Conductors and Conductance terms Factors affecting conductance Kohlrausch's law and its applications Galvanic cell (b) Construction of cell (c) Salt bridge and its functions (a) Cell representation Electrode potential Reference electrode (a) Primary reference electrode (b) Secondary reference electrode [Electrochemical series and its applications |Nernst's equation and its applications [Some special cells (a} Concentration cell (b} Reversible cell e\f/e|z ze: z g z 5 Bod & gf Be [ E g = w x ° z Ee Oo Ww al w (a) Qualitative aspect (b) Quantitative aspect (Faraday’s law) [Exercise-IIl (Analytical Questions) [Exercise-IV (Assertion & Reason) =|F a NEET SYLLABUS Flectrochemistry : Conductance in electrolytic solutions, specific and molar conductivity variation of conductivity with concentration, Kohlrausch's Law, Galvanic cells, Redox reactions, EMF of a cel, standard electrode potential, Relation between Gibbs eneray change and EMF of a cell, electrolysis and electrolytic cells, Laws of electrolysis (elementary idea), dry cell, lead accumulator, fuel cells, corrosion.OBJECTIVES After studying this unit, we will be able to : describe an electrochemical cell and differentiate between galvanic and electrolytic calls; apply Nernst equation for calculating the emf of galvanic cell and define standard potential of the cell; derive relation betuieen standard potential of the cell, Gibbs energy of cell reaction and its equilibrium constant; define resistivity (p), conductivity (x) and molar conductivity (A, of ionic solutions; differentiate between ionic (electrolytic) and electronic conductivity; describe the methods for measurement of conductivity of electrolytic solutions and calculation of their molar conductivity; Justify the variation of conductivity and molar conductivity of solutions with change in their concentration and define A* (molar conductivity at zero concentration or infinite dilution); enunciate Kohlrausch law and learn its applications; understand quantitative aspects of electrolysis; describe the construction of some primary and secondary batteries and fuel cells; explain corrosion as an electrochemical process. In awanging the badies in order of their electrical nature, theve is faumed an electva- chemical system which, ix mug opinion is mare fit than any ether ta give an idea of Chemistry. dons Jacob Berzelius4.0 INTRODUCTION Electrochemistry is the branch of physical chemistry which deals with the study of interconversion of chemical energy and electrical eneray ELECTROCHEMICAL CELL oot Galvanic cell or Voltaic cell Electrolytic cell. * Chemical energy + Electrical energy + Electrical energy > Chemical energy * Spontaneous redox reaction 4.1 CONDUCTORS ‘Substances which allow electric current to flow through them are called conductors. Examples - Metals, Aqueous solution of acids, bases and salls, fused salts and impure water ete. Conductors are of two types - @ + Nonspontaneous redox reaction (i) Metallic conductors or electronic conductors {i Electrolytic conductors or ionic conductors Metallic conductors : The conductors which conduct electric current by the movement of electrons without undergoing any chemical change are known as metallic conductors. Metals - Cu, Ag, Fe, Al etc, nion metals - graphite Electrolytic conductors : Those substances which conduct the electric current through ions in aqueous solution or molten state are called electrolytic conductors. Strong electrolyte : Electrolytes which are completely ionized in aqueous solution are called strong electrolte. Ex. : Salis, strong acid and strong base Weak electrolyte :- Electrolytes which are not completely ionized in aqueous solution are called weak electrolytes. Ex. : All carbonic acids (except sulphonic acid), CH,COOH, HCN, NH,, amine, etc. Difference between metallic and electrolytic conductor Metallic conductor Electrolytic conductor (Charge cartier are free electrons [Charge carrier are free ions, (i) Flow of electricity takes place without Flow of electricity takes place by chemical changes aniy chemical change at electrodes. G3) No transler of matter takes place. Transfer of matter takes place in the form of ions iv) Resistance is due to vibrations of Kernels | Resistance is due to inter ionic attraction and viscosity of mediurn. () The resistance increases with the The resistance decreases with the increase increase in temperature jin temperature. ()_Faraday’s laws of electrolysis are not followed, | Faraday's laws of electrolysis are followed 413Peta asa 4.2 ELECTROLYTIC CONDUCTANCE {a) Resistance (R) :- Metallic and electrolytic conductors obey ohms law according to which the resistance of a conductor is the ratio of the applied potential difference (V} to the current () flowing Rev Ris expressed in fins (b) Conductance (G) - Ibis the property by virtue of which it favours flow of current. The conductance of 1 a conductor is equal to reciprocal of resistance |= 3 ‘unit of G is mho or ohm” or Siemens (S). (©) Specific resistance/Resistivity (p) ~The resistance (R) of a conductor is directly proportional to its length (£) and inversely proportional to its area of cross section (A) t R=px Ife=1om, A=1 cm, therefore p=R 2 VeAx é= 1m? Therefore resistance offered by 1 cm? electrolytic solution is known as resistivity. Unit of p > ohm em: {d) Specific conductance/ Conductivity (x) :- 1 Its defined asthe reciprocal of specific resistance, x = é R-py K=GxG" Specific conductance = Conductance x Cell constant Hence specific conductivity ofa solution is defined as the conductance offered by 1 cm*of electrolytic solution. [Unit of x is ohm”! cm” Cell constant : G = ts unit is emr* 114.Bee chetty {e) Molar conductance = (A_, ,0r p): Its defined as the conductance of all the ions produced by one mole of electrolyte present in the given volume of solution, A, RXV \V= Volume of solution containing 1 mol of electrolyte. If concentration of solution is M - mol per ltre then 1000 Aa = Unit — ohm em? mol”! (f) Equivalent Conductance (A,,0F7,,) = Itisdefined as the conductance of all the ions produced by one gram equivalent of the electroiyle in the given volume of solution. 