CORROSION SCIENCE : Introduction : Most metals (except noble metals like pt, Au, etc) exist in nature in combined

form as oxides carbonates hydroxyl carbonates , sulphides , chlorides etc. During their extraction process , these are reduced to their metallic state from their ores. During extraction of metals, considerable amount of energy is required, consequently, isolated pure metals can be reduced in existed state. Therefore they have a natural tendency to revert back to combined state. Hence , when metal are put in to use in various forms, they are exposed to environment (such as dry gases, moisture, liquid etc. the exposed metal surface begins to decay (i.e., convention into more stable metal compounds.) In other words destruction of the metal state at the surface. This type of metallic destruction may be due to direct chemical attack by the environment or electrochemical attack (similar to reaction in Daniel cell). Definition : Its defined as the destruction of metal or alloys by the surrounding environment through chemical or electrochemical changes. CLASSIFICATION: Corrosion may occur either in a dry environment or in an aqueous medium. Dry corrosion: This involves the direct attack of dry gases mainly through chemical reactions. An important dry corrosion process is the attack by air or oxygen to form an oxide layer over the surface of metal. Wet corrosion: which is common reaction in aqueous medium . the conducting surface of the metal undergoes an electrochemical reaction with the moisture Andrew oxygen present in the atmosphere. This process can be explained on the basis of the electrochemical theory. Problems duel to corrosion: The process of corrosion is slow and occurs at surface of metals. But due to corrosion losses are enormous. (i)it will destruct the life of the equipment /plant/bridge etc. (ii)due to corrosion around 1/4th of world protection of iron is goes waste. Losses due to corrosion, cannot be measured in terms of the cost metals alone, but high cost of fabrication into the equipment/machine tools/structure should also be considered.

Due to corrosion 2 to 2.5 billion dollars per annum all over the world is going to waste. This loss varies from county to county depending on the climate. In India the direct loss due to corrosion amounts to 200crores per annum. Electrochemical theory of corrosion[single metal][wet corrosion method]: (i)According to electrochemical theory, corrosion of metals takes place due to the formation of anodic and cathodic regions on the same metal surface or when two metals are in contact with each other in the pressure of a conducting medium. (ii)At the anode region oxidation reaction takes place and the metal get converted into its ions by liberating electrons. Consequently, metal undergoes corrosion at the anodic region. (iii)at the cathodic region, reduction take place. Since metal cannot be reduced further, metal atoms at the cathodic region are unaffected by the cathodic reaction. Some constitutions of the corrosion medium take part in the cathodic reaction. (iv)the electrons liberated at the anodic region migrates to the cathodic region constituting corrosion current, the metal ions liberated at the anode and some anions liberated at the cathode diffuse towards eachother through the conducting mediumrange and form a corrosion products some where between anode and cathode. This can be explained by taking Fe metal as an example. (v)due to the following regions, their formation of anodic and cathodic region of metal may arise (a)crackness in surface film (b)presence of impurities in the bulk of the metal. (c)difference in oxygen concentration along the metal surface. CORROSION : AT ANODE: M Ex: Fe At cathode: Since metal cannot be reduced further, metal atoms at the cathodic region are not affected . therefore the cathodic reaction depending on the nature of the electrolyte. There are three possible ways in which the reduction can take place. (a)if the solution is deaerated and acidic, the cathodic reaction involves evolution of hydrogen. 2 M+ + neFe
2+

+ 2e-

2H+ + 2e-

H2

(b) if the solution is deaerated and almost neutral the cathodic reaction involves evolution of hydrogen gas and hydroxyl ions. 2H2O +2eH2 + 2OH-

(C) if the solution is deaerated and almost neutral or alkaline oxygen or water are reduced to OH- ions. O2 + 2H2O +4e4OH-

CORROSION of iron produced Fe 2+ ions and OH- ions at the anode and cathode sites respectively. These ions diffuse towards eachother. Since small Fe2+ ions diffuse more rapidly than OH- ions. Their combination occurs more commonly near cathodic region. 2 Fe
2+

+ 4 OH -

2 Fe(OH)2 (INSOLUBLE ppt) ( Ferrous hydroxide)

In an oxidizing environment, it is oxidized to ferri oxide and the yellow rust is , hydrated ferric oxide. 4 Fe(OH)2 + O2 +2H2O Types of corrosion: Depending upon the nature of the metal, environment, stress and strain on the material etc, the metal exibit different types of corrosion , they are (i)Differential metal corrosion. (ii)Differential aeration corrosion ex:pitting corrosion, water line corrosion (iii)Stress corrosion. Ex: inter crystalline corrosion (1)Differential metal corroin[galvanic corrosion] (i)When to dissimilar metals are in contact with each other a potential difference is setup resulting in a galvanic current. (ii)A metal placed high in the electrochemical series is said to be anodic to the one placed below it. Ex: Fe is anodic to Cu, Ni, and Sn(tin) Fe act as cathode when it is contact with Zn, Mg. Fe gets corrodes when it is contact with Cu and Ni; But Zn and Mg gets corrodes when these connect with Fe. 3 2[Fe2O3.3H2O][Rust]

(iii)the rate of differential metal corrosion depends primarily on the amount of the current passing from anode to cathode i.e; on the difference in electrochemical potential, higher the difference faster is the rate of corrosion. Ex: (i) It is iron and copper in contact with an aerated solution of NaCl. A current flows between the two electrodes spontaneously and electrons flow from Fe to Cu, indicating that Fe is the anode and Cu is the cathode. The reaction that take place same as the reaction discussed under electrochemical theory.
e - f low

Fe

Cu

OHFe2+ corrosion product

EX: if a piece of iron combined with copper metal

e - f low

Fe Fe2+ anodic site

Cu 2OH cathodic site

Ex: (iii)
e - f low

Fe 2OH -

Zn Zn2+

cathodic site

anodic site

Differential aeration corrosion: (i)The difference in oxygen or air concentration on the surface of the metal develops a galvanic cell. 4

The part of the metal exposed to higher oxygen concentration acts on the cathodic region and the part of the metal exposed to lower oxygen concentration acts as anodic region, consequently the poorly oxygenated region undergoes corrosion. At anode: (less oxygen concentration) M Mn+ + ne- (oxidation)

At cathode :( more O2 concentration) O2 + 2H2O + 4e4OH- (reduction)

(ii)C orrosion of metals arises as a result of the formation of oxygen concentration cell due uneven supply of air on the metal surface is known as differential aeration corrosion. (a)Pitting corrosion: (i)Pitting corrosion results when small particles of dust get deposited on a steel surface (fig). the proton covered by the dust will not be well aerated compared to the exposed surface. (ii)The covered portion thus becomes anodic with respect to the surface exposed. In the pressure of electrolyte and moisture it starts corrosion by that formations of a pit takes place. (iii)Once a pit is formed the rate of corrosion increases. This is because of the formation of small anodic area (surface).

At anodic region: At cathodic region:

Fe O2 + 2H2O +4e-

Fe2+ 4OH2Fe 2+ + 4 OH2Fe(OH)2

2Fe + O2 + 2H2O

(b) Water line corrosion: (i)The water line corrosion takes place due to the formation of differential oxygen concentration cells. (ii)The part of the metal below the water line is exposed only to dissolve oxygen while the part above the water is exposed to higher oxygen concentration of the atmosphere thus part of the metal below the water act as cathode and free from corrosion. A distinct brown line is formed just below the water line due to deposition of rust. 5

EX: water storage steel tanks Ex: Ocean going ship EX: It is common in water lifting pipes under water. (iv)though ocean going ships suffering differential aeration corrosion, ships sunk under water the difference in oxygen concentration between top and bottom of the ship is negligibly small. Thus the ship is exposed to almost uniform concentration of air and doesnt undergo differential aeration corrosion. (3)Stress corrosion: (i)while fabricated the instrument or a structure due to welding , bending, pressing, reverting and quenching, the stress will be developed on their metal surface. (ii)In corrosion environment, the stress portion behaves anodicaly with respect to unstressed portion, undergoes corrosion. (iii)At the stress portion, the atoms are somewhat displaced (exited state) creating an anodic zones of higher potential. These zones are very active and are attacked even by mild corrosion agents. (iv)It has been found that the presence of both stress and a specific corrosion environment are required for corrosion to occur. Ex: Inter crystalline corrosion (or) caustic embrittlement: (i)It occurs at the stress areas such as reverts, joints and bent portion of steam boiler and heat transferred equipments at high pressure, in which alkaline water attacks the mild steel. Iron under stress boby con.NaOH in the crack Cell representation (ii)The water of the steam boiler is softened by the addition of small amounts of Na2CO3, which makes water alkaline due to the action of Na2CO3 at high pressure. Na2CO3 + H2O 2 NaOH + CO2 Dilute NaOH(in boiler water) iron main

(III)the NaOH, thus formed move in to the crack by capillary action. Duet to the evaporation of water in this cracks the concentration of NaOH in these cracks increase.

(IV)this corrosion environment attack the metal steel (Fe bonds) and as result sodium ferroate (Na2 FeO2) is formed. This sodium ferroate undergoes hydrolysis, depositing magnetite (Fe3O4) 3Na2FeO2 + 4H2O 6Na2FeO2 + 6H2O + O2 6NaOH + Fe3O4 + H2 12 NaOH + 2 Fe3O4.

(V)NaOH regenerated in the process, continues to maintain corrosive environment and continues the corrosion. (VI)The iron in contact with concentrated alkali, being under stress, becomes anode while stress free iron surrounded by dilute alkali becomes cathode. Corrosion takes place at the stress region. The continuation of caustic embrettlement of boiler parts often results in boiler failure or boilers explosion. FACTORS AFFECTING THEIR RATE OF CORROSION: There are several factors which influence the rate of corrosion. (i)Nature of metal. (ii)electrode potential (iii)Nature of the corrosion production (iv)the ratio of anodic and cathodic regions. (v)temperature (vi)pH (vii)presence of oxidizing agent (viii)polarization at anodic and cathodic regions. (i)Nature of the metal : In general, the metals with lower electrode potential are susceptible for corrosion, than the metals with high electrode potential. (ii)Electrode potential[different in potential between anodic and cathodic region] (a)When two dissimilar metals are electrically connected in presence of an electrolyte, the metal which is higher up in the electrochemical series undergo corrosion. (b)The rate of corrosion depends upon the difference in their position, higher the difference, faster is the rate of corrosion. 7

(iii)Nature of the corrosion product The nature of the corrosion product largely decides the rate of further corrosion. The corrosion product formed on the surface of the metal may or may not act as a protective layer. (a)If the corrosion product deposit is insoluble, stable, uniform and non porous it acts as a protective film preventing they further corrosion of the metal i.e; A thin invisible, continues film formed on the surface acts as a barrier between the fresh metal surface and the corrosion environment. (b)On the other hand, if the corrosion production is soluble, unstable, nonuniform and porous the corrosion continues. In such cases the fresh metal surface is exposed continuously to the environment. (c)Metal like Al, Cr, Ti etc are highly passive as their oxides as corrosion products in oxidizing environments. (d)Metals such as Fe, Zn, Mg etc do not form any protective film and are highly susceptible for continous corrosion when exposed to oxidizing environment. (iv)The ratio of anodic and cathodic areas The rate of corrosion largely depends on the relatives size of anode and a cathode. (a)If the metal has a small anodic and large cathodic area(i.e; the ratio of anode to cathode is small) then the corrosion is more intensive and faster in rate. This is explained as follows At anode oxidation takes place and electrons areas liberated. At the cathode these electrons consumed when the anode is smaller and cathode region is large, the electrons liberated at the anode, are rapidly consumed, at the cathode region. This process makes the anodic reaction to take place faster .thus increasing the corrosion rate. (b)If the cathode is smaller, the consumption of electrons will be slower and the corrosion reaction as a whole will be slower. Ex: A broken coating of tin on iron surface, tin is cathodic to iron and the small exposed part of iron acts as anodic region and rest of the large tin coated surface acts as cathodic region. Because of small ratio of anodic to cathodic area, the corrosion rate is very high. (V)temperature : The rate of chemical reaction, in general , increases wityh rises in temperature. Corrosion process is one such chemical reaction. Therefore the rate of corrosion 8

