Lecture 12: Mixed Potential Theory Bimetallic Couples

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Lecture 12 Mixed Potential Theory Bimetallic Couples

Keywords: Bimetallic Couples, Area Ratio, Exchange Current Density.

Application of the mixed potential theory to some bimetallic systems can now be considered.

Iron Platinum couple

A very noble metal coupled to a very active metal, when significantly enhanced corrosion of iron in a corrosive medium can be expected.

iaFe= icH(Pt)

+ i H(Fe) - Pt ia c

Where ia and ic represent anodic and cathodic current densities and A is relative surface area. Since corrosion rate of platinum in the couple can be neglected due to its very high nobility,

iaFe= icH(Pt)

+ i H(Fe) c

Pictorial representation of half cell reaction with respect to corrosion of iron when present alone and when present in contact with platinum (assuming equal areas) is illustrated in Fig 12.1.

1 Course Title: Advances in Corrosion Engineering Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore

Lecture 12: Mixed Potential Theory Bimetallic Couples

NPTEL Web Course

Fig 12.1 Corrosion of iron in the absence and presence of platinum (as bimetallic couple) in acid medium.

Presence of platinum in the couple is very significant due to the following factors: a) Provides additional cathodic surfaces for hydrogen reduction. b) Exchange current density for hydrogen reduction on platinum is very much higher than that on iron ( A/cm2 on Fe) c) If the area ratio of platinum to iron (larger cathode in contact with smaller anode), is increased, the effect of coupling with platinum on the corrosion rate of iron will be magnified. for Pt is 10-2 A/cm2 compared to 10-6

The corrosion rate of an active metal such as iron or zinc thus depends on a) What cathodic metal they are coupled with in relation to the exchange current density for the reduction reaction. b) pH and nature of the cathodic reactant For example, if the Fe-Pt couple (having higher cathode to anode surface area ratio) is exposed to neutral pH solution where oxygen reduction is the cathodic reaction (instead of H2), the expected effect of noble metal (Pt) would be not so significant since the exchange current densities for oxygen
2 Course Title: Advances in Corrosion Engineering Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore

Lecture 12: Mixed Potential Theory Bimetallic Couples

NPTEL Web Course

reduction on both the surfaces are nearly same. Also, if lead metal is coupled with iron instead of platinum in acid solution, the effect of coupling on anodic oxidation of iron would be rather negligible, since the exchange current density for hydrogen reduction on lead is very much lower than that on iron.

Iron Zinc couple

Understanding the behavior of the iron-zinc couple in a corrosive environment is important since galvanizing is universally used to protect steel structures from corrosion. The role of zinc as a sacrificial anode is of industrial significance. To analyze the corrosive behavior of iron in presence of zinc,

iaFe = icH(Zn)

icH(Fe) iaZn

It is known that iaZn>>icH(Zn)

Enhanced Zinc oxidation rate would lower the rate of corrosion for iron. The effect zinc depends on the ratio of icH(Zn) / iaZn and iron will be protected as long as this ratio is smaller.

The relative areas of the two metals in a couple influence its galvanic behavior. Increasing cathodic surface areas for a fixed anode area will increase the anodic corrosion rate proportionately. Similarly, if the anodic surface areas are increased for a constant cathode area, anodic oxidation rate can be lessened.

Effect of exchange current density for the cathodic reaction on two noble metals (gold and platinum) on the corrosion behavior of an active metal such zinc can now be examined.
3 Course Title: Advances in Corrosion Engineering Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore

Lecture 12: Mixed Potential Theory Bimetallic Couples

NPTEL Web Course

From the EMF series, E0Au/Au+++ = + 1.42V E0Pt /Pt++ = + 1.2V

Gold is nobler than platinum,

However, in the galvanic series, the above position is seen to be reversed (platinum nobler than gold). Behavior of two types of noble metal-active metal couples on the anodic corrosion behavior in an acid solution can be understood taking into consideration Au Zn and Pt Zn couples. Exchange current density for hydrogen reduction on platinum and gold are 10 -2 A/cm2 and 10-6 A/cm2 respectively. Under the circumstances, higher corrosion rate (icorr) for zinc can be expected when coupled to platinum than when contacted with gold (cathodic surface area remaining similar in both cares).

4 Course Title: Advances in Corrosion Engineering Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore

Lecture 12: Mixed Potential Theory Bimetallic Couples

NPTEL Web Course

Effect of cathodic surface area on the corrosion rate of an anodic metal is illustrated in the figure given below. An active metal M is coupled to a noble metal N in an acid solution. Two surface areas for the noble metal N is considered, namely, 1cm2 and 10cm2.

Fig 12.2 Effect of change in cathodic surface area on the corrosion rate of an active metal

Corrosion rate for M is the highest when coupled to 10 cm2 of N compared to 1 cm2 of N (see Fig. 12.2). Unlike the case with coupling of an active metal with a very noble metal (such as platinum or gold) effect of coupling of two corroding metals in a corrosive acid medium can also be analyzed in the following lines (assuming equal areas). a) The combined potential of the couple (eg:- Fe Zn) will lie in between the uncoupled corrosion potentials of the two metals. b) The corrosion rate of the most active one among the couple (Zn in case of coupling with Fe) will always be enhanced, with a simultaneous decrease in
5 Course Title: Advances in Corrosion Engineering Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore

Lecture 12: Mixed Potential Theory Bimetallic Couples

NPTEL Web Course

the corrosion rate of the relatively noble metal (iron for example in contact with zinc). c) It is generally true in case of all galvanic couples that their corrosion behavior is determined by their electrode potentials, exchange current densities, relative surface areas and magnitude of overpotentials.

6 Course Title: Advances in Corrosion Engineering Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore