Chapter 2

Basic Chemistry and Basic

Basic Chemistry
Corrosion Theory

and Basic
Corrosion Theory
 Definition of Corrosion
Basic Chemistry and Basic
Corrosion Theory

“Corrosion is the deterioration of a

substance (usually a metal) or its properties
because of a reaction with its environment.”
 Terms and Definitions
Basic Chemistry and Basic

• Elements
Corrosion Theory

• Atoms
• Ions
• Compounds
• Acidity & Alkalinity
• Oxidation & Reduction
• Electrochemical Circuits
 Elements
Basic Chemistry and Basic

Elements - All matter is made up of

Corrosion Theory

elements. These elements are the

“building blocks” of the physical world and
are composed of atoms.
 Atoms
Basic Chemistry and Basic

Atoms - consist of a nucleus and orbiting

electrons.
Corrosion Theory

• Nucleus
• protons = positively charged particles.
• neutrons = neutral particles.
• Number of protons equals the number
of electrons.
•An atom has no net electrical charge.
The Bohr Model of an Atom
ELECTRONS

NUCLEUS

ORBIT
 Ions
Basic Chemistry and Basic

Ions - electrically charged atoms are referred to

Corrosion Theory

as ions.
• Anion - negatively charged because number
of electrons is greater than number of protons.
• Cation - positively charged because number
of protons is greater than number of electrons.
 Compounds (Molecules)
Basic Chemistry and Basic
Corrosion Theory

• Composed of two or more atoms.

• A water molecule is composed of one
oxygen and two hydrogen atoms (H2O).
Water Molecule

Oxygen
Atom

Hydrogen Atoms
 Acidity and Alkalinity
Basic Chemistry and Basic

• Acid
Corrosion Theory

– Higher concentration of H+
ions than OH– ions

• Alkaline
– Higher concentration of OH–
ions than H+ ions
 Acidity and Alkalinity
Basic Chemistry and Basic

• pH is important in corrosion and cathodic

protection work.
Corrosion Theory

• For some metals such as steel, the rate of

corrosion increases appreciably below a pH of
about 4.
• Between 4 and 8 corrosion rate is fairly
independent of pH.
• Above 8, the corrosion rates tend to
decrease.
 pH Scale
Neutral pH = 7
Acid pH < 7

0 Alkaline pH > 7 14

Acid Neutral Alkaline

ph = –log [H+]
 Acidity and Alkalinity
Basic Chemistry and Basic

• The corrosion rate of some metals such as

Corrosion Theory

aluminum, lead and zinc tend to increase in

alkaline environments above a pH of about 8.
• This is because the protective oxide film on the
surfaces of these metals is dissolved in by
alkalis as well as strong acids.
• Metals which corrode under low and high pH
conditions are termed amphoteric metals.
Corrosion Rate of Steel
CORROSION RATE

1 4 8 12
pH
Corrosion Rate of
Aluminum and Lead
CORROSION RATE

1 4 8 12
pH
 Electrochemistry
Basic Chemistry and Basic

Electrochemistry is the division of

Corrosion Theory

chemistry that deals with the transfer of

electric charge in chemical reactions.
 Electrochemical Reactions
Basic Chemistry and Basic

• Oxidation reaction
Corrosion Theory

– Occurs when electrons are given up by an

atom or molecule
– Decreases negative charge
• Reduction reaction
– Occurs when electrons are gained by an
atom or molecule
– Increases negative charge

In a corrosion cell, both oxidation and reduction

reactions occur.
 Oxidation Examples
Basic Chemistry and Basic
Corrosion Theory

Atom Ion + Electrons

Fe Fe++ + 2e-

Fe Fe+++ + 3e-
Anodic Process (half reaction)
ELECTROLYTE e-
e -
e -
Fe++ e- -e- e-
e -
Fe++ Fe e- e
++

Fe++ Fe++
e- ANODE
e-
Fe ++ e -
e-
Fe ++
e- e-
e -
e -
Fe ++ Fe ++
e-
 Reduction Example
Basic Chemistry and Basic
Corrosion Theory

Ion + Electron Atom

H+ + e- H

2H2O + O2 + 4e- 4OH-

Cathodic Process (half reaction)
e-- H2 H2
e
H0 H+
e -
e - H0

CATHODE e- e-
e- H0
H +
H+
-e H
- +
e -
e - + H+
e-
e H
e e-H0 H+
-

e- H+
- e
-
e H +
H0
ELECTROLYTE
Electrochemical Circuits
Metallic Path

-
e

+ ions
A
 - ions C
Electrolytic Path

Conventional Current Flow

 Electrolyte
Basic Chemistry and Basic

Electrolyte - a solution containing

Corrosion Theory

dissolved chemical compounds that

dissociate into positive and negative ions.
 Ionization
Basic Chemistry and Basic

Ionized molecules dissociate into

Corrosion Theory

ions when dissolved in water.

