CAT 1

Water Technology: Hard and soft water, Units of Hardness (numerical

problems). Disadvantages of hard water: Scale and sludge, caustic
embrittlement, priming and foaming,corrosion. Estimation of hardness:
EDTA, alkali titration method (numerical problems). Softening methods:
Lime soda (numerical problems), zeolite, ion exchange,
mixed bed deionizer, treatment of municipal water. Desalination:
Desalination of sea water, brakish water, electrodialysis, reverse osmosis.

Corrosion:
Dry Corrosion – Oxidation, corrosion by other gases,
Liquid metal corrosion
Wet Corrosion: Hydrogen evolution corrosion, Oxygen absorption corrosion
Galvanic Corrosion, Concentration Corrosion
 Corrosion
Corrosion is a process of deterioration (destructive) and
unintentional degradation of a material (loss of solid material)
caused by its environment (chemical or elctrochemical)

Corrosion is a process “reverse extraction of metals”

Reversion of base metal to its oxide form

Base metal is unstable with respect to oxidation

Metallurgial
Iron Ore Operation
Iron Metal
Corrosion

Rust
 Theories of Corrosion and Mechanism of Corrosion

1. Chemical or Dry corrosion

This type of corrosion occurs mainly through the direct chemical action
of environmental or atmospheric gases such as oxygen, halogen,
H2S, SO2, N2 and anhydrous inorganic liquid with metal surfaces in
immediate proximity

2. Electrochemical or Wet corrosion

This type corrosion occurs

i) where conducting liquid in contact with metal

ii) when two dissimillar metal or alloy are either immersed or

dipped partially in a solution
 Chemical or Dry corrosion

1. Oxidation Corrosion
2. Corrosion by other gases
3. Liquid Metal corrosion
 Oxidation Corrosion

Dry corrosion or oxidation occurs when oxygen in the air reacts

with metal without the presence of a liquid.

Oxygen present in atmosphere attacks metal surface resulting

in the formation metallic oxide which is corrosion product and this is
known as oxidation corrosion

The basic reaction involved in dry corrosion is:

M M2+ + 2e-

1/2O2 + 2e- O2-

1/2O2 + M M2+ + O2- (MO)

 Oxidation corrosion Mechanism

Oxidation first occurs at the surface of the metal resulting the formation of M2+.
Oxygen changes to its ionic form (O2-) and reacts with metal ion to form
metallic oxide. This form as a film or scale on surface of the metal.
Layer is called film when thickness is <300A and layer exceeds this thickness called
scale

Nature of the film decides further action

Corrosion stops if the metallic oxide film produced is barrier for oxygen to penetrate
for further oxidation

On the other hand, if the oxide film is porous or volatile, further corrosion occurs by
the diffusion or direct contact of oxygen in its ionic form with metal ion to produce
additional oxide film
 Metallic oxide film
Film can be 1. Stable 2. Unsatble 3. Porous 4. Volatile

Stable: Film is fine-grain of oxide which forms a compact surface adhered

tightly to the metal surface. Oxides of Al, Sn, Cu, are this type.
Oxide layer produced on the surface of this metal are impervious in nature and
Stops oxygen to attack through diffusion

Unstable: This type oxide layer are mainly produced on the surface of the noble
metals which decomposes reversibly to the metal and the oxide is liberated in the
form of oxygen
Eg. Oxides of platinum, silver
Porous : This type oxides have minute pores. Hence oxygen can diffuse towards
fresh metal present under the oxide film to continue the corrosion
Metal like Fe fall under this category

Volatile: Volatile oxides layer volatize as soon as they are formed theory by leading
Further corrosion directly
Oxides of Mo belongs to this type
 Pilling-Bedworth Rule

This rule sates that:

Oxide layer is compact, non-porous as well as protective if the volume of metallic

oxide is equal to or greater in volume to metal surface preventing corrosion.
Metals like Al forms forms oxide whose volume is greater than the volume of the
metal. Film : Non-porous: rate of oxidation rapidly decreases to zero

On the other hand volume of the metallic oxide is less than the volume of metal,
then the oxide file is porous and hence film is non protective. Because it can not
block oxygen diffuse towards fresh metal surface

