metal surface.
(d) Minimize stress: Stress levels for the selected material, such as the influence of tensile,
compressive, or shear stressing; alternating stresses; vibration or shock loading; service
temperatures (thermal stressing); fatigue; and wear (fretting, friction) must be considered
during designing, fabrication, and operation

D. USE OF INHIBITORS
Inhibitors are substances which are added from outside to reduce the rate of corrosion.
Inhibitors reduce the rate of corrosion either by forming a layer which acts as a barrier between the
material and environment and retarding the anodic or cathodic or both processes.
(a) Cathodic inhibitors: They retard the rate of cathodic reaction and hence the overall rate of
corrosion. In acidic medium, the cathodic reaction taking place is
2𝐻 +(𝑎𝑞) + 2𝑒 − → 𝐻2 (𝑔) 𝑟𝑒𝑑𝑢𝑐𝑡𝑖𝑜𝑛 𝑎𝑡 𝑐𝑎𝑡ℎ𝑜𝑑𝑒

Module 22_Corrosion Chemistry (Part 2): Page 6 of 10

 (b) Organic inhibitors like amines, mercaptans, substituted ureas, which have a lone pair of
electrons, reduce the rate of cathodic reaction considerably by reacting with H+.
(c) Anodic inhibitors: inhibitors which retard the rate of anodic reaction by polarizing. These
inhibitors generally form a layer in between the material and environment. E.g. Chromates,
phosphates, tungstates.

E. PROTECTIVE COATING
Coatings are used to isolate the anode and cathode regions. It provides a physical, continuous
effective barrier in between metal and the environment. Thus, there is no direct interaction of metal
with the environment and the rate of corrosion decreases. Coatings also prevent the diffusion of
oxygen or water vapor that initiates corrosion or oxidation.
Temporary coatings, such as grease or oil, provide some protection but are easily disrupted.
Organic coatings, such as paint, or ceramic coatings, such as enamel or glass, provide better
protection; however, if the coating is disrupted, the small anodic site that is exposed undergoes
rapid, localized corrosion.
(a) Metallic coating. Metal is coated on base structures by electrolysis or electrodeposition. In
electrolysis, the electrolytic solution of the metal ion whose coating is to be provided is
electrolyzed and the base metal (the cathode) is coated by using a direct current. The anode
is either made up of the coating metal itself or an inert material of good electrical conductivity
like graphite. The electrodeposition depends upon temperature, current density, time, and
composition of electrolytic bath. Metallic coatings can be sacrificial or noble.
Table 5.5.1 Sacrificial vs. Noble coatings
Sacrificial Coating Noble Coating
Base metal is coated with a metal which is more Base metal is coated with a metal which is more
reactive than the base metal. noble that the base metal.
Protects the underlying base metal sacrificially. Protects the base metal due to its noble
character and higher corrosion resistance.
Known as anodic coating as the reduction Known as the cathodic coating as the reduction
potential of coating metal is less than that of the potential of coating metal is more than that of
base metal. the base metal.
If there are pores, discontinuities or breaks in If there are pores, discontinuities or breaks in
such a coating, the base metal corrodes until all such a coating, intense localised corrosion takes
the coating metal is consumed. place because of the small anodic area and large
cathodic area. Therefore, multiple coating is
preferred.
Zn, Cd, Al are generally used as sacrificial Ni, Ag, Cr, Pb, Au etc. used generally for noble
coating. e.g. Galvanised iron (GI) pipes are coatings. e.g. Coating of Sn on Fe
coated with Zn

(b) Organic coating. These coatings are inert organic barriers like paints, varnishes, or plastics
applied on metallic surfaces and other constructional materials for both corrosion prevention
and decoration. Paint is a dispersion mixture of one or more pigments, generally particles of
metallic oxide (TiO2, Fe2O3, Pb3O4, BaSO4) in a vehicle (liquid consisting of drier, thinner, and
binder). Qualities of a good paint includes provision of a good barrier, inhibiting action, long
life at reasonable cost, ability to reflect the light, and it should be fast in color (does not fade
quickly).
(c) Inorganic coating. They are also known as chemical conversion coating and are inorganic
surface barriers, produced by chemical or electrochemical reactions brought at the surface of
base metal. Such coatings are particularly used as excellent bases for paints. Important
conversion coatings are: phosphate, chromate, oxide or anodized coating. Inorganic coatings

Module 22_Corrosion Chemistry (Part 2): Page 7 of 10

 include porcelain enamels, chemical-setting silicate cement linings, glass coatings and linings,
and other corrosion resistant ceramics.

