MODULE III

CORROSION SCIENCE AND E-WASTE MANAGEMENT

Corrosion Chemistry: Introduction, electrochemical theory of corrosion, types of corrosion,

differential metal and differential aeration. Corrosion control-galvanization, anodization and
sacrificial anode method.
Corrosion Penetration Rate (CPR) – Introduction and numerical problem.
E-waste Management: Introduction, sources, types, effects of e-waste on environment and
human health, methods of disposal, advantages of recycling. Extraction of copper and gold from
e-waste.
Self-learning: Recycling of PCB and battery components

CORROSION
Introduction
Corrosion is defined as the destruction and consequent loss of metals through chemical or
electrochemical attack by the environment.
Ill effects of corrosion

 Contamination of product
 Damage of metallic equipment.
 Inability to use metallic materials
 Lose of valuable materials such as blockage of pipes, mechanical damage of underground
water pipes
 Accidents due to mechanical loss of metallic bridges, cars, aircrafts etc.

Global losses of corrosion

 Efficiency loss.
 Equipment shut down due to corrosion failure and cost of replacing the corroded
equipment.
 Sudden failure of equipment due to corrosion can cause an explosion, fire, release of a
toxic product, and/or construction collapse which challenges the safety measures.

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 An escaping product from corroded equipment or corrosion product itself can cause
pollution hence may result serious health problems.
Electrochemical Theory of Corrosion:
Principle: According to electrochemical theory, corrosion of the metal take place due to the
formation of anodic and cathodic regions on the same metal surface in the presence of a
conducting medium. At the anodic region oxidation reaction takes place and the metal gets
corroded into ions liberating the electrons. Consequently, metals undergo corrosion at the anodic
region. At the cathodic region reduction reaction takes place. Metal ions in the cathodic region
are unaffected by the cathodic reaction.
The electrons liberated at the anodic region migrate towards the cathodic region
constituting corrosion current. The metal ions liberated at the anode and some anions formed at
the cathode region diffuse towards each other through the conducting medium and form a
corrosion product somewhere between the anode and the cathode. Corrosion of metal continues
as long as both the anodic and cathodic reactions take place simultaneously.
Corrosion reactions:
At the anodic region:
At anodic region, iron is liberating Fe2+ ions and electrons,
Fe →Fe2+ +2e-
At the cathodic region:
The chemical species present in the surrounding of cathode under goes reduction by accepting
electrons coming through metal from the anodic region. Depending on the surrounding medium,
there are four possible reduction reactions at the cathodic region,
1) Hydrogen liberation takes place in the absence of oxygen.
(a) In acidic medium and in the absence of oxygen the cathodic reaction is
2H++2e-→H2↑
(b) In neutral or alkaline medium and in the absence of oxygen, hydroxide ions are
formed with simultaneous liberation of hydrogen
2H2O+2e- →2OH─+ H2
2) Absorption of oxygen takes place in the presence of oxygen.
(a) In acidic medium and in the presence of oxygen
2H+ +1/2O2 +2e- →H2O

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(b) In neutral or alkaline medium and in the presence of oxygen hydroxide ions are
formed by the following reaction.
H2O+1/2O2 +2e- →2OH─
Corrosion of iron produces Fe2+ and OH─ ions at the anode and cathode sites respectively.
These ions diffuse towards each other to produce insoluble Fe (OH)2.
Fe2++2OH─→ Fe (OH) 2
. In an oxidizing environment it is oxidized to ferric oxide and the yellow rust is hydrated
ferric oxide.
4 Fe (OH) 2+ O2+2H2O →2 [Fe2O3. 3H2O] (rust)
In the presence of limited oxygen ferrous oxide is converted into magnetic oxide of iron
(Fe3O4) and is known as black rust.
3 Fe (OH) 2+1/2 O2→ [Fe3O4. 3H2O] (black rust)

Types of Corrosion:
(1) Differential metal corrosion (Galvanic corrosion)
(2) Differential Aeration corrosion
1. Differential metal Corrosion
Definition: When two dissimilar metals are in contact with each other a potential difference is
set up resulting in a galvanic current.
Principle: The two metals differ in their tendencies to undergo oxidation, the one with lower
electrode potential or the more active metal acts as anode and the one with higher electrode
potential acts as cathode. The anodic metal undergoes corrosion and the cathodic metal is
generally unattacked.