Alkali metals like Li, K, Na, the alkaline earth metals like Mg, and metals like Fe
Produce oxide films whose volume is less than the volume of metal. As a result,
Oxygen can diffuse through the pores of the film and corrosion is continuous process
 Corrosion by other Gases

Corrosive effect depends on the chemical affinity between gases and metal and the
gas involved

Degree of attack depends upon the formation protective or non protective film on the
surface of the metal

If the film is non-porous and protective, attack by gas is less

Eg. AgCl film is from Cl2 attack on Ag metal

If the film is porous and non protective, surface of the whole metal will be destroyed
Eg. Dry Cl2 gas attack on Sn metal
 Hydrogen Corrosion or Hydrogen
Embrittlement
Dry corrosion attack by hydrogen gas on metal is known as
Hydrogen Embrittlement.

This is due to the the formation of atomic hydrogen as a result of chemical or

electrochemical reaction occuring at the metal surface under a specific environment

For ex. Aqueous solution of H2S in the diffused caused evolution of atomic hydrogen
at the Iron surfaces

Evolved atomic hydrogen readily in to the metal and collects in the voids where it
recombines to give molecular hydrogen. This increases the pressure of hydrogen in
VOIDS and produces blisters and fissures.

This causes lowering of strength and ductility of the metal . The corrosion attack by
atomic hydrogen is also possible at high temperature under specific environment
H 2S + Fe F eS + 2H

H2 + H H2
H eat
H2 H + H
 Liquid Metal Corrosion

Liquid metal corrosion is due to chemical action of flowing liquid metal at high
temperature on solid metal or alloy

This type corrosion occurs in devices used in nuclear power

This type corrosion involves either

i) Dissolution of solid metal in liquid metal
ii) or internal penetration of liquid metal into the solid metal

Both of these are weakening the solid metal

 Theories of Corrosion and Mechanism of Corrosion

2. Electrochemical or Wet corrosion

This type corrosion occurs

i) where conducting liquid in contact with metal

ii) when two dissimillar metal or alloy are either immersed or

dipped partially in a solution
 Electrochemical Corrosion

This occurs due do the existence of separate anode and cathode area
or parts, between which current flows through the conducting solution

At anode oxidation takes place (loosing electron), Hence anode metal

destroyed by either dissolving in conducting solution or forming
combined oxide film
 Electrochemical Corrosion
At anode oxidation takes place (loosing electron), Hence anode metal
destroyed by either dissolving in conducting solution or forming
combined oxide film

Metal Mn+ + ne-

Mn+ Dissolves in solution

MO (Metal oxide)
 Electrochemical Corrosion
At Cathode reduction takes place (gaining electron). Cathode metal is
already reduced form. It can not be further reduced,
Hence dissolved constituents in the conducting medium accepts the
electron at cathodic site to form some ions like OH- and O2-
Metalic Ions an anodic part and non metalic ions at cathodic part
diffuse towards each other through conducting medium to forma
corrosion product some where between anode and cathode
Anode
Metal Mn+ + ne-
ne-
Flows towards cathode

Cathode

Medium
½ O2 + H2O+ ne- n OH-
 Electrochemical Corrosion
This involves

1. Formation of anodic and cathodic part and in contac

with each other
2. The presence of conducting medium

3. Corrosion of anodic area only

4. Corrosion product somewhere between anodic

and cathodic areas
 Electrochemical Corrosion
At anode oxidation takes place (loosing electron), Hence anode
metal destroyed by either dissolving in conducting solution
or forming combined oxide film
At Cathode site electrons are consumed by dissolved
constituents in the conducting medium.
Electron consumption at cathodic site takes place either by

a) Evolution of hydrogen or

a) Absorption of Oxygen depending on the nature of the

corrosion environment
 Evolution of hydrogen type corrosion
This type corrosion occurs usually in acidic(H+) environment

Consider metal like Iron (Fe), at anodic reaction is dissolution of iron

as ferrous ions with liberation of two electrons

Fe Fe2+ + 2e-
These electrons flow through the metal from anode to cathode
where H+ ions (of acidic solution) are eliminated as hydrogen gas.

