ALO. 5 Ei = @ Conductors allow the electric current to pass|& Rod or plate of metal which is kept immersed. in electrolytic solutions through them but non conductors ey + Twotypes (insulators) do not. g “Aaide catia g Oxidation occurs Reduction occurs 2] Chargeisnegative ‘Chargeis positive @ Produces ions either in molten state or in 3} ingalvaniccell ingalvaniccell aqueous state ig ‘Chargeis positive Chargeisnegative | HRCTROIGT é inelectrolyticcell inelectrolytic cell Strong Electrolyte Weak Electrolyte E (® Sees oe Seen [> Almost 100% ionized > Very less ionized] |¥|® _ Itis combination of fio electrodes or two half cells. eg.S.A,SBsaltofS.A} leg. WB. of WB. ‘Types of cells: 2 SB i Electrolytic cells,” anic cells Electrical energy — 3 ‘Chemical ene Siemen mt ohm m |5)_ Cell constant (b)’ It is the ratio of distance between the two electrodes to the area of plates. cmt a m? Hy CK: It is the conductance of electric current, through 1 molar sol" & the distance between ohmr'cm? mole | Siemen mmole? fondu viele It is the conductance of electric current, through 1 Normal sol" & the distance A= eS) ohmtcm? eq? | Siemen m? eq!"] Electro z i F ik ionic conduct “Conductivity is due to mobility of free electrons | 1. | Conductivity is due to mobility of free ions from negative to positive end towards oppositely charged electrodes 2 During conduction matter is not transferred 2. | During conduction matter is transferred in the form of ions 3.| Passage of current may bring only 3. | Passage of current brings in physical as physical changes well as chemical changes 4.|" The conductivity power is high 4. | The conductivity power is relatively less 5.| An increase in temperature decreases 5. | With an increase in temperature. conductivity conductivity due to increased thermal increases due to the increase in the degree of vibration of particles or resistance increases ionisation and increase in the mobility of ions. At infinite dilution for a electrolyte A,B, ALAB,) = a8 +yn2, ANA.B,)= 22A° + yX2B- IMP: - 1. 2. 3. 0 | Zine eM = cattode lzns0, solu cuso, solution as pgs Principle. It is Primary Reversible galvanic cell. Working j) AtAnode (oxid®) Zn(s) > Zn™(1M) + 2¢~ AtCathode (Red) Cu*(IM) +#2e"(s) + Cu(s) Net Rea® Zn(s)+Cu**(1M)-> Zn™(IM) + Cu(s) Voltage 1.1 V (at 298 K) ion SS Representation 75 | Zn§0,ll CuSO, Cu T = REC = RCC» RCC RCC» RCC RCC + RCC + RCC Ke © Zn rod > ~v * Sol" +ve © Excess ions © Neutralised b « Zn dissolves at anode ‘* Cu deposits at cathode When E,, = 1.1 V « No flow electron © No flow current * No reaction (CasesTIT| When E,,> 1.1 V ‘* Flow of electrons -> Cu to Zn © Flow of current Zn to Cu * Zn deposited at cathode © Cu dissolves at anode 5 res 'Prof.Motegaonkar S.R. M.Sc.Chem.Gold Medalist SET/NET-JRF,GATE, DRDO,TIFR qualifiDef: The potential difference across the electrical layer whic is created at the rod-electrolytic solution interface. The electrode potential depends upon the following factors- (a)Nature of the electrode (b) Concentration of the ions in solution (c) Temperature ‘Types of electrode potential!” Oxidation potential : (E,,) ‘The