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At the anode), Fe→ Fe2+ + ne-

At the cathode H2O + ½ O2 + 2e- → 2OH-
Fe2++2OH─→ Fe (OH) 2
2Fe (OH) 2+1/2O2+H2O → [Fe2O3. 3H2O] (rust)

Process: When two metals having different electrode potentials are in contact with each other in
the presence of an electrolyte, one metal acts as a cathode whereas the other acts as an anode.
This leads to an electrochemical reaction as a result of which, the anode is dissolved into the
electrolyte. Galvanic corrosion can only occur when there exists an electric conducting path
connecting the metals and when an electrolyte which can offer a channel for the migration of
ions is present.

Differential Metal Corrosion

Examples:
(1) Steel pipes joined to Copper plumbing, undergo galvanic corrosion, since Steel acts as the
anode.
E0Fe+2/Fe = - 0.44 V E0Cu+2/Cu = +0.34 V
(2) Steel screws or rivets used on Copper sheet, or screws and washers of unlike metals.
(3) Steel propeller shaft in Bronze bearing.

2. Differential Aeration Corrosion

Differential aeration corrosion occurs when a metal surface is exposed to differential air
concentrations of Oxygen concentrations. The part of the metal exposed to higher oxygen
concentration acts as a cathodic region and the part of the metal exposed to lower oxygen
concentration acts as anodic region.

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Corrosion of metal arising as a result of the formation of an oxygen concentration cell

due to uneven supply of air on the metal surface is known as differential aeration corrosion.
At the anode (less O2 concentration), Fe → Fe2+ + ne-
At the cathode (more O2 concentration), H2O + ½ O2 + 2e- → 2OH-
Fe2++2OH─→ Fe (OH) 2
2Fe (OH) 2+1/2O2+H2O → [Fe2O3. 3H2O] (rust)

Eg.:- 1. Part of the nail inside the wall, being exposed to lower oxygen concentration than the
exposed part, under goes corrosion.
2. Paper pins inside the paper gets corroded, and the exposed part is free from corrosion.
3. Metal under dirt, dust, scale or water undergoes corrosion.
Water line Corrosion:
Principle: Water line corrosion is a case of differential aeration corrosion. The water line
corrosion takes place due to the formation of differential oxygen concentration cells. The part of
the metal below the water line is exposed only to dissolved oxygen (acts as anode) while the part
above the water is exposed to higher oxygen concentration (acts as cathode) of the atmosphere.
A distinct brown line is formed below the water line due to deposition of rust.
At the anode (less O2 concentration), Fe → Fen+ + ne
At the cathode (more O2 concentration), H2O + ½ O2 + 2e- → 2OH-
Fe2++2OH─→ Fe (OH) 2
2Fe (OH) 2+1/2O2+H2O →[Fe2O3. 3H2O] (rust)

Water - line Oxygen

Cathode

Corroded part (anode)

Examples:
(1) Ships that are left in the water for extended periods of time can be at risk of waterline
corrosion.
(2) Steel water tanks in which water is stored for a long period.

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Corrosion Control
(a) Galvanisation
Galvanisation is a process of coating a base metal surface with Zinc metal. It is an anodic
coating which is produced by coating a base metal with more active metals which are anodic to
the base metal. Eg.: Iron is coated with anodic and active metals like Zn, Mg, and Al.
Galvanisation is carried out by hot dipping method.

The galvanization process involves the following steps.