One should apply coatings with caution. When painting, for example, do not paint the less noble
material without also coating the more noble material; otherwise, imperfections in coatings can cause
greatly accelerated attacks that are concentrated on the less noble metal. Keep such coatings in good
condition.
If only one surface can be painted, the more noble surface should be chosen to reduce or
eliminate the cathode area.
In cases where the metals cannot be painted and are connected by a conductor external to the
liquid, the electrical resistance of the liquid path may be increased by keeping the metals as far apart
as possible. This is not practical in most cases.

F. CATHODIC PROTECTION
We can protect against corrosion by supplying the metal with electrons and forcing the metal to
be a cathode. Cathodic protection suppresses the corrosion current that causes damage in a corrosion
cell and forces the current to flow to the metal structure to be protected. Thus, the corrosion or
metal dissolution is prevented. If electrons enter through the external circuit or if current enters the
structure from the electrolyte then the structure is protected. This is affected by either of the
following ways:
(a) By appropriate galvanic coupling. A sacrificial anode is attached to the material to be
protected, forming an electrochemical circuit. The sacrificial anode corrodes, supplies
electrons to the metal, and thereby prevents an anode reaction at the metal. The sacrificial
anode, typically Zn, Al, or Mg and its alloys, is consumed and must eventually be replaced.
Applications include preventing the corrosion of buried pipelines, ships, off-shore drilling
platforms, and water heaters. This type of protection is used for underground pipelines, ship
hulls, boat hulls, water tanks. The sacrificial anode block is replaced by a fresh one, when
consumed completely.
(b) Impressed current cathodic protection. An impressed voltage is obtained from a direct current
source connected between an auxiliary anode and the metal to be protected. Essentially, we
connect a battery so that electrons flow to the metal, forcing the metal to become the
cathode. An insoluble anode/electrode like graphite, platinum, stainless steel or high silica
iron and is connected to the metallic structure to be protected.
This method has certain advantages over sacrificial cathodic protection since it is
controlled from the outside and no anode has to be replaced making it good for long-term
operation. This method is used for the protection of water mains, electrical cables,
transmission towers, condensers, etc.

G. PASSIVATION (ANODIC PROTECTION)

Metals near the anodic end of the galvanic series are active and serve as anodes in most
electrolytic cells; however, if these metals are made passive or more cathodic, they corrode at slower
rates than normal. Passivation is accomplished by producing strong anodic polarization, preventing
the normal anode reaction; thus, the term anodic protection.
We induce passivation by exposing the metal to highly concentrated oxidizing solutions. If iron is
dipped in very concentrated nitric acid, the iron rapidly and uniformly corrodes to form a thin,
protective iron hydroxide coating. The coating protects the iron from subsequent corrosion in nitric
acid.

Module 22_Corrosion Chemistry (Part 2): Page 8 of 10

 We can also cause passivation by increasing the potential on the anode above a critical level. A
passive film then forms on the metal surface, causing strong anodic polarization, and the current
decreases to a very low level.
A prime example of passivation is that of titanium or aluminum called anodizing, wherein a thick
oxide coating is produced. The different thicknesses of the coating formed results in the appearance
of different colors and is often employed in decorating jewelry/decorative objects made from these
metals. Another application of passivation is the formation of a Ta2O5 oxide layer on tantalum wires
which are used to make capacitors.

