44 | Engineering Chemistry ~1 2.1 INTROD le) Electrochemistry is a branch of physical chemistry which deals wi relationship between electrical energy and chemical changes. | th the | | A material which allows electric current to pass through it is cate da conductor. 2.1.1] CLASSIFICATION OF CONDUCTORS Conductors Metallic (or) Electronic Electrolytic (or) lonic conductors conductors | Conductivity is due to movement Conductivity is due to movement of ions of electrons Eg: Strong clectrolytes (KCI, NaCl) Eg: All metals, aqueous solutions ‘Weak electrolytes (CHsCOOH, NH.OH) of acid base 2 ELECTRODE POTENTIA! A metal (M) consists of metal ions (M"*) with valence electrons. When the metal (M) is placed ina solution of its own salt, any one of the following reactions will occur. (i) Positive metal ions may pass into the solution M— M* +ne (oxidation) (ii) Positive metal ions from the solution may deposit over the metal. M™ +ne — M (reduction)we , oo Electrochemiswry l4s xample t | when Zn electrode is dipped in ZnSO, solution, 2+ ions, Now the Zn electrode attains Zn goes into the solution ras a negative charge, due to th jation of valence electrons on the metal, the negative charges develosed on thé | ni S Ie electrode attract the positive ions from solution. Due to this attraction th iti sips remain close to the metal. eResitive | i Example 2 i When Cu electrode is dipped in CuSO, ), solution, Cu** ions from the solution deposit over the metal. Now, the Cu electrode attains a Positive charge, due to the accumulation of Cu" ions on the metal. The positive charges developed on the electrode attract the negative ions from solution. Due to this attraction the negative jons remain close to the metal. Zn rod Zn? ion solution (a) Zn electrode in (b) Cu electrode in ZnSO. Solution CuSO, Solution Oxidation process Reduction process Figure 2.1 Electrode potential @ Watch Animation in the CD-ROM Thus, a sort of layer (positive (or) negative ions) is formed all around the met- al. This layer is called Helmholtz electrical double layer. This layer prevents further passing of the positive ions from (or) to the metal. A difference of poten- tial is consequently setup between the metal and the solution. At equilibrium the Potential difference becomes a constant value which is known as the ¢lectrode_ Potential of a metal.A 2 46 | Engincering Chemistry -1 Joctrons is called the oxidat;, » to lose H Thus, the tendency of an electrode to lo: jectroms inedlled the >to gain el tential and the tendency of an electrode to 4" potential. on p tetig, Factors affecting electrode potential jon depends on The rate of the above reaction depends ¢ 1. The nature of the metal. 2. The temperature. taal ion 3. The concentration of metal ions in solutio: Single Electrode Potential (E) It is the measure of tendency of a metallic electrode to lose (or) gain electrons When is in contact with a solution of its own salt. Standard electrode potential (E") It is the measure of tendency of a metallic electrode to lose (or) gain electrons, whe, it is in contact with a solution of its own salt of 1 molar concentration at 25°C. 3 EXPRESSION FOR ELECTRODE POTENTIAL NERNST EQUATION Consider the general redox reaction, kK Mv tne ===> M6) For this reversible redox reaction, the free~ener; ‘gy. change (AG) and its equilibrium constant (K) is related by the following equation. (Vant Hof: Isotherm) 4G =-RTInK+RTIn Products] [Reactants] Ae Products] =AG°+ RTIn Products] [Reactants] eae (--RTInK = AG®, the standard free energy change) The change in free energy is related to electrical energy as ~4G = nFE and ~AG’ = nFE°, (2.2)y electrical energy is produced at the expense nce of free en en sipvalency,FisFaraday and iselectrical energy, cena Electrochemistry |47 1 | wher" a bat tuting the Equation 2.2 in Equation 2.1, we get, [Products] {Reactants] pividing the Equation 2. 3 throughout by—nF, 28 -(Sr) Ce) (ne) “_(RT) (1 h ESE iE ita [+ activity of the metal, (M]=1] | _pFE=-nFE° + RTIn (2.3) M™] 2.303RT 1 E=E°— log —— ] r = i + nF iM] i 9, 2303RT i q E=E° + log IM" ] (2.4) | when the values of R, Fand T are substituted the Equation 2.4 becomes R=8314 JK" Amole?; F = 96500 coulombs ; T= 298 K) oe Be Bg ee tog IM] (25) where Eis the electrode potential and E? is the standard electrode potential. similarly for oxidation potential, 0. om log [M™] (26) B= Eu — for electrode potential. and 2.6 are Faowna as Nernst I Equations Equation 2.5ae ‘ : a Be arin Electrochemistry | 51 d the potential of the cell in which the followin 8 Feaction takes pl SC. Ziq + Cu? (0.01M) > Cu, + Zn a Pesta **(0,.2M) where E°(Zn™* /Zn) =~ 0.76V; E° (Cu** /Cu) =o34y | solution The electrode reaction and the net cell reaction of the above cell is | AtAnode : Zn—Zn**(0,2M) +2e | AtCathode: Cu?*(0.01M) + 2e— Cu Zn + Cu** (0.01M)— Zn™*(0.2M) + Ca | n=2 Bea = Ex — Bt = Boyt pou ~ Evan pany | =0.34- (-0.76)V =1.10V «. According to Nernst equation, E,. for the given cell Fog = Et, — 2508RT |, [Zn (product) nF [cu (reactant) _ 2308-8314 298, (0.2) 2. 96500 8 (0.01) =1.10- 0.0296(1.3010) =1.10- 0.03844 Potential of the cell = 1.0616 V 2.4 REFERENCE ELECTRODE An electrode whose electrode potential is already known and is used to determine the potential of other electrodes is called a reference electrode. Some important reference electrodes are hydrogen gas electrode, calomel electrode, Quinhydrone electrode, etc. =1.10 STANDARD HYDROGEN ELECTRODE (GAS ELECTRODE) (SHE) A gas is bubbling in a solution forms this kind of electrode, Example: gen electrode, Figure 2.21 chemist 52| Engineering In hydrogen electrode, H, Bas is bubbled Yn a solution of Hcl. C ing place in the equilibrium reaction taking place i electrode is 2H! +20e 2 HT In this electrode an acid resistant metal (uch as Pi) is used for conducting pur- pose, The cell reaction may be represent- edas [Pt,H,| H* oe The standard electrode potential of SHE is given by Eon "OV : ea] Figure 2.2 Hydrogen electrode 2B CALOMEL ELECTRODE (METAL-METAL INSOLUBLE SALT ELECTRODE) It consists of a metal and a sparingly soluble salt of this metal dipped in: solution of a soluble salt having the same anion, e.g. calomel electroé. (Figure 2.3), This electrode consists of mercury, solid mercurous chloride and a solution ¢ KCL. It may be written as Hg | Hg,Cl,) | KCl(saturated solu n) The electrode behaves both