(1) The metal surface is washed with organic solvents to remove organic matter on the
surface
(2) Rust and other deposits are removed by washing with dilute sulphuric acid.
(3) Finally the article is well washed with water and air-dried.
(4) The article is then dipped in a bath of molten zinc, maintained at 425 – 430C and
covered with a flux of ammonium chloride to prevent the oxidation of molten Zinc.
(5) The excess Zinc on the surface is removed by passing through a pair of hot rollers, which
wipes out excess of Zinc coating and produces a thin coating.
One advantage of gavanisation is that, even if the coating is ruptured, the base metal does not
undergo corrosion. The exposed surface of the metal is cathodic with respect to zinc. Therefore,
galvanisation is also known as sacrificial coating.
(b) Anodization
Anodization is generally produced on nonferrous metals like Al, Zn, Mg and their alloys
by anodic oxidation process. It is a type of inorganic coating where surface layer of the metal is
converted into a compound, by chemical or electrochemical reactions, which forms a barrier
between the underlying metal surface and the corrosion environment
In anodization of aluminium, clean, polished aluminium is taken as anode and immersed
in an electrolytic cell containing chromic acid. Inert electrodes like lead is generally used as
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cathode. The anodic oxide film formed on Al in bath as aluminium oxide, which is porous. The
pores are finally sealed by dipping in hot water to produce Al2O3 .H2O, which acts as a non-
porous protective layer preventing corrosion.
Anode reaction: 2Al + 3H2O → Al2O3 + 6H+ +6e-
Cathode reaction: 6H+ + 6e- → 3H2

(c) Sacrificial anode method:

In this method, the protected metal structure is converted into a cathode by connecting it
to a more active metal. This active metal acts as an auxillary anode Zn, Mg and Al are the
common auxillary anodes and are more reactive undergo corrosion, protecting the metal
structure. Since the anodic metals are sacrificed to protect the metal structure, the method is
known as sacrificial anode method. Exhausted sacrificial anodes are replaced by new ones as and
when required.
Eg.;1. A magnesium block connected to a burried oil storage tank
1. Mg bars are fixed to the sides of ocean going ships to act as sacrificial anodes.
2. Mg blocks are connected to buried pipe lines.

Anodic Reaction : Mg → Mg2+ + 2e

Cathodic Reaction : ½ O2 + H2O + 2e →2OH-

Mg
Under
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steel Pipe line
tank
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Mg Mg

Corrosion Penetration Rate (CPR)

The Corrosion penetration rate is the speed at which any metal or alloy deteriorates in a specific
corrosive environment through chemical or electrochemical reactions. It is also defined as the
amount of weight loss per year in the thickness of metal or alloy due to corrosion. The Corrosion
penetration rate also referred as corrosion rate.
Corrosion penetration rate depends on following factors;
1. Nature of metal.
2. Nature of corrosive environment/medium.
3. Nature corrosion product.
4. Speed at which corrosion spreads in the inner portion of metal.
The Corrosion penetration rate is calculated using the following formula;

CPR =

Where,
W is weight loss after exposure time.
T is exposure time in corrosive medium.
D is the density of metal or alloy.
A is surface area of exposed specimen.
K is constant.
Numerical Problem on CPR:
1. A thick steel sheet of area 400 cm2 is exposed to air near the ocean. After one-year period
it was found to experience a weight loss 375 g due to corrosion. If the density of the brass
is 7.9 g/cm2 calculate the corrosion penetrating rate in mpy and mmpy (given K= 534 in
mpy and 87.6 in mmpy).
To calculate CPR in mmpy:

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Given CPR in mmpy

K 534 87.6

W (wt loss) 375 g 375 x 1000 mg

ρ 7.9 g/ cm3 7.9 g/ cm3

A 400 cm 2 400 cm 2
t 1 year 1 x 365 x 24 hrs

CPR =

CPR =1.186 mmpy

To calculate CPR in mpy :

Given CPR in mpy

K 534

W (wt loss) 375 g 375 x 1000 mg

Ρ 7.9 g/ cm3 7.9 g/ cm3

A 400 cm2 400 X 0.155 inch2

T 1 year 1 x 365 x 24 hrs

(1 cm2 = 0.155 inch2)

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CPR =

CPR = 46.67 mpy

2) Calculate the CPR in both mpy and mmpy for a thick steel sheet of area 100 inch2 which
experiences a weight loss of 485g after one year. (Density of steel=7.9g/cm3).
To calculate CPR in mmpy :