increase as the temperature increases. Increase in corrosion increases the conduction of the corrosion medium, which also contribute to the increase in the corrosion rate. (vi)pH : in general, the rate of corrosion is high when the nature of the environment is acidic. (a)if the pH<3, severe corrosion occurs even in the absence of air due to the continues evolution of hydrogen at the cathodic region. (b)if the pH>10, corrosion of the metal practically ceases, due to the formation of a protecting coating of hydrogen oxide of iron. (c)between pH 10-3, the presence of oxygen is essential for corrosion of iron. (vii)presence of oxidizing agent: The presence of oxidizing agents in the environment increases their corrosion rate of the metal. Even noble metals undergo corrosion in the presence of oxidizing agents. Polarization at anodic and cathodic region: (a)during the process of corrosion, the polarization of anode or cathode decreases the rate of corrosion substantially. (b)because of anodic polarization the tendency of anodic metal surface to undergo oxidation decreases, I,e. the rate of dissolution of metal as metal ions is decreased. This is generally duel to increase in the concentration of ions of the dissolved metal at their vicinity of the electrode (concentration polarization), or due tro the formation of a protected film covering the anode. Because of anodic polarization, the anode reaction becomes slower Anderson overall corrosion rate decreases. (c)cathodic polarization retards cathodic reaction. This is due to chemical polarization of the cathode.i,e. hindering they combination of cathode reactant with the electron.the retarded movement of the cathodic reactant to the cathodic surface or retorted removal of the cathodic reaction product fromm the surface of the cathode also make the cathodic reaction slower. (d)for the corrosion to continue, both cathodic and anodic reaction should take place simultaneously. The slow rate of one of reaction makes their corrosion reaction slower. (e)the presence of depolarizers reduces the polarization effect. In some instances, addition of complexing agent can chelate they ions of the different metal, reducing their concentration almost to zero and consequently decreases anodic polarization notably.as a result corrosion process accelerates considerably. Such complexing agents in this cases are termed as anodic depolarizers. Similarly oxidizing act as

cathodic depolarizer by absorbing electrons from cathode surface. Oxygen itself actually as cathodic depolarizer. CORROSION CONTROL: THE corrosion in general can be controlled by preventing the formation of galvanic cells. The methods commonly used to control corrosion of metal are the following (i)design and selection of the material. (ii)protective coatings (a)Inorganic coatings (i)anodizing (ii)phosphating (b)organic-coatings- paints and enamels. (iii)metal coatings (a)anodic metal coating. (b)cathodic metal coating. (iv)corrosion inhibitors (v)anodic protectors (vi)cathodic protectors (1) design and selection of the material: corrosion can be controlled by selecting proper material which resist the corrosion environment and design them suitably during fabrication. selection of the material: (i)differential metal corrosion reduced by avoiding the use of the two dissimilar metals. If theirs is unavoidable the position of the metal chosen shall be a close as possible in the galvanic series. (ii)to reduce the rate of corrosion, the anode material must be as large as possible while the cathode should be small. Design: (i)an insultor should preferably be used at the contact point of the two dissimilar metals. However a porous insulator such as asbestos, wood should not be used, since it absorbs and holds liquids whicher act as electrolytic conductors. 10

(ii)whenever possible the equipment should be supported on legs instead of on large blocks to facilitate free circulation of air and prevent the formation of stagnant pool or damp area. Similarly shares corners should be avoided. The equipment should be designed in such a way that it can be easily wept free from dust to reduce the corrosion due to pitting Andrew differential aeration effect.

la rg e bla ck- po or d esign b etter d esign

sharp edge

smooth edge

poor design

better design

Protective coating: (a)metal coatings: 1.the base metal(substrate) is covered with a layer of other metal, this process is referred as metal coating. 2.there are two types of metal coatings. ANODIC METAL COATING: (i)The metal coating which are anodic to the base metal is called anodic metal coating. (ii)in order to protect the metal from corrosion, any metal which is higher up in the galvanic series such as Zn, Mg, etc are coated on iron(base metal). (iii)the characteristic features of anodic coating is that the base metal on which the coating is done will not get corroded even if the coating falls if at some places. this is due to the formation of large anodic and small cathodic areas. (iv)anodic metallic coating is carried out by using their following methods.