as the cathode as well as the anode and thi depends upon the connected co-electrode, if the current flows from the left to the right, the calomel electrode wi behave as an anode and send mercurous ions into the solution, The releas! Thea ous ions combine with Clr ions given by KCl to form meregrous chlort Thus there will be removal of chloride ions from the solution.54 | Engineering Chemistry = 1 Usually saturated solution of KCI is used Therefore whe 0.2422 V aT elena aca Nts 2.5 DETERMINATION OF ELECTRODE We can determine the relative electrodes value of the electrode potential of a a me as constant. This electrode ig 4) fixing the potential of one of the as Reference electrode. knoy, For this purpose, the potential of a standard hydrogen electrode in 14 been arbitrarily fixed as zero. An example is illustrated below with ole a ‘ Figure 2.4. Teco ey. tion of the electrode potential of a zinc electrode elect of wt deve Defi Determinal sele ton $ ! {| 2nred \ Ex IM ZnSO. Figure 2.4 Determination of electrode potential of Zn In thi i i - cell. The omit ae is coupled with SHE to form a complet canbe determined as ‘lignes . From this value, the electrode potential of zint ‘cellElectrochemistry |35 where E,= Reduction potential of the right-hand side el a . si E, = Reduction potential of the left-hand sid ce eee _ lee Boa = Beste ~ Bznaeyzn 0-76 = 0~ E, Scrode ‘22+ /2m Epas/n = 0.76 Vv | E ELECTRODES (SE) on Ake The glass electrode is fabricated from a special i «containing 22% Na,O and has low electrical resictaitg sdb Staion tivity. The membrane potential is selective towards a given ion. Thus thes i electrodes are selective towards hydrogen ions, but at higher pH, the tential of which is affected by other cations, especially Na* ions.This led to ae idea of geveloping ion-selective electrodes. B Definition The electrodes, those are not specific for a given ion, but possess certain selectivity towards a given ion are referred to as ion-selective electrodes. Ion-selective electrodes consist of specially prepared membranes placed between two electrolytes as in the case of glass electrodes. Example: Glass electrode b.6.1| GLASS ELECTRODE Glass electrode is otherwise called as internal reference electrode. A glass electrode consists of a thin - walled glass bulb containing Pt electrode in 0.1M HCl as shown in Figure 2.5. The glass electrode may be represented as Pt, HCl (0.1M) | Glasspintinurn wire 0.4 MHI “Thin Walled Glass Bulb Glass membrane advanta 5 Glass electrode anf # de 2. ‘Measurement of pH of a solution using Glass Electrode mi i The glass electrode is placed in the solution under test and it is coupled ys 4 saturated calomel electrode. Ee [ Potentiometer Sia, id Saturated Calomel r) Electrode Glass ‘Saturated KC! solution x Electrode salt bridge |—Hgzclz Be 4 1 Solution of unknown pH Figure 2.6 Determination of pH by using, glass electrode ‘The emf of the cell is measured. Fr as follies, ‘om the emf, the pH of the solution is calculat#!Electrochemisny |§7 Eu =E, -E, Eon = Eo - Eats Bout = 0.2422 —[ Be,” ~ 0.0591 tog tH'y] = 0.2422 — E°4-0.0591 log [H"] advantages } 1, Itis simple and can be used easily. | 2, Equilibrium is achieved rapidly. 3, The results are accurate. 4. Itis not easily poisoned, Limitations 1, It cannot be used in pH above 12. 2. It is necessary to use special potentiometers because the glass membrane shows a high electrical conductivity. HAE] TYPES OF ION-SELECTIVE ELECTRODES Depending upon the nature of membrane, ion-selective electrodes are generally classified as, a) Cation-sensitive type: Its selectivity order is Ht > Kt > Nat > NH,*, Li*....>> Ca** b) Anion sensitive type: F>Cl>NO, > CN >S* etc., eT eYeT reer ES (OR) EME SERIES “The arrangement of various metal electrodes in the order of increasing Dales of standard reduction potential with respect to standard hydrogen electrode is called electro chemical series”. |58 | Engineering Chemist ~! al of some of the electrodes is given in 4 "fy The standard reduction potent ing Table 2.1 . table 21 Electrochemical series rere 1 z g calcttl bated Pattee aces Hahah fF 4 i Lehi Lit +e Li Ate —KyK | Kite +K aA - Cat Ca | Ca #20 Ca | 7 Na‘ / Na Na*+e—Na | | Mg*/ Mg [Mgt +2e—-Mg | iat, . | Ar/Al AP" +3e" —> Al } [Zn® / Zn Zn + 2e—Zn a id Cr / Cr Cr+ 3e > Cr rr | Fe*/Fe Fo" + Je Fe : L_N*/ Ni Ni? + 2e° Ni = [— Sn" /Sn_ Gn® + 2e—> Sn | [Pb /Pb Wee bE i Fe* / Fe Fe | Fe* +3e" Fe 2H*/H, ” 2H* + 2e- —H, ste | a | Tora aer pa | 5 Ag’ / Ag. Age >Ag +080 = : Pet / Pt Pt + de Pt ae . : AalA " . = Reduction | DET u Au’ +e>Au 41.50 v b = Nk 5 —| 5 pa EY Et ae +287 | Cathodic : APPLI FRB) appuication oF me SERIES (SIGNIFICANCE OF EMF SERIES) 1 Calculation of single electrode Potential The emf of a sin; gle electri using Nernst equation, ode at a particular temperature can be calcu! aid60 | Engineering Chemistry ~ I gen from acids 1 potential E? will displace the hy droge, fo, 6. Displacement of hyar Metals with negative reductior s tion. saan will displace H,. (ie) Metals above H, in the emf series Example +H, T Zn+H,SO, > ZnSO, E’m =—0.76 volt acid (tyyr076 ) Zinc displaces hydrogen from an ) ‘The metal with positive reduction potential will not displace the hydrogen fe Nig ib. Ele an acidic solution. ‘Ag+ HSO, —+ No reaction (E%,, = + 080 vy) - _spo} a cell means an assembly of a set of electrodes name, In electrochemistry, anode and cathode and an electrolyte. Cells are classified into two types depent ing upon their inter-conversion. a. Electrolytic cell It is the cell which converts electrical energy is to chemical energy. ie. te supplied electrical energy is used to bring out the chemical change. Eg: Electrolysis of HCl Here two platinum electrodes are connected with external battery and immer parnally in an aqueous solution of HCl. When electricity is passed through platinum electrodes, electrolysis occurs which causes the evolution H, gas cath ode and Cl, gas at anode. Cell Reaction At Anode: 2Cl — Cl, t+ 2e (Oxidation) At Cathode: 2H* + 2e- > H, t (Reduction) aElectrochemistry | 61 Chlorine gas Platinum el Pipe 27 Eye cetnumancote | siete | | b. flectrachemical cells An electrochemical cell is one in which electri | ‘ical e1 i spontaneous redox reaction. nergy is generated by a | r i CTROGHEMIGAL © Flectrochemical cells are of three types: 1, Galvanic cell 2. Concentration cell 3. Fuel cell. 1. Galvanic or Voltaic cell This is a device to produce electrical energy by means of a chemical change (redox reaction) (eg) Daniel cell. A Daniel cell consists of a Zn electro! tion takes place) and a copper electro tion takes place). The two solutions are separal Figure 28, As soon as the salt bridge is introduced de dipped in ZnSO, solution (where oxida- de dipped in CuSO, solution (where reduc- ted by a salt bridge, as shown 1n the electrode reactions start. Cell reactions At the anode (negative electrode) Zn > Zn + 2e (oxidation)G2] Engineering chemist! athode (positive electrode) At the ci (reduction) Cu +2e— Cu Overall cell reaction zn + Cu® > Zn® + Cu Hence, E,., = E,- E, Eq = emf of cell E, = Reduction potential of the right-hand side electrog, ‘Ode. E, = Reduction potential of the left-hand side electrod, le. Uses of Salt bridge 1. Itis employed to eliminate the liquid junction potential. 