Corrosion Mechanisms

and
Prevention
Introduction to Water Chemistry
y
 Atomic Structure

10 P Valence Shell

ƒ All atoms have the same number of electrons as protons

ƒ Protons are positively charged and are contained in the nucleus
ƒ Electrons orbit around the nucleus at very high speeds
ƒ The outermost orbital of an atom is called the “Valence Shell”
ƒ Most atoms like to ha
have e 2 electrons in the innermost orbital and
require 8 electrons in their outermost orbital to be stable
 Compounds
p

ƒ Compounds are atoms that have bonded to

form a molecule

ƒ There are two types of compounds:

1 Covalent Compounds
1.

2. Ionic Compounds
 Covalent Bonds

ƒ Two or more non-metallic

non metallic elements share each other’s
other s
electrons

ƒ This happens because each of the atoms do not have

enough electrons in their valence shell
 Covalent Bonds

1P

8P

1P

Example : An oxygen atom has 8 proton and 8 electrons. It

h 2 electrons
has l t iin th
the fifirstt orbital
bit l and
d only
l 6 iin th
the outer
t
orbital.
It bonds with 2 hydrogens which have 1 electron each to
fulfill its requirement of 8 electrons in the outer orbital. This is
how H2O is formed.
 The Properties of Water
Polar Covalent Bond

Hδ+
Οδ¯

Hδ+

ƒ When Oxygen and two hydrogen atoms share electrons to form

H2O the electrons are more attracted to the larger Ο atom than
H2O,
they are to the smaller H atoms. For this reason, they spend most
of their time orbiting the Ο atoms and less time around the H atom.
ƒ As a result, the Ο atom in water has a PARTIAL NEGATIVE charge,
and the H atoms each have a PARTIAL POSITIVE charge.
 Ionic Bond

Na+ Cl ¯
11 P 17 P

ƒ Ionic bonds involve at least one metal and one non-metal

ƒ The
Th metalt l ion
i has
h more protons
t than
th electrons
l t so it is
i positively
iti l charged
h d
(Cation: Ca++, K+, Ba++, Fe++).
ƒ The non-metal atom will have more electrons that protons so it is negatively
charged (Anion: F¯
F , Cl
Cl¯)).
ƒ The non-metal anions can also be compounds (OH¯, HCO3¯, CO3¯ ¯, SO4 ¯ ¯)
 Ionic Bond

Na+ Cl¯

+ –

ƒ The charged ions are attracted to each other like magnets

due to these electrostatic charges
 The Properties of Water
Dissolution of Salts
Ο δ¯ Ο δ¯
Ο δ¯

Ο δ¯ Na+ Cl ¯ Ο δ¯

Ο δ¯

ƒ The partial negative charge of the oxygen atom in the H2O

molecule is attracted to the positively
Οδ¯ chargedΟsodium
δ¯

Š The partial positive charge of the Hydrogen in the H2O molecule

is attracted to the chloride.
Š This is known as dissociation of the ions.
Corrosion Mechanisms
 Corrosion

• Metal exposed to aerated water is oxidized

• Oxidation is defined as a loss of electrons
and can only occur in the presence of an
electron acceptor known as the “oxidizer”
• The most well known oxidizer is oxygen.
 Anodic Reaction

• When a solid metal is oxidized, it becomes

ionized and dissolves in water.
• The site at which metals dissolve into the
solution becomes the Anode.

Anodic Reaction:

M Æ Mn+ + n e-
where:
M = metal involved
n = valence of the corroding metal species
e = electrons
 Ionization of Solid Metals
by oxidation at Anode

Fe++

Ο
Οδ¯
26 P

ΟΗ¯
Cathodic
Hδ+
Anodic Οδ¯

Hδ+
ΟΗ¯
 Anodic Reaction

• For example, if iron (Fe) was exposed to an

aerated, corrosive water, the anodic reaction
would
ld be:
b
Fe Æ Fe2+ + 2e-
• Ferrous Ions (Fe2+) would dissolve in water
• The electrons would flow to the Cathode
Cathode.
 Dissolution of Ferrous ion in Water

Ο δ¯ Ο δ¯

Ο δ¯ Fe2+
Fe2+

ƒ The partial negative charge of the oxygen atom in the H2O

molecule is attracted
Οδ¯ to the positively charged ferrous ions
Š This is known as dissolution ofδions
ions.
Ο ¯
 Anodic Reaction

Aerated Water
O2
O2 O2 O2 O2

O2

O2 O2

O2 O2
O2 O2

- Cathode - + Anode + - Cathode -

e- - Fe2+ - e-
ee-Fe2+
- e- -
Fe2+
e e2+
Fe2+ Fe e
Fe2+ e-
e e-
-
2+- Fee-
2+
Fee
e- Fe2+ e2+
-
e- Fee- -
e

Fe Æ Fe2+ + 2 e-
 Cathodic Reaction
• Hydrogen evolution (acids):
2 H+ + 2 e- Æ H2
• Oxygen reduction (acids):
½ O2 + 2H+ + 2 e- Æ H2O
• Oxygen reduction (neutral or base):
½ O2 + H2O + 2 e- Æ 2 OH-

Note:: More than one oxidation and more than one

Note
reduction reaction can occur during corrosion
 Cathodic Reaction

• At the cathode, reduction of oxygen

would occur:
½ O2 + H2O + 2e- Æ 2(OH)-
• Reduction is defined as the acceptance
of electrons by an oxidizer.
• In this case, oxygen accepts the
electrons
e ect o s lost
ost by tthe
e iron.
o
 Reduction of Oxygen at Cathode