2 Age RXV \V = Volume of solution containing 1 ea of electrolute. If concentration of solution is N - gram equivalent per litre then x1000 [Unit - ohm? cm’ eq? © Relation between A,, and A, «1000 1000 Age M and aoe slp We know that Normality = Valeney Factor x Molarity. So |Aes Illustrations "Illustration 1. The resistance of a 1N solution of salt is 50 ©. Calculate the equivalent conductance of the solution, if the two platinum electrodes in solution are 2.1 cm apart and each having an area of sx1000 11000 1). Solution. N wt Mlustration 2. Which of the following have maxirnum molar conductivity. (0.08 M solution and its specific conductivity is 2 x 102.0 ern Gi) 0.1 M solution and its resistivity is 50 9 em, 1000 2, 1000 4 ot Solution. Aye RGROO 8 2x 10% x Tg = 250 -*cm? mol , _xx000 Ld 21000 ot crema? nn aa Ag = SO gy 7200 2 cm? mot So, the molar conductivity of 0.08 M solution wil be greater than 0.1 M solution Mlustration 3. The conductance of a salt solution (AB) measured by two parallel electrodes of area 100 cm? separated by 10.cm was found to be 0.0001 £27. volume enclosed between two electrodes contain 0.5 mole of salt, what is the molar conductivity (Sem® mor} of salt at same cone. ajooL (B)0.02 {C)2x105 {Dj none of these {20 1; G= 0.0001 S, V = 100 x10 = 1000 cm = 1 litre 000m? “oem i a ® =GGt=0.1 x0.0001 = 10% _ &x1000 _ (0.1 «0,0001) x 1000 Ae 05 = 0,02 S em?mot! 15Pre-Medical 43 116 FACTORS AFFECTING ELECTROLYTIC CONDUCTANCE (@) Inter ionic attraction :-If inter ionic attraction between ions of solute is more, then the conductance will be less. (6) Polarity of solvent :- If solvent has high dielectric constant then the ionization and conductance will be higher. (€) Viscosity of medium :- On increasing the viscosity of medium, the conductance decreases. (d) Temperature = Asthe temperature of electrolytic solution is increased, the conductance mcreases because K.E. of the ions increases and al ypes of attraction forces decrease and the viscosity of medium decreases, (@) Dilution =~ (0 On increasing the dilution conductance (G) increases. For strong electrolyte with dilution interionic force of attraction decreases therefore conductance increases. For weak electrolyte with dilution degree of dissociation (a) increases therefore conductance increases, (i) With dilution specific conductance decreases because with dilution number of ions in 1 ml solution decreases (ii) With dilution equivalent and molar conductance increases because with dilution normality or molarity creases Determination of molar conductance of electrolytes at infinite dilution Debye Huckel Onsager equation — . A, =As.—bVE only for strong electroltel where A,, = molar conductance at concentration C, molar conductance at dition, b = constant and its value is same for a particular type of electrelyte. C (mol /L)* + Ifagraph is plotted between A, us VC a straight ine is obtained for strong electrolyte. On extrapolation this line touches A, axis, Therefore A‘ for strong electrolyte can be found out from intercept. For weak electrolyte the slope of curve is not constant so it can not be extrapelated to obtain A | |Chemisiry 4.4 KOHLRAUSCH'S LAW OF INDEPENDENT MIGRATION OF IONS. At infinite diution when dissociation of electrolyte is complete; each ion makes a definite contribution towards equivalent conductivity of any electrolyte irrespective of the nature of other ion associated with it This law states that the equivalent conductivity of any electrolyte at infinite dilution (A, ) isthe sum of equivalent ionic conductivities of the cation and anion given by the electrolyies at infinite dilution. [Az = Aer as] Where 22 = equivalent conductance of cation at infinite dilution, 2ef = equivalent conductance of anion at infinite dilution. For AB, -xA" + vB In terms of moler conductances of cation and anion T ne) + gine th Where 2% = Limiting molar conductance of cation dey y= Limiting molar conductance of anion y= charge on cation X= charge on anion Ho nc AS =: Where x = Stoichiometric coefficient of cation y= Sloichiometric coefficient of anion illustrations Mustration 4, Calculate A‘ of oxalic acid, given that +h: Az, Na,C,0, = 4002+ em? eq? AS H,SO, = 700227 em? molt Ag Na,SO, = 450Q-tem? eq! Solution A H,C,0, = 700 + 800 - 900 = 6009"! cm? molt 4.5 APPLICATIONS OF KOHLRAUSCH'S LAW : (a) To calculate conductance of weak electrolyte. (b) To calculate degree of dissociation : A lent conductance at ncentrati Degree of dissociation a=2-= Stent Conan a Az, equivalent conductance at infinite dition A, a-4e An (©) Tocalculate dissociation constant of weak electrolytePre-Medical mas (@)_ Solubility (5) and K,, of any sparingly soluble salt. Sparingly soluble sait means salt with very less solubility Saturated solution of sparingly soluble salt can be considered as infinitely ditute solution. «1000 Ina saturated solution of sparingly soluble salt. M = Solubility (S}. A, (saturated) = A= © Tonic conductance (4) and mobility of ions (u) In electrolyte solution the ionic conductance of any ion isdlirectly proportional to their mobility or speed of ion. how foracation 2, & u, orfic=Fu,] where F = 96500 C forananion 4, &u, or =F uy @ Transport number/Hittorf's number(t) ‘The current flowing through an electrolytic solution is carried by ions (cation and anion). ‘The fraction of total current carried by an ion is called its transport number, transport number of cation (t.) = oS me a transport numberof anton ) = 52 =A fue Illustrations Hlustration §. Equel volumes of 0.015 M CH,COOH & 0.015 M NaOH are mixed together. What would be molar conductivity of mixture if conductivity of CH,COONa is 6.3 x10 S em? (1) 8.4 cm? mol? (2) 84 S cm? mo (8) 4.2 S cm? mol (4) 42S cm? moh Sol 0015 6.3x10* x1000 84 § can’ mot® lution [Sal] = <5" Mt a= Fo jg79 ~~ 84S em! mol 2 Mlustration 6. The dissociation constant of n-butyric acid is 1.6 «10° and the molar conductivity at infinite dilution is 380 x10 $ mmol", The specific conductance of the 0.01 M acid solution is (1) 1.52 «10° S mt (2) 1.52 x10? S mt Q)1.52 x10? S mrt (4) None co? 0.01xa" Solution = og PEM = Toy 1.6x10* An = ¥iL6x107 = 0.04; TRE Bey = 0.04 380 x10 _ x10? “Mt jew 00498010 0.01 695.195 gy! 10 118Chemistry Illustration 7. The conductivity of a saturated solution of Ag,PO, is 9 x10" Sm” and its equivalent conductivity is 1.50 x 10+ S m? equivalent’. The K,, of Ag,PO, is (1)4.32 x10 (2) 18x10" — (3) 8.64. x10" (4) None of these 1000 4000 No 1.50 x 104 x 10*=9x10%x10? x Qy; N=6x10% Kx Solution N_ 6x10" a = 2x10 mol /L S=M ny 3 AgPO,, <> 