2. It builds up electrical connectivity between the two electrolytic lytic solu, tion, Copper sulphate solution Figure 23) ic Galvanic cel nic cell V Watch Animation in the CD-RO! e CD-ROM2n 121m) = _ ‘The following points oa | cam) [ca | | jectzochemical cell e Noted | 1, The cell is made up of tw. 'O electrodes, an anode and a cathode. i ith regard to the representation of an 9 The electrodes are separat double vertical ling, DY 4 ®Alt bridge which is indicated by a 3, The anode is always written ca on th I ji ree oe indicated a the ce i efthand side andthe cathode is || 4, Anode is represented by writing th both separated by a vertical ie e metal first followed by the metal ion, a ‘he tions, 5, Cathode is represented by writing the metal ion first followed by the me i metal, both separated by a vertical line. 6. The electrolyte concentration is mentioned in brackets. b.11 NERNST EQUATION FORA 'GALVANIG CELL Eg: Daniel cell [Zn | Zn** (Ci) 1Cu® (C,) Cu Ey =Ey -E. 2.303RT 2.303RT S ae -[Fem* a logic [Peet OORT ogi | “Tre - 2303RT ,_ [Cu] = [Por aE rm ‘Aa 108 FA 2303RT , Ca. log nF Gq OF A CELL “the difference of potential, which ial to the lower ELECTROMOTIVE FORGE (EMP) : Electromotive force (EMF) is defined as, F electrode of higher potenti Causes a flow of current from one | __ Potential of other”. It is expressed in volts, Vv.Ww | Electrochemistry io hemistry 65 on bY YK, i K, cell C, is put into the 1h ; , Pen, | fpeated to find the corresponding Circuit. The above procedure is ; Fy 29 the emf of cell C, is calculated using the te equati Sig EME FC, distance mye : | fea SE OF CS, distance AX, eas | , Sof Wr i | ich f The emf measurements are useful in finding the end point of volumetric he analysis. Thisiscalled potentiometrictitrati tr i indicator electrodes. ation. Theend pointcanbemeasured using ‘d There are three types of potentiometric titrations. They are S 1. Acid-base titrations 2. Precipitation titrations 3. Oxidation-reduction (Redox) titrations fel OXIDATION - REDUCTION (REDOX) TITRATIONS Titrations in which both oxidiation and reduction reactions take place simultaneously is called oxidation - reduction (or) redox reactions. Here, an inert electrode like Pt electrode is used as the indicator electrode. This may be coupled with a saturated calomel electrode to form a complete cell. Example: Titration between ferrous sulphate and potassium dichromate in the Presence of dilute sulphuric acid. cid is titrated against 50 ml of ferrous sulphate solution containing sulphuric acid i Potassium dichromate. Initially the solution contains Fe* ions only. When ‘e** ions. Hence, the potassium dichromate is added, Fe® ions will be oxidised to F ‘ solution will now contain both Fe” and Fe* ions. The reaction may be given as, Fe™ 3 Fe™ +e / Now, the emf of this redox system is given according to the Nernst equation a5,ering Chen : ccs | a | ‘sat bridge = | principle cond Hach paste duc | of com’ Magnet Strror Vom ave 2.10 Potentiometric Titration | mol | a. Fe? = Fe™ +e" b. Now, the emf of this redox system is given according to the Nernst equations, @ bor sean FT a ° + 0.0591 1 FE E+ 08 [Fe] e. Hence, as the concentration of Fe* goes on increasing, the potential or emfofth —_cid-I cell will also increase. The emf increases slowly at first and rapidly towards te ca end point. If a plot is drawn between volume of potassium dichromate againt emfand AE / AV, the shown in Figure 2.11 graph will be obtained. — Vol. of Kxcrs0, ——__ Figure 2.11 Oxidation ~ reduction titratio, a bei the « conc the in t ally ‘unt (in rey mc Vol. of KeCr207 ——— nsRE 74 | Eng reering Chemistry - fee ON Qe, co ‘Any process of destruction of solid metallic material through an unvvan, a chemical (dry medium) or electrochemical (wet medium) attack by its enviggs ee rent is Known as corrosion. 3.U Reason for corrosion in metals Metals in pure form possess high energy and low stability. To attain stay, form metals undergo oxidation to form their metallic compounds with liberatg, of energy- — omioa Metal <2 Metallic compound + Energy (high everey) ey (low energy) Corrosion ‘ee SOT (oxidation) PEEKS xy Rese Or KOO OI ROGRoe Metallic S2he+ Energy | B62 comy und < XR Reco e 1.Co Nesesnetetetatataentata [High Energy state] (reduction) [Low Energy state] abot Figure 3.1 Corrosion processes resu ; Se witl Two examples of corrosion are: the 1. Formation of rust on iron articles. Re 2. Formation of a green layer on the surface of copper. 13.2 TYPES OF CORROSION er 0 assified into = T (On the basis of the medium of attack, corrosion can be cl types. 1. Chemical corrosion or dry corrosion. 2. Electrochemical corrosion or wet corrosion.‘Nteg ito, table Ation, ne | | | | | Corrosion and Corrosion Con CHEMICAL CORROSION (or) DRY CoRROSION =e his pe Of corOSION occurs mainly thro : ugh the di amospheric gases like oxygen, halogens, eee siete action a fnment. This type of corrosion may be classified int thee ee ha 4, Corrosion by oxygen. a 2, Corrosion by hydrogen 3. Liquid-metal corrosion Metal imal —_ae bx! | + XI 1. Corrosion by oxygen This type of corrosion is otherwise called oxidation-corrosion. It is brought about by the direct action of oxygen on metals in the absence of moisture, This resulis in the formation of a metal oxide film. Once the metal surface is covered with a mono layer of oxide, the growth of oxide film commences perpendicular to the metal eurface and results in the formation of a thick oxide Jayer. Reactions M = M¥+2e (loss of electron) 0, +2e ~ Oo (Gain of electron) (Corrosion product) M*¥+0Q2 = MO The product of corrosion is forme don the metal surface as shown in Figure 33.chemistry 76 | Engineering Chemist? a the metal surface plays an impoy, fies ant, layer ig volatile in nature (such ag \. ide layer isv S Moc’ If the ose ide Iayer is unstable (Such as Ay, ph jc, In this case corrosion is not POSsible th 2 Co corrosion is not possible aya, by formed o} The nature of the oxide in oxidation-corrosion: oH a eS as ‘oxygen fae tim ——>| otal —— ‘oxi 1S A ye MOO jor <0! 