CME511

MEE525
MAT511

Principles of Corrosion
Lecture 2
Basic Principles and Electrochemical Reactions

SPRING TERM 2022

 Corrosion
• Many different specific environments
where corrosion can occur
• Most general case is immersion/exposure
to a bulk aqueous solution
– Atmospheric corrosion: aqueous solution is a
condensed thin layer, but overall principles for
the most part are the same
• Rusting: Iron or carbon steel
• Non-ferrrous metals: corrode
– Example: “White rust” describes corrosion
product on zinc (galvanized steel)
Corrosion In Prime Time!
 Degradation Processes
• In absence of a chemical environment:
– Fracture (failure under applied stress)
– Fatigue (failure under repeated cyclic stress)
– Wear (sliding of materials on each other)
– Erosion/cavitation (mechanical damage from
movement of liquid or collapse of vapor
bubbles)
– Radiation (interaction of elementary particles
resulting in distortion of metal lattice)
Environmentally Assisted
Degradation
 Basic Principle
During corrosion, the rate of
oxidation must equal the rate of
reduction in order for the system
to maintain charge neutrality.
Zinc Corroding in HCl
Overall reaction: Zn + 2HCl ZnCl2 + H2

-
Zn Zn + 2e
+2

Anodic reaction

2H+ + 2e- H2 (g)

Cathodic reaction
(Cl- not involved)
 Other Examples
Fe + 2HCl FeCl2 + H2

2Al + 6HCl 2AlCl3 + 3H2

• These reactions are quite similar in that they all involve hydrogen reduction;
• They differ only in the oxidation (anodic) reactions;
• Therefore, hydrochloric acid corrosion is simplified, since in every case the
cathodic reaction is the evolution of H2;
• This is also true for other acids such as:
• Sulfuric, phosphoric, hydrofluoric and water-soluble organic acids
such as formic and acetic;
• Sulfate, phosphate and acetate do not participate in the
electrochemical reaction
The anodic reaction is always
oxidation of a metal to its ion:
-
Ag Ag + e
+

- -
M M +n
+ne Fe Fe + 2e
+2

-
Al Al + 3e
+3
Common Cathodic Reactions

Hydrogen evolution 2H+ + 2e- H2 (g)

-
Oxygen reduction O2 + 4H+ + 4e 2H2O

Oxygen reduction O2 + 2H2O + 4e

-
4OH
-

(neutral or basic solutions)

Metal ion reduction M+3 + e

-
M+2

Metal deposition M+ + e
-
M
• H2 evolution is a very common cathodic
reaction
• Acid or acidic media frequently encountered
• O2 reduction is very common;
• Metal ion reduction and metal deposition are
less common
• Most frequently found in process streams
• All of these reactions consume electrons
 How many reactions can occur
simultaneously?
• During corrosion, more than one oxidation and
reduction can occur;
• More importantly, more than one reduction reaction
can occur on the surface at a time;
• Ex: Zinc in aerated HCl
– Hydrogen evolution and oxygen reduction
– Since rates of oxidation:reduction must be equal, the
increase in total reduction rate increases the rate of zinc
oxidation
– Therefore, acid solutions containing oxygen are more
corrosive than “air-free” acids.
Zinc Corroding in Aerated HCl

-
Zn Zn + 2e +2

2H+ + 2e- H2 (g)