3 Ag’ + PO,” K, 38S K, = GS". S = 278! = 27 (2x105% = 4.32 x10 BEGINNER'S BOX- 1. The resistance of LN solution of CH,COOH is 250 ©, when measured in a cell of cell constant 1.15 eny?. The ‘equivalent conductance will be (1) 4.6 27 cm? eq? (2) 9.2 OF cm? eq* (3) 18.4.07.cméeq? (4) 0.023 Qrem’eq* 2. The specific conductivity of N/10 KCI solution at 20°C is 0.012 2" cm! and the resistance of the cell containing this solution at 20°C is 56 ©. The cell constant is (1) 4.616 cm (2) 0.672 em (8) 2.173 cm (4) 3.324 om? 3. Molar conductances of BaCl,, H,SO, and HC! at infinite dilutions are x,, x, and x, respectively. Equivalent ‘conductance of BaSO, at infinite dfution willbe w eos) @ fx, =yotl 26, +¥-2e) w fits el 4. — Theionization constant of a weak electrolyte is 25 x 10°¢ while the equivalent conductance of its 0.01 M solution is 19.6 Som? eqy*, The equivalent conductance of the electrolyte at infinite dilution (in $ cm® eq” ) willbe (39.2 (2)78.4 (3) 392 (4) 196 5. Which has maxmium conductivity (1) (CANHY, Cl] (2 ICHNH), CLIC GV ICHINH),CHCL, (4) [CHNH.ICt, 19Pre-Medical 4.6 120 GALVANIC CELL : Working princi Whenever a metal strip is putin its electrolytic salt solution then a potential between the metal and the liquid phase (Electrolytic salt) ANODE : Some metals (which are reactive} ate found to have tendency to go into the solution phase when these are placed in contact with their ions or their salt solutions. For example : Zn rod is placed in ZnSO, solution face oF Cet Zing electrode A, © fees ‘yfindericalcepactor How Zinc afome became zine Tone al the electrode surtace ‘The Zn atom or metal atoms will move in the solution to form Zn’?. After some time following equilibrium will be established Znls) > Zn® 420° There will be accumulation of sufficient negative charge on the rod which will nt allow extra zinc ions to move in the solution. i.e. solution will be saturated with Zn’* ions, The extra positive charge of the solution will be more concentrated around the negatively charged rod. An electrical double layer is developed in the system and hence a potential is created between the rod and the solution which is known as electrode potential © On anode oxidation will take place. (release of electron), © The electrode potential is represented by Eng, CATHODE = Cu rod, ! ‘Very soon 2 dynamic 80, ‘equilibrium is created and become a cu" coylinderical capacitor How copper ton is sohting states ‘accapls tno electron ant became 3 ‘aturl czpper of the deste| | Chemistry eee or ‘Some metals (Cu, Ag, Au etc.,) are found to have the opposite tendency Le. when placed In contact with their aqueous ions, the ions from the solution will get deposited on the metal rod. The following equilibrium will be established CuP(aq) +2e° > Culs). So rod will have deficiency of electron (become positive charge], Extra negative charge will surround this positively charged rod and form double laver. An electrical double layer is developed in the systems and hence a potential is created between the rod and the solution which is known as electrode potential eathode reduction will take place.igain of ¢ } © Electrode potential can be represented by = Fe .ycuss Construction of cell : @ Ithas two half-cells.each having a beoker containing a metal strip that dips in its aqueous salt solution. The metal strips are called electrodes and are connected by a conducting wire, # Two solutions are connected by a salt bridge. ‘® The oxidation and reduction half reactions occur at separate electrodes and electric current flows through the wire. Zinc {anode}, Copper (cathodo} nls)—-Zn""aq)22—Cu4agh 26 = us) Salt Bridge and its functions : Salt bridge is inverted U-tube containing solution of inert electrolyte with ager-agar or gelatin to convert into semi solid form. Tons of inert electrolyte do not involve in any chemical change. ‘The electrolyte in salt bridge should be such that spead of it's cation is nearly equal to speed of it's anion Ex. KCI, KNO,, NH,NO, IfAg™ , Ha,"*, Pb, TH ions are present in a cell then KCI is not used because there can be formation of precipitate of AgCl, Hg,Cl., PCI, or TIC| Functions © It connects the solution of two hall cell to complete the circuit, © _Itmaintains the electrical neutrality of the solution in order to give continuous flow or generation of current. © If the salt bridge is removed then voltage drops to zero. © Ie prevents the liquid -liquid junction potential. The potential difference which atises between two solutions when they brought in contact with each other. Cell Representation : We require two half cells to produce an electrochemical cell, which can be represented by following few rules; © The anode half-cel! is akways written on the left followed on the right by cathode half cell The separation of two phases (slate of matter) is shown by a vertical line ‘The various materials present in the same phase are shown together using commes. The salt bridge is represented by a double slash (Il) ‘The significant features of the substance like pressure of a gas, concentration of ions ete. are indicated in brackets immediately after writing the substance. 2n(s) | ZnSO, aq) I CuSO faq) | Culs) —_]a tttPre-Medical 4.7 ELECTRODE POTENTIAL: © The potential developed between metal electrode and ils ions in solution is known as electrode potentiat © The potential developed between metal electrodes and the solution of fs ions al 1 M concentration at 1 bar pressure and 298 K is known as standard electrode potential. e ‘There are two types of electrode potential :~ (a) Oxidation Potential (O.P.) © The electrode potential for oxidation half reaction Mis) + Moaq) + ne- © Tendency to get oxidised. © Greater the 0.P. greater will be the tendency to get ox (b) Reduction Potential (R.P.) © The electrode potential for reduction half reaction Mfaq) + ne- -» Mis) © Tendency to get reduced. © Greater the R.P. greater will be the tendency to get reduced. ° Electrode potential depends upon : © Concentration of the solution. © Nature of the metal. © Pressure temperature conditions. ! 