tendency of getting oxidised. (i) Reduction potential : (E,,,) The tendency of getting reduced. EQUI. Eox; of an element is same in magnitude but opposite in sign to the Ered. (ice. Eoxi= - Exed) By conventions, the electrode potential is represented by reduction potential (Eyeq)- + Standard Electrode»Potential . aoe ee q standard conditions SE ii. An electrode in which pure and dry hydrogen gas is| bubbled at 1 atm pressure around a platinised| platinum plate immersed in 1 MH ion solution is called SHE. It is a primary reference electrode. ROC + RCC RCC“ RCC «RCC» RCC RCC RCC RCC RCC Working i) Act as Anode H,(g, 1 atm) — 2H*(1M) + 2e ii) Act as Cathode 2H*(IM) + 2e > H,(g, latm) iii) Difficulties in setting SHE fa) It is not easy to handle 'b) Its difficult to obtain pure and dry H, gas. () It is difficult to maintain latm pressure. d) It is difficult ot maintain 298 K temperature. le) It is difficult maintain concentration of HCl 1M. f) Itis difficult to prepare ideal platinised Pt - plate iv) Voltage v) Representation bs 8 Glass wool plug Principle It is a metal - sparingly soluble salt electrode. It is as a secondary reference electrode. Working i) Act as Anode 2Hg() + 2CI(sat) > Hg,Cl,(s) + 2e° ii) Act as Cathode Hg,Cl,(s) + 2e- > 2Hg (1) + 2CI(sat) iii) Advantages of calomel electrode fa) It is easy to construct and transport and convenient to handle. Ib) The potential of the electrode is reproducible and remains constant. ic) No separate salt bridge is required for its combination with other electrode.iv) Voltage It depends upon concentration of KCI. KClcone [srr | DCE (0.1M) +0.33V NCE (1M) +0.280V SCE (Saturated) +0.242V v) Representation Kel Hg,¢), | Hg mm ME or ‘cell’potential & Nernst Equation 1. Gibbs energy changes for cell rea”. AG? = - nF E°,,, 2. Standard cell Pot. & equ™ constant 3. Nernst equ* 1. For electrode Case-I: For metal - metal ion electrode Ey Bo ogi] 2 Case-II: For hydrogen electrode 0.0591 log tH 2 Puy If P,, =Tbar, E,= 0.0591 log [H*] Ey =~ 0.0591 pH Case-III: For calomel electrode E, = 0.280 - 0.0591 log [Cl] Pau ae TREC + ROG > RCC = RCC > REC + RCC - RCC > RCC = RE 2. For EMF of cell .. 2303RT Fa Bn Tp log Q : 0.0591 at 25°C, Boy = Pa 7 log Q 10 The arrangement of various metals and non metals on the basis of E° values which ate calculated using SHE is called EME series ‘The eleciochemical Geties- Electrode reaction (Reduction) Element Standard electrode reduction potential F volts i Li -3.05 K C+ ROC RCC + RCC» RCC > RCC» RCC» REC + RCC + RCC -0.44 - 0.408 -025 054 dl 5 0.00 Cu = | cut+2e>Cu = +0.397 L 1, +2e 20 +0538 Ag Agite Ag $0.79 Hg Hg"?+2e > Hg $0,885 Br, Br, +2¢°—>2Br +108 cl, Cl+2e + 2cr +136 Aw Au’ +3e> Au +150 Fy F,+2e—> 2F +287 Characteristic of electrochemical series -ve SRP => electrode acts as anode wrt ve SRP => electrode acts as cathode wrt SHE SHE rics PORT CooMe cele eena—— - Application of electro-chemical series (i) Reactivity of elements 1 + Reactivity of metals 2 E> + Reactivity of non metals « E° 1 (ii) Electropositive character of metals o BP (iii) Displacement reactions Metal having less