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Effect of coupling of an active metal to an noble metal

Zn with Pt

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The rate of hydrogen evolution is decreased on zinc and increased on platinum because the
io on pt (10-3 A cm-2) is higher than Zn (10-10 A cm-2).

The rate of oxidation of zinc is increased significantly on coupling and zinc dissolves
vigorously. Nothing happens to platinum because Pt has more + ive reduction potential than Zn.

Platinum is an excellent catalyst for reduction of hydrogen and zinc is a poor catalyst.

If the area ratio of Pt to Zn (larger cathode in contact with smaller anode), is

increased, the effect of coupling with Pt on the corrosion rate of zinc will be magnified.

The corrosion rate of an active metal such as zinc or iron thus depends on

1. Cathodic metal they are coupled (i.e., exchange current density

for the reduction reaction is the controlling parameter)

For example, if Pb metal is coupled with Zn instead of

Pt in acid solution, the effect of coupling on anodic
oxidation of Zn would be negligible, since the io for
hydrogen reduction on Pb is very much lower than that
on Zn.
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2. pH and nature of the cathodic reactant

For example, if the Zn-Pt couple is exposed to

neutral pH solution where oxygen reduction is the
cathodic reaction (instead of H2 evolution), the
expected effect of noble metal (Pt) would be not
so significant since the io for oxygen reduction on
both the surfaces are nearly same.

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Effect of galvanic coupling of zinc with gold and platinum:

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According to the thermodynamic approach, the difference between the potential of zinc
(Eo = —0.76V) and gold (Eo = 1.50V) is higher than the difference between the potential of
the zinc (Eo = —0.76V) and platinum (Eo = +1.2V).

So, the Zn-Au couple should corrode faster than Zn-Pt couple according to the
thermodynamic approach.

Surprisingly, Zn-Pt couple corrodes faster than Zn-Au couple, because the hydrogen
reduction rate is the highest on a platinum surface (io = 10-3A cm-2) compared to on gold (10-
6A cm-2). The reduction rate of hydrogen is very low on Zn surface (i = 10-10A cm-2).
o

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Effect of change in cathodic surface area (anode-cathode area ratios):

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The icorr of uncoupled zinc is lower than the icorr of zinc coupled either to Pt
(l cm2) or Pt (10 cm2).

The icorr of Zn coupled to Pt (10 cm2) is highest. The corrosion potential of coupled platinum
shifts to more noble values as the area of platinum surface is increased from l cm2 to 10 cm2.

The smaller the anode to cathode ratio as in the case of Zn coupled to Pt (10 cm2), the
larger is the magnitude of corrosion.

If the anodic surface areas are increased for a constant cathode area, anodic oxidation
rate can be lessened.

Avoid a small anode to cathode area ratio to minimize the risk of

serious galvanic corrosion.