Pilling Bed Worth Rule According to this rule, it can be defined that an oxide is protective or non- protective by means

of the volume of the oxide. Therefore , an oxide is protective if the volume of the oxide is as least as great as the volume of the metal from which it is formed. On the other hand, if the volume of the oxide layer is less than the volume of the metal from which it is formed, the oxide layer is porous and hence non protective, because it can not prevent defined that an oxide is protective or non protective by means of the the approach of oxygen to the metal surface below. For example, alkali and alkaline earth metals (Li,Na,K,Rb,Be,Ca,Sr,etc) on oxidation produce oxide deposits of smaller volume than the respective metals from which they were formed. This results in the formation of a porous layer through which oxygen can diffuse to bring about further attack on the metal thus corrosion continues non stop. On the other hand, heavy metals like Al, forms oxide of greater volume than the metal from which they were produced. These non porous continues oxide films prevent the diffusion of oxygen and hence therefore of further attack decreases with increase in the thickness of the oxide film. However as the film grows thicker, their tendency to crack and scale out becomes greater and particularly at high temperature intermittent attack of metal may take place at the exposed parts of the metal.( due to cracking of the oxide film). The ratio of the volume of the oxide to the volume of the metal consumed is known as Pilling Bed Worth Ratio. Pilling Bed Worth ratio = Volume of the oxide formed Volume of the metal consumed

Wet Corrosion or Electrochemical Corrosion Theory The modern electrochemical theory is based on Nerst theory, according to which all metals have a tendency to pass into solution. If a Zn electrode is dipped in a solution of Zn sulphate, the positive Zn ions in the metal electrode are in a continuos vibration and occasionally an ion receive sufficient energy to escape from the metal and pass into surrounding solution.Then the electrode acquires a negative charge , thus each Zn++ passing from metal to solution leaves the electrode deplected of two electrons. Zn ions in solution are attracted to the negatively charged Zinc electrode and some of the ions may be redeposited on the solid electrode. Thus an equilibrium between positive ions in solution and the metal is rapidly established. In the case of Copper, the tendency for Cu++ to go into solution is lesser and their tendency to plate out on the Copper electrode is greater. The tendency of a metal to pass into solution when immersed in a solution of its salt is measured in terms of its electrode potential. If a metal having higher electrode potential comes into contact with another metal having a lower potential, a galvanic cell is set up and the metal having higher electrode potential becomes anodic and goes into solution to a measurable extent. If the surrounding liquid is sufficiently acidic, H2 gas will be evolved at the cathodic metal while the anodic metal dissolves. If the acidity of the surrounding liquid falls below a certain value, the rate of dissolution of the anodic metal slows down and is controlled by the rate rate at which oxygen can diffuse to the cathode and depolarize the corrosion cell. The extent of galvanic corrosion depends upon the difference in the electrode potentials of the two electrode and their respective areas. The greater the difference in the potential of the cathode and anode, the greater will be corrosion. Also the smaller the area of the anode as compare to the cathode the more severe will be the attack. (3) Stress Corrosion Mechanochemical effects are collectively called Stress Corrosion . Mechanical failure of a metal is hastered by a corrosive atmosphere. Caustic embrittlement is a typical example. In boilers used for raising steam the water may be occasionally alkaline. The alkali attracts the boiler plates, consequently to this the boiler plates become brittle. More often this failure occurs near the rivets. After repeated cyclic stresses a metal fails the number of such cycles after which failure occurs is reduced in the presence of a corrosive. This corrosion fatigue is a general phenomena common to most metallic materials. There is a specificity to the metal corrosive combination which would cause cracking. For example , Stainless steel crack in chloride environment but not in Ammonia, whereas Brass crack in Ammonia atmosphere but not in chloride.

