10) Corrosion Corrosion is the oxidative deterioration of a metal, such as conversion of iron to rust [Fe 0, - xH,0], the tarnishing of silver (due to formation of Ag,0), development of a green coating on copper and bronze. Corrosion is basically an electrochemical phenomenon. A metal is oxidised by loss of electrons to oxygen and forms metal oxide, Mechanism of corrosion Let us consider the example of rusting of iron. The spot of an iron object, where oxidation occurs is'called the anode. Atanode, Fe(s) —> Fe**(aq) +207; E°=0.44V Electrons from the anode move through the metal and go another spoton the metal and reduce O, in presence of H" ions. This spot where reduction takes place is the cathode. At cathode, O(s) + 4H" (aq) + 4e” —3 2H,0(), E° =1.23 V Note TheH*ionis produced when CO, ges csslved in water forming HCO, which releases ions, 0, + HO —+ H,C0,+ H* + HCO. Net reaction, 2Fe(s) + Oo(g) + 4H" (aq) —> 2Fe** (aq) + 2H,0(1) Eu =1.67V Fe?* ions move through water on the surface of the iron object. If water present is saline, it will help more in carrying the current in the electrochemical cell formed. Fe®* ions are further oxidised by atmospheric O, to Fe* (as Fe) and comes out as rust in the form of a hydrated iron (Ii) oxide represented as Fe,0, - x0 4Fe?* (aq) + 0. (9) + 4H,0(l) —> 2Fe 205 (s) + 8H" air Oe Water °: droplet Fe QF e(s) — Fe** (aq) + 2e7 Oxidation, @0,(4)+ 21,01) + 4e°—+ 40H (aq) Reduction Fe? (aq) Fe? (aa) FE (aq) 2822570504. 285,0 (us) Fig. 3.9 (a) A water droplet on the surface of ron forms an electrochemical cell which leads to rusting. Atmospheric oxygen iplays a major partin the corrosion. HY ions produced in this reaction help further in rusting. Fe +2H* —>Fe* +H, Impurities present in iron also enhance rusting by setting a number of miniature cells. Rusting of very pure iron takes place very slowly. Prevention of corrosion Corrosion of iron can be prevented or at least minimised by shielding the metal surface from oxygen and moisture. It can be done by using following methods. () Barrier protection A coat of paint, thin flim of oil, grease etc., are very effective for a while, but rust begins to form as soon as the coating is broken or scratched or chipped. (ii) Electrical protection or cathodic protection Metals such as Gr, Sn, or Zn afford a more durable surface coating for Fe. The steel used in making automobiles is coated by dipping into a bath of molten zinc, a process known as galvanisation. Since Epa = AAV, Ea gq =~ 0.16 V Hence, zinc is oxidised more readily than iron,” and it, in turn, reduces Fe”* (formed during oxidation rusting) to Fe. Fe” +Zn—> Zn™ +Fe, Eoy=1.20V This reaction is spontaneous in forward direction hence, Zn can reduce Fe** to Fe. As long as the zine and iron are in contact, the zinc protects the iron from oxidation even if the zine layer becomes scratched. ‘The technique of protecting a metal from corrosion by connecting it to a second metal that is more easily oxidised is called cathodic protection. (iii) Sacrificial protection or sacrified anode Underground steel pipeline is protected by connecting it through an insulated wire to a state of magnesium (Fig. 3.9(b)) which acts as a sacrified anode and corrodes instead of iron. In this, easily oxidised Mg acts as anode, pipeline behaves as cathode, the moist soil is the electrolyte. At anode Mg —> Mg” (aq) + 2e7; E°=2.37V Scanned with CamScannerAt cathode 0, (9) + 4H" (aq) + 4e” —> 2H,0(0} E°=1.23V Mg tt : rn orage tani Fig. 3.9 (2) Cathodic protection of an iron storage tank (cathode) by magnesium, amore electropositive metal | 11 Commercial cells or batteries “Any cell or batteries that we employ as source of electrical ‘energy is basically an electrochemical cell. If a number of cells are arranged in a series then this arrangement is collectively called as battery. In this, the anode of each cell connected to the cathode of the adjacent cell and the voltage provided by the battery is the sum of the individual cell voltages. The electrochemical cells can be broadly classified into following two categories. 