11

(1)cladding: this process mainly used with metal sheets. For ex: the iron sheet to be protected is cladded(sandwiched) between two sheets of the anodic metal and squeezed by rolling under pressure & heat. (2)hot dipping: it involves dipping the base metal in molten anodic metal. The coating metal should melt at relatively lowest temperature and the base metal must withstand this temperature without undesirable changes in its properties. (3)if we coat Zn on iron then that process is called galvanization. GALVANIZATION.: the process of galvanization is carried out as follows, (i)the base metal first treat with organic solvent to remove grease or oil material present on it. (ii)again treat with dil. H2SO4 to remove rustic or oxide layer present on it. (III)the metal is treated with fluxes ZnCl2 and NH4Cl for best adhesion property. (iv)finally the base metal dipped into the zinc at 430-4700C. (V)the excess zinc is removed from the surface by rolling or wiping etc. Tinning: the processes of coating a thin film of molten tin on the base metal surface by hot dipping technique is called as tinning. The process as follows. (1)treatment with organic solvents-remove grease or oily layer. (2) treatment with H2SO4 to remove rust or oily layer. (3) treatment with ZnCl2 and NH4Cl flux to improve adhesion properties. (4) the base metal dipped into the molten Tin-to coat tin on base metal. (5) treatment with palm oil - to avoid oxidation. The tinning process mainly used in food storage cans etc. metal spraying: It is done by flame spray technique, where metal used is fed ionto the mouth of a handle pistol and melted by an intense gas flame. the metal parts formed are sprayed by an air blast on to the surface to be coated. (i)cathodic metal coating: (i)in this the base metal is coated with a cathodic metal such as tin, nickel, chromium and iron. 12

(ii)in this coating, the coating must be absolutely free from gaps, otherwise rapid corrosion of the base metal takes places as a result of the formations of large cathodic and small anodic areas. (iii)the coating must completely cover the surface without leaving a pin hole. A superior method such as electroplating are adopted to give cathodic metal coating. (iv)tinning 2.INORGANIC COATINGS: These are chemical conversion coatings. (i)here a surface layer of the metal is converted in to a compound, by chemical or electrochemical reactions, which forms a barrier between underlying metal surface and the corrosion environment. (ii)the chemical conversion coating are different from other types of coating in the sense that, they are integral part of the metal itself. (iii)in addition to the corrosion resistance, thin type of coatings also provides increased electrical insulation and enhanced adherence for Paintsville aand other similar organic coatings. (iv)there are two types of inorganic coating methods. (i)anodizing (ii)phosphating

Anodizing: (i)some metals like Al,Mg,Ni etc and their alloy due to passivation effect exhibits much higher corrosion resistance than expected from its position in the galvanic series. Def: Anodizing is a process in which a protective passive oxide film is artificially(chemically or electrochemically) produced on certain metals. It is also called as anodic oxidation process. Process: In which base metal is made as anode, in an electrolytic bath of suitable composition and passing direct electric current. The most commonly used baths area chromic acid, sulfuric acid, phosphoric acid, oxalic acid etc and lead in generally used as a cathode.

13

When we apply external EMF, at anode oxidation takes place(Al Al3+ + 3e- ). The Al3+ get combined with the oxygen and formed Al2O3 on the anode. This oxide layer is a porous and provides good adherence for paints and dyes. The strength and corrosion resistance of the anodized film can be increased by the so called sealing, which involves heating if boiling water or steam or metal salt solution. This treatment changes porous alumina at the surface of the coating into monohydrate (Al2O3.H2O ), which occupies more volume therby the pores are sealed . (II)PHOSPHATE COATING: (1)phosphate coating is a process in which a thin films of metal phosphate coating gets deposited on the metal surface due to the interaction of surface atoms of their base metal and certain metal phosphate in aqueous solution of phosphoric acid. Process: the phosphating bath contains three essential components (i)free phosphoric acidic (H3PO4) (II)A primary metal phosphate like Fe, Mn, Zn phosphates. (III)an accelerator like nitrates, nitrites, chlorates, H2O2 etc.. (iv)pH - 1.8 to 3.2 (2).the reaction include their dissolution of metal as ions, forming a phosphate without the bath solution which subsequently gets deposited on the surface of the metal. Application: 1.the phosphate coating is as an under layer for paint finishing. It is standard pretreatment before painting of automotive bodies and other steel sheet fabrication such as refrigerator and washing machines etc.. 2.phosphating is widely applied for the protection of metal parts of machinery, which cant be painted such as nuts, bolts etc.. (3)ORGANIC COATING : paints and enamels Paints: the function of organic coating mainly two (i)the coating serve to keep out air and moisture from the base metal surface or act as a barrier between base metal and corrosion environment. (ii)the pigment (red lead, zinc chromate etc) or or drying oils (linseed oil, wood oil, etc ) present in the paint often exerted an inhibitive action by electrochemical and other means. 14

