HES202 ] CBCS - BC) OL GNEERING| EY www hkbk.edu.in ee eeu sstn) Crore 3 HKBK Dept of Chemistry Cope ct gon rt MODULE3 Corrosion and Electrode System “Corrosi is defined as the destruction or deterioration of ‘metals or alloys by the surrounding environment through chemical or electrochemical reactions”. Corrosion may occur either in dry environment or in an aqueous medium. Dry Corrosion (Chemical Corrosion): Dry corrosion occurs by direct attack of atmospheric gases such as oxygen, hydrogen sulfide, halogens, and sulfur dioxide on the metal forming oxide layer Wet corveiion (Electrochemical Corrosion): Wet corrosion occurs in presence of an aqueous solution of electrolyte & atmospheric oxygen by setting up of tiny galvanic cells on the metal surface. Electrochemical Theory of Corrosion according to this theory, when a metal is exposed to the atmosphere following electrochemical changes occur. i) Formation of Anodic & Cathodic sites takes place leading to formation of tiny galvanic cells. The electrons are liberated at anodic site & are taken up by the cathodic site. ii) The metal dissolves at the anodie site (oxidation) i.e. corrosion takes place at the anodic site. iii) Reduction of H2O & O2to OH- & Hzoceurs at the cathodic site. J Electrochemical theory of corrosion is explained by exposing Iron to the atmosphere. When a small piece of Iron metal is exposed to the atmosphere, formation of Anodic and Cathodic sites takes place on the surface of Iron and following electrochemical changes occur. At Anode ‘Oxidation of Fe takes place resulting in corrosion. Fe ——+ Fe? 2e—oxidation. 7 At Cathode ‘The clectrons liberated at anode flow to the cathode & cause reduction of H2O & O2 at the cathode, The reduction process depends on the nature of electrolyte ie, atmospheric moisture ‘or water film. D> ‘the moisture or water film is aerated & neutral. (Oz & HzO reduce to OH ~ions. 220 + 02+ 4e —> 40n- D) If the moisture or water film is deaerated & neutral. 10 reduces liberating Hz gas & OH ~. 2204+2e ——> Inf+20Hn- ©) Ifthe moisture or water film is deaerated & acidic. 1 ions reduce toHe gas, 2it+2e——> Th Peal Sansulle Pathapalye Fabredaen MSc PEDCBCS - BCHES202 FRIATRENGINEEHING | csc www, hkbk-edu.in Dept of Chemistry MODULE 3 ch settles down between the The Fe? & OW ions combine to form the corrosion product, which SET ae Fe (OH): Iron Hydroxide Further Fe (OH)2 oxidizes to hydrated Ferric oxide. 4.Fe(OH):+2H20+0: ——+ 2(Fer0s31n0) — Rust Types of Corrosion 1. Difforential metal corrosion. 2. Differential aeration corrosion. 1. Differential Metal Corrosion, p ‘When two dissimilar metals are in contact, potential difference arises due to the formation of tiny galvanic cells & corrosion occurs at the anode, A metal placed high in the lectrochemical series acts as anode & the other metal acts as cathode. ‘Thus Iron (Fe) is anode to Sn, Cu, Ni and hence Iron (Fe) undergoes corrosion. On the other hand Fe acts as a cathode to Mg & Zn, as a result, Mg & Zn undergo corrosion in presence of eg, aot i Fe cu Fe an > l|<_ => |< In this bimetallic couple Iron as anode undergoes corrosion & Copper as cathode is protected. This is because Iron is above Copper in the galvanic serics, If Fe is coupled with Zn, Zinc as anode gets comroded & Fe as cathode is protected. This is because Zn is above the Iron in galvanic series. ‘The rte of conesion depends on th amount of sent passing fiom cathode to anode Higher the difference in the reduction potentials of two metals; higher is the rate of comosion fan instance potential difference between Fe & Cuismore than that ofbetween Fe & Sn, Therchg Fe corrodes faster in presence of Cu than in presence of Sn, “In general in a bimetallic couple, the metal which is more anodic gets corroded & the other metal which becomes cathode is protected”, Hence, Bolt and nuts are always made ir metal. of sit 2. Differential aeration corrosion, ‘The difference in concentration of Oxygen over the surface of a