Chapter 4

Corrosion electrochemistry

This chapter presents two subjects:

I. Corrosion Reactions
II Corrosion Rates

I. Corrosion Reactions
Metallic corrosion has been defined in Chapter 2 as an
electrochemical reaction, involving the transfer of electrons. It is also
a chemical reaction which involves oxidation and reduction.
Oxidation (Anodic) reactions

1 5

2 6

3 7

4 8

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

oxidation or anodic reaction is

M0 M+n + ne (A)

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The counter reaction for oxidation is the “reduction” or cathodic reaction”
which is a decrease in valance charge or consumption of electrons.
Cathodic (Reduction) reactions:
Reduction of hydrogen ions.
2H+ + 2e H2
(Hydrogen evolution)
Oxygen reduction in neutral solutions
O2 + 2H2O + 4e− 4OH−

Metal deposition
Cu +2 + 2e Cu (metallic copper)
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

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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+ + 4e
Cathodic reaction: O2 + 2H2 O + 4e- 4
Overall reaction: 4Fe + 3O2 + 2H2O 4Fe (OH)2

Fe(OH)2 is the primary corrosion product of iron, called ferrous

hydroxide , it has the color of green to greenish black rust . 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 rust; it has the color of red – brown rust. It can form a mineral
called hematite.

Some typical cathodic reactions:

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 a. Hydrogen ion reduction
2 H+ + 2e - H2
Important in acidic solutions.

b. Reduction of water
2 H2 O + 2e - H2 + 2
Occurs normally in natural waters.

c. Oxygen reduction
O2 + 4H+ + 4 e- 2 H2 O
Occurs in aerated acidic solutions.

d. Oxygen reduction of water

O2 + 2H2 O + 4e- 4
Important in natural, aerated waters.

e. Ferric ion reduction

Fe +3 + e- Fe +2
Occurs under acidic, turbulent conditions (e.g., acid cleaning).

f. Metal deposition

M +n + ne → M e.g. Cu+2 + 2 e → Cu

g. Sulfate ion reduction

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

h. Bisulfide reduction
2HS + 2e 2S + H2
Examples on Chapter 4
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Example 4.1
Write the oxidation and reduction reactions which occur during the
reaction of aluminum by air free sulfuric acid.
Answer:
Oxidation reaction: Al Al+3 + 3e

Reduction reaction: 2H+ + 2e H2

Example 4.2

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

Answer:

Oxidation reaction: Fe Fe+2 + 2e

Reduction reaction: 1. 2H+ + 2e H2

2. O2 + 4H+ + 4e 2H2O
3. Fe+3 + e Fe+2
Example 4.3

Write the oxidation and reduction reactions for the corrosion of SS304
alloy in aerated HCl.

Answer:
Oxidation reaction: 1. Fe Fe+2 + 2e
2. Cr Cr+3 + 3e

Reduction reaction: 1. 2H+ + 2e H2

2. O2 + 4H+ + 4e 2H2O
II Corrosion Rates

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 Important Laws
 Basic Electricity Review
Ohm's Law
Volts = amperes * Ohms
V=I¿ R

Electrical charge (q)

q = amperes ¿ time
=I¿ t
Resistance (R)
t
ρ
R= Ac

Electrical Energy (E)

E=V¿ I¿ t=V¿ q

Basic Law for Corrosion

Faraday's Law
(4.1)

Where
= (net mass produced or consumed) in grams
I = current in amperes (A)
k = electrochemical equivalent
t = time (seconds)
F = Faraday = 96500 C/eq
M = molecular weight
Remark: I, is an indication of corrosion rate.

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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

 Faraday’s equation
Δ G = ΔE * (- n F)

Δ G = Free energy change of the corrosion process.

ΔE = Potential difference (Volts) – driving force.
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¿ 96494 C.

Corrosion Rate Calculations

Corrosion rate can be expressed in different ways. The most common ways
are:
1- Weight loss (gives general corrosion on the surface)
2- Penetration loss.
3- 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 is:

C.R.= (4.2)

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 Δm = mf - mi (in milligrams)
Time in days
Area in dm2
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.

2. Penetration loss: This method is based on the loss of thickness. The

corrosion rate expression is:

Thickness loss
C.R. = Time (4.3)
Thickness: mills, inches, and mm
Time: Years
1 mil = 0.001'' = 0.025mm
40 mils = 1mm

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 in Table 1.

Table 1: Some conversion factors for the corrosion rate:

To get mdd To get mpy

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 Multiply by Multiply by
mpy 0.696 D mdd 1.437/D
ipy 696 D ipy 1000
mmy 27.4 D mmy 39.4
D is the density in g/cm3

3. Corrosion current: The corrosion current (Icorr.) can be obtained

from the knowledge of the theoretical weight loss ( m) and the time
(t) of exposure according to Faraday's law:

m = (k) (t) (Icorr) (4.1)

Where m in grams, t, in seconds, k is the electrochemical equivalent in

grams per coulomb (g/C), and I = current in amperes (A)

Few relations are obtained from eqn. (4.1) as shown in Table (2):

Table 2: Relationships among corrosion rates

and current

mdd = 89.55 ¿ 103 i M/n (4.4)

gmd = 8.955 ¿ 103 i M/n (4.5)
mpy = 1.287 ¿ 105 i M/n ¿ D (4.6)

ipy = 1.287 ¿ 102 i M/n ¿ D (4.7)

mmy = 3.27 ¿ 103 i M/n ¿ D (4.8)

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

Corrosion Rate for an alloy:

Definitions
ai = the atomic weight of the (i) species in the alloy
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 ni = the number of electrons exchange of the (i) species in the alloy

f i = mole fraction of the (i) species in the alloy

= number of equivalents of the (i) species in the alloy

= total number of equivalent.

