Beruflich Dokumente
Kultur Dokumente
Thermodynamics –
the equilibrium between metals and their
environment
Corrosion tendency of metals
Qualitative picture of what can happen at a given
pH and potential
But…
Real potential = E
2Hads → H2
w I i
Faraday’s law: (2)
At AnF nF
2.3RT 1 2.3RT
1 0.337 log 2
0.337 log(Cu 2
)
nF (Cu ) nF
Contd..
2.3RT 1 2.3RT
2 0.337 log 2
0.337 log(Cu 2
)S
nF (Cu )S nF
Contd..
it
(Cu 2 ) S (Cu 2 )
DzF
2 iLt
(Cu )
DzF
2.3RT i
Conc 2 1 log1
nF iL
il
k
IR Drop
When polarization is measured with a potentiometer and a
reference electrode-Luggin probe combination, the measured
potential includes the potential drop due to the electrolyte
resistance and possible film formation on the electrode surface
The drop in potential between the electrode and the tip of Luggin
probe equals iR.
Effect of temperature,
concentration and
velocity of the aqueous
environment on combined
polarization is shown in
the figure
Combined Polarization
Stern-Gray Equation:
Δ iappl βc βa
icorr
2.3 Δφ βc βa
The Area Effect
Usually cathodic reactions are slower than anodic
reactions
For a cathodic reaction to occur, there must be available
sites on the metal surface. Corrosion cells will not work
when the cathodic area is too small for surface sites
In a galvanic cell, the anode/cathode area ratio is an
important factor for severity of corrosion attack
A large cathode causes severe attack on a small anode
If we cannot avoid situations for galvanic corrosion, we
may reduce thinning by making the anode material of
large surface area and cathode of smaller area.
The Area Effect
Copper plates with steel rivets in Steel plates with copper rivets in
seawater seawater
Steel rivets severely attacked Tolerable corrosion of steel plate
Large cathode/small anode Small cathode/large anode
Influence of Polarization on Corrosion Rate