Definition of Terms

Matter
Element
Compound
Mixture
Atom
Molecule
Ion
Electrolyte
Matter
Matter is any substance that has
weight and occupies space.
Element
An element is a substance that cannot
be broken down by chemical reactions
Elements are the basic building blocks
of all matter
Examples Iron, Oxygen, Hydrogen,
Gold
Periodic Table
PERIODIC
TABLE
Common Elements
Iron, Fe
Copper, Cu
Sodium, Na
Chlorine, Cl
Oxygen, O
Compound
A compound is a combination of two
or more elements
A compound is a pure substance
A compound has a fixed composition
Examples of compoundscarbon
dioxide, ferric oxide, salt, water
Mixture
A mixture is a combination of elements and/or
compounds held together by physical rather
than chemical forces
Mixtures do not have fixed compositions
Examples of mixturesair, soil, most rocks
Atom
An atom is the smallest particle of an
element
An atom consists of a central nucleus that
has a positive charge surrounded by
electrons that have an equivalent negative
charge
Atoms are electrically neutral
ELECTRONS
NUCLEUS
ORBIT
Bohr Model of an Atom
Molecule
A molecule is the smallest particle of an
element or compound that retains all of the
properties of that compound or element
The smallest particle of an element
hydrogen gas is H
2 ;
oxygen gas is O
2
The smallest particle of a compoundwater
is H
2
O; ferric oxide is Fe
2
O
3
Oxygen
Atom
Hydrogen Atoms
Water Molecule
Ion
An ion is a charged atom or molecule
An atom or molecule with a net
negative charge is a negative ion,
also called an anion
An atom or molecule with a net
positive charge is a positive ion, also
called a cation

(Atoms or molecules become ions by
transferring electrically charged
particles.)

Electrolyte
An electrolyte is a liquid solution
containing ions
An electrolyte can conduct an electrical
current by the movement of ions
Bonding Forces
Van der Waals inert gases

Ionic dissimilar charged ions such as
NaCl

Covalent shared valence electrons
such as O
2

Metallic valence shell electrons
Corrosion reactions are
sometimes called
Electrochemical Reactions

Oxidation/Reduction Reactions

Redox Reactions

Corrosion Cells
Oxidation
Oxidation occurs when
electrons are lost from an
atom, compound, or ion
Oxidation reactions increase
the positive charge of the
atom, compound or ion
Oxidation occurs at the
anode in an electrochemical
reaction
The electrons remain in the
metal and may move freely
within the metal
Reduction
Reduction occurs when electrons
are added to an atom,
compound, or ion
Reduction reactions increase the
negative charge of the atom,
compound or ion
Reduction occurs at the cathode
in an electrochemical reaction
The electrons are supplied from
within the metal and move to the
cathode from anodic sites
Anodic Reactions
Electrons are given up in
anodic reactions
Positive charge increases
Negative charge decreases
Anodic reactions are called
oxidation
The electrons remain in the
metal and may move freely
within the metal
Anodic Reactions
Generic: M
O
M
n+
+ ne

Iron: Fe
o
F e
++
+ 2e


Fe
o
F e
+++
+ 3e


Fe
++
F e
+++
+ e


Aluminum: Al
o
Al
+++
+ 3e


All anodic reactions make the reacting
metal more positive and produce
electrons
Cathodic Reactions
Electrons are gained in cathodic
reactions
Negative charge increases
Positive charge decreases
Cathodic reactions are called
reduction
The electrons are supplied from
within the metal and may move to
the cathode from other sites
Cathodic Reactions
Generic: R
+
+ e

R
O

Hydrogen Reduction:
H
+
+ e

H
O

2 H
O
H
2
Oxygen Reduction:
2 H
2
O + O
2
+ 4 e

4(OH

)
O
2
+ 4 H
+
+ 4 e

2 H
2
O

All cathodic reactions make the
reacting material more negative
(less positive) and consume
electrons
Electron vs. Conventional Current Flow
Which direction is conventional flow in this cell?
Which direction is conventional flow
in this cell?
The Corrosion Cell
Metallic corrosion is an electrochemical
reaction which involves:
a transfer of electrons
oxidation - loss of electrons (corrosion)
reduction - gain of electrons
(protection)
migration of ions
Corrosion Cell Drawing
4 Requirements for a Corrosion Cell
Anode
Areas that give up electrons
Cathode
Areas that receive or consume
electrons
Metallic Path
Areas that transport electrons
Electrolyte
Areas that transport ions
Anode
Which direction
is conventional
flow in this cell?
Which direction
is electron flow
in this cell?
We now know how corrosion happens
it is electrochemical
The electro part is the electrons
The chemical part is the ions


Next we need to know what causes
this process to happen.
Review
Most corrosion of metals is
electrochemical
There are 4 requirements for
electrochemical corrosion to
occur
Corrosion can be controlled by
removing or slowing any of the
4 requirements
What causes electrons to flow
in a corrosion cell?
Corrosion cells are created when there
is an imbalance or non-equilibrium
energy balance, causing a movement of
energy from high levels to lower levels.