 Components of a
Basic Chemistry and Basic

Corrosion Cell
Corrosion Theory

• Anode (oxidation reaction)

– corrosion
• Cathode (reduction reaction)
– no corrosion
• Electrolyte (cations and
anions)
• External path (usually
metallic)
 Anode Reactions
Basic Chemistry and Basic
Corrosion Theory

Oxidation of the metal where the atom has

become more electropositive.

Mo Mn+ + ne-
Feo Fe++ + 2e–
Alo Al+++ + 3e–

Hgo Hg+ + 1e–

 Cathode Reactions
Basic Chemistry and Basic
Corrosion Theory

Reduction of the metal where the species being

reduced becomes more electronegative.

•Oxygen Reduction
2H2O + O2 + 4e– 4OH–
•Hydrogen Reduction
H+ + e– H
 External (Metallic) Path
Basic Chemistry and Basic
Corrosion Theory

Allows electron charges to flow from

anode to cathode.
 Electrolytic Path
Basic Chemistry and Basic
Corrosion Theory

• Cations move toward the cathode.

• Anions move toward the anode.

 Electrolyte
Basic Chemistry and Basic

• An ionized solution capable of conducting

Corrosion Theory

electricity.
• Ions are the principle charge carriers in
an electrolyte.
 Electron and Ion Flow
e- e- e- e- e-
-
e- e-
e- Direction of Electron Flow
e-

e- e- ELECTROLYTE e-
e-
e- - e- + e -
e
ee- e
- + e- e- e-
+ ee-
CATHODE
CATHODE + ANODE
ANODE
+
Conventional Current–Effective
Flow of Positive Charges
Electron Flow
e- e- e- e-
e-
e- - e- e-
e
e- - e
-
e- e
e- e- e- e-
e- e-
e- e-
e- e-
CATHODE ANODE

ELECTROLYTE
 Single Corrosion Cell
Microscopic View

CATHODIC ANODIC SITE

SITE e- -
- e
-
- e e e-
e
e - e - e -+ e- e -
H H H Fe++ Fe++
H +
Fe++ Fe++
H+ H2 OH-
H+ Fe++ OH-
H+ Fe++ OH-
H+ Fe(OH) Fe(OH)2
H+ 2
Fe(OH)2
Multimeters
Voltmeter Circuit Connection
E
+ _

VOLTS

I _
+
RA RB RC

Parallel Connection
 Voltage Measurements
Basic Chemistry and Basic
Corrosion Theory

• Driving voltage of galvanic anode system

• Rectifier voltage output
• Structure-to-electrolyte potential
• Voltage drop across a pipe span
• Voltage across a current shunt
 Polarity Sign
20 mV Voltage measurement is positive
_
+

ur re nt
C
Sign of Voltage for Dissimilar
Metals
.600 V
Voltage
measurement
_
+ is positive

Noble Active
 Sign Convention
Basic Chemistry and Basic
Corrosion Theory

If a voltmeter is connected such that

the positive terminal is to the more noble
metal and the negative terminal to the
more active metal, the reading is positive.
 Voltmeter Connections

Pipe-to-Soil Potential Measurement

Voltmeter Meter display is a Voltmeter

.900 v -.900 v Meter display is a
postive reading. negative reading.
_ Record a negative _ Record a negative
+ +
P/S Potential. P/S Potential.
Reference
Cell Reference
Cell

Electrolyte Electrolyte
Pipe Pipe
Reference Electrodes
(Half Cells)
 Copper-Copper Sulfate

Reference Electrode
Connection
for Test
Removal
Lead
Cap
Copper Rod
Clear
Window Saturated Copper
Sulfate Solution
Porous
Undissolved Copper
Plug
Sulfate Crystals
 Use and Care of CSE
Basic Chemistry and Basic

• Keep clean.
Corrosion Theory

• Cap when not in use.

• Clean porous plug.
• Keep free of contamination.
• Keep spares in field.
• Keep fresh electrode for calibration.
• Record temperature when in use.
• Shield from direct sunlight.
Basic Chemistry and Basic
Corrosion Theory

Driving Force
For Corrosion
Elevation Difference
Causes Water to Flow
Direction
of

W
at
er

Elevation Difference
Fl
ow
Energy Cycle of Steel

IRON OXIDE BLAST FURNACE BESSEMER

PIPE MILL STEEL PIPE

REFINING PROCESS
CORROSION PROCESS

IRON OXIDE
PIPE CORRODING
Basic Chemistry and Basic
Corrosion Theory

MAGNESIUM
ALUMINUM
ZINC
STEEL
COPPER
CARBON
SILVER
PLATINUM
GOLD
 Energy Required to Convert
Ore to Metal
Basic Chemistry and Basic