The requirement for a good paint: (i)adhesion must be good and its physical appearance also to be good. (ii)the film formed should be continues, uniform and resistant to air and water. (iii)should be chemically inert to corrosion environment. (iv)should have reasonably long life. Process: before painting, surface preparation is required (i)surface preparation: degreasing removing of scales and impurities. (ii)primer: such as phosphate coating. (iii)fillers: such as nitrocellulose, epoxides etc.. are applied on the well dried prime surface in order top improve the external appearance of the paint and to produce a smooth coatings. Enamels: which are the hard material containing over 90% calcium and magnesium salts which provide corrosion resistance to the material which are using at elevated temperatures. CATHODIC PROTECTION: Cathodic protection is a method of protecting a metal or alloy from corrosion by converting it completely into cathodic and no part of it is allowed to act as anode. Principle: metals normally undergo corrosion dy electrochemical process with the formation of anodic and cathodic regions in contact with eachother. The corrosion of metal takes place at the anodic region whereas at the cathodic region the metal is unaffected. Therefore, corrosion can be prevented by eliminating the anode sites and converting the entire metal intolerance cathodic area. There are two-year methods of cathodic protection. (i)sacrificial anodic method. (ii)impressed current method. (i)sacrificial anodic method: In this method, the base metal structure is converted into a cathode by connected it to a more active [higher up in galvanic series or less noble]metal. This active metal actually as an auxiliary anode. Mostly Zn, Mg, Al are the common auxiliary anodes used in this method. These metals being more active, acts as anode and undergo destruction Andersen protecting the metal structure. 15

Since the anode material sacrificed to protect the metal structure, the method is known as sacrificial anode method. Exhausted sacrificial anodes are replaced by new ones as and when required. Ex: 1. A Mg block connected to buried oil storage tank. 2.Mg base areas fixed to the side of ocean going ships. 3.Mg blocks area connected to the buried pipe lines. Advantage: Disadvantages (i)The method is simple. expenditure for (ii)low installation cost. consumed anodes. (iii) minimum maintenance cost. (iv) Doesnt require power supply. (II)IMPRESSED CURRENT METHOD: (1)In this method, by applying a direct current large than the corrosion current. (2) The base metal is made cathodic by connecting it to the cathode of the external source of current the anode of the source is connected to an inert electrode(lead or graphite) (i)involves recurring Replacement of

Protect Metal cathode

anode

inert electrode

(3)The metal structure being cathode, doesnt undergo corrosion. Anode being inert, remains unaffected [electrons for protection are supplied by a source of direct current]. Advantages: (i)One installation can protect larger area of metal. 16

(iii)low maintenance cost. Disadvantages: (i)It is very expensive, because it needs continues current. (ii)If the impressed current is not uniform on the entire surface of the protected structure, localized corrosion takes place on the protected metal. ANODIC PROTECTION: (i)The prevention of corrosion by impressed anodic current is called anodic protection. (ii)The method is based on the formation of a protective film on metals by externally applied current. Generally, when a metal is made as anode and current is applied, the dissolution rate of the metal tends to increase but in the case of passive metals with active transition like nickel, chromium, titanium and their alloys, application of suitable anodic current makes them passivated and decrease the rate of dissolution of metals. If we plot the graph potential applied & corrosion current.

E D C EP A ipassive icritical

trans passive region

protection range B

log i

Observation from the graph: (i)when known potential applied initially the corrosion current increases as shown in fig. as AB indicating dissolution of the metal. This trend continues until the current reaches a critical value and passivation due to the development of oxide layer sets in. this potential is called passivating potential [ EP ]. (II)Above EP , the current flow decrease and reaches a minimum value, called the passivating current ipassive the decrease in current due to the formation of passive film on the metal. 17