Fe++

Οδ¯
Ο
26 P

ΟΗ¯
Cathodic
Hδ+
Anodic
Οδ¯

Hδ+
ΟΗ¯
 Corrosion
Electrochemical Cell
O2 Aerated Water
O2
O2 O2
O2
O2 O2 O2

O2 O2
O2
O2

δ+
Hδ+ δ+
δ+δ+
HH Hδ+ Hδ+ Hδ+ Hδ+ HHδ+δ+Hδ+ HHδ+δ+ Hδ+ Hδ+ Hδ+ H
H
H
δ+
δ+
Hδ+
δ+ H
Hδ+
H δ+
δ+

+ Anode +
OH
OH
OH - - OH
OHOH --OH
-- -
O
OOHO
OH
22 2O O
O222
-- -
OOO22OH
2 OO 2 OOH
δ- -O OH
δ-
2
--
O2OHO
- δ-
O2OH
OO2OH
- δ-- - δ-
OH
2O O Oδ-OOH 2
-- δ- OH
OH-O - -
OH O2OHO 2
O
- δ- O OH
OH
δ-
δ-
Oδ- ---
2 O O222
e- - Fe2+ e-- e-
ee-
-
- Cathode - Fe2+
e Fe
e-e-
Fe
2+ 2+ e2+ e-
Fe Fe2+
e
2+- Fe2+
- - Cathode -
Fee e-
e -
- Fe 2+
Fee2+
-
e e-
e-

2Fe0 Æ 2Fe2+ + 4e- (anodic)

O2 + 2H2O + 4e- Æ 4(OH)- (cathodic)
 Corrosion
Electrochemical Cell
• The anodic and cathodic reactions would be:
2Fe0 Æ 2Fe2+ + 4e- (anodic - oxidation)
O2 + 2H2O + 4e 4 - Æ 4(OH)- (cathodic
( th di - reduction)
d ti )
--------------------------------------------------
2Fe + O2 + 2H2O Æ 2Fe2+ 2 + 4(OH)
( )-

• At the cathodic site

site, pH at the steel surface can be
as high as 10 – 11.
Precipitates:
• Fe2+ + 2OH- Æ Fe(OH)2 (Ferrous Hydroxide)
 Oxidation of Dissolved Iron

• Ferrous ions (Fe2+) are oxidized to less soluble

Ferric Ions (Fe3+) in the presence of oxygen

4Fe2+ Æ 4Fe3+ + 4e-

O2 + 2H2O + 4e- Æ 4(OH)-
-----------------------------------------------
4Fe2+ + O2 + 2H2O Æ 4Fe3+ + 4(OH)-

Precipitates:
Fe3+ + 3OH Æ Fe(OH)3 Ferric Hydroxide
 Oxidation of Dissolved Iron
OH- O2
Fe3+
OH- OH- O2
OH- O2
O2 Fe3+
OH- O2 O2
Fe3+ OH-

OH-
OH- -
OH OH Fe3+
- A
Aerated
t d Water
W t O2
OH-
Fe3+
O2 OH- OH- - 3+ OH- O2
OH- Fe
OH
OH- OH- OH- OH-
O2 Fe3+ OH-
Fe Fe
3+ 3+ OH -
OH- O2
OH- OH- FeOH
3+ -
O2 OH- OH-
O2
O2 OH- O2
OH-
O2 O2
O2 O2

O2
O2

O2
O2
O2 O2
O2
O2
O2
O2
O2
Hδ+ HH H
δ+δ+δ+ δ+ δ+δ+ δ+
H HH H Hδ+ Hδ+ Hδ+Hδ+ Hδ+Hδ+ HHδ+δ+ Hδ+HHδ+δ+ Hδ+
OH - O-2δ-δ-
- - δ-
OOH
OH - - - - - OH- - -δ-- - OH- -OH --
OO
O OH
OH
OO2OOH OO OHOH
O22OOH OH O OHOHO
OH OH OH
OH O- δ-
O OH
2 2 OO2 2O2 O
- -OH
OHO2OH
OH - - OH
- O
OOH
- δ-
OH -OH
OH - δ-- -
2O2 OO2
δ-
222 O 22O2O δ-
2 OO2 2 2 O O 22 O22O 2O
δ-

ee
- -
e-2+- e- - 2+ e- - Fe 3+ ee
--
eFe
Fe- 2+
3+
e Fe
- Fe
Fe2+ e
3+Fe
Fe 3+ e Fe
Fe Fe
3+ 2+ e Fe2+
Fe2+
3+ Fe3+ 2+
ee- - Fe
Fe2+
3+ e-
Fe 3+
- Fee-
Fe
Fe ee
2+
3+
-
e-e-
Formation of Passive Layer at Cathode
Fe2+ + 2OH- Æ Fe(OH)2 (Ferrous Hydroxide)
( )2((s)) + O2(g) Æ 4H2O(l)
6Fe(OH) ( ) + 2Fe3O4.H2O(s)
( )
Green Hydrated Magnetite
Fe3O4.H2O Æ H2O + Fe3O4 Black Magnetite
g (passive
(p layer)
y )
4Fe(OH)2 + O2 + 2H2O Æ 4Fe(OH)3 (Ferric Hydroxide)
Fe(OH)3 Æ FeO(OH).
FeO(OH) H2O Æ FeO(OH) + H2O
2FeO(OH) Æ Fe2O3.H2O Hydrated Ferric Oxide
( d Brown Rust))
(Red
Fe2O3.H2O Æ Fe2O3+ 2H2O (alpha
(alpha or gamma)
gamma)
Formation of Passive Layer at Cathode