2 hy -O, 5 Yor ! D ' = Ewe 90 po ¢ 7 |4¢—— oxide film / environment - Metal / Oxide interface Figure 3.3 Mechanism of Oxidation corrosion Pilling - Bedworth ratio The ratio of the volume of the metal oxide formed to the volume of the metal cur sumed is called “Pilling-Bedworth ratio”. 1. If the volume of metal oxide formed is less than the volume of meté ite, Volume of the metal oxide formed Volume of the metal consumed consumed, the oxide layer is porous and non-protective. E ? i " “ample: Alkali and alkaline earth metals such as Na, Mg, Ca etc unde! 80es this type of corrosion, 2. If the volume of the metal oxi | of metal consumed, the oxice xide formed is greater than the volume layer is non-porous and protective.im, “} Por Corre rast n | ample + Hem meas su on ad Comsion Conn S Ay 120, | corrosion, a8 Pb, Sn, ote oss PD wit ©: undergoes this type iby carosion by hydrogen Pe of hy Stoig yriytrosen em" f : f ' eo this type of corrosion takes place when metal vj Hs gases Pipes carry hydrogen and brittlement Fe + HES — FeS + 2H (Atomic hydrogen) | The atomic hydrogen diffuses readily | yoids. There it combines with another ai H+H>Ebt 5 atic of i | | During the pane em ° an hydrogen high pressure is developed and causes cracks on the metal. This process is called hydrogen embrittlement. into the metal and coll — tom of hydrogen forming meleuhe ing molecular nment @ rrr rrsteninneconom 1) Decarburisation See. | At high temperatures, the molecular hydrogen is dissociated into atomic | H, 2928 metal con- C+ 4H >CcH,? hydrogen, When alloys like stel is exposed to this environment the stom hydro- ines with carbon in steel forming methane i My of metal gen diffuses into the metal and com forming man Men these gases gets collected in the voids high pressure is developed results in cracking of the steel. seviak t in steel and the quality of e of carbon conten This results in the decreas 5 4 decarburisa Steel decreases. This process is called as @ Watch Animation in the CD-ROM tion” of steel.78 | Engineering Chemistry -! 3. Liquid metal corrosiow ai al flows over a solid i smpocuss wher eanollerl NCES ST metal. dissolution of the solid ‘metal or diffusion of the liquid into the solid metal 2 take place. @ waren animation in the CD-ROM ELECTROCHEMICAL CORROSION (OR) WET CORROSION Condition 4, Wet corrosion takes place where a conducting liquid is in contact wig, metal. = 2. Italso happens when two dissimilar metals or alloys are either immerse or dipped partially in a solution. Mechanism It involves flow of electrons from the anodic to the cathodic areas. [At the anodic area, oxidation takes place M — M™ +ne (oxidation) (Eg) Fe > Fe*+2e At the cathodic area, reduction reaction occurs. Iron Metal Acidic Environment 0" ws At tr T| Corrosion and Corrosion Control \79 tal aration of tydrogen Sor Big, ae eta he This type of cathodic reaction occurs j fivacld teense . ce in acidic environment. | The overall reaction is Fe + 2H* + Fe + Ha} | D. Absorption of oxygen (formation of rust) wig, | Ms sateen This type of cathodic reaction occurs i ‘urs in neutral aqueous soluti en solytesin the presence of oxygen. aa 1hQr+ H:0 +2e > 208F The overall reaction is Fe+ 20H — Fe(OH): | |<—— oxide film Figure35 Absorption of oxygen PE corrosion [tin ore a If enough oxygen is present, the ferrous hydroxide is oxidised to ferric hydroxide, a product called yellow rust.80 | Engineering Chemist ~ 1 and electrochemical corrosion Difference between chemical a ical_and_electrochemica ‘The difference between chemica i consi tabulated in Table 3.1. A sabe 3.1 Chere an elctrctiemical corrosion 1, This occurs 2 IItis duc to the direct chemic of gases on metals. al action | It is due to the formation a large number of tiny pa, vanic cells. Vea It involves electrochemical~ reactions (redox). Only heterogeneous metal ~ [3 | Itinvolves chemical adsorption. Z| Indry corrosion, even a homoge- neous metal surface gets corroded. undergoes wet corrosion, Corrosion occurs at anode The corrosion products accumulate 5. at the same spot of corrosion. and the products accumu- late at the cathode. 6. __ | In this case uniform corrosion is Pitting corrosion is more observed. frequent in this case. 3.3 GALVANIC COR RN Definition Wh ae hen two dissimilar metals (Zn and Cu) are coupled together and exposed toi electrolyte, the m i y more anodic metal undergoes corrosion. This type of corrosion is knowt® galvanic corrosion”. Example (i) Figure 3. higher inemt =e wloonen Zn- Fe couple in which more active zinc which ode which is lower in emf peas and undergoes corrosion and iron acts asc iron undergoes corrosion whien gens ol) represents Fe - Cu couple in whit emf series. In this metalli ich is more active when compared with copp it ic couple Fe acts as anode and Cu me as cathode. ExamCorros fon and Corrssio "Control |B Less active Cathode active Anode Tess active Figure 3.6 Cathode Zn Zn+20 Electric et | (Less noble) anode is attacked (tore noble ‘cathode is protected | Zn cu Figure 3.7 Galvanic corrosion @ Watch Animation in the CD-ROM. | ee Ee a ee Reactions Anodic reaction oan Zn — Zn’ +2e (oxidation) wn as Cathodic reaction (i) Inacidic medium ch is 2H* +2e" > Het a (i) In neutral solution with oxygen ich rin %2Qr+ HO + 2e° + 20H82 Engineering Chemist! Examples ; tal around copper wire. 1. Corrosion of soldered me! bearing. on of steel shaft in bronze connected to copper plumbing. 2. Corros 3. Corrosion of steel pipe 4, Steel screw ina brass marine hardware corrodes. Control ; i .d by selecting two dissimi 1. Galvanic corrosion can be controlled by s¢ 6 ae mea he electrochemical serie ’ are very close ii 2. Itcan also be avoided by connecting two dissimilar metals *hrOUgh ing, ing materials. . 