Standard emf series

• EMF series • Metal with smaller

o
V metal o
metal V
metal
corrodes.
Au +1.420 V • Ex: Cd-Ni cell
Cu +0.340
-
more cathodic

Pb - 0.126 +
Sn - 0.136
Ni - 0.250 o
Co - 0.277 V =
Cd - 0.403 0.153V
Cd 25°C Ni
Fe - 0.440
Cr - 0.744
more anodic

Zn - 0.763 1.0 M 1.0 M

Al - 1.662 Cd 2+ solution Ni 2+ solution
Mg - 2.262
Na - 2.714
K - 2.924
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 Galvanic series
• Ranks the reactivity of metals/alloys in seawater

Platinum
Gold
more cathodic

Graphite
(inert)

Titanium
Silver
316 Stainless Steel
Nickel (passive)
Copper
Nickel (active)
Tin
Lead
more anodic

316 Stainless Steel

(active)

Iron/Steel
Aluminum Alloys
Cadmium
Zinc
Magnesium
3
Galvanic Cell e flow

Anode Cathode
Zn Cu
(0.76) (+0.34)

Zn  Zn2+ + 2e Cu2+ + 2e  Cu

oxidation Reduction

Zn will corrode at the expense of Cu

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 Anodic/cathodic electrodes

Anodic/cathodic phases at the

microstructural level

Differences in the concentration of the

Metal ion
How can galvanic cells form?
Differences in the concentration of
oxygen

Difference in the residual stress levels

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 Different phases (even of the same metal) can form a galvanic couple at the
microstructural level (In steel Cementite is noble as compared to Ferrite)
 Galvanic cell may be set up due to concentration differences of the metal ion in the
electrolyte  A concentration cell
Metal ion deficient  anodic
Metal ion excess  cathodic
 A concentration cell can form due to differences in oxygen concentration
Oxygen deficient region  anodic
O2 + 2H2O + 4e  4OH
Oxygen rich region  cathodic
 A galvanic cell can form due to different residual stresses in the same metal
Stressed region more active  anodic
Stress free region  cathodic

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8
9
• The term 'polarization' derives from the early 19th-century
discovery that electrolysis causes the elements in an electrolyte to
be attracted towards one or the other pole.

• Thus, initially 'polarization' was a description of electrolysis

itself.

• In time, as more electrochemical processes were invented, the

term 'polarization' evolved to denote any (potentially
undesirable/desireable) side-effects that occur at the interface
between electrolyte and electrodes.

• Polarization isolate the electrode from the electrolyte,

impeding/delaying reaction and charge transfer between the two.

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• Polarization is a mechanism that typically results in a
change in the potential of an electrode during electrolysis,
when the anode’s potential becomes noble than that of the
cathode. It has the effect of decreasing the output voltage
of batteries, increasing the voltage required for electrolysis
cells or lowering currents.

• Polarization can also be described as a deviation from

equilibrium due to an electric current passing through a
galvanic cell.

• Polarization may occur at the cathode (cathodic

polarization) or at the anode (anodic polarization).

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12
• In electrochemistry, polarization is a collective term for
certain mechanical side-effects (of an electrochemical
process) by which isolating barriers develop at the interface
between electrode and electrolyte.

• These side-effects influence the reaction mechanisms, as well

as the chemical kinetics of corrosion and metal deposition.

• These mechanical side-effects are:

• activation polarization: the accumulation of gasses (or other
products) at the interface between electrode and electrolyte.
• concentration polarization: uneven depletion of reagents in
the electrolyte cause concentration gradients in boundary
layers.

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