Thermodynamics
Thermodynamics
Thermo = heat (energy)
Dynamics = movement
Thermodynamics = the movement of
energy
Energy naturally flows from sites with
high energy to sites with lower energy
Thermodynamics can predict if corrosion
will happen under specific conditions but
cannot determine the rate
Potential or emf (Electromotive Force)
Electrical (electrochemical) potential is a
measurement of energy level
More negative potentials indicate higher
energy levels
Potential is measured in volts
Potential Measurement
Detection of anodes and cathodes can
be accomplished in many cases with a
voltmeter and reference electrode.
A corrosion potential is made by
comparing a metal sites voltage to a
reference electrodes voltage.
Corrosion Potential
Reference Electrodes
Reproducible Potential
Hydrogen electrode = arbitrary zero
Calomel Mercury Potassium Chloride
Saturated, 1 Normal, 0.1 Normal
Silver/Silver Chloride
Wet type Potassium Chloride
Saturated, 1 Normal
Dry Type Seawater
Copper/Copper Sulfate Saturated
0.7755 V
Comparison of Potentials Measured
Using Different Reference Electrodes

Hydrogen Reference Electrode
0.000 V
0.850 V
Saturated Calomel Reference Electrode
+0.2415 V
Copper / Copper Sulfate
+0.3160 V
0.534 V
Metal Surface
Copper- Copper Sulfate
Reference Electrode
Copper Rod
Saturated Copper
Sulfate Solution
Undissolved Copper
Sulfate Crystals
Porous
Plug
Visual
Window
Reference Electrode Potentials
Reference Electrode
Hydrogen
Calomel (Saturated)
Calomel (Normal)
Calomel (0.1) Normal
Silver/Silver Chloride (Saturated)
Silver / Silver Chloride (Normal)
Silver /Silver Chloride (Dry in
Seawater)
Copper / Copper Sulfate
Potential (Volts)
0.000
+ 0.2415
+ 0.2800
+ 0.3337
+ 0.2250
+ 0.2222
+ 0.2500

+ 0.3160

Corrosion Potential
The voltage difference between a corroding
surface and a reference electrode is a
potential
Galvanic Series
Listing of metals in order of potential
Different for different environments
Different than the emf series
Does not give corrosion rates
Galvanic Series in Seawater
Active Magnesium
End Zinc
() Aluminum Alloys
Carbon Steel
Cast Iron
13 % Cr (Type 410) Stainless Steel (Active)
18-8 (Type 304) Stainless Steel (Active)
Naval Brass
Yellow Brass
Copper
70 - 30 Copper-Nickel
13 % Cr (Type 410) Stainless Steel (Passive)
Titanium
18-8 (Type 304) Stainless Steel (Passive)
Noble Graphite
End Gold
(+) Platinum
The Nernst Equation
Used to calculate the change in potential
that results from changes in the
electrolyte.
ln
nF
RT
E E
reaction products
reactants
Electromotive Forces Series
OxidationReduction (redox) Potentials
M

M
n+
+ ne

Pure metals
In solutions of unit activity of
reactants
Predicts corrosion of a single
metal
Pourbaix Diagrams
Predicts stability of substances
Considers potential and pH
Predicts possibility of corrosion
Predicts corrosion product
composition
Evaluates effect of changes in pH or
potential
0.0
1.0
2.0
-1.0
-2.0
0.0
1.0
2.0
-1.0
-2.0
-2 0 2 4 6 8 10 12 14 16
-2
0 2 4 6 8 10 12 14 16
P
O
T
E
N
T
I
A
L
,

S
.
H
.
E
.

(
v
o
l
t
)

pH
Fe
Fe
++
Fe
+++
Fe
2
O
3
Fe
3
O
4
a
b
HFe O
2
-
Pourbaix Diagrams
Faradays Law
Relates weight of reacting material to current flow

nF
Mtl
W
Kinetics
Defines corrosion rate
Usually predicts corrosion current density
Corrosion rate is proportional to current
density
Evans ( E vs log i ) diagrams
E-Log I Plots Evans Diagrams
Potential plotted against log of current
Useful for evaluating polarization effects


E

More Positive
(+)

More Negative
()
Log i
Open Circuit Potentials

More Positive

(+)

x

Open circuit potential
of the cathode

E


More Negative
(-)

x
Log i
Open circuit potential
of the anode
Anode Polarization



More Positive
(+)
E
Anode Polarization
More Negative
()
Log i
x
x
Cathode Polarization



More Positive
(+)
Cathode Polarization
E
More Negative
(-)
Log i
x
x
Combined Polarization Complete Cell




More Positive
(+)

x
E
Corrosion
Current

x
More Negative
(-)
Log i
Area Effects
Reaction intensity is dependent on
current density
Current densitycurrent per unit
areasuch as mA/cm
2

Current density affects polarization
Area Effects - Smaller Cathode
More Positive
(+)
x

E


New

Original
Corrosion
Current

x Corrosion
More Negative Current
()
Log i
More Positive
(+)
x

E


x

More Negative
()
Log i
Area Effects - Smaller Anode
Original
Corrosion
Current
New
Corrosion
Current
Types of Electrochemical Cells
Any difference in potential can result in an
electrochemical corrosion cell
Difference in MetalGalvanic Corrosion Cells
Difference in Concentration Concentration Cells
Difference in Surface Activity - Active/Passive Cells
Difference in Temperature Thermogalvanic Cells

Reversal of Potential Zinc-Iron


More Negative
Potential of Zinc

Potential

Potential of Iron
More
Positive
100 F
Temperature
140 F
180 F
Passivity
Formation of passive films of reaction
products:

May occur naturally
Stainless Steels
Nickel Alloys
Titanium

May be formed chemically or
electrochemically
Oxidizing solutions
Applied current
Transpassive
Passive
Active
Corrosion Rate
Oxidizing
Power
Passivity
Summary
Thermodynamics
Kinetics
Nernst Equation
Faradays Equation
Polarization
Passivity