• A strong tenacious protective oxide film is formed

composed of Fe3O4 (magnetite) with an outer
layer composed of α-Fe2O3 and γ- γ-Fe2O3. The
oxide film inhibits diffusion of Fe2+ and O2-
which prevents further corrosion.
• The passive film acts as a barrier to prevent
exposure of steel to oxygen
• Magnetite is also extremely soluble under normal
temperature conditions when pH<9
pH<9.7
7
 Types of Corrosion

• General corrosion
• Galvanic Corrosion
• Concentration Cell Corrosion
• Dealloying
• Erosion Corrosion
• Microbiologically
c ob o og ca y Influenced
ue ced Co
Corrosion
os o
 General Corrosion

• General corrosion is when anodic dissolution

is equally distributed over the entire metallic
surface.
• Microscopic
Mi i anodes
d and
d cathodes
h d are
continuously changing their electrochemical
behavior from anode to cathode cells
resulting in a corrosion rate that is nearly
constant
co sta t at aall locations.
ocat o s
 General Corrosion

Aerated Water
O2
O2 O2 O2 O2

O2

O2 O2

O2 O2
O2 O2

+- Anode
Cathode+- -+Cathode
Anode +- e- - Fe2+
- Cathode
+ Anode- +
e-- e-- 2+ ee-
2 Fe 2 -
F 2+
e- - Fe2+ - -
e- e e- -
Fe2+ e- - Fe2+ e-- e e2+ e Fe
ee-Fe2+
- e- -
e e2+ e-Fe2+ e e e2+ Fe2+
e Fe2+
Fe e -
e-eFe
2+
Fe2+Fe Fe2+ Fe
e-eFe
2+
e-
Fe2+- e- Fe2+ e- - 2+- Fee-
Fee
2+
- Fee
2+- e e- 2+- Fee-
Fee
2+
e-
e-
e-

Fe Æ Fe2+ + 2 e-
General Corrosion
 Galvanic Corrosion

• Galvanic corrosion occurs when two different

metals are in contact and exposed to a corrosive
environment.
• The more “noble” metal is the one that is less
susceptible to oxidation in a given environment
and will attract the electrons of the other metal.
• The less noble metal will become the anode and
will suffer from accelerated attack while the
more noble metal (cathode) is protected.
 Galvanic Series in Seawater at 25 °C (77 °F)
Corroded End • Magnesium
(anodic, or least noble) • Magnesium alloys
• Zinc
• Galvanized steel or galvanized wrought iron
• Aluminum alloys
• Mild steel
• Wrought iron
• Cast iron
• Ni-Resist
Ni Resist (high
(high-nickel
nickel cast iron)
• Lead
• Tin
• Copper alloy (yellow brass, 65% Cu)
• Copper alloys (admiralty brass)
• Copper C11000 (ETP copper)
• Copper alloys (silicon bronze)
• Copper alloy (copper nickel, 30% Ni)
• Type 304 stainless steel (passive)
• Type 316 stainless steel (passive)
• Type 904 L stainless steel
• Duplex 2205 stainless steel
• Silver
• Titanium
Protected End • Gold
(Cathodic, or more noble) • Platinum
 Galvanic Corrosion
• Example: Zinc will corrode when connected to iron.
• The zinc is less noble and will oxidize more easilyy
than the iron
• Thee eelectrons
ect o s will flow
o to tthe
e iron
o making
a g itt tthe
e
cathode.
Zn Æ Zn2+ + 2e- (Anodic reaction)
½ O2 + H2O + 2e- Æ 2(OH)- (Cathodic reaction)
• The
Th formation
f i off hydroxides
h d id increases
i the
h pH
H at
the surface where the iron is in contact with water
forming a less corrosive environment – this is
known as “cathodic protection”.
 Galvanic Corrosion

O2 Aerated Water
O2
O2 O2
O2
O2 O2 O2

O2 O2
O2
O2

+ Anode +
Zinc
δ+
Hδ+ HH δ+
δ+δ+
Hδ+ Hδ+ Hδ+ Hδ+ HHδ+δ+Hδ+ HHδ+δ+ Hδ+ Hδ+ Hδ+ H
H
H
δ+
δ+
Hδ+
δ+ H
Hδ+
H δ+
δ+

OH
OH
OH - - OH
OHOH --OH
-- -
O
OOHO
OH
22 2O O
O222
-- -
OOO22OH
2 OO 2 OOH
δ- -O OH
δ-
2
--
O2OHO - δ-
O2OH
OO2OH
- δ-- - δ-
OH
2O O Oδ-OOH 2
-- δ- OH
OH-O - -
OH O2OHO 2
O
- δ- O OH
OH
δ-
δ-
Oδ- ---
2 O O222
e- - Zn2+ e-- e-
ee-
-
- Cathode - Zn2+
e Zn
e-e-
Zn
2+ 2+ e2+ e-
Zn Zn2+
e
2+- Zn2+
- - Cathode -
Zne e-
e -- Zn 2+
Zne2+-
-

Steel e e
e- Steel

Zn0 Æ Zn2+ + 2e- (anodic - zinc)

½ O2 + H2O + 2e- ↔ 2(OH)- (cathodic - steel)

 Galvanic Corrosion
• Differences in composition or surface condition
of similar metals can result in galvanic corrosion
cells.
• New pipeline installed in a repaired section will
corrode more rapidly than the old pipe to which
it is connected.
• The old pipe will have a protective rust layer
that will make the iron in the new steel easier to
oxidize by comparison
comparison.
• The new pipe will become the anode and will
suffer an accelerated loss in mass
mass.
 Concentration Cell Corrosion

