seaeiag eanaarmpe PETE (NITK)- Surathkal Department of Chemistry 1. Introduction, Definition, Different theories( types) of Corrosion Mechanism 2. Theory of Electrochemical Corrosion 3. Factors Affecting Corrosion rate> Corrosion Science: > Corrosion is a natural phenomenon, a chemical process and most significant problem across the globe. > Generally a Slow process > Mainly taking place on the Metal SURFACE > Corrosion Science isa field of InterdisciplinaryWhy do Metal-Undergo Corrosion 2222? > Metals have a tendency after production and during usage to revert back to its lower energy, more stable state > The tendency is known as the Law of Entropy. It is very rare to find metals in their pure state naturally, more commonly, they are combined with other elements to form oresDefinition: Any process of deterioration and consequent loss of a solid (metallic) material, through an “unwanted chemical or electrochemical attack by its environment, starting at its surface, is called corrosion. The term corrosion is sometimes also applied to the degradation of plastics, concrete and wood, but generally refers to metals. (OR) Corrosion is defined as the process (or result) of unwanted attack on a metal by its environment. Eg.: Rusting of iron - layer of reddish scale and powder of oxide (Fe,O,); formation of green film [CuCO, + Cu(OH),] on the surface of copperDry OR Direct OR Chemical Wet OR Corrosion Electrochemical Corrosion Oxidation Liquid Metal . Corrosion Z Corrosion Corrosion by Other Gasese Direct chemical action of environment/atmosphere with metal surfaces in proximity in absence of moisture e Three types of chemical corrosion: a) Oxidation corrosion- direct action of oxygen at low or high temperature Low temperature - Alkali and alkaline earth metals- rapid oxidized High temperature- all metals (except noble metals) - oxidized 2M———_ 2M™ + 2ne Metal ions 2.0, 2ne7-———— 010° oxide ions 2M + 1/20) 2M™ + nO?© Oxidation -Surface of metal © Resulting metal oxide scale- barrier ° Diffusion of metal outwards - more rapid- metal ion smaller © Diffusion of oxygen inwards meta tte ne” (Oxidation) Reaction at meta Direction of electrons conduction Mal oxide scale formes by direct a reaction amas tion ay 24 POEM lore ‘atl on ugh sale Fig. Oxidation mechanism of meta Se Seer ZThin layer of oxide on metal surface e Nature of film decides further action ° If film is: 2 i. Stable: >» Fine grained in structure » Adhere tight to parent metal surface > Impervious nature » Protective coating in nature » Oxidation corrosion is prevented » e.g. Aluminum, lead, tinIf film is : ii. Unstable: = > Oxide layer formed decomposes back into the metal and oxygen > No oxidation corrosion is possible Eg. Ag, Au and Pt Fig. 2. Unstable oxide layer. oatIf film is : iii) Volatile: > Oxide layer volatilizes > Metal is exposed for further attack » Rapid and continuous corrosion » Eg. MoO, i 5 \ Volale 4 ce meta! oxide —~Ficeh alitecs ie. Fig. 3. Volatile oxide layer. 10If film is : . iv) Porous: > Presence of pores and cracks » Atmospheric oxygen have access to underlying surface of metal » Continuous corrosion > e.g. Iron, Steel Porous Further attack Fig, 4. Porous oxide layer. Il“An oxide is protective or non-porous, if the volume of the oxide is atleast as great as the volume of the metal from which it is formed” “If the volume of the oxide is less than the volume of metal, the oxide layer is porous and hence, non- protective as it cannot prevent the access of oxygen to the fresh metal surface below” e Alkali/Alkali earth metals form oxides of volume less than the volume of metals- leads to corrosion e Aluminum- oxide volume is greater than the volume of metal- non porous layer- rate of oxidation is zero 12OIrrosi © Gases like SO,, CO,, Cl,, H,S, F, react with metal and form corrosion product © Corrosive effect depend on the chemical affinity between the metal