1. Primary cell In these type of cell, redox reactions occur only once and the cell becomes dead after sometime. They cannot be recharged or used again, e.g. dry cell like Leclanche cell, mercury cell. () Lectanche cell Itis called dry cell as it has constituents in dry powdered or paste form and not in solution form. The electrodes of this cell are. At anode zinc metal can ‘At cathode inert graphite rod surrounded by a paste of MnO, and carbon black Electrolyte moist paste of NH,Cland ZnCl, in starch (2) neta ep en Pitch seal ) | zinc container (anode) | Graphite cathode) MnO, + C Paste NH(Cl + ZnCl. Paste Fig, 3.10 The dry cell Reactions involved Atanode — Zn(s) —> Zn?*(aq) + 2e7 At cathode 2MnO,(s) + 2NHj (aq) + 227 —> Mn,09(s)+ 2NH() + H,0y Note Oxidation tate of tn changes rom +4 in Hn, tinh, Net reaction Zn(s) + 2NH +2MnO2—> [Zn(NHy)_Cla] +Mnz03 +H,9 ‘Alkaline dry cell is a modified version of the Leclanche cell in which the acidic electrolyte NH, Clis replaced by ‘an alkaline (basic) electrolyte (NaOH or KOH). It involves reactions. At anode Zn(s) + 20H" (ag) —> Zn0(s) + H,0(0) + 26" At cathode 2Mn0 9(s) + H,0() + 2e° —> MnO (s}+ 20H” (aa) Oe __ Net» Znls)+ 2MnO,(s) ——> _ZnOl) + Mny0,(3) '* Thus, cell potential is independent of concentration of OH ions. # Corrosion in alkaline medium takes place slowly as compared to acidic medium hence, alkaline batteries have longer life. Alkaline cell also produces higher power and more stable current and voltage because of more efficient ion transport in the alkaline electrolyte. (i) Mercury cell Ithas Anode Zine and mercury amalgam Cathode Paste of carbon and HgO Electrolyte Moist HgO mixed with KOH Reactions involved Anode, Zn(s) + 20H (aq) —> ZnO(s) + H,O() + 227 Cathode, HgO(s) + H,0() + 2e” —> Hg(l) + 20H” (aq) Net “Znle) + HgO (s) —> ZnO(s) + Hg() ‘* Net reaction does not involve any ion i.e. OH”hence, cell potential is independent of OH” concentration. Therefore, the cell gives a constant potential of 1.35V. Scanned with CamScanner2. Secondary cells qtisa chemical device in which may be stored in the form Tr chemical energy and energy may be drawn out when required. « Itcan be recharged by passing an electric current through them. ‘« Itcan be used over and again « Ttacts as an accumulator or storage cell '« It shows reversible reactions. ()Nickel-cadmium batteries Nickel-cadmium or ‘ni-cad’ batteries are rechargeable torage batteries. They have longer life but more expensive. Positive plate Separator Negative plate Fig, 3.11 Nickel-cadmium batteries ‘Anode; cadmium metal, Cathode ; nickel (II) compound like NiO{OH) supported on nikel. Electrolyte KOH Reactions involved during Atanode ; Cals) + 2017 (aq) —* Ca(OH) (s) + 227 At cathode ; NiO(OH\s) + H,0() + e7 —> Ni(OH),(s) + OH” (aq) Discharging Net: Cd(s)+ 2NiO(OH)(s) + 2H,0) Fagg ischarge Recharging CA(OH) o(sf + 2Ni(OH) »(s) When cell if recharging, the reactions are reversed. wyetin ce : (i) Lead-storage batteries ‘A typical 12-V battery consists of six cells connected in series, each cell providing a potential of about 2 V. ‘Anode A series of lead grids packed with spongy lead Cathode A series of grids packed with lead dioxide. Electrolyte An aqueous solution of H,SO,, 38% by weight. « Discharge of