• Concentration
Concentration--cell corrosion occurs because
of differences in the environment surrounding
the metal.
• This
Thi form
f off corrosion
i commonly
l occurs in
i
localized areas where small volumes of
stagnant solution exist.
exist
• Normal mechanical construction can create
crevices
i att sharp
h corners, spott welds,
ld joints,
j i t
fasteners, flanged fittings, couplings,
threaded joints,
joints etc
etc…
 Concentration Cell Corrosion
O2 O2
O2
Aerated Water
O2
O2
O2 O2
O2
O2
O2 O2
O2
O2

O2
δ+ δ+ Hδ+
Hδ+ δ+δ+
HH Hδ+ Hδ+
OH
OH-- - OH-- δ- - δ- - -
OH OO22OH
2 O OOH
O22 O OOHOH
2 O2OHO - δ-

e- - 2+ e-
eFe Fe e-2+
e - Fe2+
-
e
e-- 2+
eFe

Oxygen Cell: The metal surface exposed to water

with lower dissolved oxygen will become the anode
(oxidizes and dissolves), while the surface exposed
to higher dissolved oxygen levels will become the
cathode. (Crevice Corrosion)
 Concentration Cell Corrosion

• Higher dissolved oxygen provides a

driving force for cathodic reaction
• Reduction of oxygen would occur:
½ O2 + H2O + 2e- Æ 2(OH)-
• The area with lower dissolved oxygen
will become the anode
F Æ Fe
Fe F 2+ + 2
2e-
 Concentration Cell Corrosion
Pi i
Pitting
• Pittingg occurs in the presence
p of an oxygen
yg cell
only if a break exists on the passive film (such as
a scratch)
• Any area containing stagnant water will consume
oxygen by cathodic reaction as corrosion occurs.
• While the remainder of the surface is continuously
supplied with oxygen rich water, the stagnant area
now contains
t i a very low
l oxygen concentration
t ti
• The dissolved oxygen differential causes the
stagnant
t t area tto b
become th
the anode.
d
 Concentration Cell Corrosion
Pi i
Pitting
• The surroundingg metal surface becomes the cathode,,
and is protected due to the locally increased pH.
O2 + 2H2O + 4e- Æ 4(OH)
( )-
• At the anode, Ferrous ions continue to dissolve into
the water.
Fe Æ Fe2+ + 2e-
• As the dissolved Ferrous ions diffuse towards the
cathodic areas, they are oxidized and form a porous
ferric hydroxide
y p
precipitate
p that covers the pit.
p
4Fe2+ + 10H2O + O2 Æ 4Fe(OH)3(s) + 8H+
 Concentration Cell Corrosion - Pitting
O2 O2
O2 O2
O2

O2
O2 Aerated Water
O2 O2
O2
O2
O2 O2

O2 O2
P
Passive
OH- i Layer
L
OH- OH- OH- OH- OH-
Hδ+ Hδ+ Hδ+ Hδ+
OH- OH- OHOH
-
P OH
Passive
-
i Layer
-
LOH -

- Oδ-OHO
-
OH- OH-
Oδ- Oe2 - e
Fe --
2+ 2
e- Fe
2+
e
OH
- Cathode - +e-Anode
Fe
+ 2+
- Cathode -
e-
Fe2+ e-
e-
eFe- 2+
e-
Fe2+ e-
e-
eFe
-
2+
e-
Fe2+
e--
e
eFe-
2+
e- 2+ e-
Fe
- 2+ e
-
eFe
e 2+ e-
-
Fe
eFe- 2+ e-
eFe- 2+ e-
- 2+ e
-
eFe
e -
Fe2+ e-
-
e

2Fe0 Æ 2Fe2+ + 4e- (anodic - oxidation)

½ O2 + H2O + 2e- Æ 2(OH)- (cathodic - reduction)
 Concentration Cell Corrosion
Pi i
Pitting
• In the ppit,, the ferrous ions hydrolyze
y y to ferrous
hydroxide ions, resulting in the formation of acid
protons:
Fe2+ + 2H2O ↔ Fe(OH)2 + 2H+
• The pH begins to decrease at the anode causing
a higher rate of dissolution of the iron.
• The presence of chlorides in the water
intensifies this effect as hydrochloric acid forms
2Cl- + Fe2+ + 2H2O ↔ 2HCl + Fe(OH)2
 Concentration Cell Corrosion - Pitting
O2 O2
O2 O2
O2

O2
O2 Aerated Water
O2 O2
O2

O2
O2 O2
O2 O2 O2

- Cathode - OH-
- Cathode -
Fe2+
H+ OH-

H+

2+ OH
-
OH
Fe
-

H+ Fe
2+

H+

Fe2+
OH-
Fe2+

OH-

H+
H+
Fe2+

Fe2+ + 2H2O ↔ Fe(OH)2 + 2H+ (anodic – oxidation)

Concentration Cell Corrosion - Pitting
 Dealloying

• Dealloying is a corrosion process in which one

of the elements is preferentially removed from
an alloy.
• The affected area becomes weak
weak, brittle
brittle, and
porous but there is no obvious change in the
size or shape of the component.
• Dealloying occurs in underground cast iron
water mains and can result in breaking of the
pipe when water pressure is suddenly
increased.
 Concentration Cell Corrosion
Dealloying
Aerated Water
O2
O2 O2
O2 O2
O2

O2
O2

O2 O2
O2
O2

O2

C Fe C Fe C Fe C Fe
Fe++ e-
e- C Fe C Fe C Fe C Fe

Fe C Fe C Fe C Fe C Fe
Fe++ e-C Fe C Fe C Fe C
e-

C Fe C Fe C Fe C e-Fe++
Fe C Fe C Fe C Fe C Fe
e-

Fe C Fe C Fe C Fe C Fe
Fe++ e-C Fe C Fe C Fe C
e-
 Erosion Corrosion
• Erosion corrosion refers to the repetitive formation
and destruction of a metal
metal'ss protective surface film.
This typically occurs in a moving liquid.
• The formation of a protective film can be due to the
cathodic process which creates an oxide layer on
the p
pipe
p surface.
• The destruction of the protective film is mechanical
due to high
g velocityy flow of water,, especially
p y if it
contains suspended solids.
• Erosion corrosion often occurs in copper heat
exchanger tubes.
 Erosion-Corrosion Process

