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How does corrosion occur?
ELECTROCHEMICAL CORROSION
Ex: consider the corrosion of zinc in an acid solution
Two reactions are necessary:
Zn Zn2 2e
-- oxidation reaction:
-- reduction reaction:
2H 2e H2 (gas)
H+
Oxidation reaction
Zn Zn2+
H+
Zinc
flow of e
2ein the metal
H+
H+ +
H
H+
H2(gas)
H+
reduction reaction
Acid
solution
H2(gas)
Mn+ H+
ions
H+
e-
25C
e-
ne -
2e -
metal, M
metal, M
ne -
e-
Platinum
e-
Mn+
ions
H+ 2e H+
H2(gas)
Platinum
-- Corrosion
25C
o
Vmetal
0 (relative to Pt)
o
Vmetal
0 (relative to Pt)
more anodic
more cathodic
EMF series
metal
Au
Cu
Pb
Sn
Ni
Co
Cd
Fe
Cr
Zn
Al
Mg
Na
K
o
Vmetal
+1.420 V
Ex: Cd-Ni cell
+0.340
o
o
V
<
V
Cd corrodes
Ni
Cd
- 0.126
- 0.136
+
- 0.250
DV o =
- 0.277
0.153V
- 0.403
- 0.440
Cd
Ni
25C
- 0.744
- 0.763
- 1.662
1.0 M
1.0 M
- 2.363
Cd 2 + solution Ni 2+ solution
- 2.714
Adapted from Fig. 17.2,
Data based on Table 17.1,
Callister & Rethwisch 8e.
- 2.924 Callister 8e.
4
V V 0.153 V
o
Ni
o
Cd
Cd
25C
Ni
1.0 M
1.0 M
Cd 2+ solution Ni 2+ solution
VNi VCd
Cd
RT X
V V
ln
nF Y
o
Ni
o
Cd
Ni
XM
YM
Cd 2 + solution Ni 2+ solution
n = #eper unit
oxid/red
reaction
(= 2 here)
F=
Faraday's
constant
= 96,500
C/mol.
GALVANIC SERIES
more anodic
(active)
more cathodic
(inert)
FORMS OF CORROSION
Stress corrosion
Uniform Attack
Oxidation & reduction
reactions occur uniformly
over surfaces.
Combined action of
stress & corrosive
environment
Selective Leaching
Corrosion along
grain boundaries,
often where precip.
particles form.
g.b.
prec.
attacked
zones
Fig. 17.18, Callister &
Rethwisch 8e.
Pitting
Preferred corrosion of
one element/constituent
[e.g., Zn from brass (Cu-Zn)].
Intergranular
Erosion-corrosion
Forms
of
corrosion
Galvanic
Downward propagation
of small pits and holes.
Fig. 17.17, Callister &
Rethwisch 8e. (Fig. 17.17
from M.G. Fontana,
Corrosion Engineering,
3rd ed., McGraw-Hill Book
Company, 1986.)
Metal oxide
Metal (e.g., Al,
stainless steel)
Zn 2+
zinc
zinc
2e - 2e steel
steel
pipe
e-
Cu wire
Mg Mg 2+
anode
Earth
e.g., Mg Anode
Adapted
from Fig.
17.22(a),
Callister &
Rethwisch
8e.
CORROSION RATE
10
PREDICTION OF CORROSION
RATES
Polarization = displacement of electrode
potential from its equilibrium value
2 types of polarization : activation or
concentration
Magnitude displacement = Overvoltage ()
11
Activation Polarization
12
Concentration Polarization
Under what conditions is concentration
polarizing rate controlling?
the reaction rate is high and/or
the concentration of active species in the
liquid solution is low.
13
SUMMARY
Metallic corrosion involves electrochemical reactions
-- electrons are given up by metals in an oxidation reaction
-- these electrons are consumed in a reduction reaction