battery When the cell gets discharged (providing current) acts as an electrochemical cell. The reactions involved are ‘At anode Pb(s) + HSO; (aq) —> PbSO, (5) + Ht + 2e7, E° = 0.296 V At cathode PbO, (s) + 3H* (aq) + HSO;j (aq) + 26° —> PSO , (s) + 2H,010, E' 1.628 V Net Pb(s) + PbO,(s) + 2H” + 2HSO; (aq) —> 2PbSO ,(s) + 2H,0(), E° =1.924 V Characteristics ‘There is no need for the cell to have separate anode and cathode compartments because the oxidising and reducing agents are both solids (PbO. and Pb) that are kept away from coming in contact by the presence of insulating spaces between the grids. + Sulphuric acid is consumed during discharging and ‘when the concentration of H,SO, falls to 1.20 gm Lit requires recharging. ‘+ Recharging the battery _A “run-down” lead storage battery can be recharged by using an external source of direct current to drive the cell reaction in the reverse non-spontaneous direction. ‘Actually it forces the electrons to flow in opposite direction resulting in the deposition of Pb on the anode and PbO» on the cathode. In this case battery behaves like elecizolytic batteries. ‘The reactions involved are At cathode (negative pole) PbSO 4 (s) + 2e7 —> PD(s) + SOF (aq) At anode {positive pale). 4s: PbSQ (3) + 2H,0.—9 PbO pts) + SOF (aq) +44" (aq) + 26 Net reaction: eotse of 2PbSO 4 () + 24,01) —> Pb(s) +PbO 29) + 4H (aq) Scanned with CamScanner‘The recharging process becomes possible because PbSO, formed during process is solid and stick to the electrons. Therefore, it can easily lose or gain electrons during, lectrolysis. ; ore re mo TL) TL co Source of direct curent Discharging ” Recharging Fig, 3.12 Lead storage battery (@) Construction ofa lead storage battery (©) Changes occurring during discharging and recharging ‘of battery. (ii) Fuel cells A fuel cell is a galvanie cell in which one of the reactants is a traditional fuel such as CH, or H, or CO. Reactants are not contained within the cell but instead are continuously supplied from an external reservoir. * Electrodes are made of porous carbon impregnated with metallic catalysts (Pt, Ag or metal oxide), electrolyte is hot aqueous KOH. * Electrolyte Concentrated KOH or NaOH + Catalysts Generally Pt or Pd or Ag Reactions involved The fuel (gaseous H) and the oxidising agent (gaseous ©,) do not react directly but instead of flow NOTE! Thuymodrymamic Spficieny of fust Cor ages -nfe? Bu Bone Cae xlro 4 2 HD KGS X23 mm aa? : NEE ge 239300 Tmt! ym = A4-xyoo = ~ FE : ; sa Tae = 37.39 Ka/mat » $ For, Hyn0, fuel Cott, _ = 20 “a Wgt Hon (04) PH Ha0(1)4 40, E=- 083 "Us a 97.39 8 (A\ehe-—> 40H" (48), +040 = 23489 ¢ rou, O,(6) + an,o()rhe > , = RSE gay over, reaction 2Ha (87409 (6) A4Q0(8) Ect 24133 into separate cell compartments where Hy is oxidised x anode and O, is reduced at the cathode. Atanode 2H, —> 4H + 4e~ 4H +40H” == 4H,0 a ‘2H,(g) + 40H (aq) —> 41,00) 44> At cathode 02(g) + 2H,0U) + de” — > 4OHT (aq) eet Net reaction 2H,(g)+ O2(g) —> 2H,00) Catalyst used in this cell, increases the rate of electrode reactions. ‘Advantages (0 Fuel cells are pollution free cell, are light in weigh, and have high reliability. (ii Efficiency of fuel cell is very high (about 70%). Anode =, + Catnode = =o (HORNHOW) snoenbe poveiueou09 Fig. 3.13 Fuelcell Disadvantages (@ It is very difficult to handle gaseous fuels. (ii Catalyst used are very costly, (ii) Electrode preparation is very difficult and time taking. Uses ‘The primary use of this kind of cells is in space craft, where by product (H,0) can be used for other purposes ® well. These cells are also used in other vehicles like electric cars, submarines ete. ° = 0-40-(-0.89)¥ Scanned with CamScanner