4.8 REFERENCE ELECTRODE : © The potential of a single electode cannot be determined but the potential difference between two electrodes can be accurately measured using 2 reference electrode. . © An electrode is chosen asa reference with respect to which all other electrodes are valued, | © There are two types of reference electrodes, ! (a) Primary reference electrode : Standard hydrogen electrode (SHE) Representation : Pt, H,(a) | H* (1M) When aets as anode HA{g) = Hyg) === 2H" + 2e" (at 1 atm) Eitaue'(eq) = SOP Pi black When acts as cathode ‘electrode © Tocalculate standard potential of any other electrode a cellis coupled with standard hydrogen lectrode (SHE} and it's potential is measured that gives the value of electrode potential of that electrode. (b) Secondary reference electrode : @) Calomel electrode (Hg,Cl,) - Representation: PI Hg-Hg,Cl,,, | KCI, When acts as cathode SHE: +e + Hg+ Chis ae! - When acts as anode Hg + Ces > 5 HazClyy +€ 92Chemistry Silver-silver chloride electrode - Representation : PtlAg-AgCl,, | KCl. When acts ascathode AgCly +e” > Agy + Clin) When acts asanode Agus + CT asi > AgCly +e" 4.9 CELL POTENTIAL (E°,,) : E*,, = SRP of cathode ~ SRP of anode = SRP of cathode + SOP of anode = SOP of anode ~ SOP of cathode 4.10 ELECTROCHEMICAL SERIES Arrangement of different elements in increasing order of SRP is known as electrachernical series or activity series. Electrode Reaction SRP (at 298 K) i, Tere > Li) =305V K Ki +e 9 KG) = 2.93 Ba Ba? + 20 > Ba -291V Ca Cart + 2e > Cals) -287V e Na Nat +e > Na(s) -2n1V 3] Mg Mg"? + 2er > Ma(s) =237V a Al AB + 3e- > Al -1.66V = Mn Mr? + 2e- > Ma -118V oy HOM +e > $H,+OH | -0.828V pa 3 Zn Zn"? + Be > Znls) -0.76V Fy fad cr Crt + Be > Crs) -O.74V $ ° Fe Fe® + 2e° + Fe -044V rs 3 cd Cd 420° > Cals) -0.40V FS) 5 Co Co® + 2e + Co ~0.28V g S Ni Nit? + Ze > Nils) ~0.24V o ca Sn Sn*? + 2e" + Sn(s) -014V 2 £ Pb Por? + 2e" > Pols) -0.13V Fa H, 2H" + 2e- > Ha) 0.00V iH Cu Cut + 2e + Cuts) 034V z L I+ 2e + 2b O54 Fe Fet +e + Fe 077 Hg Hg, + 2e" > Hat) 079V Ag Ag: +e > Ag 0.80V Hg Ha + Hat) 0.85 Br, Br, + 2e-— 2Br 1.06 V Pr? + 2er > Pr 120V oO, 40, + 2H) + 2e + HO | 1.23V a, Cl, +e > 2Cr 136V Au Aur? +3e" > Auls) 140V F, E+ 2e » 2F 287VPre-Medical 4.11 APPLICATIONS OF ELECTROCHEMICAL SERIES () Oxidising and reducing power - f 1 Oxidising power a SRP 4 GO Red sop a he feducing power «. SRP (ii) Reactivity of metals ~ 1 Reactivity of metal a SOP 4 ae * In ECS reactivity of metal decreases from top to bottom. * Liis most reactive metal. . (iii) Reactivity of non-metal - ! 1 Reactiityof nonmetal @ SRP & Sop + INECS reactivity of non-metal increases from top to bottom, © F, is most reactive non-metal. {iv) Displacement reactions in solution - More reactive metal / non-metal displaces less reactive metal / non-metal in their solution. + Cu +2 AgNO, + CulNO), + 2Ag Ag + CulNO)), ~+ No reaction © 2KI+ Cl, +2KCl +1, 1, + 2KC1-> No reaction (¥) Metal above hydrogen displaces H, from dilute acid solution, + 2n+HSO aq) > 2nS0,+ H@) : Cut H,SO, (dilute) + No reaction 1 4.12 NERNST EQUATION + I gives relation between electrode potential/ EMF of cell and concentration of electrolytic solution. Walther Nernst derived a relation between free energy change (4G) and Reaction quotient (Qh i AG=AG'+RTInQ a) ‘where AG and AG*are free energy change and standard free energy change; 'Q is reaction quotient. “AG = nFE and -4G*= nFE? Thus from Eq. (1), —nFE = -nFE?+ RT InQ Where - R= gas constant, T = temperature (in K) F = Faraday (96500 coulomb mot), n= number of e- gained or lost in balanced equation. oyChemistry AL25°C, above equation may be unten ag E=E°- 2°27 N gal Eg 0.0591, PI a Rl In general, for a redox cell reaction involving the transference of n electrons ah +B cC + dD | 0.0591, ICh(D} 0 : = Dig og Ea Ebi | Bea Bow Sapp oe 4.13 APPLICATIONS OF NERNST EQUATION () Calculation of electrode potential (Egy or Eo.) ~ M'" +ne° Resto" 5 M(s) 0591, [MI iM 1 IM") IM" increases, then Ey, increases (i) Calculation of electrode potential and pH of hydrogen electrode - I 2H + 26> Hg) Egy a2, 2.082 jg Pie eee Te 0.0591, 1 Ey Ew = Ete 5 oF { Py, is taken f atin] Ep = 0.0591 log [H*} Ex = -0.0591 pH), Ege = +0.0591 pH] ) Calculation of EMF of cell (E,.) ~ eg. Zn(s) + Cu’(aq) 2 Zn (aq) + Cus) 0.0591, [Zn Ea Ean aig If [Cur] increases, then E, increases I 20" increases, then E, ,decreases 125Pre-Medical (iv) Prediction and feasibility of a cell reaction - For a feasible cell reaction AG=-ve (AG =—nFE, Ey= te (¥) Calculation of equilibrium constant (K,) and AG’ - From Nest equation — 0.0591, 0591, og PI “Sir] P! At equilibrium, E.,=0 and fl =K, Egg = EOy — E°, = 0. 0591 logK, ei » _2.303RT Eiy= 5 boak., APE, = 2,303 RT log K,, AG =-2.303RT oak, Illustrations Ilustration 8. Write cell representation for the following redox reaction, Sn** (aq) + 2Ag* (aq) > Sn** (aq) + 2Agis}. Solution The cell consists of a platinum wire anode dipped in Sn*? solution and a silver cathode dipped in Ag” solution therefore Pt(s) ‘Sn*{aq), Sn* (aq) || Ag’ (aq) | Agts). Illustration 9. Calculate the EMF of a Daniel cell when the concentration of 2nSO, and CuSO, are 0.001 M and 0.1M respectively, The standard EMF of the cell is 1.1 V. Solution Zn{S) + CuSO, ~» ZnSO, + Cu Zn © _ 0.0591 ] 0.0591 E> Bout 3 9 foe 211 og OS IMlustration 10. Calculate E° and E for the cell Sn! Sn® (1M) | Pb'*(10-"M} | Pb, ES (Sn?'I Sn) = -0.14V, E?(Pb*| Pb) = -0.13V. Is cell representation correct? 1,159 Solution =Ei, rw Ese 0.13 -[-0.14) = + 0.01V o, 0.0591, [Sn 00 =e a 001 Pel ps 08 V cell with not work Mustration 11, Calculate the equilibrium constant for the reaction Fe’ +Ce” = Fe + Ce, IGiven: E%,..,.. = 1.44 V:E°, 0.68 V] 2.303 RT robert Take = 0.06 at 25°C, log 4.68 = 0.67 Solution Fe + Cott st Fe + Co = 144-068 = 0.76 = tog k,; K~ 4.64 x<10® aemass fllustration 12. Solution. Mlustration 23. ‘Solution. Mlustration 14, Mlustration 15. Solution Chemistry The 0.1M copper sulphate solution in which copper electrode is dipped at 25°C, Calculate the electrode potential of copper electrode {Given E%,.» /c, = 0.34V] Cu? + 2e° Cu Eg Ely 0.059 jog [Product en Reactant) Heen=2 so E= 0.3429 lego E = 0.34 ~ 0.03 = 0.31 Volts ‘The EMF of the cell Cr 1Ce* (0.1M) || Fe“ (0.01M) | Fe (Given Egss¢, =— 0.75, Efe, g,=- 0.45 V) Half cell reactions are At Anode [Cr+ Cr? + Se] x2 At Cathode [Fe*? + 2e-+Fe] x3 Over all reaction 2Cr + Fe?» 2Cr* + 3Fe E®,, = Oxidation potential + Reduction potential = 0.75 + (-0.45) = 0.30 = 0 2:089 [Product] Fa 8 Reactant) ~ =0.20-24 = 0,26 Volt. For the cell Pt ! H(0.4 atm) | H'(pH=1) | H*tpH = 2) | H, (0.1 atm) | Pt ‘The measured