(iii)if the potential is further increased, the metal remains unattacked up to a particular particular potential is reached(CD). In this range [ EC-ED ] corrosion rate of the metal is very low. at this potential the anodic protection can be achieved. so to maintain this potential we can use potentiostat. Process: The anodic protection to a structure is applied by using a device called potentiostat. It is an electronic device that maintenance a metal at a constant potential w.r.t reference electrode. The anodic protection of steel tank containing H2SO4 is shown below. The potentiostat has three terminal, one connected to the storage tank, another to an auxiliary cathode, another is connected to reference electrode corresponding to passive range.
POTENTIOSTAT

Auxiliary electrode H 2 SO4

Ref erence electrode

Anodic corrosion successful if it follows these conditions. (i)the metal or alloy readily get passivated by applying anodic current. (ii)it requires smaller current to maintain passive state , high corrosion resistant at low energy consumption. LIMITATIONS: (I)it limits only for passive metals. (II)installation cost is very high. (III)we cannot reduce corrosion to zero. CORROSION INHIBITORS: 1.the rate of corrosion is reduced by the use of certain chemicals called corrosion inhibitors. These inhibitor slow down the anodic or cathodic reaction occurring in the corrosion process by forming a protective film over the anodic or cathodic region. 18

2.they are mostly used to provide protection to systems in which corrosion environment is recirculated or confined for a longer period such as I C Engine, recirculation cooling water systems and pipe lines for transporting etc.. 3.the inhibitor provide protection against corrosion by retarding either anode or cathodic reactions. On the basis of this property, they are broadly classified as (i)anodic inhibitor and (ii)cathodic inhibitors. (i) ANODIC INHIBITOR: (i)Oxidation of the metal is the reaction that occurs at anode sites during corrosion i.e, in rusting of iron, Fe2+ ions are formed at the anodic region. If the formation of Fe2+ is prevented, the cathodic reaction stops thereby corrosion process retarded. This is achieved by the addition of anions such as chromates(CrO4- ), tungstate(WO4- ), molibdate(MoO4-), phosphate(PO4-) etc..these anions combine with metal ions formed at the anodic region, forming the sparingly soluble respective salts. These compounds formed area deposited on the anodic sites forming protective films, which act as barrier between the fresh metal surface and the corrosion medium it avoids the further corrosion. (ii)anodic inhibitors are found to be effective only when sufficient amount of the inhibitor is added in to the corrosion medium. (II)CATHODIC INHIBITORS: At cathode reaction are
2H+ + 2e H2 2OH - + H2 4OH 1

2H2 O + 2e 2H2 O + O2 +4e

2 3

if the reaction occurring at the cathodic areas are controlled then it is possible to inhibit they corrosion of metals. The two important type of cathodic reaction are liberation of hydrogen or absorption of oxygen. Therefore the cathodic reaction can be stopped by preventing / retarding the liberation of hydrogen or by preventing / retarding the absorption of oxygen. INHIBITION OF HYDROGEN: (i)the liberation of hydrogen at cathode can be prevented either by preventing or retarding the diffusion of H+ ions to the cathode. 19

(II)the diffusion of H+ ions to the cathode is prevented by the addition of certain organic compounds which contains nitrogen or sulfur. Urea, thiourea, aliphatic amines, & hetero cyclic compounds are widely used as cathodic inhibitors. (iii)such substances, when added to the corroding environment, are adsorbed on their cathodic sites forming a protective film. INHIBITORS OF OXYGEN ABSORPTION: (i)the absorption of oxygen can be reduced by removing the oxygen from the corrosion medium or by simply decreasing the diffusion rate of oxygen to cathode. The objective is achieved by adding reducing agents are oxygen scavengers such as hydrazine, sodiumsulphite etc.. these substances remove oxygen from the corroding environment by reducing it.
N 2 H4 + O 2 2Na 2SO 3 + O2 N 2 + 2H2 O 2Na 2SO 4

(II)the second objective is achieved by adding salt such as ZnSO4, MgSO4, NiSO4 etc.. in to the corrosion medium. The cation of the salts migrate towards the cathode surface & react within cathodically formed alkali to deposit their hydroxides on the cathodic sites
Zn2+ + 2OH M g2+ + 2OH Zn(OH) 2 Mg(OH) 2

(III)THE action of an inhibitor depends on their nature of the metal to be protected as well-known as corrosion environment. It is therefore, necessary to choose an appropriate inhibitor for particular system.

20