and the gas Degree of attack depends on whether film is: a) Protective or non-porous ¢ Extent of attack decreases ¢ Film protects metal from further attack ¢ Eg.: AgCl film formed from the attack of dry Cl, on Ag surface b) Non-protective or porous © Surface of whole metal is gradually destroyed ¢ Eg.: Dry Cl, gas attacks on tin forming volatile SnCl, Attack of H,S on steel forming FeS scale 3¢ It takes place when anhydrous liquid/molten metal attacks on the metal surface ¢ When liquid metal comes in contacts with solid metal, it leads to weakening of solid metal due to : © It dissolves in liquid OR ¢ Penetration of liquid metal into solid metal e.g. Mercury dissolves most of the metals by forming amalgams, thereby corroding them 14JEORY OF EL » Electrochemical corrosion (Wet corrosion): Flow of electron-current between the cathodic and anodic areas Two possibiliti i. Conducting liquid is in contact with metal ii, Two dissimilar alloys/metals are either immersed or dipped partially ina solution ie At anodic area: oxidation occurs- anodic metal is destroyed- metallic ions are formed » Corrosion always occurs at anodic areas.... Why ?? At cathodic area: reduction occurs-do not affect the cathode- many metals cannot be further reduced-nonmetallic ions are formed M ——~— M™ + ne-™ (Oxidation) Metal ions M™ ———=_Dissolves in solution 5e Anodic reaction M M™ + = ne- (Oxidation) e Cathodic reaction: More complicated... bec. It involves constituents of corrosion medium and depends on the nature of corrosion environment Consumes electrons in 2 ways: a) Evolution/liberation of hydrogen b) Absorption of oxygen 16a) Evolution of hydrogen: ¢ Possible, when anodic area is large & cathodic area is small; Oxygen is absent ° ¢ Inacidic environment... e Eg. Dissolution of Fe as ferrous ions with the liberation of electrons Fe ———= Fe** + 2e7 (Oxidation) 2Ht + 2e° ——— HA Fe + 2Ht ——=— Fe + Hy4 © Ht ions of acidic solution gets eliminated as H, gas 17Fig, 5. Mechanism of wet corrosion by hydrogen evolution, 18= e Displacement of Ht ions from the acidic solution by metal ions e Anode-very large areas © Cathode- small areas ¢ In Neutral/alkaline medium and in absence of Oxygen............ hydroxide ions are formed along with liberation of hydrogen 19e Absorption of oxygen : Takes place when e Anode-very small areas Cathode- large areas e Atmospheric Oxygen is present Eg. Rusting of iron Surface of iron- thin film of oxide © Oxide develops some cracks- creates-which act as anodic area ¢ Rest of well metal parts-act as cathode 20Absorption of oxygen : In Neutral/alkaline medium and in presence of Oxygen...... hydroxide ions are formed 2H,0 + O, + 4e° —» 40H In acidic medium and in presence of Oxygen...... 4H' +0) +4e° —»2H,0 Overall Reaction: a Reet 20H == - He(OH); + Fe* and OH ions originate from anode and cathode + Smaller Fe?* ions diffuse more rapidly than OH * Combine near the cathode Corrosion occurs at anode and rust is deposited at or near the cathodeAbsorption of oxygen Fig. 6. Mechanism of wet corrosior ‘oxygen absorption. where corrosion 22igh oxygen is present: 4 Fe(OH), + O, + 2H,0 ——» 4Fe(OH); ° Fe,O,.H,O - yellow rust ¢ Limited supply of oxygen: Corrosion product- black magnetic oxide of iron:Fe,O, 23° effects of increased oxygen content: » favors cathodic reaction - more OH" ions > removes more electrons - accelerates corrosion at anode Accelerates both corrosion and rust formation 24.Rate and extent of corrosion depends on: > Nature of the metal > Nature of the corroding environment 251. Nature of the metal: e The tendency of a metal to undergo corrosion is dependent on the nature of the metal. Metals with lower reduction potential aree more reactive and therefore undergo corrosion easily whereas metals with higher reduction potential do not undergo corrosion easily. e The tendency of metal to undergo corrosion decreases with increase