potential at 25°C is @-o1Vv 2)-0.5V (3)-0.041 V Anode reaction: H,{0.4 atm) -» 2H* (107 M) + 2e~ Cathode reaction; 2H* {10 M) + 2e-—> H, (0.1 atm) (4}-0.030V H{0.4 aim) + 2H* (10 M) + 2H" (10 M) +H, (0.1 atm) cell reaction 9.059 5, (1040.1) Ea Peg ayo) TB egy BL6OVE Eo ray 8 140V, then Es... willbe Mois (2) 2.945 V (3) 1.255V (4) none Aut +e —> Auls) FP= 169V Al); AG? ‘Aue + 3e-—> Auls) F=140V (2); AG} From (2}— (1) Aus + Zen —> Aur £3); AGS AG; =AG)-AG> = 2xF XE? =-3 xP x1.40 + 1 x1,69 xF F=1255V 127Pade Eins The value of electrode potential does not depend on stoichiometry of half reactions as itis an intensive prop. erty. © Gibb’ free energy is extensive property. © Inelectrolytic call, cathode is negative terminal whereas in Galvanic cell cathode is positive terminal © Cellreaction is spontaneous, if AG =-ve or Es 4ve © Cell reaction wil be in equilibrium, if eg. AG=0 or © Work done by a cell : @ Let’ faraday charge be taken out of a cell of EMF" E' then work done by the cell willbe calculated as Work = Charge xPotential = nF XE. fi) Work done by cell = Decrease in free energy so-AG = nFE or W_,, = + nFE*, where E°is standard EMF of the cell. 1. Calculate E°,,, for following cell ZnlsM2nZ, HAs !Ag(s) Ey. ., =-0.76V: By, ,,=0.90V (1) 0.04V (2)-1.56V @Q156V (4) 0.84 2. Standard EMF of a galvanic cell involving 2¢ transfer is found to be 0.591 V at 25°C. Cakualte equilibrium > constant for cell reaction (1) 20° 2) 10" ) 10% (a) 200 3. Calculate cell potential at 298 K for following galvanic cell Cds}! Ca"*(aq,){0.1M) || H ‘x (0.1M)1H,(9,0.5 atm}! Pt Ey yasey = 0.400 (10.38 (2)~ 0.38 (3) 0.36 (4)-0.36 4. Calculate E°,,of following galvanic cell at 298 K ; Cals)| Cacas if Fe““aq | Feds) Ej =-287V : Ex yee = OAV ()2.46V 2)-2.46V (3.28V 4)~3.28V 5. Given Eayigg = O.B0V. Byghigg 237 V, Bayicy 20.84 V, Bygiigg = 0.79 V. Which of the following statement is correct (1) AgNO, can be stored in copper vessel {2} Mg(NO,), can not be stored in copper vessel (8) CuCl, can be stored in silver vessel (4) HgCi, can be stored in copper vessel 6.1/2 H,g) + AgCls} 1H (aq) + Cr fag) + Ag is) occurs in the galvanic cell (1) Ag/AgCis| | KCI Gol | AgNO, fa) Ag 2) PV/H,Q) | HCl so} || AgNO, (sol) | Ag (3) PVH,Q) | HCI so) | CF 1 AgCl (so) 1 Ag (4) PL/HL{g) KC! 0) || AgCl ol) | Ag 128Chemistry | 4.14 SOME SPECIAL CELLS (A) t t | @) CONCENTRATION CELLS A concentration cell is a form of galvanic cell that has two equivalent half cells of the same material having difference only in concentrations. For such cells anode and cathode are same so E’, = 0. eg. Pt, Hyg} (P, atm) 1H’ (C,) || HC.) 1H.) (P, atm), Pt Anode Reaction: —_Hi{P,) —> 2H*(C,) + 2e Cathode Reaction: 2H(C,) + 2e° > HP.) Cell Reaction: H{?,) + 2H"(C,) —> 2H"(C,) + HP) 0.0591, (PL Ea Ean a SiR) ¢ = 9020591. [ExT Pe So, Eas, z 1S] , 0.059, fc, Case 1: IfP,=P, = LatmEy= 2] c - tog IE = -0.059 val ¥.C, > C, then E,,, > 0 and call will be spontaneous. 0.059, IP, Case2: ifC,=C, at = 2g 2] Pi =P, IP, >P, then E,, > 0 and cell will be spontaneous. REVERSIBLE CELLS : ‘Those cell's in which chemical reactions are reversed by applying external emf in opposite directions known as reversible cells. A daniel cells said to be reversible if it follows two conditions () When E,, > 1.1 V (emf of danie! cal); coll reactions reversed (i) When E,, = 1.1. V (emf of daniel cel; equilibrium wilt be established. + Ingeneral secondary cells ae reversible in nature. When E,.> 1.2 {i No flow of electron or current (i) Electron flow from Cu to Zn and current {i No chemical reaction flow from Zn to Cu. (i Zinc is deposited at the zine electrode and 129Pre-Medical Bao ALteN, 4.15 ELECTROLYSIS The process of chemical decomposition of an electrolyte by the passage of electricity is called electrolysis or electrolytic dissociation. It is carried out in electrolytic cell where electrical eneray is converted into chernical energy. For electrolysis two suitable electrodes are immersed in the solution of an electrolyte. When an electric potential is applied between the electrodes, the positive ions move towards the cathode and negative ions move towards the anode. The gain of electrons (decrease i oxidation number) means reduction takes place at the cathode and loss of electrons {increase in oxidation number) means oxidation takes place at anode, Electrolytic cell ‘There are two aspects of electrolysis (A) Qualitative aspects of electrolysis :- In qualitative aspect products formed at electrode are identified. At electode product formation depends on Following (Nature of electrolyte (2) Nature of electrodes : The metal strip at which current enters is called anode; anode is positively charged in electrolytic cell. On the other hand, the electrode at which current leaves is called cathode, Cathodes are negatively charged, There are two types of electrodes (2) Attackable : The attackable electrodes participitate in the electrode reaction. They are made up of reactive metals like Zn, Cu, Ag etc in their respective solutions. In such electrodes, atom of the metal gets oxidised into the corresponding cation, which is passed into the solution, Thus, such anodes get dissolved and their mass decreases. © Helectrodeis active, at cathode, metal goes on depositing and at anode metal is dissolved. ‘The process is called electroplating, 6) Non-attackable : Nomattackable electrodes do not participate in the electrode reaction as they made up of unreactive elements lixe Pt, graphite etc. Such electrodes do not dissolve and their mass remain same. © Among the two cations, that cation is discharged at the cathode which has higher reduction potential. Among the two anions, that anion will be discharged at the anode ‘which has lower reduction potential or higher oxidation potential @ The discharge of NO;, POY and SO; ions at anode does not commonly take place from aqueous solution. (ii) Concentration of electroistic solution, Examples of electrolysis : (a) Electrolysis of Molten Sodium Chloride NaCl gg —? Na + Cr Reaction at anode (oxidation): 2C —> Cl,(g) + 2e~ Reaction at cathode (reduction) : 2Na* + 2° —+ 2Nal) 180 qGrin {b) Electrolysis of Sodium Chloride Solution ‘On electrolysis of aqueous solution of NaCl, the possible species involved in half-reactions are Na‘, Cl and H,0. i ‘The possible cathode hall-reactions are t Nat, + & —» Na, Et = -2.71V 2H,0, + 2e —+ H,, + 20H, B= - 0.83V i Under the standard conditions, H,O is to be reduced in preference to Na‘, Hydrogen is evolved at the cathode. ! The possible anode half-reactions are ! 