O2
Aerated Water
O2
O2 O2

O2
O2
O2

O2

O2
O2 O2
O2

Passive Film

Base Metal
Microbiologically Influenced Corrosion

• Anaerobic bacteria survive best in the absence

of oxygen
• Aerobic bacteria need oxygen to survive
• Anaerobic bacteria can exist in the inner parts
off corrosion
i deposits,
d it while
hil the
th outer
t parts
t are
inhabited by aerobic bacteria.
Microbiologically Influenced Corrosion
Anaerobic Bacteria

• Sulfate Reducing Bacteria (SRB) are anaerobic

bacteria that reduce sulfate to hydrogen sulfide.
SO42- + 8H+ + 8e- Æ S2- + 4H2O
• Symptoms of SRB-
SRB-influenced corrosion are
hydrogen sulfide odor, and black iron sulfide
deposits.
S2- + 2H+ Æ H2S
S2- + Fe2+ Æ FeS
Microbiologically Influenced Corrosion
Aerobic Bacteria

• Certain Aerobic Bacteria can produce

aggressive organic and inorganic acids.
• Acids
A id produced
d d by
b bacteria
b t i accelerate
l t
corrosion by dissolving oxides (the passive
film) from the metal surface
• Acids also consume the OH- ions which
accelerates the rate of the cathodic reaction
(Le Chatelier’s Principle).
 Biogenic Sulfuric Acid Attack
• H2S produced by anaerobic bacteria is oxidized
byy oxygen
yg to form elemental sulfur.
2H2S + O2 Æ 2S0 + 2H2O
• Sulfur adheres to the inner surface of the pipe
pipe,
where it becomes available as a substrate for
the sulfur oxidizing bacteria Thiobacillus
thiooxidans.
• The sulfur is oxidized by the aerobic bacteria
into sulfuric acid causing corrosion of steel and
cement p piping.
p g
S0 + H2O + 3/2 O2 Æ H2SO4
Microbiologically Influenced Corrosion
Aerobic Bacteria

• Iron
Iron--oxidizing bacteria are aerobic bacteria
which oxidize ferrous ions to less soluble ferric
ions.
ions.
Fe2+ Æ Fe3+ + e-
• The resulting ferric ions precipitate as ferric
hydroxides forming tubercules in the pipes.
 Oxidation of Dissolved Iron
OH- O2
Fe3+
OH- OH- O2
OH- O2
O2 Fe3+
OH- O2 O2
Fe3+ OH-

OH-
OH- -
OH OH Fe3+
- A
Aerated
t d Water
W t O2
OH-
Fe3+
O2 OH- OH- - 3+ OH- O2
OH- Fe
OH
OH- OH- OH- OH-
O2 Fe3+ OH-
Fe Fe
3+ 3+ OH -
OH- O2
OH- OH- FeOH
3+ -
O2 OH- OH-
O2
O2 OH- O2
OH-
O2 O2
O2 O2

O2
O2

O2
O2
O2 O2
O2
O2
O2
O2
O2
Hδ+ HH H
δ+δ+δ+ δ+ δ+δ+ δ+
H HH H Hδ+ Hδ+ Hδ+Hδ+ Hδ+Hδ+ HHδ+δ+ Hδ+HHδ+δ+ Hδ+
OH - O-2δ-δ-
- - δ-
OOH
OH - - - - - OH- - -δ-- - OH- -OH --
OO
O OH
OH
OO2OOH OO OHOH
O22OOH OH O OHOHO
OH OH OH
OH O- δ-
O OH
2 2 OO2 2O2 O
- -OH
OHO2OH
OH - - OH
- O
OOH
- δ-
OH -OH
OH - δ-- -
2O2 OO2
δ-
222 O 22O2O δ-
2 OO2 2 2 O O 22 O22O 2O
δ-

ee
- -
e-2+- e- - 2+ e- - Fe 3+ ee
--
eFe
Fe- 2+
3+
e Fe
- Fe
Fe2+ e
3+Fe
Fe 3+ e Fe
Fe Fe
3+ 2+ e Fe2+
Fe2+
3+ Fe3+ 2+
ee- - Fe
Fe2+
3+ e-
Fe 3+
- Fee-
Fe
Fe ee
2+
3+
-
e-e-
Microbiologically Influenced Corrosion
Effects of Biofilms on Corrosion
• Some types of aerobic bacteria form protective
biofilms (slime).
(slime)
• The aerobic bacteria consume the oxygen in
the outer layer
y of the biofilm leavingg an oxygen
yg
free environment that allows anaerobic
bacteria to thrive.
• The difference between dissolved oxygen
concentration beneath the biofilm vs. outside
the biofilm creates an oxygen cell – the area
b
beneathth the
th biofilm
bi fil becomes
b the
th anode.
d
• The slime allows water and nutrients to enter
but can filter out certain toxic compounds that
are harmful to the bacteria.
 Effects of Biofilms on Corrosion