3, By making cathodic area smaller and anodic area larger. DIFFERENTIAL AERATION CORROSION Definition This is a kind of electrochemical corrosion occurs due to the development, y varying concentration of oxygen or any electroiy: concentration cell formed b on the surface of the metal. The less oxygenated area acts as the anode and will get corroded. The meg oxygenated area acts as the cathode and is protected from corrosion. Example (i) When a Zn metal is partiall corrosion. ly dipped in electrolyte undergoes this typet Reactions Atanode (less oxygenated surface) Zn Zn* + 2e (oxidation or corrosion) At cathode (more oxygenated surface) %O2+H,0 + 2e 20H- (reduction)lopment of electrolyte The more | | Lis type of More oxygenated part (cathode) Znrod Fost :0 +20°-» 2011 Se Lnowatarcom | Corroding anode | Zn» Zee be (Loss oxygenated ma Figure 3.8 Differential aeration Corrosion ‘Watch Animation in the CD-ROM pample (ii) pitting Corrosion Pitting is a localised attack on a [rein lant > mig 2 bag) metal resulting in the formation of pit | fi | al ancace ER | Gano v4 RNs cates | around which the metal is relatively unat- around which the meta! is rae" tacked. The pitting corrosion takes place when, a | metal surface is covered by a drop of water, Figure 39 Fitting corrosion sand, dust, scale etc, Letus consider a drop of water on a metal surface as shown in Figure 3.9. The area covered by the drop of water acts as an anode due to les: xygen-concentration and suffers pitting corrosion. The uncovered area (freely exposed to air) acts as a cathode due to high oxygen concentratior Therate of corrosion will be more, wien the area of cathode is larger and The ST" ofanode is smaller. Therefore, more and more material is removed form the same spot. Thus a small pit is formed on the surface of the metal. ode Fe — Fe + 2e"I 84 | Engineering Chemistry ~ At Cathode \ Formation of OH ions. = % 0; + H;O + 2e > 20H a Net Reaction i, If enough oxygen is present, the ferrous hydroxiq fpifeicerted, S18 Ong |W ferric hydroxide, a product called yellow rust is formed. ‘i o 4Fe(OH), +O,+2H,0 ——> 4Fe(OH), e J F (Fe,O; -H,0) a yellow rust é Example (iii) (a) Crevice corrosion A Bos Crevice between different ‘Anode Cathode ga ~ metallic objects is in contact with liquids, it becomes anodic region due to less oxygen exposer and suffers crevice corrosion. The more oxygenated areas acts as the cathode as shown in Figure 3.10. Loss aerated ©) Pipeline corrosion , (onodi) Buried pipelines pass- ing from one type of soil to another for example, from clay. (less aerated) to_sand (more aerated) may get corroded due to differential aeration, More aerated (cathodie) Clay Figure 3.11 Pi eT PipelinecorrosionFy xij. ise, Te to | "the corrosion. Conn 70 85 n and Corrosi z ” Control | ad wire-fence ‘ pnt s ; ’ e A wire fence in which the e wires Cross are less ere SSS Oxygen. the rest of the fence a weythan ne fence and hence sion occurs at the wire crossings, | 4 . me the Tess oxygenated wire crossings ef sanode and the remaining area acts act ‘ a cathode. area ; ny Figure 3.12 Corrosion on wine f S INFLUENGING CORROSION Ae 5.1 | NATURE OF THE METAL o 1, Position in galvanic series In general metals above the hydrogen in emf series gets corroded easily due their anodic nature. When two metals or alloys are in electrical contact (conducting liquid), the more active metal undergoes corrosion. Eg: Zn= more active metal Cu= Noble metal ‘The greater the distance between two metals, in electrochemical series greater is 2. Over voltage the increase in the rate of Jhanism of corrosion, Inhy it cl In hydrogen evolution me tage. conosion is related to decrease in hydrogen over V i is 0.7 volt. By addin; 8g: The normal hydrogen over voltage of Zn in 1M H:SO1 is on vet ‘ ya _ 8 small amount CuSO, as impurity to Zn metal, the hydrog ion takes place. reduced to 0.33V and the increase in the rate of corrosion takes P| 3. Relative areas of anode and cathode ill be more. So, If the cathodic area is larger, the demand for electrons wilf 1 86 | Engineering Chemistry-1 anodic area mailer and cathodic 5 s area j ne severe, if the Sa, jon will b idit) gui re increases with the increasing ¢. 2° ur L centage of corrosion ine § Sony, ie The percentags ee vs extent of the impurities. ae : we extent c ve purity of zine 99.999 [99.99 [99.95 oe for 0 purity of zinc 19,99 : Corrosion rate | 1 1650 | 5000 | Bet ati {nit 100% pure metal will not undergo any type of corrosion, but Presing, and HS it in in otal creates heterogenity, that result galvanic corrosion, 4 anos impurities in me ct | 5. Physical state of metal pe " _ a ! b The rate of corrosion is influenced by grain size, orientation of ey. stress etc. If the grain size of the metal is small the rate of corrosion will tej, = natu etc. ih 5 Metal parts under stress become anode and undergo stress corrosion, Pr | ii 6. Nature of the surface film cates)’ | i In aerated atmosphere, all metals get covered with a thin film of my; the PE oxide. The ratio of the volumes of the metal oxide to the metal is knownas'saz_ 6, For HH volume ratio’. Greater the specific volume ratio, lesser is the oxidation Corrosig } / rate. part HI 7. Solubility of corrosion products Inelectrochemical corrosion if the corrosion product is soluble in the cored ing medium corrosion proceeds at a faster rate. On the other hand if the cone sion product is insoluble (eg. PbSO;) it acts as a protecting layer. If the corrosion product is volatile (MoO), corrosion rate is faster. SF soil ay NATURE OF THE CORRODING ENVIRONMENT & 1, |. Temperature “eases with increase of temperature. At hig! — en f diffusion of the ions increase in a chemical reaction. Hen the rate of Corrosion increases,: s te Corrosion and Corrosion Control |s7 ‘dit | ow miditY Su, | pumidity of air is directly related to rate of corrosi te ay ses i humid conditions in the Presence of atm sion. The rate of corrosion | incre ser humidity the moisture in the air eet Se TIE Ba8eS like C higher ity sture in the air acts as electrolyte e At i | forsetting electro chemical corrosion, a co of corrosive gases fe nas In industrial areas, atmosphere is polluted wit Senge, | yh SDH E> thereby increasing the rate of corrosi mosphere, the presence of chloride ions increases t fect of pH Crystal Generally acidic medium is more corrosive than aqueous medium. which