metal devel i cell resulting in corosion. The metal surface where the concentration of Osis high Rane Suthode, sine cathodic reactions involve the reduction of O2 and the surhoe when concentration of O> is less becomes anode, ider a strip of pure Fe is partially immersed vertically ina sohition of aerated Nac ern {On is higher atthe surface ofthe solution and eathodic reaction nog Prof Sanatle Palpelya Fabruditn FeO Me Al to Fe So Po may ow He As As@) HKBK S829 | a Dept of Chemistry \ wwwebkbk.edu.in Applied Cherulstry for Computer Science & Engineering stream MODULE 3 per portion of the strip becomes cathode. Whereas the concentration ‘of Oxygen is less at the lower portion & it becomes anode. The oxidation of metal i.e. corrosion occurs at lower portion of the Fe strip immersed in NaCl and electrons pass from bottom to the top of the strip and reduction of H:O & Os occur at upper portion of Fe strip . The corrosion product is formed in between anodic & cathodic sites & not on active electrode surface. reduction 2 hence the up Fe —> Fe##+ 2c —Anodic reaction —at bottom. O2+2H2 0 + 4e —* 40H ~~ Cathodic reaction —at top. ‘Therefore well-aerated region of the metal becomes cathode & less aerated region becomes anode, resulting in corrosion. This is known as differential aeration corrosion. Oo Few! Cathode 2H:0 +0) M4e—> 4 OH > j—> Aerated Nacl > Anode ‘This phenomenon of deferential aeration corrosion explains a) Water line corrosion. —_b) Pitting corrosion a) Water line Corrosion ‘When water is stored in Iron tanks, it is generally found that the maximum amount of corrosion takes place just below the water level. The area above the water line is highly oxygenated acts as cathode é& is protected. The area just below the water line becomes anode & intense corrosion occurs. This is termed as water line corrosion, This type of corrosion is observed in ships floating in seawater and water storage tanks. _ CBCS - BCHES202 b) Pitting Corrosion When a large drop of water or an electrolyte or dust particles is placed on the surface of a clean sheet of Iron, the concentration of O> will be less at the bottom of the drop & becomes 1 anode, while O> will be moreat the surface area & becomes cathode, Hence corrosion statts at the bottom of the drop causing pits or cavities at the bottom. ‘Water Drop ocgy HKBK ESR 2) ww webkbkedy- Dept of Chemistry Applied cheinistry for Computer Science & Engineoring si ™ MODULE 3 Corrosion Control Ture and every metal always try to attain & vrosion through electrochemical reactions. by various techniques. The total system in the universe is dynamic in nal more stable state, In this process metals undergo co! h Conosion cannot be totally prevented butit can be controlled effectively nodizing — 1, Surface Conversion coatings Phosphating % CE . ing (Galvanizing) _—— 2. Metal coating Cathodic metal coating (Tinning) Gaerificial ‘Anodic Method——_ 3. Cathodic Protection << Impressed Current Method 4 1 Inorganic Coatings Anodizing: ‘When metals like Al, Ti, Cr, Vanadium, Zirconium ete. are made as anode in presence of chromic acid, H2SO,, oxalic acid or phosphoric acid, a thin layer of oxide is formed, which acts. as a protective layer. 7 Anodizing isan electrochemical process in which aluminium metal surface is converted - into a decorative, durable, corrosion resistance surface by formation of passive oxide : layer”. a Anodizing of Aluminum: ‘The aluminium metal object surface is degreased & polished. Alum is made as anode & platinum electrode as cathode in 3 — 10% chromic acid at. ‘a current density of 10-20 mA/Cm:. A thin oxide layer (Al:Os) of 2— 8 micron: fommed. The higher thickness can be obtained by addition of 102% Hs SO, &1 density of 160 mA fem? which gives 24-mieron thickness, The aqueous solution of dye at 50 ~ 60°C which gives colour. Finally the & Co acetate followed by boiling water to improve corrosion resistance. ‘Applications: - In Air crafts, window frames and utensils to de core