Aerated Water
O2 O2

O2 O2 O2

O2

O2
O2
BIOFILM
O2 O2
O2 O2
O2 AerobicO2 O2
O2
O2
O2
O2 Anaerobic
O2
O2
O2
O2
O2
δ+
Hδ+ HH δ+
δ+δ+
Hδ+ Hδ+ Hδ+ O2 Anaerobic Hδ+ HHδ+δ+Hδ+ HHδ+δ+ Hδ+ Hδ+ Hδ+ H
H
H
δ+
δ+
Hδ+
δ+ H
H δ+
δ+
Hδ+
OH
OH
OH
-- - - - OH
OH
OH-- - --OH OH - δ- O2 -- δ- OH- -
O
OOHO
OH O O
O
22 2 222 OO O OH
222 OO 2 OOH
δ- -O OH
δ-
2
--
O2 O O2OH
OO2OH
- δ-- - δ-
OH
2O O Oδ-OOH OH-O
2
OH O2OHO 2
O
- δ- O OH
OH
δ-
δ-
Oδ- ---
2 O O222
e- - Fe2+ e-- e- - e- -
Fe2+
e e e Fe2+
Fe2+ Fe2+ e
Cathode Fe2+
e- - Cathode
e-e- Fee 2+- Fe2+
e
e- -
Fe2+
Fee2+
-
e e- -
e

Anode
Controlling Corrosion
 Corrosion Problems

• Consumer
C complaints
l i t about
b t Red
R d Water
W t
• Compliance
p with EPA’s Lead and Copper
pp Rule
 Degassifiers:: Effect on Alkalinity
Degassifiers

• Florida groundwaters contain a high amount of H2S

• Degassifiers are used to remove the H2S in the
permeate.
• Degassifiers also completely remove CO2.
• If Caustic Soda is added to water without CO2, pH
increases more easily, but water has no buffering
capacity.
• The hydroxides are consumed by acids in the
distribution system resulting in a pH drop
 Degassifiers:: Effect on Alkalinity
Degassifiers

• In order to resolve this problem, many plants inject

CO2 gas into their permeate prior to caustic dosing
dosing.
H2O + CO2 H2CO3
H2CO3 + OH- HCO3- + H2O
HCO3- + OH- CO32- + H2O

• Alkalinityy can also be added byy blending

g the p
permeate
with a small amount of feedwater or water from a
neighboring lime softening plant.
 Alkalinity – Effects on Corrosion

• Alkalinityy provides
p buffering
g capacity
p y in water systems
y
CO32- + H+ HCO3-
HCO3- + H+ H2CO3
• Buffering is the ability to minimize pH fluctuations
resulting from introduction of acids or bases

• Certain types of bacteria in the distribution system can

produce organic and inorganic acids as byproducts of
th i metabolism
their t b li ((ie
(iiie.. Sulfur
S lf O Oxidizing
idi i B Bacteria)
t i )

• Some corrosion byproducts can hydrolyze producing

f
free acid byproducts (ie
(ie.. Fe2+
2 + 2H
2 2O Fe(OH)
(O )2 + 2H
2 +)
 Alkalinity – Effects on Corrosion
Iron
• At pH 7 – 9, tuberculation and precipitation rate
of iron hydroxide increases BUT dissolved iron
decreases
• Experiments using 100 year old cast iron pipes
taken from a Boston distribution system showed
that decreases in alkalinity from 30mg/L to 15
mg/L as CaCO3 at a constant pH resulted in an
immediate increase of 1.5 - 3.5X in iron release.
• Corrosion of cast iron and mild steel are
minimized when alkalinityy g
greater than 60 mg/L
g/
as CaCO3
 Alkalinity – Effects on Corrosion
se
Releas
Iron R Iron

15 ppm 30 ppm 60 ppm

Alkalinity
Alkalinity – Effects on Corrosion
Iron
 Alkalinity – Effects on Corrosion
Lead
• Lead release is significantly lower when
alkalinity is between 30 and 74 mg/L as CaCO3
than when alkalinity is <30 mg/L as CaCO3
• Corrosion of Lead Solders occurs mainly by
galvanic corrosion – alkalinity >74ppm does
not reduce lead release into drinking water.
• A pH of at least 8 is required to minimize lead
corrosion to acceptable levels
• pH of >9.2 is optimal for reduced lead
concentrations in drinking water
 Alkalinity – Effects on Corrosion
Lead
ease
d Rele
Lead

15 30 45 60 74
ppm ppm ppm ppm ppm
Alkalinity
 pH – Effects on Corrosion
Lead
0.20
L)
n (mg/L
olved

0.15 0.128
fro m Corrrosion
Lead Disso

0.10

0.05 0.035
0 008
0.008 0.004
0.00
6.7 8.5 9.2 10.5
pH
 Alkalinity – Effects on Corrosion
Copper

• Alkalinity
a y <25
5 mg/L
g/ as CaCO3 increases
as s
uniform corrosion of copper.
• However, copper corrosion also increases
when alkalinity is >74 ppm due to the
formation of soluble cupric bicarbonate and
carbonate
b t complexes
l – this
thi effect
ff t iis made
d
worse if the pH is also < 7.8
• At pH>8
H 8 copper corrosion
i that
th t occurs will
ill
be non-uniform or pitting corrosion.
 Alkalinity – Effects on Corrosion
C opp er R eleease Copper
n W ate r
in

1
15 2
25 3
35 4
45 55 6
65 75 8
85 9
95
Alkalinity
 Alkalinity – Effects on Corrosion
Copper

• Copper
pp is least soluble at pH>9.
p Chlorine
in water oxidizes copper surfaces to form a
protective passive
p p layer
y that prevents
p
further corrosion. This passive film will
dissolve if pH<9.
p
 Alkalinity
30 45

Iron

Copper

Lead

15 25 35 45 55 65 75
Alkalinity
 Corrosion Inhibitors

Two types of corrosion inhibitors:

1. Anodic Inhibitors
Inhibitors:: Form a film on the anode
to prevent water from directly contacting the
metall surface
f

2. Cathodic Inhibitors:
Inhibitors: Form a precipitated
barrier at the cathode to reduce the flow of
electrons.
 Anodic Corrosion Inhibitors

• Anodic Inhibitors work by passivation.

