® Oy M** + 26 At the oxide filnvenvironment interface M | Vi0 +26” —+0?- The overall reaction is } M+ ‘20, ——>M”* + 0 = MO (Metal-oxide film) | Nature of oxide film The nature of oxide film formed on the metal surface plays an important role in oxidation corrosion. (i) Stable oxide layer A stable oxide layer is a fine-grained in structure, and gets adsorbed tightly to the metal surface. Such a layer is impervious in nature and stops further oxygen attack through diffusion. Such a film behaves as a protective coating and no further corrosion can develop. ‘Example: Oxides of Al, Sn, Pb, Cu, ete are stable oxide layers. - (ii) Unstable oxide layer ___ Unstable oxide layer is mainly produced on the surface of ble metals, which decomposes back into the metal and oxygen. Metal oxide <-> Metal + Oxygen » Oxides of Pt, Ag, etc are unstable oxide layers. Volatile oxide layer The oxide layer volatilizes as soon as it is formed, the metal surface for further corrosion. le: Molybdenum oxide (MoO) is volatile. Scanned with CamScannerScanned with CamScannerCorrosion and its Inhibition 10.7 Collection of these gases in the voids deve, ney lop very high Pressure, which causes cracks "yt Process is called hydrogen embrittemena” on metal. This } (®) Decarburisation At higher temperature atomic hy | 2 a di thermal dissociation of molecu hydrogen” formed by the Heat H,—>24 when steel is exposed to this environment, the at 4 : - tomic hy readily combines with carbon of steel and Produces sree C+4H—scy,t Collection Of these gases in the voids develop very high Pressure, which causes cracking. Thus the Process of decrease in carbon content in steel is termed as “decarburisation” of steel, 10.5.3 Liquid-metal corrosion This is due to the chemical action of flowing liquid metal at high temperature. The corrosion reaction involves (i) either dissolution of a solid metal by a liquid metal. (or) (ii) liquid metal may penetrate into the solid metal. Wet corrosion occurs under the following conditions i) When two dissimilar metals or alloys are in contact with oe, each other in the presence of an aqueous solution or 7 moisture, - Gi) When a metal is exposed to varying concentration of oxygen or any electrolyte. Scanned with CamScanner10.8 Enginooring Chemistry Under the above conditions, one part of the metal becomes anode and another part as cathode Mechanism of wet corrosion (i) In anodic part, oxidation (or) dissolution of metal occurs M—>M?* +26" (i) In cathodic part reduction reaction occurs, which depends on nature of the corrosive environment (a) If the corrosive environment is acidic, evolution occurs at cathodic part. 2H" + 2e° ——>H,T hydrogen (b) If the corrosive environment is slightly alkaline (or) neutral, hydroxide ion forms at cathodic part. YO, + 2e° + HO ——>20H™ Thus, the metal ions (from anodic part) and non-metallic ions (from cathodic part) diffuse towards each other through conducting medium and form a corrosion product between anode and cathode. (a) Hydrogen evolution type corrosion “All metals above hydrogen in the electrochemical series have a tendency to get dissolved in acidic solution with simultaneous evolution of hydrogen gas” (Fig. 10.3). Example: When iron metal contacts with non-oxidising acid like HCI, Hz evolution occurs. At anode " Iron undergoes dissolution to give Fe’* ions with the liberation of electrons. Fe ——>Fe”* + 2e” (Oxidation) Scanned with CamScannerFig. 10.3 Hydrogen evolution type At cathode The liberated electrons flow from anodic to cathodic part, 2H? + 2e° ——>H,1 (reduction) )) Absorption of oxygen or Formation of hydroxide type corrosion * The surface of iron is usually, coated with a thin film ‘oxide. However, if the oxide film develops some crack and anodic areas are created on the surface while maining part’ acts as cathode (Fig. 10.4). fron metal contacts with a neural solution of ‘of oxygen, OH™ ions are formed. Scanned with CamScannerScanned with CamScannerHere, the more acti electrode potential) acts Setive metal (with more 3 (with less negative electrode ®t! the | ooo . SS active Potential) acts as cathode Fig. 10.5(a) & (b) Galvanic corrosion r represents Zn-Fe couple, in which zine poe ae in emf series) dissolves in preference (less acti tal) i.e., Zn acts as anode-and undergoes ‘and Fe acts as cathode. Scanned with CamScanner10.12. Other Example for Galvanic Corrosion Steel screw in a brass marine hardware corrodes. This is due to galvanic corrosion. Iron (higer position in electrochemical series) becomes anodic and is attacked and corroded, while brass (lower in electrochemical series) acts as cathodic and is not attacked. : Galvanic corrosion can be minimised by providing an 2 ing material between the two metals. uy Differential aeration or concentration cell corrosion This type of corrosion occurs when a metal is exposed ) to varying concentration of oxygen or any electrolyte on the surface of the base metal. Example: Metals partially immersed in water (or) conducting solution (called water line corrosion). If a metal is partially immersed in a conducting