2Chigg —> Clyy + 207 Be = - 136V | THO, —> On, + 4H, + 4° Ee = - 1.23V | Under the standard-state conditions, H,O is to be oxidized in preference to Cl. But since i electrode potentials, depend on concentrations it tums out that when the solution is concentrated enough in Cl, Cl, is the product; but in dilute solution, O, is the product. : Starting with very dilute NaCI solutions, the oxidation potential of Cl is very : negative, so H,O is reduced in preference to Cl. But as the NaCl ' concentration increase, the oxidation potential of Cl increases until eventually i CI is oxidized in preference to H,0. The product changes from 0, to Cl,. The half-reactions and cell reaction for the electrolysis of aqueous sodium chloride to Chlorine and hydroxide ion are as follows: 2HO, + 2e —> Hy + 20H%,, (cathode) . 2Ch,y—> Clay + 2e (anode) 2H,0, + 2Ch,, —> Hay + Chy + 20H, Because the electrolysis started with sodium chloride, the cation in the electrolyte solution is Nat. On evaporation of the electrolyte solution, sodium hydroxide NaOH is obtained. (c)_ Electrolysis of Molten lead bromide using inert (pt/graphite) electrodes. Cathode (reduction) : Pb + 2c" > Phi} E*= 0.126 VV } Anode (oxidation): 2Br + Brja)+2e FE =-1.08V Overall reaction Poe? + 2Br- ~» Pbis) + Brg) Ey = 0.126 ~ 1.08 =~ 1.206 V E,,> 1.206 V (a) Electrolysis of aq CuSO, using inert (pt/graphite) electrode Cathode (reduction) : Cu + 26° + Cu(s) B= 0.34V 2H,O() + 2e- > H,\g) + 20H'taq) EP = -0.83V ‘At cathode reduction of Cut* (aq) will be prefered over reduction of water as its standard reduction potential is more, than that of water. ‘Thus reaction at cathode : Cu + 2e" ~» Culs) Anode (oxidation): 2S0} + S,0} + 2e EB =-1.96V 2H,O() > Og) + 4H +4e EY =-1.23V At anode oxidation of water is preferred over oxidation of sulphate ion as its standard oxidation potential is more, than that of sulphate ion. ‘Thus reaction at anode : 2H,O(é) + O,(g) + 4H* + 4e~ After electrolysis solution will become acidic (pH < 7) ; E181Pevodei CO) 132 ) (a) 8) Electrolysis of aq. CuSO, using Cu electrode. Cathode (reduction): Cu + 2e" + Cu FP=+0.34V 2H,O(4) + 2e° + Hig) + 20H = -0.83V At cathode reduction of Cu (aq) will be preferred over reduction of water as its standard reduction, potential is more, than that of water. ‘Thus reaction at cathode Cut + 20° > Cufs) Anode (oxidation): S03 -» S,03 + 2e" Fe, = 1.96 2H,O(6) > O,lg) + 2H +4e° EP 1.23 Culs) + Cut + 2e~- £2 =-0.34V At anode oxidation of copper solid is prefered over oxidation of water and sulphate ion as its standard oxidation potential is more than that of water and sulphate ion, ‘Thus reaction at anode ; Culs) + Cu + 2e~ Itis example of electrolytic refining and there will be no change in the pH and concentration of electrolyte Electrolysis of dilute H,SO, : Cathode (reduction) 2H? + 2e" + Hyg) E=0 2H,0) + 2¢ > HJg)+ 20H E* -0.83 due to less avaitabiity of H’ ions, it will not participate in formation of H, gas therefore reduction of water will take place. Anode (oxidation) S0j? > $,0,° + 2e" E'=-1.96V 2H,0() > 0,,g) + 2H + de E°=-123V oxidation of water is preferred over oxidation of sulphate ion as its standard oxidation potential is more, than that of sulphate ion. Electrolysis of concentrated H,SO, Cathode (reduction) 2H 4 2e" > Ha) B=0 2H,O(} + 2e > Hig) + 20H E*=-0.83V due to reduction of H* ions, formation of H, gas takes place. Anode (oxidation) S07? > $,0,% + 2e- E'=-1.96V 2H,O() + O,(0) + 2H' + 4e- P= -123V due to oxidation of SO} ions, formation of persulphate ion (8,0, takes place. QUANTITATIVE ASPECTS OF ELECTROLYSIS 1 mole electron = N, electron = 96500 coulomb = 1 Faraday Mite o Me Gul ag > oe Traiow, Ung + nF charge discharges. = 1 mol of Mion 1 21 F charge discharges = = molof Mion 1 = 2M = 1g equivalent of Mion Hence |t mole e = 1 F = 1 g equivalent] i.Chemistry FARADAY’S LAWS OF ELECTROLYSIS (a) First law of electrolysis = ‘Amount of substance deposited or liberated af an electrode is directly proportional to amount of change possed through the solution WaQ W = amount of substance deposited, Q = charge in coulomb w=zQ Z = electrochemical equivalent when Q-= 1 coulomb, then W=Z Thus, amount of substance depasited by 1 coulomb charge is called electrochemical equivalent. Let Lampere current is passed till 't’ seconds. Then,Q= it», W=Zit 1 Faraday = 96500 coulomb = Charge of one mole electrons One faraday is the charge required to liberate or deposit one gram equivalent of a substance at corresponding electrode. Let Eis equivalent weight then ‘E” gram will be liberated by 96500 couloms. 1 Coulomb will berate a gram E Elt 2B. wel By detinition, 500 56500 Wt umber of g eq = number of faraday) E ~ 96500 (b) Second law of electrolysis : When same amount of charge is passed through different electrolyte solutions connected in series then weight of substances deposited at electrodes are in ratio of their equivalent weights. L<. WEL PRODUCTS OF ELECTROLYSIS OF SOME ELECTROLYTES ‘¢In electrolytic celi D.C. current is used. eo 133 Electrolyte Electrode Product obtained {Product obtained at at anode cathode ‘Aqueons NaCl Pt or Graphite a, H, w Fused NaCl Ptor Graphite a, Na (a) | AqueousNeOH | Ptor Graphite °O, H, z (iv) Fused NaOH Ptor Graphite 0, Na i (| AqueousCuso, | Ptor Graphite °, cu j (ui | Aqueous Cu, Copper Cu oxidises to Cu? fons ca i (ai) | Aqueous CuCl, Copper Cu oxidises to Cur? ions ou 3 (si) Ditte HCL Por Graphite a, H, fx) | Dilite H,S0, Pror Graphite °, H, t) | Cone. H,S0, Pt or Graphite 5,0; H, i (x) | Aqueous AgNO, | Prof Graphite o, Ag i si Dilute NaCh Pror Graphite ©. H, + For electrolysis AG = +ve, So itis non-spontaneous processPre Medical Rasy Tilustrations Mlustration 16 How much electric charge is required to oxidise : {a} 1 mole of H,0 t0 0, (0) 1 mole of FeO to Fe, Solution (2) The oxidation reaction is H,O—> 40, + 2H! + 2e° 1 mole 2 mole Q = 2F = 2 x96500 = 1.93 «10°C (0) The oxidation reaction is FeO + THO 4Fe,0, +H +e Q= F = 96500 coulomb Mlustration 17 One mole of electron passes through each of the solution of AgNO,, CuSO, and AICI, when ‘Ag, Cuand Al are deposited at cathode. The molar ratio of Ag, Cu and Aldeposited are (Qaeded (2)6:3:2 (96:3:1 ()1:3:6 Solution Deposited equivalent willbe same eq, Ag= 1 mole Ag Leg. Cu = 1/2 mole Cu eq. Al= 1/3 mole Al = ratio vd doeae i Mlustration 18 Exactly 0.4 faraday electric charge is passed through three electrolytic cells in a series, frst containing AgNO, second CuSO, and third FeCl, solution, How many grams of each metal will be deposited assuming only cathodic reaction in each cell Solution ‘The cathodic reaction in the cell are respectively, ' Ag + © —> Ag Tmole 1 mole 108g 1 Cu + Be —> Ge mole 1 mole 635g 2F and Fe 4 3e —+ Fe mole 1 mole 56g 3F Hence, ‘Ag deposited = 108 x0.4 = 43,2 g 63.5 Gu deposited = —>~ x0.4= 12.79 56 and Fe deposited = x04 = 7.479 Mlustration 19 An electric current of 100 ampere is passed through a molten liquid of sodium chloride for 5 hours. Calculate the volume of chlorine gas liberated at the electrode at NTP. Solution ‘The reaction taking place at anode is 2Cr Cl, + 2e 710g 71.0g 2x 96500 coulomb I mole Qe ixt = 100 x5 x 60 x 60 coulomb ‘The amount of chlorine lberted by passing 100 x 5 x 60 x 60 coulomb of electric charge. 1 = 3796500 * 100 x5 x60 x60 = 9.3264 mole Volume of Cl, liberated at NTP = 9.3264 x22.4 = 208.91 L neARLEN Chemisty Ilustration 20 How long a current of 2 A has to be passed through a solution of AgNO, to coat a metal surface ‘of 80 cm? with 5 um thick layer? Density of silver = 10.8 g/cm’. =M M__ 4 Solution a-¥5108- FocEalot > M= 10.8 x400 x10 Exlxt 4 108 x2 xt SG5H0 10.8% 400x104 =F = t= 193 see BEGINNER'S BOX-3 1. Lhe of 1 M CuSO, solution is electrofysed. After passing 2 F charge, the molarity of CuSO, willbe (y/2 eM @M @)zew 2, Same quantity of current is passed through molten NaCland molten Al,O,,. 4.6 g of Na was deposited in one cell, the mass of Al deposited in other call is (0.99 (189 27g (43.69 3. A certain current liberates 0.5 g of hydrogen in 2 hr. How many grams of copper cen be deposited by the same current flowing for the same time in a copper sulphate sohution? (1279 (2)15.9¢ 3)31.89 (4) 63.59 4, A quantity of electric charge that brings about the deposition of 4.5 g Ai from Al‘ al the cathode will also produce the following volume (STP} of H.(a) from H* at the cathode 44.8 L (2224. G12 (@)5.6L 5. A current of 9.65 ampere is passed through the aqueous solution of NaCl using suitable electrodes for 1000 s. The arnount of NaOH formed during electrolysis is (2.09 (24.09 316.09 (4) 8.09 6, If 0.224 L of H, gas is formed at the cathode, the volume of O, gas formed at the anode under identical conditions, is (0.224 L. (2)0.448 L. (3) 0.112 L. daa 4,16 COMMERCIAL VOLTAIC CELLS. Batteries can be classified as primary and secondary. Primary batteries can not be returned to their original state by recharging, so when the reactants are consumed, the battery is “dead” and must be discarded. Secondary batteries are often called storage batteries or rechargeable batteries. The reactions in these batteries can be reversed; thus, the batteries can be recharged. (A) Primary cells : Dry cells and mercury cells The most familiar type of battery is the dry cell which is cn acompactof Leclanche cell knawn aftr its discoverer Leclanche (fig. In this ce, the anode consists of a zine container end the cathode isa graphite rod surrounded by powdered MnO, and carbon. The space between the electrodes is filed with a moi paste of NH,Cland ZnCl, The electrode reactions are complex, but they can be written approximately as follows Anode Znls)-—» Zn"? + 2e Cathode MnO, + NH,* + €&—> MnO(OH) + NH, In the cathode reaction, menganese is reduced from the Znce Ne, + 44+ oxidation stae to the 3+ slate. Ammonia isnot liberated as Carbon black ‘a gas but combines with Zn* to form Zn(NH,),2 ion. Dry cells + NH,CL do not have an indenfiite life as acidic NH,Cl corrodes the zine ‘Reomarial oy ea control container even when not in use. Dry cells have a potential (eee ee aie of approximately 1.25 to 1.5V. 135Pre-Medical Mereury cell, suitable for low current devices like hearing aids, watches, etc. consists of zinc ~ mercury ‘amalgam as anode and a paste of HgO and carbon as the cathode. The electrolyte is a paste of KOH and ZnO. The electrode reactions for the cell are given below Anode Znlt1g) + 20H" —> ZnOfs) + H,0 + 2e- Cathode HO + HO+ 2e-—» Hall) + 20H Anode _ Cathode ‘The overall reaction is represented by ZnlHig) + HgO{s) —s Zn0s) + Hal) ‘The cell potential is approximately 1.35 V and ‘remains constant during its life as the overall reaction does not involve any ion in solution whose concentration ccan change during its lifetime. (B) SECONDARY OR RECHARGEABLE BATTERIES ‘The most important secondary cell is the lead storage battery. It consists of a lead anode and a grid of lead packed with lead dioxide as cathode. A solution of sulphuric acid (38 percent by mass or having density 1.30.gm cm’ is used as an electrolyte. Cathode Negative plates: i lead grids filed with spongy lead Positive plates: i lead grids filed with PbO, 1 7g : The Lead storage battery i When the cell discharges, it operates as a voltaic cell. The lead is oxiised to Pb ion and lead plates acquire a negative charge. ‘At Anode: Pols) ——> Pb? + 2e- eon) Pb** ions combine with sulphate ions of solution to form insohible PbSO, Ph? + SO,* —-» PoSO, (Precipitation) if) Overall reaction Pb{s) + SO,* — PbSO,6) + 2e The electrons given by Ph are used at cathode (PbO, electrode) At Cathode : PoO,s} + 4H* + 26° —» Pb + 2H,O (i Pb? +SO,? —+ PbSO, (Precipitation) onl PDO,s} + 4H + SO,%+ 2e-—> PLSO,69) + 2.0Hoa “Therefore the overall cll reaction during discharging Pb{s) + SO, —> POSO,6) + 2e° PRO,s) + 4H + SO? + 2e—» PbSO,() + 2H,O Pb{s) + PbO, {6} + 2H,SO, —+ 2PbSO,(s) + 2H,0 ‘When a potential slightly greater than the potential of battery is applied, the battery can be reacharged. During recharging the cel is operated like an electrolytic cell ie. now electrical energy is supplied to it from an external source. The electrode reactions are reverse of those that occur during discharge ‘At Cathode: — PPSO,[s} +22" —> Pbis) + S07 At Anode: — PLSOJs) + 2H,O—> PbO) + 4H* + S0,7+ 20° 2PbSO,s) + 2H,O —> Pois) + POs) + 2H,S0, tis clear that H,SO, is used up during the discharge & produced during reacharging reaction of cel The discharging process of the storage cell is based on the principles of electrochemical cell, whereas the charging