is impor- h acidic gases like, CO, SO: ion. Similarly in the marine the rate of corrosion. be high’ | nature of fons | Presence of anion like silicate leads to the formation of insoluble metal sili- | cates, which inhibits further corrosion, where as the presence of Cl- ions destroys the protective film there by increasing the corrosion. ‘specie 6. Formation of oxygen concentration cell rrosion | More oxygenated part of the metal becomes cathode and the less oxygenated part becomes anode, resulting in the formation of oxygen concentration cell. | Eg. More oxygenated area orrod- 2H,O +O; + de’ — 40H: (cathodic reaction) corro- rosion Less oxygenated area: Fe —» Fe* + 2e (anodic reaction) Corrosion of buried pipe lines, cables etc., are due to the differential aeration in soil. 3.6 CORROSION CONTRO! _ The rate of corrosion can be controlled by eith er modifying the metal or the88 | Engincering Chemistry = 1 SQN contron OF CORROSION BY MODIFYING THE METAL 7. By selection of the metal Noble metals are used in ornaments and in surgical instruments, a most immune to corrosion. 's they in 2. By using pure metal Pure metals have higher corrosion resistance. Even a small amount o imp, rity may lead to severe corrosion. 3. By alloying Corrosion resistance of many metals can be improved by alloying. For exan, ple, stainless steel containing chromium produce a coherent oxide film, Whig, Protects the steel from further attack. 4. By proper design (i) Avoid galvanic corrosion ti Galvanic corrosion will occur when two different metals are jive) such a case galvanic corrosion is prevented by a. Selecting the metals as close as possible in the electrochemical series. b. Selecting smaller area for cathode and larger area for anode. Stee! | | } | ©. Inserting an insulating material between the two metals as in Figure 3.13. | i \ “41 Coppor Copper Poor design Good design Figure 3.13 Insulation avoids 8 (ii) Proper Drainage in Tanks Tanks and other mplete liquid shou alvanic corrosion containers must be desi; Id be drained igned in such a way that, the off as shown in Figure 3.14.Conasion ie and Corrosion Controt | g9 Has | compote PS aE he, rainage can Ry ‘drainage rt oF, | a, ici | 4 Avoid sharp comers and bends = —_] aides E h i Poon Sharp comers should be avoided to reduce corrosion * Which — i ned. In Poor design Good design | | 23.13, | Poor design Good design | Figure 3.15 Corrosion prevention using curved pipeline | (ie) Avoid Crevices Crevices allow moisture and dirt, which results in increased elec- tochemical corrosion. This can be prevented by filling the crev- ites with a filler as in Figure 3.16. Veled joints produce crevice comosj eh bY so welded joints are coli Figure 3.16 Minimizing crevice corrosion9 | Engineering Chemistry <1 of CATHODIC PROTECTION Br i ple g:ttesion may be controlled by cathodic protection. It is based on th, Psa! Ciple that the metal to be protected is converted to cathode thereby Prevent | aE ns | Corrosion. There are two types of cathodic protection methods. | as j 4) Sacrificial anode method In this method, the metal to be protected is connected to a more anog, so that all the corrosion is concentrated at the more anodic metal. econ | pra | re Cisintandaly pam | igure 3.17 Sacrificial anodic protection Qwnen Animation in the CD-ROM ic Mey Sacrificial anode E.g. protection of iron pipeline. Pipelines (made of Fe) are connected by a Copper wire to Mg or Zn metal. The\, F or Zn undergoes corrosion because itis more anodic than iron. Therefore, they, ©) or Zn is said to be the sacrificial anode. This is depicted in Figure 3.17. Applications of sacrificial anodic protection | | Insta copper wie | Sacrificial Zn (or) Mg | nul Sacrificial anodic protection of ship _| Us + s o Ps a. This method is used for the Protection of ships and boats. Sheets of Mg* so Zn are hung around the hull of the ship as shown in Figure 3.18. Za th Mg will act as anode compared to iron (ship or boat is made of iron),* Corrosion concentrates on Zn or Mg. Since they are sacrificed in the prot’Lon ® th | Y Prey. Pr "even ih. vy Co "asin and Corrosion Conte |9 | ofsaving iron, they are called sacriticiy a tection of underground pipelines anodes, ‘cal *3.19(@)- bles fi nm 's from soi ™ soil corrosion as in Figure _insertion of Mg sheets into the water bo as shown in Figure 3.19(b), “FS Prevents the formation of rust Insulated veo | | | Sacre Zor my | { (6) Underground pipetine | Figure 3.19 \ b) Impressed current method oe Pp See es at exthode | Ande ‘Sa Under ground pipe line Graphite anode ‘sexi Fo igure 3.20 Impressed current cathodic protection In this method, an impressed current is applied in the opposite direction to nullify the corrosion current and the corroding metal becomes the cathode. Usually, a sufficient d.c. current is applied to a buried pi node. The graphite anode is buried in backfill (mixture o peline through a graphite f gypsum, bentonite and tact between the anodic part and lum sulphate) to increase the electrical con! dl “surrounding soil.92 | Engineering Chemistry -1 i; 2 Control of corrosion by altering the en vironmen 1. Deareation a metal surface inc The presence of increased amount of Ona cdiasolvedd oxygen by ses the | rate of corrosion. De-areation involves Si oni Iealso removes discon e of temperature together with mechanical agitation. ed %, of water. 2. Deactivation ving dissolved oxygen by adding sing | Deactivation is a process of remo chemicals in aqueous solution. Example Sodium sulphite : 2Na;SOs + O2 > 2NazSOs Hydrazine + NsHy + Q2 > Ne + 2H20 3. Dehumidification In this method, moisture from the air is removed by Jowering the relative humidity of the surrounding air. This is done by adding silica gel (or) alumina, which adsorbs moisture preferentially on its surface. | 4, Alkaline neutralisation | ‘The acidic character of the corrosive environment (H:S, HCl, CO:, SO: ete) | can be neutralised by spraying alkaline neutralizers. (NH3, NaOH, lime etc.) 5, Using Corrosion inhibitors These are organic or inorganic substances when added in small quantities to | the corrosive environment decreases the corrosion of metal. | a) Anodic inhibitors These agents form sparingly soluble salt at the anodic area which acts as a protective layer, thereby preventing further corrosion. E.g. Chromates, Phos- phates, Tungstates of transition metals. b) Cathodic inhibitors In acidic solutions the main cathodic reaction is evolution of hydrogen. 