Most Potassium
Magnesium
Corrosion Theory

Energy
Required Beryllium
Aluminum
Zinc
Chromium
Iron
Nickel
Least Tin
Energy Copper
Required Silver
Platinum
Gold
 Faraday’s First Law
Basic Chemistry and Basic
Corrosion Theory

The weight of any material deposited on

the cathode (or liberated from the anode)
is directly proportional to the quantity of
electric charge passing through the circuit.
 Faraday’s Law
Basic Chemistry and Basic

Wt = K I T
Corrosion Theory

Where Wt = weight loss, kg

K = electrochemical equivalent, kg/A-yr
I = Amps
T = Years
Electrochemical Equivalents
Metal Kg/A-Yr Lb/A-Yr
Carbon 1.3 2.86
Aluminum 3.0 6.5
Magnesium 4.0 8.8
Iron/Steel 9.1 20.1
Silicon/Chromium/Iron 0.5 1.0
Nickel 9.6 21.2
Copper (monovalent) 20.8 45.8
Zinc 10.7 23.6
Tin 19.4 42.8
Lead 33.9 74.7
 Polarization
Basic Chemistry and Basic
Corrosion Theory

• The change from the open-circuit

potential as a result of current across
electrode/electrolyte interface.

• As polarization increases corrosion

rate decreases.
Polarization Diagram (Evans) for
a corrosion cell
+
P EOC
o
t
e EPC
EM
n EPA
t
i
a EOA
l
_
I CORR
log I
 Activation Polarization
Basic Chemistry and Basic
Corrosion Theory

The energy used to cause the

reduction reaction to proceed.

•Oxygen Reduction
2H2O + O2 + 4e– 4OH–

•Hydrogen Reduction
H+ + e– H
 Concentration Polarization
Basic Chemistry and Basic
Corrosion Theory

The change in voltage of an electrode

due to concentration effects at the
electrode/electrolyte interface.
Basic Chemistry and Basic
Corrosion Theory

Corrosion Rate
Factors that Affect the
 Anode/Cathode Ratio
Basic Chemistry and Basic
Corrosion Theory

The effect of current concentrated on a

small area will be greater than the effect
of the same amount of current on a
larger area.
Basic Chemistry and Basic
Corrosion Theory Large Anode - Small Cathode
Basic Chemistry and Basic
Corrosion Theory
Small Anode - Large Cathode
 Influence of the Environment
Basic Chemistry and Basic

on Corrosion Rate
• Moisture Content
Corrosion Theory

• Electrolyte Conductivity
• pH
• Oxygen Concentration
• Temperature
• Stress
• Aeration
• Agitation
 Causes of Corrosion
Basic Chemistry and Basic

• Dissimilar Metals (Galvanic)

• De-Alloying
Corrosion Theory

• Stresses
• Differential Moisture
• Temperature Differences in the Metal or
Electrolyte
• Dissimilar Soils
• Oxygen Concentration Cell
• Metal Ion Concentration Cell
• Microbiological Influences
Practical Galvanic Series
Material Potential*

High Potential Magnesium -1.75

Magnesium Alloy -1.60
Zinc -1.10
Aluminum Alloy -1.05
Clean Carbon Steel -0.50 to -0.80
Rusted Carbon Steel -0.20 to -0.50
Cast/Ductile Iron -0.50
Lead -0.50
Steel in Concrete -0.20
Copper -0.20
High Silicon Iron -0.20
Carbon, Graphite +0.30

* Potentials With Respect to Saturated Cu-CuSO4 Electrode

Dissimilar Metals Corrosion
Graphite-Zinc Battery

Zin
c
Carbon rod

Negative terminal
 De-Alloying
Basic Chemistry and Basic
Corrosion Theory

• Graphitization of Cast Iron

• De-zincification of Brass
 Stressed Areas
Basic Chemistry and Basic

• Cold Worked
Corrosion Theory

– Threads
– Bends
• Welding
– Residual Stress
– Heat Affected Zone
Differences in Moisture
Content

Cathode Anode Cathode Anode Cathode

Temperature Difference
Corrosion Cell COMPRESSOR
STATION

Hot
Gas
E
D
N O
A
CATHODE
Cooler
Gas
Conductivity and Salt Concentration

Soil with Low Concentrations

of Dissolved Salts

Anode Cathode Anode

Soil with Higher Concentrations

of Dissolved Salts
 Oxygen Concentration
Corrosion Cell
Oxygen Oxygen
Penetration Penetration
Pavement

Cathode Anode Anode Cathode

Little or
No Oxygen
 Oxygen Concentration
Corrosion Cell
High Oxygen
Concentration
(Cathode)

Example of
Low Oxygen Crevice
Concentration
(Anode)
Corrosion
Sulfate Reducing Bacteria
AST Bottom MIC