1
EW =

The equivalent number, EQ N

The corrosion rate of any alloy may be estimated from Eqn.(4)

C.R. = C (4)
Where , , i = the current density in
Two common equations for the corrosion rates of an alloy are:

1. C.R. in mpy = 1.287 ¿ 105 (i) (EW) / Dav (5)

2. C.R. in mmy = 3.27 ¿ 103 (i) (EW) / Dav (6)

Example 4.4
A specimen has a surface area of 100 in2. Weight loss = 7.3216 grams for 50
days. Find the C.R. in mdd.
Solution:

cm =6.4516 dm
2
(100)(2.54)(2.54 ) 2

A = 100 in2 = (10)(10) cm 2 /dm 2

= 7.3216 gram = 7321.6 milligrams

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 C.R. =

7321.6 mg
2
=22. 6970 mdd
= (6. 4516 dm )(50 days )

Example 4.5

What is C.R. in mpy if the specimen in Example (1) is from steel?

gm
1.437 3
( ), cm
C.R. = mdd D for steel, D = 7.87

1. 437
= (22.6970) ( 7 .87 ) = 4.1443 mpy

Example 4.6

What is the corrosion current density in A/cm2 for zinc corresponding to

a corrosion rate of 0.05 ipy.

Solution

Apply Eqn.4.7: ipy = 1.287 ¿ 102 i M/n ¿ D (4.7)

Reaction: ,n=2

Required data: M = 65.37 g/mole , D = 7.14 g/cm3

Given Data: C. R. = 0.05 ipy

Insert all numerical values in Eqn. (4.7), we obtain:

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0.05 = 1.287 ¿ 102 (4.57773) (i)

i = 0.8487¿ 10-4 A/cm2 = 0.8487 A/m2

Example 4.7

A zinc specimen exposed to an acidic solution loses 25 milligrams during

12 hours exposure:
(a) What is the equivalent current flowing due to corrosion?
(b) If the specimen area is 200 cm2, what is the corrosion rate in mdd?
(c) What is the corrosion rate in mpy?

(a) What is the equivalent current flowing due to corrosion?

Solution
Reaction: ,n=2

(a) Use Eqn. (4.1):

(4.1)

Where

= (net mass produced or consumed) in grams

I = current in amperes (A)
k = electrochemical equivalent
t = time (seconds)
F = Faraday = 96500 C/eq
M = molecular weight

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Essential Data:

, M = 65.37 g/mole ,
t = (12 hr) (3600 s/hr) = 43200 s , n = 2 , F = 96500 C/ eq
k = 3.387E-4
Answer: I = 1.707E-3 A

(b) If the specimen area is 200 cm2, what is the corrosion rate in mdd?

Use Eqn. (4.2):

Weight loss
C.R.= ( Time )( Area ) (4.2)

To obtain C.R. as mdd, we need the following data:

Weight loss = (mg) = 25 mg

Time in days = 12/24 = 0.5 day
Area in dm2 = 2 dm2
Answer C.R. (mdd) = 25 mdd (b)

(c) What is the corrosion rate in mpy?

Use Eqn. (4.6):

mpy = 1.287 ¿ 105 i M/n ¿ D (4.6)
Required data:

M = 65.37 g/mole , n=2 , D = 7.14 g/cm3

Answer: C.R. (mpy) = 5.04 mpy (c)

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Example 4.8
Calculate the C.R. for 304 SS alloy in mpy equivalent to 1 μ A/cm2 ?
The alloying elements of SS 304 are
19% Cr, 9.25 % Ni balance = Fe (other elements are small <1% )

Element fi ni ai Di (g/ cm2)

Cr 0.19 3 52 7.1
Ni 0.0925 2 58.71 8.9
Fe 0.717 2 55.85 7.87

EW =

Apply Eqn. (5)

−6

¿ 10
5
(1× 10 A /cm2 ) (25 .12 )
C.R =1.287 7 . 82

= 0.413 mpy

Guidelines for the Corrosion Rate

For handling chemical media whenever the attack is uniform, metals are
classified into three groups according to their corrosion rates and intended
application.
These classifications are as follows:
a) When the C.R. < 0.15 mm/y (<0.005 ipy) — Metals in this category
have good corrosion resistance to the extent that they are suitable for
critical parts, for example: valve seats, pump shafts , impellors and
springs.

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b) When the C.R. is in the range of 0.15 to 1.5 mm/y (0.005 to 0.05 ipy).
Metals in this group are satisfactory, if a higher rate of corrosion can be
tolerated, for example: Tanks, piping, valve bodies, and bolt heads.
c) When the C.R >1.5 mm/y (> 0.05 ipy) — usually not satisfactory.

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