2H! + 2e > H,¥ Corrasio Psion and Corrosion Cant | pit ions can be decreased by addin, 93 4 8 inhibitors i "e, pa tioure® Hors like amines, mercaptans, ur ‘eas, i ' Plans, urea i Sth | qn solutions the formation of hydroxide ion, o, veg 10 +%02+2e — 204. ¥ Causes corrosion 0, . above reaction _ be controlled by adding Haga: innibitors like Mg, Zn or Ni which are capable of formar ss ¢°,ConoUME OF the ides which acts as protective layer, 6 insoluble metal hydrox- B Some | 7 PROTECTIVE COATING The corrosion factor demands the use of expensi jon resi omer ec deere he we operivsin san es problems, some other protective materials are needed to protect aii from its surroundings. These materials are called protective coatings, Protective coatings form a continuous physical barriers between the coated-surface and its relative environment. lumina, characteristics of protective coatings 1. They must be chemically inert to the environment. 2 They should prevent the penetration of the gases and other materials present in the environment to the base material (j.e., metal to be protected) Inparting properties The following properties are imparted to the base materials. ities to 1. Wear-resistance 2. Hardness 3. Electrical properties 4. Oxidation resistance 5. Thermal-insulating properties 6. Decoration94 | Engineering Chemistry -1 i : jon mi one or more pigments in q yp, Paint is a mechanical dispersion alee of elal seeee ican 4 Deh drying oil and thinner. When paint is applies ona “acy-plement ft inner ey, rates, and the drying oil slowly oxidises forming a dry pigment film on the surface, Mey Requisites of good paint A good paint possesses the following characteristics. 1, It should spread easily over the protected surface. 2. It should possess high covering power. 3. It should form a quite tough film. 4. Its film should not get cracked on drying. 5. It should protect the base metal from corrosion 6. The film should be glossy. 7. The film should be stable. 8. It should possess high adhesion capacity. Constituents and functions of paints 1. Pigment Pigmentis an essential constituent of paint. It is a solid colour bearing substant. which provides desirable colour to the paint. It's functions are to a. Provide opacity to paint. b. Provide strength to paint. ¢: Provide desired colour to paint, 4. Give aesthetical appeal. (ie., pleasing to look at) ©. Give protection by reflecting harmful uv-light, £. Provide resistance against abrasion/ wear and tear. 8 Increase resistance of the paint film to weather covv Corrosion and Corrosion Comet |os p.Jmprove the impermeability of paint gi im to Moisture, ems , 7 White lead, ZnO, tithophone . Red lead, Ferric oxide. | 3 Green Chromium oxide EL Blue Prussian blue 5. | Black Carbon black a Brown _| Brown umbre Characteristics of good pigments Good pigments should be a. opaque b. chemically inert c. non-toxic d. freely mixable with film-forming constituent oil stance, e. cheap, 2. Vehicle or drying oil / int, These are glycerides of Vehicle is a film-forming constituent of the paint. high molecular weight fatty acids consisting of conjugated double bonds. CH; COOR | CH COOR | CH; COOR The most widely used drying oils are linseed oil, 'ydrated castor oil. soyabean oil and96 | Engincering Chemistry -1 Functions of drying oils Drying oil supplies. a. Toughness b, Durability c. Water-proofness Mechanism of drying of oils The oil film absorbs oxygen at the double bonds and forms : oxides and hydroperoxides. They isomerise, polymerise and condense to fom highly cross-linked macromolecular film. Reactions wet paint film (oll + Oil film + pigment + Pigment + extender + drier drier + thinners) Pigmented film gy ‘cross «linked structure) Oxidation and Evaporation polymerisation of oll ——",. of thinner undar the catalytic influence of drier Figure 3.21 Drying of a paint film 3. Thinners Thinners are another important constituents of Paint, which are highly volt tile solvents, The functions of thinners are to, a. Reduce the Viscosii ty of the paint b. Dissolve vehicle and the additives in the vehicle Penetration, Power of the vehicle & Increase the Clasticity of the paint film, Petoxides, dipg. | Bh arr INP 2 otCorrosion and Corrosion ; a sion Control |97 inners used are i r amon thi turpentine, mineral g iit i kerosene, methylated naphthalene ete Pirits, benzene, naphtha, toluol, isi Driers Driers are oxygen-carrier catal through oxidation, polymerisation and brittle film. sts, They enhance the drying of the elves and condensation, They tend proten e tend to produce hard The more effective driers are resinates, linoleates, tungstates of Co, Mn, Pb, and ipen Zn. form |. extenders or fillers Extenders are low refractive index materials which are added to a. Reduce the cost | b. Increase long durability of the paint | c. Provide negligible covering power d. Reduce the cracking of dry paint film e. Increase random arrangement of pigment particles f. Behave as carriers of pigment colour Examples: barytes (BaSQ,), tale, asbestos, silica gypsum, mica, magnesium silicate, calcium sulphate, etc. 6. Plasticizers Plasticizers are one of the constituent of paint, which are added to a. Provide elasticity to the paint film b. Minimize surface cracking on plasticizers used are tricresyl phosph tylphthalate. ate, triphenyl phosphate, tri Antiskinning agents __ Antiskinning agents are added to prevel film. nt the gelling and skinning of the Examples : Polyhydroxy phenols.98 | Engineering Chemistry - 1 METALLIC COATING Surface Preparation for Met allic Coatings : Importance of cleaning metallic articles before metallic Coating (el, deposition) are sh 1. To impart corrosion, abrasion, wear, thermal and impact resistance 2. To provide electrical or thermal conducting surface 3. To provide enhanced optical or thermal reflectivity to the surface i 4. To manufacture good quality electrical and electronic ¢ capacitors, circuit boards, etc. Methods ‘Omponents lig i 1. Solvent cleaning : Itis used to remove oils, greases and fatty substancespy | Onmé iH applying organic solvents like naphtha, toluene, acetone, etc followed 5; 1 cleaning with steam and hot water. This treatment provides a metal su. face which is suitable for metallic coating. 