Electrochemical or Wet Corrosion

This type of corrosion occurs when aqueous solutions or liquid electrolytes are present. This type is more frequently encountered then the chemical type , when a large number of tiny galvanic cells are formed on a metal surface or when two different metals surface come into contact with each other in the presence of moisture this mechanism occurs. Here two partial reactions occur, one at each electrode . The anodic reaction always the dissociation of the metal ( Corrosion ). M (s) ===========Mn+(aq) + ne-If the corrosion medium is highly acidic or if air is excluded from the system , hydrogen evolution is more likely than the oxygen absorption
M(s) ======== Mn+(aq) + ne--

Cathodic reaction may be (1)oxygen absorption or (2) Hydrogen evolution or (3) Metal deposition. All of these the first two are more probable. 2H+ + 2 e-- ======== H2 (g) If the solution is sufficiently aerated , oxygen absorption occurs. In fairly acidic medium the rkn_ O2 + 2H2O + 4 e- ========2 H2O occurs In alkaline or neutral medium, the reaction occurs O2 + 2H2 O + 4 e--- ==========4OH--- occurs. Metal ion reduction and metal deposition occurs only in special environments such as chemical plants.

During corrosion more than one oxidation or one reduction reaction may occur. If, for example, more than one reduction occur, then the oxidation viz Corrosion will be faster than when only one reduction occur. This is because the total rate of oxidation, must be equal to that of reduction.

Types of corrosion

(1) Pitting Corrosion Pit is a blind hole (cavity) or a through hole (perforation) with a depth layer than the surface cross section . Formation of a pit on a metal surface is the result of highly localized attack.

The mechanism of pitting most often involves the Setting up of differential oxygen concentration cells A drop of water rusting on a metal surface . Dissolved Oxygen concentration is more near the periphery of the drop than at the centre. Therefore the area of the metal in- contact with the extreme ends of the drop are well oxygenated. While the metal part in the contact with the drop centre is starved of oxygen. The former area becomes cathodic to the latter. Metal at the centre get corroded while corrosion product gather at the periphery of the drop. As the anodic area is tiny as compared to the cathodic area, more and more material is removed at the same spot. Thus a hole is formed. The bottom of the pit so formed is further removed from the atmosphere thus becoming a better anode. This is the reason for the autocatalytic nature of the pitting. (2) Waterline corrosion This type of corrosion is generally occurs in the case of Iron dipping partially in stagnant water. The position near the waterline is well aerated and acts as a cathode, areas deep inside are acts as anode since oxygen concentration is smaller. Corrosion takes place in anodic areas and the reduction of oxygen to OHions occur at the cathodic area. The Fe2+ and OHions interact at the region between the anode and cathode to give Fe(OH)2 , which is subsequentaly oxidized by dissolved oxygen to rust. With longer times of the corrosion , the anodic area slowly shifts upwards until whole specimen is corroded.

Factors affecting the corrosion are (1) Temperature With increase in temperature of environment the reaction as well as diffusion rate increases, thereby corrosion rate is generally increases. (2) Humidity The higher the moisture content in the atmosphere , the greater is the rate and the extent of the corrosion because moisture acts as medium for oxygen in air and behaves as an electrolyte in air, e.g. atmospheric corrosion of iron is slow in dry air as compared to moist air. (3) pH Acidic media are generally more corrosive than alkaline and neutral media. The amphoteric metals such as Al, Zn, Pb, are dissolve (corroded) in alkaline solution. The corrosion rate of iron in oxygen free water is slow, until pH is below 5. The corresponding corrosion rate in presence of oxygen is much higher. Zinc is rapidly corroded, even in weakly acidic so. lutions such as carbonic acid suffers minimum corrosion at pH = 11. (4) Nature of Electrolyte Chloride ions present in the medium destroy the passive film and corrode many metals and alloys. On the contrary, some anions like silicates may form an insoluble product (silica gel ) which inhibit corrosion. (5) Presence of impurities in atmosphere Atmosphere in the vicinity of industrial area , contains corrosive gases like so2 and fumes of Hcl & H2SO4. In the presence of these gases the acidity of liquid, adjacent to the metal surfaces, increases and its electrical conductivity also increased. This consequent results in an increase of corrosion on the exposed metal surface. Similarly, in Marine atmosphere presence of Na+ and Clleads to increase the conductivity of liquid layer in contact with the metal surfaces thereby increases the corrosion. (6) Presence of suspended particales. (7) Formation of oxygen concentration cell (8) Conductance of corrosion medium.