E° value can displace another metal having greater E° value from salt solution | Non metal having greater E° value can displace | another non metal having less E° value from salt solution. Metals having -ve E° values displace hydrogen from dilute mineral acids. (iv) Reducing power of metals «25 (v) Oxidizing “ot (vi) Thermal stability of ® ai ‘metallic oxides “5 (vii) Products of electrol of metal * Preferential of non metal | (viii) Corrosion * Tendency to undergo corrosion of métals «. RCE TREE T RCE TREE + RECT REE RCE RCE HCE (+) Brass cap |——Zn container [——Paper spacer | Paste of Mn0,+ carbon |——Graphite rod Paste of NH,CI + ZnCl, e (is) Ekteaction of melo : ig] MnO, prevents the collection of H, gas on Metal having fess E° vaiue.can be usediin'the|*| ~ ‘mOeS cs Bente extraction of another metal having greater E° | ANE a er a eee value Jo] Hag +2Mn025) > M2034) +20) eg, Zn is used in extraction of Ag and Au by|"| NH, produced combines with Zn to form cyanide process (leaching) 3| complex which makes reaction irroersible S| zn*(aq) + 4NH,(aq) > [Zn(NH,),*(aq) + Ttis the compact form of Galvanic cell. '@ COMMERCIAL CELLS v v has cells Secondary Cells Fuel Cells Les Cannotbe recharged and] [* Canbe recharged and hence can be] [* The heat of combustion of fuel is hence cannot be reused. reused. converted into electrical energy “8: dry cell, mercury cell le.g, lead storage battery, NICAD cell_ | _|e.g. H,-O, fuel cell. TiAlkaline dry cell Electrolyte + NaOH or KOH © At Anode (oxid) Zn(s) + 20H:,,.> ZnO, + H,O() + 2e- © At Cathode (Red”) 2Mn0, (s) + H,O(l) 2e° > Mn,0,(s) + 20H(aq) The alkaline dry cell has longer life than acidic dry cell because in acidic dry cell NH,Cl corrodes Zinc vessel & decreases life Zn(s) + 2H"(aq) > Zn™ + H,(g) ECU RSTME Mele Pb plates. Spongy lead packed with Principle It is Secondary, I Working 1) Discharging ( i) At Anode (oxid" Pb(s) + SO} (aq) > PbSO,(s) + 2e" ii) At Cathode (Red*) — PbO, Plate (+ve) PbO,(s) + 4H'(aq) + SO} (aq)+ 2e" > PbSO((s) + 2H,0() iii) Net Rea" PD(s) + PbO,(s) + 4H"(aq) + 2 SOF (aq) > 2PbSO,(s) + 2H,0() iv) Voltage 2V v) Representation 2 © NSPS Charging + (Voltage > 2 V applied) During all reactions reversed EINE, At Anode 1. Gas Fuel-> 2, Liquid fuel > CH,OH, HCHO, N,H, 3. Oxidant > =/4. Catalyst > I5, Electrolyte eae cee ee eee Mee eee eA ieee ese 3yNickel-Cadiiitimn (NICAD) cell (1.4 V) At anode -> Cd electrode Ca(s) + 20H, > Ca(OH),(s) + 2e" (Oxia) At cathode —> NiO, electrode NiQs(5)+2H,0() +26" ~> Ni(OH),(s)+20H™(ag) Cd (s)+ NiO2(s)+2H,0() + Cd(OH),(s)+Ni(OH),(5) cz I/Flow, batter: PT ny 2H,(g) + 40H (aq) > 4H,0() + 4e- At Cathode 0,(g) + 2H,O() + 4e- > 40H-aq) Net Rea" 2H,@)+0,(@) > 2H,00) Voltage 1.23 V Representation re tiles ely Most of the chemical energy released in the formation of O-H bond is directly converted into electrical energy rather than into heat energy of combustion reaction. H,CO,CO,CH,CH, CH, CHa oO, Pt, Pd, Ag, CoO KOH, NaOH, H,PO, oeelectrolysis. + The phenomenon of decomposition of electrolyte by passing electricity is called The electrolytic solution used is either molten. or