• The Corrosion Inhibitor precipitates on the metal
surface, filling in any gaps in the existing oxide
layer
layer.
• The precipitated Corrosion inhibitor forms a thin
insoluble film which provides a barrier between
the metal and the water, preventing migration of
ions from the solid state to the solution state.
• As long as the reaction at the anode is prevented,
electrons will not flow to the cathode.
 Anodic Protection
PO43- PO43-
O2
PO43-
Aerated Water PO43- PO43-

O2
PO43- PO43- O2 PO43-
O2 O2 PO43-
O2 O2
PO43-
PO43-
O2 PO43-
PO43- PO43-
PO43-
PO43- O2 O2
PO43- PO43- O2
O2 PO43- PO43- PO43- 3- PO43-
PO4 + Anode + PO43-
PO
PO43-
3-
PO4 43- O2
PO43-
PO43-
PO43- PO43- PO43-
O2 PO43- PO43- O2 PO43-
PO43-

Fe2+ Fe2+ Fe2+ 2+ Fe2+

Fe2+
Fe Fe2+ Fe2+
Fe2+
Fe2+ Fe2+ Fe2+
Fe2+ Fe2+ Fe2+ Fe2+
Fe2+

Protective iron phosphate film forms at the anode

3Fe2+ + 2PO43- Æ Fe3(PO4)2
 Anodic Corrosion Inhibitors

Problems Associated with Underdosing

• Underdosing orthophosphates will only coat some

of the anodic sites leaving others exposed
• Severe pitting corrosion will occur as the oxidation
concentrates
t t att th
the unprotected
t t d anodic
di sites.
it
• This type of problem is often found at sites where
phosphoric acid is used as a corrosion inhibitor
 Non-continuous Passive Film - Pitting
O2 O2
O2 O2
O2

O2
O2 Aerated Water
PO43- O2 O2 PO43-
O2 PO43-
PO43- O2
PO43- O2 O2
PO43-
O2 O2
OH- OH- OH- OH- OH- OH- Hδ+ Hδ+
OH- OH- OHOH
- - OH- OH-
Hδ+ Hδ+

- Oδ-OHO
-
OH- OH-
Oδ- Oe2 - e
Fe --
2+ 2
e- Fe
2+
e
OH
- Cathode - + - Cathode -
e- Anode
Fe2+ +
e-
Fe2+ e-
e-
eFe- 2+
e-
Fe2+ e-
e-
eFe
-
2+
e-
Fe2+
e--
e
eFe-
2+
e- 2+ e-
Fe
- 2+ e
-
eFe
e 2+ e-
-
Fe
eFe- 2+ e-
eFe- 2+ e-
- 2+ e
-
eFe
e -
Fe2+ e-
-
e
 Anodic Corrosion Inhibitors
• Orthophosphate: Effective in distribution
systems at moderate dosages
• Silicate: Very effective but require extremely
high dosages
• Molybdate: The best of the anodic corrosion
inhibitors but high dosage and high cost
prevent its use for large scale systems
systems.
• Borate: Boron is a possible carcinogen so this
is only used in industrial systems.
• Nitrite: Nitrite is useful in oxygen free systems
such as chillerss bu
su but iss not
o us
used
d in drinking
d g
water systems.
 Cathodic Corrosion Inhibitors
• Cathodic Corrosion Inhibitors work by
precipitating hydroxide, carbonate or phosphate
films at the cathode:
• Precipitation of these salt films occurs due to the
increased pH from hydroxyl ions produced by
reduction of oxygen
• These salt films are thick and sometimes visible
• The films formed at the cathode restrict diffusion
of dissolved oxygen to the metal surface
surface.
• The salt films are also poor electronic
conductors and so oxygen reduction does not
conductors,
occur on the film surface.
surface.
 Cathodic Protection
Zn2+
Zn2+ Zn2+ Zn2+

O2 Aerated Water
O2
O2 O2 Zn2+ O2
Zn2+ Zn2+
Zn2+ Zn2+
O2
Zn2+ Zn2+
O2
Zn2+ Zn2+ O2 Zn2+
O2 O2 Zn2+
Zn2+ Zn2+ Zn2+ Zn2+
O2 Zn2+
Z 2+
Zn Zn2+ Z 2+
Zn Z 2+
Zn
Zn2+ Zn2+ Zn2+
Zn2+ Zn2+ Zn2+ Zn2+ Zn2+ Zn2+
Zn2+ Zn2+ 2+2+
ZnZn
Zn2+ Zn2+ 2+2+ Zn2+
Zn
Zn2+Zn Zn2+ Zn2+Zn
Zn 2+ 2+
Zn2+ O2
Zn2+ Zn2+ 2+ 2+
ZnZn
Zn2+
Zn2+ Zn2+
OH
OH- - -
OH OH
OH
OH
-- - OH- - -
OH
OH OH-- -
OH
OH OH
- --
OH
OH - - - OH
OH
OH
OH OH
OH
OH- - OH-- -
OH-OH
OH OH
-OH - - - OH
-OH OH-OH
-
OH
OH OH
- --OH-- - OH-
OH OH-

e- e
- e- - Fe2+ e- 2+ e--
e Fe e2+
- - e-
Fe2+ Feee
2+
Fe- 2+ Fe
e-ee-
Fe2+ e- - Cathode - e- -Fe2+
e

Prevents Reduction at the Cathode:

½ O2 + H2O + 2e- ↔ 2(OH)-
If reduction is prevented, oxidation will not occur
 Cathodic Corrosion Inhibitors
• Zinc: Effective in distribution systems at
moderate dosages
• Calcium: Recent studies dispute effectiveness
of calcium carbonate as corrosion inhibitor
• Magnesium: Theoretically will provide
corrosion inhibition when Magnesium
hydroxide is formed at high pH
• Polyphosphate: Claimed to form a protective
layer on steel, copper and lead – most studies
show it is ineffective in absence of calcium or
zinc.
 Cathodic Corrosion Inhibitors

Zinc
• This is the most superior of the Cathodic Inhibitors
• The zinc works byy pprecipitating
p g as a zinc hydroxide
y
(Zn(OH)2) on the cathodic surface, inhibiting the
reductions.