Given CPR in mmpy

K 534 87.6

W (wt loss) 485 g 485 x 1000 mg

ρ 7.9 g/ cm3 7.9 g/ cm3

A 100 inch 2 100 X 6.45 cm 2

t 1 year 1 x 365 x 24 hrs

1inch2=6.45cm2

= 87.6 X 485 X 1000

7.9 x 100 x 6.45 x 365 x 24
=
= 0.9518 mmpy

To calculate CPR in mpy :

Given CPR in mpy

K 534 534

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W (wt loss) 485 g 485 x 1000 mg

ρ 7.9 g/ cm3 7.9 g/ cm3

A 100 inch 2 100 inch 2

t 1 year 1 x 365 x 24 hrs

534 X 485 X 1000

7.9 x 100 x 365 x 24
= 37.424 mpy

E waste Management
All electronics and electrical items which is discarded on completion of their useful life
together is called as E-waste.

Sources of E-Waste:
1. Computer peripherals: monitor, keyboard, mouse, motherboard, laptops, CDs etc
2. Telecommunication device: phones, cell phones, routers, pagers, fax machine etc.
3. Household appliances: washing machines, vacuum cleaners, toasters, drying machines,
refrigerators, irons, air conditioners etc.

4. Industrial electronics: sensors, medical device, automobile device etc.

5. Electrical devices: switches, wires, bulbs etc

TYPES OF ELECTRONIC WASTE

 Fridges, freezers and other cooling equipment.

 Computers and telecommunications equipment.
 Consumer electronic devices and solar panels.
 TVs, monitors and screens.
 LED bulbs.
 Vending machines.

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Effects of e-waste on environment and human health

• Improper handling and processing of e-waste may lead to entry of toxicants in

human food chain as well as the environment by contamination of water, air
and soil E-waste is rich in toxic metals, polyaromatic hydrocarbons (PAH),
PCBs, polybrominated diphenyl ethers (PBDEs) and some other pollutants
like polyvinyl chloride phthalates

• Several studies have been done on the effects of e-waste contaminants such as
metals (Cd, Pb, Cr, Be, Hg), organic pollutants (PAH, PCB etc.) on soil
enzymatic activity, soil community and altering physical and chemical
properties of soil.
• A number of studies have found that children contain significantly higher
concentration Pb and Cd resulting in lower cognitive skills and also results in
respiratory problem.

• Metals like antimony, arsenic, chromium, cadmium, etc. may cause harmful
effects on humans when they enter in the body via several means. These
metals accumulate in the plants and then in animals and humans through the
food chain. When comes in contact with humans for example lead (Pb)
adversely affects behaviour and learning capabilities.

• The metals such as Fe, Ni, Cr, As, Zn, Pb, and Cd etc. These aberrations are
indicative of the fact that leachates of e-waste are capable of inducing somatic
mutation and cytotoxicity.

Methods of E-waste Disposal:

 Landfilling. This refers to the practice of essentially digging a massive hole in the
ground, filling it with waste and then covering it back up with soil. While the pits are
lined with clay or plastic with a leachate basin to prevent toxic waste from leeching into
the surrounding environment, some substances such as cadmium, lead, and mercury
inevitably finds their way into the soil and groundwater, causing contamination.

 Acid Bath: Soaking electronic circuits in powerful sulphuric, hydrochloric, or nitric acid
solutions separates metals from the electronic pathways. The metals can then be recycled
and used in the manufacture of new products. However, the highly hazardous acid waste
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needs to be very carefully disposed of to prevent it from finding its way into local water
sources – essentially trading one waste disposal problem for another.

 Incineration: A very crude e-waste disposal method that involves burning the waste in an
extremely high temperature incinerator. This has the twin benefit of significantly
reducing the waste volume and generating energy that can be repurposed for other
applications. Unfortunately, the process of burning the components which make up
electronic waste also produces vast quantities of toxic gasses – including cadmium and
mercury – which are released into the atmosphere.

 Recycling: Many items of e-waste can be dismantled and their component parts
repurposed into new products. E-waste recycling techniques can recover precious metals
from circuit boards and be melted down to make new devices or used for other products
such as jewellery.