process is based upon the principles of electrolytic cells. n factor for H,SO, during charging and discharging is equal to one. manne ‘A. The battery consists of sin two-voll cells connected in series, 1B Esch component call is composed of severe! negative end positive ‘lectrades made of pure. ‘spongy lead and lead oxide, Poo, respectively; connected in'parailel, are ‘mmnersed ie a dilute solution of sulturie acid, lates in'8 solution srvga, eng Po (spongy) (€) Nickel - Cadmium {"Ni - Cd") batteries : ‘They are used in variety of cordless appliances such as telephones, video camcorders, and cordless power tools, are lightweight and rechargeable. The chemistry of the cell utilizes the oxidation of cadmium and the reduction of nickel (II) oxide under basic conditions. At cathode: INiQ(OH) (8) + H,O(} + e+» NOH),{s} + OH faq) x2 Atanode: Ca{s) + 2 OH" > Ca{OH),(3) + 2e~ Net cell reaction : 2NiO(OH4s) + Cais) + 2H, (J 2N(OH), fs) + Ca(OH), (5) As the active masses of all reaction components are independent of their amount. The cell delivers constant EMF throughout. 137Pre-Medical (D) Fuel Cells Its possible to make batteries in which the reactants are fed continuously to the electrodes. Electrical cells that are designated to convert the free energy from the combustion of fuels such as hydrogen, carbon monoxide or methane directly into electrical energy are celled fuel cells. (One of the most successful fuel cells uses the reaction of inydrogen with oxygen to form water (fg.). This cell has been used for electric power in the Appollo space programme, The water vapours produced were condensed and added to the drinking water supply for the astronauts. Water anode (4 Fig. : A simple fuel cell {+) cathode aqueous electrolyte =o, In the cell shown in figure hydrogen and oxygen are bubbled through a porous carbon electrode into concentrated aqueous sodium hydroxide. Catalysts are incomorated in the electrode. The electrode reactions are : Atanode : At cathode + Net cell reaction : 21H {Q) + 20H faq) —> 2H,0(6) + 2e°| Og) + 2H,0(8) + de —> 40H (aa) 2H{g) + fe) — 24,01 ‘This cells runs continuously as long as the reactants are supplied. Since fuel ces convert the eneray of a fuel directly to electricity, they are potentially more efficient than the conventional method of generating electricity on a large scale by burning hydrogen, carbon fuels or by using nuclear reactor. Although theoretically we expect 100 percent efficiency in fuel cells, so far an efficiency of only 60- 70 per cent has been attained. Since fuel cells are efficient and free from pollution, efforts are being made to produce better commercially practical fuel cells. Efficiency of a Fuel Cell: f= 2S..100 Main features of different cells. Name of the ‘Anode Cathode Electrolyte cell/Battery i) Dry cell Zine Graphite NH,CI + ZnCl, MnO, +C (touching anode} {touching cathode) 2 fa Mercury cell Zinc/Mercury Paste of Hg Paste of KOH and Zn0| Amalgum and carbon i Lead storage Lead Lead dioxide H,SO, (38%) battery z fo NECd cell Cadmium Nickel dioxide KOH sol w HO, fuel cell Porous carbon Porous carbon Cone. aq. NaOH sol containing catalysts | containing catalysts i (H, passed) (0, passed) ' 138 E4.18 PREVENTION FROM CORROSION Chemistry 4.17 CORROSION Corrosion is basically an electrochemical phenomenon. The rusting of iron, the tarnishing of silver, development of a green coating on copper and bronze are some of the examples of corrosion. Corrosion causes enormous damage to building, bridges, ships and to many other articles made of irom. Incomosion, a metals cxidised by loss of electrons to oxygen anc! forms metal oxide. Corrosion of ron(which is commonly ‘known as rusting) occurs in presence of water and oxygen (ait). Akhough the chemistry of corrosion is complex taut i is understood that at one spot of an iton object oxidation occurs and that spot behaves asan anode. Anode: — Fels) —> Fe* (aq) + 2e”: (Ene = -0.44V) Electrons released at anode move through the metal and go to another spot on the metal and reduce the ‘oxygen in presence of H' ions (which is believed to be available from H,CO, formed due to dissolution of CO, in water). This spot works as a cathode : Cathode: Og) + 4H! faq) + de" —> 2H,0 (0); (@ = 1.23) Here Fe ions move through water on the surface of the iron object. (if water present s saline, it will help more in canying the current in the miniature cell thus formed and will enhance corrosion). The overall reaction of the ‘miniature cellis the sum of the cathode and anode reactions as follows : 2Fe(s) + O,{q) + 4H (aq) —> 2Fe* faq) + 2H,0(0 : EB’, = 1.67 V) ‘The Fe® ions are further oxidised by atmospheric oxygen to Fe (as Fe,0,) and comes out as rust in the form of a hydrated iron ill) oxide expressed as Fe,O,, xH,0. AFe(aq) + Og) + 4H,O(9) —> 2Fe,0,6) + 8H H+ ions produced in the above reaction help further in rusting. Impurities present in iron also enhance rusting by selting a number of miniature cell. Very pure iron does not rust quickly. Corrosion of a metal is prevented by applying ‘protective coating (such as grease, paint, bisphenol ‘or metal coatings) on metal surface. In case of iron this coating is done in two ways : i) electrolysis (Cx, Ni and Cd coating) {i) dipping iron objects in a molten metal (2n and Sn coating). Use of zinc coating to protect iron is called Galvanisation. In 40H i the of fin, But tin protects copper in thesame wayas | 5. Cotnadic protection by con a block of zine protects iron (E%o,* so. =0.34V). ‘magnesium to an iron pipe burried underground. 139Pre-Medical Instead of coating more reactive metal on iron, the use of such metals is made as sacrificial anode. This method | i i of preventing iron from corrasion is called CATHODIC PROTECTION, In this method, a plate of reactive metal (Zn or Mg) is buried beside the iron pipe or tank and connected to it by wires, Here iron becomes cathode and more reactive metal becomes anode. The reactive metal anode is sacrificed to protect the ion, Since these reactive metal pales are oxidised quic'ly, they are replaced from time to time hich is easy to do Air ust ale The rusting of iorn (Iron in contact with water forms the anode and in contact 0, + 4H + de> 2H,0 Fe > Fe + 20° with air forms the cathode, At the anode i ston is oxidised to Fe’, and atthe cathode tron ‘oxygen is reduced to water Cre eed