solution 10.6) the metal part above the solution is more aerated e become cathodic. On the other hand, the metal part jon is less aerated and thus, become anodic and ‘Waterline Scanned with CamScanner“eel + anode (less aerate) == M—sne, At cathode (MOTE Seated part) OH YO; + 1,04 26 = Preaiaced Examples for this type Of comosicn are (a) Pitting oF localised corn () Crevice corrosion. (©) Pipeline corrosion, (@) Corrosion on wite fence Pitting corrosion Pitting is a localised attack, resulting of» bole around which the meal i maga or faacon Water drop Fig. 10.7 Pitting corrosion Metal area covered by a drop of water, sand, dust. scale, ‘us consider a drop of water or aqueous NaC! resting ‘surface (Fig. 10.7). The area covered by the drop acts as an anode due to less oxygen concentration Scanned with CamScannerScanned with CamScannerScanned with CamScanner1 Chern e101 Chemical Corrosion 1. [lt occurs only in dry condition. 2 [It is due to the direct chemical attack of the metal by the environment. | surface gets corroded. product: |Even a homogeneous metal Difference between Che It al and Electeo ee “lectrochemical Corrosion occurs Presence moisture or electrolyte in it is due to the set up q a large number of cathodi. jand inodic areas. Heterogeneous surface (or Bimetallic contact is the condition. Corrosion occurs at the| mechanism. Examples: Formation of mild scale on Corrosion accumulate in the sam@lanode, while products) place, where corrosion| formed elsewhere. \ occurs. | Chemical corrosion _is|Electrochemical corrosion self-controlled. is continuous process, It follows —_adsorption| It follows electrochemical reaction. Examples: Rusting of iron in moist atmosphere. iron surface. 07) FACTORS INFLUENCING THE RATE OF CORROSION _ The rate and extent of corrosion mainly depends on (i) Nature of the metal (ii) Nature of the environment. Scanned with CamScannerCorrosion and its tnbibitor 10.7.1 Nature OF the: meta, @ Position in emf series The extent of corrosion metal in the emf series. Nex depend: $ get corroded yi; ls above FOUSIY. Lowe, T the Corrosion, a etal (OF the Undergoes corros; » The rate and Severity of corrosion depends on the difference in their positions in the emf series. Greater the difference faster is the corrosion rate, (b) Relative areas of the anode and cathode The rate of corrosion will be is larger. When the Potential) of corrosion (dissolution) (c) Purity of the metal The 100% pure metal will Of metals at anodic area, Rot undergo any type of impurities in a metal create heterogeneity and thus galvanic cells are set up with distinct anodic cathodic area in the metal. Higher the per Scot, oes i te oe es es Poe The effect of impurities on the rate of c ‘orrosion of zincNature of the surface film bring metals like Al, Cr than that of the metal n-porous and protective and pr Nature of the corrosion product is soluble in Similart 7) If the corrosion product tt will -be> faster (like MoO; on Mo medium, the corrosion rate urfa corrosion product is vc corrosion rate will be 10.7.2 Nature of the environment (a) Temperature The rate of temperature. This is bec: the rate of diffusion temperature. Hence the rate temperature. directly proportional corrosion is tion ause, the rate of chemical increases with ri of the ions of corrosion increase (b) Humidity The rate of corrosion will be more, when the b moisture acts as a solvent for in the environment is high. The the oxygen in the air to produce the electrolyte, which essential for setting up a corrosion cell Scanned with CamScannernd its Inhibition 10.19 Presence of Corrosive gases The acidic gases like. €03, 80, 4 SO4, etc. These gases produce 22>, 4 fumes of HCI, MSOs: MEE Clecirolytes whieh idic and increases the electrochemical c. aoe Frosion 4) Presence of suspended Particles « Particles like, NaCl, (NE), 1s powerful electrolyte and thus SO4 along with Moisture act accelerate the electrochemical corrosion. (e) Effect of pH The possibility of corrosion with respect to PH of the electrolytic solution and the electrode Potential of the metal is correlated with the help of a pourbaix diagram, Pourbaix diagram The pourbaix diagram for iron in water is shown in fig. 10.10. It shows clearly the zones of corrosion, immunity and passivity. In the diagram, ‘Z’ is the point where pH=7 and | the electrode potential =~ 0.4 V. It is Present in the corrosion This clearly shows that iron rusts in water under those inane In- actual practice, it is observed to be true. Passivation Scanned with CamScanner_Chrowreny 10x f From the diagram (Pig. 10.10) it is clear that of cone can be altéred by shifting the point <7 of passivity 6 % The iron will be im « ion, if the potential is changed to about extemal current. On the other hand, the corrosion of iron can also be reduced by moving into ¢ passivity region by applying positive potertial r The diagram clearly indicates that the rate of corroni: can also be reduced by increasing the pH of the solutiog » rr adding alkali. Thus the rate of corrosion will be maximum when ty corrosive environment is acidic. ic. pH is less than 7 CORROSION CONTROL a. © The rate of corrosion can be controlled by ithe; modifying the metal or the environment. 