aqeuous. The products of electrolysis obtained depends upon following. The nature of electrode used. + This is non spontaneous process and it carried out in a device called electrolytic cell. The concentration of electrolytic solutions. + During this process electrical energy is The potential values of reactions occuring at converted into electrical energy. the cathode and anode. PRR Electrolyte | Anode | Anodereaction used used Fused NaCl | Pt 2Ch > Cl +2e" Aq.NeC Pt 2Cl > Cl, +2" ‘Aq.NaCl Pt FusedNaOH | Pt AqNeOH Pt Aq-HCL ee AqHSO, |i Pt 50%HSO, | PE Aq. Na,SO, Pt 2H,O>0,+4e+4H" || Pt 2H,O + 2e-—> H, +20H" Fused Cucl, | Pt 2Cr- Cl, +26" pe CuP+2e°>Cu Aq.CuCl, Pt 2Cl—> Cl, +267 Pt Cut +20" Cu. Aq. CuCl, cu Cu Cu, +20" cu CuP+2e° Cu ! Aq. CuSO, Pt 2H,0 40, +4e+4H | Pt Cur 426° Cu Fused MgCl, | C 2Cr + Cl, +26" Steel” Cu®+2e" Cu FusedMgO | C 20" 0,44" LR Mg +-2e°->Mg FusedNaH | Pt 2H 9H, +2" Pt Na'+e—Na Aq AgNO, | Pt 2H,O > 0, +4e"+4H* Agite Ag Aq. AgNO, Ags Agte Ag+e > Ag Zn Zn +2e° Znt +209 Zn SEE Ee aa eee ee ee eta hoa red eyes eae ceaeecine@ Faraday’s Laws of electrolysis | First law “Amount deposited or liberated at the electrode during electrolysis Quantity of electricity passed through solution, TF WeQ ~ Qaixt or Weit W=Zit hence, where Q = total charge passed through the solution i= current in ampere t= time for which current flows in seconds. connected in liberated at proportional W, 1 F of electricity deposits 1 gm equivalent| irrespective of charge. For deposition of 1 mole of substance (1 gm| Atom) (Q=nxF) gRCC + ROCs RCC™ RCC “RCC > RCC = RCC RCC RCC RCE = RCC = REC = RCC RCC = REC RCC ROC REC 7 Na —% 4 23gm 7 Mg —%y 12gm Ca x hy 20gm © Cut (cuprous) 1! _» 63 gm Cu (Cupric) —#_y Sars gm For monovalent Gas (H,, Cl,)-> 1 F liberates 11.2dm> For Divalent Gas(O,)—> 1 F liberates 5.6 dm’ lo jo N,—28 5 4.66 dm? * CO, #5 11.2 dm? > CH, —#» 224 dm Prof.Motegaonkar S.R. M.Se.Chem.Gold Medalist SET/NET-JRF,GATE, DRDO,TIFR qualified+ It is electrochemical phenomenon. + During this process a tiny Galvanic cell is] formed at the surface of metal in which one part of metal acts as anode and another part acts as cathode. + Acidic oxides like CO,, SO,, SO, etc. present in | the atmosphere gets dissolved in the moisture and this solution acts as electrolyte for Galvanic cell. ‘Chemical reaction Occuring during the rusting proces: * Anode Fe(s) —> Fe® (ag) + 20°; (E°r*/re = -0.44V) * Cathode O,(g) + 4H" (aq) + 4e—> 2H,0 (6); (B= 1.23 V)|* atmospheric oxygen to Fe* (as Fe,O,) and comes out as rust in the form of a hydrated iron (Ill) oxide expressed as Fe,O,, xH,0. 4Fe*(aq) + 0,(g) + 4H,0() — 2Fe,0,(s) + 8H" | Ht ions produced in the above reaction help further in rusting. CC REC = RCC Impurities present in iron also enhance rusting by setting a number of miniature cells. Very pure iron does not rust quickly. ROC + RCC > REC» RCC = RCC IS with Zn. Tining process - Metal surface is coated with Sn. Cathodic protection- Less electropositive metal like Fe is combined with more electropositive metal like Mg, Al So that Fe becomes cathode hence it do not corrode.