08Y506 - CORROSION ENGINEERING

Lecture 2 Fundamentals of Electrochemistry

Anodic Reactions (1) Oxidation of metal to an ion with a charge. (2) Release of electrons. (3) Shift to a higher valence state.
The process of oxidation reactions in most metals and alloys are corrosion

Cathodic Reactions
Cathodic reactions are reduction reaction occurs at cathode. (a) (b)
(c) (d) (e)

2H+ + 2e > H2 (in acid solution) 02 + 4H+ + 4e -> 2H20 (in acid solution)

(f)

2H20 + 02 + 4e + 40H- (in neutral and alkaline solutions) 3+ 2+ Fe + e - Fe (metal ion reduction in ferric salt solutions) 2+ Metal deposition: M + 2e -> M ++ Ni + 2e -> Ni 2+ Cu + 2e -> Cu + Bacterial reduction of sulfate: SO42- + 8H +8e -> S + 4H20

Types of corrosion Cell

1. 2. 3. Galvanic cells Concentration cells Electrolytic cell Differential temperature cells.

4.

1. Galvanic cell
The galvanic cell may have an anode or cathode of dissimilar metals in an electrolyte or the same metal in dissimilar conditions in a common electrolyte. For example, steel and copper electrodes immersed in an electrolyte (Fig. 2.1), represents a galvanic cell. The more noble metal copper acts as the cathode and the more active iron acts as an anode. Current flows from iron anode to copper cathode in the electrolyte.

Esakkiraja N PSG College of Technology Coimbatore - 4

08Y506 - CORROSION ENGINEERING

Lecture 2 Fundamentals of Electrochemistry
Fig. 2.1 Galvanic cell

2. Concentration cells

Fig. 2.2 Concentration cell

The same electrodes are kept in a two different concentration solution make the cell active and it forms anode at high concentration solution and cathode at less concentration solution in cell. Concentration cells may be set up by: (a) Variation in the amount of oxygen in soils. (b) Differences in moisture content of soils. (c) Differences in compositions of the soil.

Fig. 2.3 Electrolytic cell

3. Electrolytic cell This type of cell is formed when an external current is introduced into the system. It may consist of all the basic components of galvanic cells and concentration cells plus an external source of electrical energy. The redox reaction in an electrolytic cell is nonspontaneous. Electrical energy is required to induce the electrolysis reaction. An example of an electrolytic cell is shown in fig 2.3, in which molten NaCl is electrolyzed to form liquid sodium and chlorine gas. The sodium ions migrate toward the
Esakkiraja N PSG College of Technology Coimbatore - 4

08Y506 - CORROSION ENGINEERING

Lecture 2 Fundamentals of Electrochemistry

cathode, where they are reduced to sodium metal. Similarly, chloride ions migrate to the anode and are oxided to form chlorine gas. This type of cell is used to produce sodium and chlorine. The chlorine gas can be collected surrounding the cell. The sodium metal is less dense than the molten salt and is removed as it floats to the top of the reaction container. Differences between a Galvanic cell and an Electrolytic cell
Electrochemical cell (Galvanic Cell) A Galvanic cell converts chemical energy into electrical energy. Here, the redox reaction is spontaneous and is responsible for the production of electrical energy. The two half-cells are set up in different containers, being connected through the salt bridge or porous partition. Here the anode is negative and cathode is the positive electrode. The reaction at the anode is oxidation and that at the cathode is reduction. The electrons are supplied by the species getting oxidized. They move from anode to the cathode in the external circuit. Electrolytic cell An electrolytic cell converts electrical energy into chemical energy. The redox reaction is not spontaneous and electrical energy has to be supplied to initiate the reaction. Both the electrodes are placed in a same container in the solution of molten electrolyte. Here, the anode is positive and cathode is the negative electrode. The reaction at the anode is oxidation and that at the cathode is reduction. The external battery supplies the electrons. They enter through the cathode and come out through the anode.

Fig. 2.4 Oxygen cell (Concentration cell)

Fig. 2.5 Differerntial temperature cell (Corrosion cell)

4. Differential temperature cells Differential-temperature cell corrosion occurs most frequently in heat-transfer equipment and piping, where substantial temperature differences exist between the inlet and the outlet portions exposed to the same electrolyte.

Esakkiraja N PSG College of Technology Coimbatore - 4

08Y506 - CORROSION ENGINEERING

Lecture 2 Fundamentals of Electrochemistry

Faradays Law of Electrolysis The First Law The mass of primary products formed at an electrode by electrolysis is directly proportional to the quantity of electricity passed. Thus: M It where I = current in amperes t = time in seconds M = mass of the primary product in grams Z = constant of proportionality (Electrochemical equivalent). It is the mass of a substance liberated by 1 ampere-second of a current (1 coulomb). The Second Law The masses of different primary products formed by equal amounts of electricity are proportional to the ratio of molar mass to the number of electrons involved with a particular reaction: M m/n Z Z = k (m/n) ---------- (2) where M = masses of primary product in grams m = molar masses (g.mol-1) n = number of electrons Z = electrochemical equivalent. Combining the first law and the second law, as in equation (1) Substituting for Z, from equation (2) into (1) M = k(m/n) It K = 1/F M = (1/F) (m/n) It Where F = Faraday's constant. It is the quantity of electricity required to deposit the ratio of mass to the valency of any substance and expressed in coulombs per mole (C (g equiv.)-1). It has a value of 96485 coulombs per gram equivalent. This is sometimes written as 96485 coulombs per mole of electrons.
Esakkiraja N PSG College of Technology Coimbatore - 4

or

M = Zit ---------- (1)

---------- (3)

08Y506 - CORROSION ENGINEERING

Lecture 2 Fundamentals of Electrochemistry

Faraday's Laws in Determination of Corrosion Rates of Metals and Alloys Corrosion rate has dimensions of mass x reciprocal of time: (g-y-1 or kg-s-1) In terms of loss of weight of a metal with time, from equation (3), we get dw/dt = mI/nF The rate of corrosion is proportional to the current passed and to the molar mass. Dividing equation (3) by the exposed area of the metal in the alloy, we get w/At = mI/nFA I/A current density (i) w/At = mi/nF ---------- (5) - ------- (4)

The above equation has been successfully used to determine the rates of corrosion. A very useful practical unit for representing the corrosion rate is milligrams per decimeter square per day (mg.dm-2.day-1) or mdd. Other practical units are millimeter per year (mmy-1) and mils per year (mpy). Corrosion rate expressions Corrosion penetration rate (mpy) = 534 w/DAT Where W Weight loss in (mg) D Density of metal (g/cm3) A Area of metal (inch2) T Time of exposure (hr)

Esakkiraja N PSG College of Technology Coimbatore - 4