• If alkalinity in the water is sufficient, a more

adhesive basic zinc hydroxycarbonate film will form
(hydrozincite),, preventing oxygen from reaching
the steel surface: 2 ZnCO3 . 3 Zn(OH)2
 Cathodic Corrosion Inhibitors

Zinc
Zi corrosion
Zinc i inhibitors
i hibit provide
id substantial
b t ti l
protection of asbestos-cement pipe by
coating the pipe and protecting it against
fiber release and water attack.
 Cathodic Corrosion Inhibitors

Calcium
• Traditionally believed to form a Calcium
Carbonate Film on the metal surface when
Calcium and Alkalinity concentrations are
sufficiently high. However, most studies show
that Calcium Carbonate by itself does not form
a protective scale on metals and is not an
effective corrosion inhibitor.
• Under certain conditions calcium has been
found to increase lead solubility
solubility.
 Cathodic Corrosion Inhibitors

Magnesium
Forms a Magnesium Hydroxide Film on the
metal surface only when Magnesium
concentration is sufficientlyy high
g (Sea
( water).
)
Magnesium hydroxide films are only stable at
very high pH.
 Cathodic Corrosion Inhibitors
Polyphosphates
yp p
• Will produce a thin, amorphous salt film ONLY in the
presence of Zinc or high levels of Calcium.
• When used alone, polyphosphate does not act towards
iron as a corrosion inhibitor but as a sequestrant, causing
a decrease in the visual observation of red water
water.
• If polyphosphate products are dosed in systems with
insufficient calcium and alkalinity
alkalinity, they will actually
increase the rate of corrosion of the steel pipe as they
sequester iron from the surface. However, since
polyphosphates
l h h decrease
d the
h appearance off red d water,
this corrosion goes unnoticed.
• Many studies have shown that polyphosphates will
increase corrosion of steel, copper and lead when used in
absence of zinc.
 Anodic/Cathodic
Corrosion Inhibitors

Products combining anodic and cathodic

p
corrosion inhibitors exhibit superior
corrosion inhibition.
 Anodic/Cathodic
Corrosion Inhibitors
• It was observed in an 18-month survey of 31 water
systems in
i Northh America
i that
h distribution
di ib i systems using i
zinc orthophosphate inhibitors had fewer coliform
bacteria than systems that did not have corrosion control.

• Coliform bacteria counts are directly indicative of

potential pathogens present in the water.
water

• The Zinc Orthophosphate does not attack bacteria – but

by reducing corrosion
corrosion, it keeps oxidizers (such as
chlorine/chloramines) active in the water instead of being
consumed by corrosion reactions (oxidation of ferrous to
ferric ions)– this reduces biologically induced corrosion.
Corrosion Coupon Tests
Port St. Lucie - JEA Plant
RO Water
 Corrosion Coupon Tests
Port St. Lucie - JEA Plant
RO Water

45 Blank
Poly/Ortho
40
C o rro ssio n R atte (M P Y )

A-751
35
30
25
40.61
20
15
24.96
10
5 1.73
0
Mild Steel
 Corrosion Coupon Tests
Port St. Lucie - JEA Plant
RO Water
6 Blank Poly/Ortho A-751
5.13
PY)

5
Rate (MP

3.91
4 3.56
osion R

3 2 73
2.73

2 1.68
Corro

1 40
1.40
1.13
1
0.18 0.12
0
Copper Brass Lead
Corrosion Coupon Tests
Port St. Lucie - Prineville Plant
RO Water Blended with Lime Softened Water
 Corrosion Coupon Tests
Port St. Lucie - Prineville Plant
RO Water Blended with Lime Softened Water

25 Blank
Poly/Ortho
C o rro ssio n R atte (M P Y )

20 A-751

15
23.82 23.62
10

5
3 16
3.16
0
Mild Steel
 Corrosion Coupon Tests
Port St. Lucie - Prineville Plant
RO Water Blended with Lime Softened Water
2.5 Blank Poly/Ortho A-751
2.16
PY)

20
2.0
Rate (MP

1.75

1.5
osion R

0.92 0.93
1.0 0.84
0.70
Corro

0 52
0.52
0.5 0.39
0.32

00
0.0
Copper Brass Lead
 Water Quality for
p
Optimal Corrosion Inhibition

ƒ Alkalinity between 30 – 45 ppm

ƒ Maintain a pH > 8.5

ƒ Products combining anodic and cathodic

corrosion inhibitors should be used for
Reverse Osmosis Permeate.

ƒ Perform
P f C
Corrosion
i C
Coupon studies
t di tto ensure
adequate corrosion control.
Ionic Bond

Fe++

26 P
 Concentration Cell Corrosion

• Metal Ion Cell: The metal surface exposed

p to
water with lower concentration of the metal’s
ions will become the anode (oxidizes and
d
dissolves),
l ) while
h l the
h surface
f exposedd to water
with higher concentration of the metal’s ions
will become the cathode
cathode.
• (Diagram or Animation for Explanation)
• Le Chatelier’s Principle