2. Alkali cleaning : It is used to remove old paint coating by applying trisodium phosphate along with soaps and wetting agents like caustic soda, and followed by rinsing with water. 3. Mechanical cleaning: It is used to remove loose rust and other impurities from the surface. This is done by applying bristle brush plus some abr: sives like sand and detergents, 4. Flame cleaning : It is accomplished by heating the metal surface witha ht flame to remove moistu re and loosely adhering scales followed lY brushing. 5. Sand-blasting : It is use for large steel surfaces, dangerous to health of this process the sand is i — . sally suitable cd for removing oxide scales. It is especially suit ; This process requires expensive equipment at 0 Tt workers, because it causes disease, ‘silicosis’ !* % introduced into an air stream, under pressure 0!” to 100 atmosphere, and the blast is impacted on the metal surface. ; ici . a 6 Pickling and etching : Acid Pickling is more convenient method 2 scale removal from themetal surface tobecoated. Itisdoneby immersing" aes "ded if metal (except Aluminium) in an acid solution, Aluminium is pick! alkaline solution.Corrosion and Corrosion Control |99 ‘Acid pickling of steel is done by dipping in warm dilute Ho, or in cold HCI solution with inhibitors, j ; 5 (lect | For articles made of copper, brass or nickel, dilute HNOs or a mixture of | dilute HNO; and dilute H,So, is used. Nce ALSO UULIN NOM CHLN OMARION e ‘The process in which the coating metal is deposited on the base metal by PENts like ing a direct current through an electrolytic solution containing the soluble altof the coating metal is called electroplating or electrode position. objectives stances by | Onmetals llowed by 1. To increase corrosion resistance metal sur 2. To increase resistance to chemical attack and wear resistance _ | 3. Toincrease hardness aPPIVINE | 4 To increase decorative and commercial values ke caustic : Onnon-metals " impuritis 1. For increasing strength some abr 2 For preservation and decoration 3. To make surface conductivity Theory of Gold electroplating lectrolyte : Gold double cyanide or AuCl salts100 | Engineering Chemistry ~1 atinized titan, Procedure it solving is first treated with organic solvents to Temove o; The base metal is first surface scales [i : , 7 remove surface scales like oxic, Brey, ete. Then with dil. HCI or H2SO, to re eS lay Tole * F athode and anode is pl leaned base metal is made as ca . Plain ‘Sa the electrolytic solution is the soluble gold double cyanide Salts of Aue, x anode and cathode are placed in the electrolytic solution. When ite is passed, coating metal ions get deposited over the base metal and q of gold coating is obtained on the base metal and optimum current deg Clty, 1-10 mA/cm*, The operating pH range is 8.5 with 100% cathode current Cfficiencigg h t 60°C. To get bright gold ‘a optimum current density is 1 - 10 mA/cm? al . To A some brighteners are added such as Hexamine, Cystine silver and nicke| Por, i Example : AuCl ionises as AuCh > Au* +3Cr- At cathode : Au ions gets deposited as Au metal ve towards the gold anode and combines with equivalent amount of Au atom to form AuCl; Au Au® + 3¢- Au*+3Cr Auch The overall teaction at anode is Au+3¢cl, AuCh + 3e- ae Copper object (Cathode) Figures,a Corrosion and C 1 : ‘orrosion Controt Slaya,, 8te, we ing i “ anige” Se 7 | Gold plating is often used in oy Ning, ically conductive | open ‘ Or 4 Org We | gectrically co ayer on ¢, ally ig ae, & €otFosion Ct oy Lap, Cur,” tov a day see ae) is Itisa process in Which a noble mot object ode) ating uniform thin coating. di al (inactive) is deposited on thout using electrical energy and deposit on the metal inthe presence of a reducing agent wi a metal surface reduces the metal ions to metal y. The reducing surface to give a Metal ions + Reducin; => di Bagent — metal + oxidised product | | 1 | deposited over metal surface | various aspects of electroless plating are: \ 1, Preparation of active surface of the object to be plated. The methods | available are a. Etching i.e., by acid treatment b. Electroplating a thin layer of the metal to be plated c. Treating with stannous chloride followed by dipping in palladium chloride solution. This provides a thin coating layer specially for plastics, and printed circuit boards. 2. Plating bath is composed of a, soluble salt of the metal to be plated. b. reducing agents like formaldehyde, hypophosphite etc. succinate ete. i ing rate 4.exaltants like succinate, fluoride etc this enhances the plating . thallium etc. to prevent the ©. complexing agents like tartarate, citrate, ©. stabilisers like thiourea, calcium, t decomposition of the plating bath solution. £ buffer solution, to control pH of bath.102 | Engineering Chemistry’! Advantages of electroless plating over electroplating z 1. No electrical energy is required. ; 2, Articles (to be plated) made of insulators, semiconductors are electro x i easily. ey Some electroless plating 1. Electroless nickel plating Pre-treatment of activation of the surface The surface to be plated is first degreased (using organic Solvents) Folloig by acid-treatment. a. metals and alloys like Al, Cu, Fe, brass etc., can be directly Plated ig nickel without any activation. b. stainless steel surface is activated by dipping in hot solution of 50% diluy SO. | Composition of bath a. Coating solution - NiCl, solution (20 g/1) b. Reducing agent - Sodium hypophosphite (20 g/ 1) ©. Buffer - Sodium acetate (10 g/1) d. Complexing agent cum exhaltant - Sodium succinate (15 g/l) . Optimum pH - 4.5 £. Optimum temperature - 93°C Net reactions At anode 7 HPOr + HO. FEPOs + 2H + 26° (oxidation Atcathode Nim 4 9,- 3 2 Ni (reductiot + = LPO; + HO + Ni+ H:POs + 2H" Redox reacion® NiePlateg Corrosion and Corrosion Control [103 yas? beappli I this method can be applied On objects h: ving intricate shapes ( getter corrosion resistance than electro, 2 (e.g. recesses) plating process, | cations vies wh Bectroless Ni plating is extensively used in electronte appliances, ait finds applications in hydraulic co; MPreSsors, pressure vessels, pumps and fuel injection assemblies, 3,Blectroless nickel coated polymers (like ABS _ plastic 8) find preferred decorative as well as functional applications, 4.Plastic cabinets with Cu and Ni are used in digital as well as electronic “instruments.