SUMMARY
• Pilling-Bedworth (P-B) ratio for material M:
(𝑀𝑊𝑜𝑥𝑖𝑑𝑒 )(𝜌𝑚𝑒𝑡𝑎𝑙 )
𝑃 − 𝐵 𝑟𝑎𝑡𝑖𝑜 =
𝑛(𝑀𝑊𝑚𝑒𝑡𝑎𝑙 )(𝜌𝑜𝑥𝑖𝑑𝑒 )
𝑃−𝐵 <1 → 𝑐𝑜𝑎𝑡𝑖𝑛𝑔 𝑖𝑠 𝒑𝒐𝒓𝒐𝒖𝒔 𝑎𝑛𝑑 ∴ 𝒏𝒐𝒏 − 𝒑𝒓𝒐𝒕𝒆𝒄𝒕𝒊𝒗𝒆
1<𝑃−𝐵 <2 → 𝑐𝑜𝑎𝑡𝑖𝑛𝑔 𝑖𝑠 𝒏𝒐𝒏 − 𝒑𝒐𝒓𝒐𝒖𝒔 + 𝒂𝒅𝒉𝒆𝒓𝒆𝒏𝒕, 𝑎𝑛𝑑 ∴ 𝒑𝒓𝒐𝒕𝒆𝒄𝒕𝒊𝒗𝒆
2<𝑃−𝐵 → 𝑐𝑜𝑎𝑡𝑖𝑛𝑔 𝑖𝑠 𝒏𝒐𝒏 − 𝒂𝒅𝒉𝒆𝒓𝒆𝒏𝒕 (𝒇𝒍𝒂𝒌𝒆𝒔 𝒐𝒇𝒇), 𝑎𝑛𝑑 ∴ 𝑛𝑜𝑛 − 𝒑𝒓𝒐𝒕𝒆𝒄𝒕𝒊𝒗𝒆
• Rate of rxn trends based on type of oxide:
porous oxide: non-porous oxide: thin protective oxide film:
𝑦 = 𝑘𝑡, 𝑦 = √𝑘𝑡 𝑦 = 𝑘 ln(𝑐𝑡 + 1)
• Faraday’s equation: shows that one-gram eq. of a metal will be deposited by 96,500 C of charge.
𝐼 𝑡 𝑀 𝑖𝐴 𝑡 𝑀
𝑤= =
𝑛𝐹 𝑛𝐹
• To minimize/prevent corrosion:
i. IMPROVE DESIGN:
- Avoid sharp bends and sharp corners to reduce impingement.
- Avoid galvanic coupling.
- Fluid systems should be properly designed.
- Avoid crevices.
- Avoid having a small anodic area and large cathodic area.
- Improve wall thickness.
- Fabricate and inspect components carefully.

ii. SELECT AND TREAT MATERIALS ACCORDINGLY:

- Consider material requirements (field chemistry, mechanical engineering, metallurgy);
- Consider overall cost;
- Consider material properties (density, modulus of elasticity, tensile strength, thermal
conductivity);
- Consider processing and fabrication;
- Improve resistance to corrosion thru refining, decreasing the concentration of impurities, or
alloying;
- Improve corrosion resistance with homogenization heat treatment;
- Select combinations of suitable metals that are as close as possible in the galvanic series.

Module 22_Corrosion Chemistry (Part 2): Page 9 of 10

 iii.CONSIDER THE ENVIRONMENT AND OP. VARIABLES:
- Remove corrosive constituents.
- Change operating variables: (i) lowering of temperature, (ii) choosing the right pH.
- Clean and do preventive maintenance.
- Minimize stress.

iv. USE INHIBITORS:

- Cathodic inhibitors
- Organic inhibitors
- Anodic inhibitors

v. APPLY A PROTECTIVE COATING:

- Metallic coatings: methods are electrolysis, electrodeposition; coatings are either sacrificial
or noble
- Organic coatings (like paint)
- Inorganic coatings/chemical conversion coatings

vi. INDUCE CATHODIC PROTECTION (forcing the base metal to become a cathode):
- By appropriate galvanic coupling (attaching a sacrificial anode to the base metal);
- By impressed current cathodic protection (attaching a battery to the system to force base
metal become a cathode).

vii. INDUCE PASSIVATION:

- forcing the base metal to undergo strong anodic polarization, a.k.a. anodizing

Self-Assessment 24
1. Explain the difference between atmospheric corrosion and underground/soil corrosion. Include
factors affecting both corrosions.
2. Describe the variables that affects a corrosive environment.

References:
1. Askeland, D.R., Fulay, P.P., & Wright, W.J. (2011). The Science and Engineering of Materials,
(6th ed). Cengage Learning. CT, USA. ISBN 978-0-495-29602-7
2. Davis, J.R. et al. (2000). Corrosion: Understanding the Basics. ASM International. OH, USA. ISBN
0-87170-641-5
3. Goel, N. & Kumar, S. (2006). Concise Engineering Chemistry (2nd Ed). AITBS Publishers and
Distributors, India. ISBN 81-7473-233-2
4. Jones, D.A. (1996). Principles and Prevention of Corrosion (2nd Ed). Prentice-Hall, Inc. NJ,
USA. ISBN 0-13-359993-0
5. Makhlouf, A.S.H & Aliofkhazraei, M. (2018) Handbook of Materials Failure Analysis:
With Case Studies from the Construction Industries (1st Ed.). Butterworth-Heinemann.
MA, USA. ISBN 978-0-08-101928-3

Module 22_Corrosion Chemistry (Part 2): Page 10 of 10