 Reuse: By far, the most environmentally friendly e-waste disposal technique is for, where
possible, devices to be reused. Many charities will gladly accept old electronic devices
that can then be refurbished and redistributed to people in more disadvantaged
communities.
Advantages of recycling

 E-waste recycling and management E-waste recycling is the developing, assembly,

buying or promoting new electronic products which are prepared from waste materials.
 E-waste recycling has multiple benefits a. Retrieving valuable materials from
electronics.
 Helps in avoiding pollution.
 Provides a shot in the arm to employment generation E-waste recycling is quintessential
because it helps in ameliorating a big threat dangling over vital natural resources.
 The deposit to be made should be sufficient to cover the recycling and transportation
cost of the product.
 Present research activities for recovering precious and base metals from waste printed
circuit boards are eyeing on Hydrometallurgical techniques
 Therefore, hydrometallurgical techniques are more comprehensive than conventional
means Step wise processes in e-waste recycling.

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 The main part of the recycling process is dismantling, that is, elimination of different
parts of e-waste that are the source of hazardous pollutants such as PCB, Hg, separation
of plastic that contains PVC, removal of CRT and separation of valuable metals like
copper, lead, silver and gold from the waste.
EXTRACTION OF GOLD FROM E-WASTE

Gold metal has good electric conductivity and chemical stability and hence it is used for
making integrated circuits of electronic devices, coating for contacts and connectors. E-wase
contains 10 times more excessive concentration of gold compared to gold ores. Among the E
waste PCBs are rich in metals. It contains around 35% of Cu, 0.16% Ag, and 0.13% gold by
weight. Several methods are pyrometallurgy, hydrometallurgy, biometallurgy, microwave
treatment etc are employed to recover precious, metals from E-waste. Among these, recovery
of metals hydrometallurgy is more economical.

Hydrometallurgy method of Extraction of gold from E waste

There are 3 stages in metal recovery by hydrometallurgy method\
1. Pretreatment stage
2. Chemical treatment stage
3. Metal recovery stage
Pretreatment stage
In the pretreatment step, e waste is manually dismantled to separate various fractions like
metals, ceramics, plastics, papers and wood. The technique such as gravity separation,
electrostatic separation, magnetic separation and eddy current separation are used to separate
metals from other fractions.
Chemical treatment stage
In this method metals are leached into solutions by treating with appropriate chemical
reagents. Several leaching agents such as thiosulfate, alkaline cyanide, and many acids such
as hydrochloric acid, sulphuric acid and nitric acids can be used to leach gold into solution.
Cyanide leaching is the most common method used to extract gold metals. Sodium salt of 3-
nitrobenzene sulphonic acid with KCN in the presence of oxygen used as leaching agent. A
water soluble dicyanoaurate gold complex is obtained in the process
4 Au + 8CN- + O2 + 2H2O 4 Au (CN)2 - + 4 (OH) -

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Metal recovery stage

In the last step metal is recovered from leach solution. Varieties of methods like electro
deposition, solvent extraction, ion exchange, adsorption, precipitation and cementation are
used to recover metals from leached solution. In electro deposition method, gold is extracted
by electro deposition of gold from dicyanoaurate gold complex. Pure gold metal is taken as
cathode and inert metal is used as anode is dipped leached solution. When current is applied
gold is electrodeposited on cathode.

Extraction of copper from e-waste.

The method involves the following steps
• Separation of copper by solvent extraction.
• The selective recovery of copper from the stage-1 leach solution was undertaken using a
previously established solvent extraction process with the salicylaldoxime in kerosene.

• As copper recovery is dependent on the initial pH of the solution, the effect of pH of the
nitric acid leach solution was studied between pH 1 and 3.5.

• It was found that the percentage extraction of copper into kerosene increases from 70 to
77% over pH 1–2.5, and then decreases from 77 to 54% over pH 2.5–3.5, leading to
maximum extraction in the pH range 2–2.5

• Other metals such as nickel were poorly extracted at these acidities, e.g. 1.2% at pH 2.5.
• Varying the concentration of kerosene from 10 vol% to 30 vol% increases copper
extraction from 50 to 99%. The organic to aqueous (o/a) phase ratios were maintained at
2:1.

• This results in a purified strip solution comprising 99.9% of the total copper content,
along with minor impurities of zinc (0.05%) and lead (0.02%).

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