-
O2 + 4H+ + 4e 2H2O
 Coupled Reactions
• Due to heterogeneous nature of metal
surfaces
• Polycrystalline metal surfaces contain an
array of site energies due to different
crystal faces (grains) and grain boundaries
• Other defects (edges, steps, kink sites,
screw dislocations, point defects)
• Surface contaminants/impurities or
adsorbed ions from solution
Corrosion of Iron in Water
The corrosion of iron can be shown as :
-
2Fe + O2 + 2H2O 2Fe+2 + 4OH
The individual half reactions are :
2Fe 2Fe+2 (aq) + 4e
-
(Anodic reaction)
- -
O2 + 2H2O + 4 e 4OH (Cathodic reaction)
The unstable ferrous and hydroxyl ions react to:
-
2Fe+2 + 4OH 2Fe(OH)2
The ferrous hydroxide is readily oxidized to:
4Fe(OH)2 + 2H2O + O2 4Fe(OH)3
 Aerated solutions vs non-aerated
solutions
• How to decrease corrosion in an aqueous
system?
– Eliminate/reduce oxygen concentration of
electrolyte;
– Eliminate/reduce contaminant metals available for
reduction;
 Corrosion of Fe in Air
(atmospheric corrosion)
 Other ways to eliminate/reduce
oxidation/reduction reactions
• Physical barrier on surface
– Nonconducting films/paints
• Corrosion inhibitors
– Interfere with anodic or cathodic rx
– Organic compounds
• Form a film or metal complex
• Increase electrical resistance of the electrolyte (or corrosive
media)
– High purity water is much less corrosive than impure or “natural”
water
• Impressed current
– Cathodic protection
• “sacrificial” anode (Zn/Mg blocks attached to motors, hulls, water heaters)
 Flint, MI: An Avoidable
Catastrophe – April 2014
- Nearly two years ago, the state decided to save money by
switching Flint's water supply from Lake Huron to the Flint
River;
- The switch was made during a financial state of emergency
was supposed to be temporary while a new state-run supply
line to Lake Huron was ready for connection;
- Soon after the switch, the water started to look, smell and
taste funny.
- Water contained iron; Flint River is highly corrosive: 19 times
more so than the Lake Huron supply (contains higher Cl-
levels)
- The State Dept. of Environmental Quality wasn’t treating the
Flint River water with a corrosion inhibitor (in violation of
Federal Law).
- Half of the service lines to homes in Flint are made of lead.
Since the water had no corrosion inhibitor, lead began
leaching into the water supply, in addition to the iron.
- A 2011 study on the Flint River found it would have to be
treated with an anti-corrosive agent for it to be considered as
a safe source for drinking water.
- Adding that agent would have cost about $100 a day, and
experts say 90% of the problems with Flint's water would
have been avoided.
Impressed Current/Cathodic
Protection Example
 Summary:
Basic Elements of Corrosion
Prevention
• Eliminate the electrolyte
• Electrically isolate the anode from the cathode
• Block or screen the cathode to prevent anions
from accessing the electrons produced by the
anodic reaction
• Coat the entire metal surface with a barrier
layer
• Alter the voltage difference between the
cathode and the anode to stop the flow of
electrons
 Solution Properties
• Acidity and alkalinity
• Ionization constant
• Solubility product constant
 Problem Example 2.1

• The corrosion of aluminum produces Al+3 ions in solution. Write an

expression for the solubility product of aluminum hydroxide. If the
concentration of Al+3 ions in solution is 1.0 x 10-6M, will aluminum
hydroxide precipitate at pH 9.0? The tabulated value for Ksp for
aluminum hydroxide is 1.3 x 10-33.
 Faraday and Faraday’s Law
• Corrosion involves simultaneous charge
transfer and mass transfer across
metal/solution interface
W=ItA
nF
W = mass
I = Current (Amps)
t= time (sec)
A= molecular (atomic) weight
n= # equivalents transferred/mol of metal
 Example 2.2

• Plain carbon steel immersed in seawater has a uniform corrosion

rate expressed as a penetration rate of 5.0 mpy (mils per year,
where 1 mil is 0.001 inches). The density of iron is 7.87 g/cm3. The
molecular weight of iron is 55.8 g/mol.

• Calculate the weight loss after 1 year exposure

• Calculate the corresponding corrosion current density in
microamperes per square centimeter (µA/cm2) assuming that the
corrosion current is given by:

Fe Fe+2 + 2e-
Measurement of Corrosion
 Homework Assignment
• Please answer problems #4, #8 and #12.