2H+ + 2e- H2
Fe + 2H+ Fe2+ +H2
 Evolution of hydrogen type corrosion

This type corrosion causes displacement of hydrogen ions from the acid
solution by metal ions
All metals above hydrogen electrochemical series have a tendency to
get dissolved in acid solution with evolution of hydrogen gas
Anodes are very large areas where as cathodes are small area
 Absorption of Oxygen type corrosion
Rusting if Iron in neutral aqueous solution of electrolytes like NaCl
solution in the presence of atmospheric Oxygen is a common example
of this type of corrosion

Surface of Iron is usually coated with at thin film of Iron Oxide.

However if this thin film develops some cracks, Anode areas are
created on the surface, while rest of the metal part acts as cathode.
Small area of anode and large area of cathode are created

At anode Iron dissolves as Ferrous ion with liberation of electrons

F Fe2+ + 2e-
e
Liberated electron flows from anode to cathode through iron metal ,
where
Electrons are intercepted by dissolved oxygen as
½ O2 + H2O+ 2e- 2 OH-
 Absorption of Oxygen type corrosion

Fe2+ ions at anode and OH- ions at cathode diffuse and when they meet
Ferrous hydroxide is precipitated

Fe2+ + 2OH- Fe(OH)2

If enough O2 is present, Fe(OH)2 is easily oxidized to give Fe(OH)3

4 Fe(OH)2 + 2H2O + O2 4 Fe(OH)3

This product is called yellow Rust Fe2O3.H2O

If the supply of oxygen is limited, corrosion product may be

even black anhydrous magnetite Fe3O4
Fe2+ forms at anode and OH- forms at cathode; Combination takes place nea
Cathode: Smaller Fe2+ diffuse faster than larger OH- .
Corrosion occurs at anode but rust deposited at or near the cathode
 Absorption of Oxygen type corrosion

Increase in oxygen content

Forces that cathodic reactions to produce more OH-

It removes more electron at anode and accelerates the corrosion at the
anode

Both of the above effect produce more reactants for rust formation

Hence Presence of Oxygen in more,

Accelerates corrosion and rust formation
 Galvanic (or Bi-metallic) corrosion
When two dissimilar metals (Zn and Cu) are electrically connected and
exposed to an electrolyte, the metal higher electrochemical series (more
negative electrode potential) undergoes corrosion
This type is Galvanic corrosion.

Zn is in higher electrochemical series where as Copper is on lower in

electrochemical series

Hence Zn forms anode and is attacked and gets dissolved

Cu acts as cathode

In acidic solutions, corrosion occurs by the hydrogen evolution type

While neutral or slightly alkaline solution, oxygen absorption occurs

Electron current flows from the anodic metal Zinc to the cathodic metal
Copper
Corrosion occurs at anode while cathodic
2+ part- is protected from the attack
Zn Zn +2e
Copper fitting on steel pipe carrying water:
Galvanic Corrosion

Copper fitting on steel pipe carrying water:

Steel pipe acts as anode, Copper acts as cathode.
Pipe is direct contact with fittings and
water is conducting electrolyte for ion migration
 Galvanic Corrosion

1. Steel crews in a brass marine hardware

2. Lead-antimony solder around copper wire
3. A steel propeller shaft in bronze bearing
4. Steel pipe connected to copper plumbing

This type corrosion can be avoided by

1. coupling metal close to the electrochemical or Galvanic series

2. Insulating material between two metals can be fixed
3. Making cathode metal smaller and anode metal larger in area
 Galvanic Series vs Electrochemical series

Lithium

Titanium

Li Li+ + e- - 3.05
Galvanic Series Electrochemical series
Galvanic Series vs Electrochemical series
In the electrochemical series (reduction electrode potential
arranged down in an decreasing order), a metal low in the
series (more negative value) is more anodic and undergoes
faster corrosion

Li corrodes faster than Mg

Zn corrodes faster than Fe
Fe corrodes faster than Sn
Cu corrodes faster than Ag
However there are exceptions to this
Ti is less reactive than Ag
Zn-Al couple, Zn is corroded
This is because, Ti and Al form strong adhering oxide layer
on their surface
It is clear that electrochemical series does not account for
all metals and alloys
 Galvanic Series vs Electrochemical series

Hence more practical series called Galvanic series have been

prepared by studying the corrosion of metals and alloys in a given
environment like sea-water

Galvanic series give real and useful information for studying the
corrosion of metals and alloys
Concentration Cell Corrosion