in the electrode potential e The reactive metals like Na, K, Mg, Zn are more susceptible for corrosion. The noble metals like Ag, Au, Pt, Pd are less susceptible for corrosion. e Some metal do show property of passivity 26it largely decides the rate of the further corrosion e If the corrosion product is insoluble, stable, uniform and nonporous, it acts as a protective film preventing the further corrosion. e If the corrosion product formed is soluble, unstable, porous and non uniform, the corrosion continues. e Some metals e.g. Al, Cr are highly passive as their oxides, as corrosion products form protective films on metal surface 273 rog' e If the hydrogen over voltage of metal is low, it is more susceptible for corrosion, When the cathodic reaction is of hydrogen evolution type. e with lower hydrogen over voltage, hydrogen gas is evolved easily and therefore rate of cathodic reaction becomes faster which also increase the rate of anodic reaction and therefore corrosion of metal becomes fast. e In metals with higher hydrogen over voltage, cathodic reaction is slow and corrosion of metal becomes slow. 28QQ 4. pH of the medium: e In general, lower the pH, higher is the rate of corrosion. e metals like Al, Zn etc. undergo fast corrosion in highly alkaline medium. e the pH of the solution also decides the types of cathodic reaction 29> highly influenced by the relative sizes of anodic and cathodic areas > Metal with small anodic and large cathodic area (i.e. ratio of anodic to cathodic area is SMALL), corrosion is intensive and faster cérrosion rate at anode > if cathode is smaller, the consumption of electrons will be slower—overall corrosion rate will be slow > Eg.: Asmall steel/iron pipe fitted in a large copper tank 306. Purity of metal: Impurities : oe = in metal Eg.: Zinc containing impurities such as Pb, Fe > Corrosion of Zn . ‘Heterogeneity leading > Rate of corrosion increases with 0 electrochemical cell increasing exposure and extent of impurities Corrosion at anodic parts 317. Position in galvanic series/difference in potential between anodic and cathodic region: > Two or more metals/alloys are in contact > Inpresence of electrolyte , > More active metal suffers corrosion > Rate and severity depends upon the difference in their positions > Greater is the difference, the faster is the corrosion of anodic metal/alloy 32> Corrosion rate is highly influenced by physical state of metal like particle size, smooth/rough surface, localized stress > Smaller grain size- enhanced solubility- corrosion rate will increase » Stress- area under stress- will act as anode and undergo corrosion 23g. Passive character of metal: > Al, Cr, Niand Sn are passive . > Exhibit higher corrosion resistance > Formation of protective thin film of oxide on metal/alloy surface > Film- Self-healing nature > Eg.: Corrosion resistance of stainless steel - passivating character of Cr 3410. Solubility of corrosion products: » Electrochemical corrosion > Solubility of corrosion product in corrosion medium - decides the rate of corrosion > Soluble- Corrosion at a faster rate > Insoluble- in the medium/ forms insoluble product (PbSO. ),in HSO,) °* © Functions as physical barrier © Suppresses corrosion 3De As temperature increases, rate of chemical reaction increases © Increase in the temperature also leads to increase in the conductance of corrosion medium 12. Humidity: © Generally, as the humidity increases, it leads to enhance the corrosion rate © The presence of moisture in the atmosphere provides the conducting medium for the formation of galvanic cell, facilitating corrosion of metal 36> Atmosphere in the vicinity of industrial area » Gases- CO,, H,S, SO,; Fumes- HCl, H,SO, « Acidity of liquid and electrical conductivity- near metal surface increases + Increase of corrosion current in electrochemical cell--- that will lead to increase the corrosion rate af