10.8.1 Control of corrosion by modifying the metal 1. By selection of the metal Selection of right type of metal is the main factor for corrosion control. Thus, noble metals are used in ornaments and in surgical instruments, as they are most immune (0 corrosion. E 2. By using pure metal ‘ i ive Pure metals have higher corrosion resistance. Even @ ; small amount of impurity may lead to severe corrosion. i ed Corrosion resistance “of many metals can be improv . For example, stainless steel containing chromium n ‘oxide film, which protects the steel from Scanned with CamScannerint = @ Corrosion ANd its Inhibition By proper design of the important , Riven below 4 Som be observed Avoid galvanic corrosion @ If two different metals are eceur, In such a case nic OMe, wal vanic corre Corrosion ) Selecting the SOrrCsION Is preven at @ Ss he metals as Gy ated by electrochemical series “85 possible = in the (b) © Fig. 10.11 Insulation avoids galvanic corrosion Drainage affects corrosion if Tanks and other containers must be designed in such & way that, the whole of the liquid should be drains! completely (Fig. 10.12). Scanned with CamScanner} 1 WA Poor design Good design ¢ affects corrosion Fig. 10.12 Draina ners and bends ould always be y smooth comers or (iii) Avoid sharp cor avoided, and Sharp comers of © corrosion ¢a 10.13) dges shi an be avoided by hence ¢! curved pipe bends (Fig Le \/ Poor design Good design Poor design Good design Fig. 10.13 Corrosion prevention using curved pipelinend dirt, which results in ion. This can be prevented by (Fig. 10.14), Poor design Good design Fig. 10.14 Minimizing crevice corrosion Example: Riveted joints produce crevice corrosion, so welded joints are preferred. 4. By cathodic protection ‘The principle involved in the cathodic protection is to force the metal to behave like a cathode. The important cathodic protection is Sacrificial anodic protection. Sacrificial anodic protection method In this method, the metallic structure to be protected is made'cathode by connecting it with more active metal (anodic srmtad, So that all the corrosion will concentrate only on Whe active metal. The artificially made anode thus gradually gets aesjed protecting the original, metalic structure, Heres Tis process is otherwise known as sacrificial anodic protection. ‘Aluminium, Zine, Magnesium are used as sacrificial anodes.igineering Chemist ised for the protection of ships and boat Sheets of Mg oF re hung around the hull of the (Fig. 10.15). Zn_or Mg_will_act_& ode_comp: (Ship or boat is made of iron) Dn con Zn or Mg. Since sacrificed in thet This method i so corn nitrate: are process of iron, they are called sacrificial anodes Sacrificial zinc or magnesium Insulated copper wire Ship hull Fig. 10.15 Sacrificial anodic protection of ship Important applications of sacrificial anodic protection are Mg (Sacrificial anode) (b) Boiler (4) Underground pipeline Fig. 10.16 Sacrificial anodic protection Scanned with CamScannerUnd Pipeline Cee 10 prevent iit? the done Fig. 10.16()), rat “ot A corrosion inhibitor is a substance corrosion of a metal, When it Sido Scabies is added to the corrosive environment. | 10.9.1 Types of Inhibitors |} L. Anodic Inhibitors | Examples: Chromates, nitrates, phosphates, tu } ions of transition elements with a high oxy ; content. € corrosion n insoluble These Anodic inhibitors are those that prevent th reaction, occurring at the anode, by forming compound with the newly produced metal ions { f I precipitates are adsorbed on the metal (Anode) surface, forming a protective film and reducing the corrosion rate. Though this type of control is effective, it may be dangerous, since severe local attack can occur, if some areas are uncovered. IL. Cathodic Inhibitors In an electrochemical corrosion, the cathodic reactions 7 mit. are of two types depending upon the environme Scanned with CamScannerIn An Acidic Solution inhibit like thioureas, subst Examples: ©, heavy metal soa In an acidic solution, the cathodic reaction i of hydrogen ie —> H,T 2H" + The corrosion can be reduced in two ways ” ions to the lown the diffusion of H © By slowi This can done by adding organic inhibitors like amines, pyridines, etc., which are adsorbed at the metal surfaces, By increasing the over voltage of hydrogen evol This can be done by adding antimony and arsenic oxides which deposit adherent film of metallic arsenic or antimony at the cathudic areas. (ii) (b) In a Neutral Solution Examples: Sodium sulphite (Na;SO;), hydrazine (Hy In a neutral solution, the cathodic reaction is H,0++40) +2." —>208r The corrosion can be reduced in two ways, () By eliminating the oxygen from the neutral solution thereby formation of OH” ions are inhibited. This can be done by adding reducing agents like Na3SO;, NoH,, etc. (i) By eliminating the OH” ions from the neutral solution " This can be done by adding Mg, Zn, or Ni salts. These Scanned with CamScannerScanned with CamScanner