Corrosion Engineering

Lecture 5
CHE 311
Corrosion electrochemistry
 Metallic corrosion has been defined in Note 2 as an electrochemical reaction,
involving the transfer of electrons.
Corrosion Reactions
 It is also a chemical reaction which involves oxidation and reduction Examples.

 Notice the increase in valence or production of electrons. General form of oxidation

or anodic reaction is
M0 M+n + ne
 The counter reaction for oxidation is the “reduction” or cathodic reaction” which is a
decrease in valance charge or consumption of electrons
Redox Reactions
 Reduction of Hydrogen Ions
 2H+ + 2e H2

 Oxygen reduction in neutral solutions

 O2 + 2H2O + 4e 4 OH−

 Metal deposition
 Cu(+2) + 2e Cu (metallic copper)
Metallic Redox Reaction
 During metallic corrosion, the rate of oxidation equals the
rate of reduction. There could be more than one anodic
reaction (e.g. alloys) and more than one cathodic reaction.
We may conclude that:
 Corrosion reactions are electrochemical in nature (electron
production & consumption).
 It is possible to divide corrosion reactions into anodic and
cathodic reactions.
 Rate of oxidation equals rate reduction.
Mechanism of Rusting
 Only iron and steel can rust. Other metals corrode and produce oxides. Normally
rust is a flaky red-brown solid product which is largely hydrated iron. The
primary corrosion product of iron is ferrous hydroxide or hydrous ferrous oxide
[Fe(OH)2], but the action of oxygen and water can lead other corrosion products
having different colors.

 The reaction processes for iron is:

 Anodic reaction: 2Fe 2Fe(+2) + 2e
 Catodic reaction: O2 + 2H2O 4 OH-
 Overall reaction: 2Fe + O2 + 2H2O 2Fe(OH)2
Mechanism of Rusting
 Fe(OH)2 is the primary corrosion product of iron, called ferrous hydroxide. With
more action of oxygen and water, another rust will form:

 2 Fe (OH)2 + ½ O2 + H2O 2 Fe (OH)3

 Fe(OH)3 is a corrosion product named ferric hydroxide. It is the principal

component of red – brown rust. It can form a mineral called hematite.
Cathodic Reactions
 Hydrogen ion reduction
 2 H+ + 2e H2
 Important in acidic solutions.
 Reduction of water
 2 H2O + 2e H2 + 2OH-
 Occurs normally in natural waters.
 Oxygen reduction
 O2 + 4H+ + 4 e 2 H2O
 Occurs in aerated acidic solutions
 Oxygen reduction of water
 O2 + 2 H2O + 4e 4OH-
 Important in natural, aerated waters.
Cathodic Reactions
 Ferric ion reduction
 Fe(+3) + e Fe(+2)
 Occurs under acidic, turbulent conditions (e.g., acid cleaning).

 Metal deposition
 M(+n) + (n)e M e.g. Cu(+2) + 2e Cu

 Sulfate ion reduction

 4 H2 + SO4(–2) S(-2) + 4H2O
 Occurs in the presence of sulfate reducing bacteria (SRB) in deaerated
environments.

 Bisulfide reduction
 2HS + 2e 2S + H2
Example
 Example 1: Write the oxidation and reduction reactions which occur during the
reaction of aluminum by air free sulfuric acid.

 Oxidation reaction: AL 3e + AL(+3)

 Reduction reaction : 2H(+) + 2e H2

 Example 2: Write the oxidation and reduction reactions for the corrosion of iron
in aerated sulfuric acid containing ferric sulfate.

 Oxidation reaction: Fe 2e + Fe(+2)

 Reduction reaction :
 A) 2H(+) + 2e H2
 B) O2 + 4H(+) + 4e 2H2O
 C) Fe(+3) +e Fe (+2)
Example
 Example 3: Write the oxidation and reduction reactions for the corrosion of
SS304 alloy in aerated HCl.

 Oxidation reaction:
 A) Fe Fe (+2) + 2e
 B) Cr Cr(+3) + 3e
 Reduction reaction :
 A) 2H(+) + 2e H2
 B) O2 + 4H(+) + 4e 2H2O
Corrosion rate
 Basic Electricity
 Ohm's Law
 Volts = amperes * Ohms
 V=I xR

 Electrical charge (q)

 q = amperes x time
 q=I xt

 Resistance (R)

L
ρ
 R= , L/A is shape factor
A

 Electrical Energy (E)

 E=V xI xt=V xq
Corrosion rate
 Faraday's Law:  m = kIt

k= M
nF
 Where:
 m = (net mass produced or consumed) in grams
 I = current in amperes (A)
 k = electrochemical equivalent
 t = time (seconds)
 F = Faraday constant = 96500 C/eq
 M = molecular weight

 Few values for k

Metal n Mwt K (g/C)
Fe 2 55.84 2.893E-4
Zn 2 65.38 3.39E-4
Al 3 17.98 6.21E-5
Corrosion rate
 Faraday’s equation
 G = E * (- n F)
 Where:
  G = Free energy change of the corrosion process.
 E = Potential (Volts)
 n = The number of electrons transferred in the corrosion reaction.
 F = Faraday = 96484 C/eq.
 1 mole of metal of valence n converted into ions gives n x 96494 C.
Corrosion Rate Calculations
 Corrosion rate can be expressed in different ways. The most common ways are:
 Weight loss.
 Penetration loss.
 Corrosion current.

 1- Weight Loss: The initial and final weight of a coupon is measured. The corrosion
rate (C. R.) expression is based on this weight loss, the time of exposure and the
area of the coupon. The rate expression
Weight is
loss
C.R.= (Time) (Area)

 The weight loss gives the average corrosion rate.

 Two common units
 1. Milligrams per day per square decimeter (mdd)
 2. Grams per square meter per day (gmd)

 Conversion factor: 10 mdd = 1 gmd.

Corrosion Rate Calculations
 2- Penetration loss: This method is based on the loss of thickness. The
corrosion rate expression is
Thickness loss
C.R.= Time
 The most common used units are mils per year (mpy), inches per year
(ipy), and millimeters per year (mmy).
 Some conversion factors between the weight loss and penetration loss are
presented

To get mdd To get mpy

Multiply by Multiply by
mpy 0.696 D mdd 1.437/D
ipy 696 D ipy 1000
mmy 27.4 D mmy 39.4

 1 mil = 0.001'' = 0.025mm

 40 mils = 1mm
 D is the density in g/cm3


Corrosion Rate Calculations

   Corrosion current: The corrosion current (Icorr.) can be obtained from the
3-
knowledge of the theoretical weight loss ( m) and the time (t) of exposure
according to Faraday's law:

m = (k) (t) (Icorr)

 Where m in grams, t, in seconds, k is the electrochemical equivalent in
grams per coulomb (g/C). Few relations are obtained between corrosion rates
and current.

Where, I is the current density in A/cm2, M is the atomic weight and n is the
oxidation state.