#le Ext) ONE O SEs ee arco cae mee arn ents Calomel Eledxode - ee Wien CALS hietantnre | we At [RELATION] « At &AE [RELATION],8. ELECTROCHEMICAL CELLS 8.1 Electrolytic Cells Electrolytic cells are devices in which electrolysis (chemical reaction involving oxidation and reduction) is carried out by using electricity or in which conversion of electrical energy into chemical energy is done. 8.2 Galvanic Cells This is a device where a redox reaction is used to convert chemical energy into electrical energy, ie, electricity is obtained with the help of oxidation and reduction reaction. The chemical reaction responsible for production of electricity takes place in two separate compartments. Each compartment consists of a suitable electrolyte solution and a metallic conductor. The metallic conductor acts as an electrode and the compartments containing the electrode and the electrolyte solution are called half-cells. When the two compartments are connected by a salt bridge and electrodes are joined by a wire through the galvanometer, the electricity begins to flow. This is the simple form of voltaic cell8.3 Daniel Cell Zine electrode ] Anode) ine sulphate (ZnSO), How sare ondge Cotton wool 3 plug Anion movement <—— —— cation movement Copper (on of ecronsy °C. Evrrent * ‘electrode (Cathode) Topper () sulphate solution (Cuso,)Oxidation half reaction, Zn(s)—>Zn** (aq) +26 Reduction half reaction, Cu’* (aq) + 36° ——>Culs) Net reaction Zn(s) + Cu" (aq)——> Zn" (aq) + Culs) Salt Bridge: A Salt bridge is usually an inverted U-tube filled with a concentrated solution of inert electrolytes. An inert electrolyte is one whose ions are neither involved in any electrochemical change nor do they react chemically with the electrolytes in the two half-cells, icance of salt bridge: The following are the functions of the salt bridge (@ _Itconnects the solutions of two half-cells and completes the cell circuit. Gi) prevents transference or dfusion of the solutions from one half-cell to the other. (ii) It keeps the solutions in two hal-cells electrically neutral. (iv) It prevents liquid-liquid junction-potential, ie, the potential difference which arises between two solutions when in contact with each other. A broken vertical line or two parallel vertical lines in a cell reaction indicates the salt bridge Zn|Zn** || Cu** |CuItis the tendency of an electrode to get duction potential: It is the tendency of an electrode to get reduced, i, to accept electrons. Mn’ +ne-——>M indard Electrode Potential: The potential difference developed between metal electrode and the solution of its ions of unit molarity (1M) at 25°C (278 K) is called standard electrode potential.1 Tal aa std ates = palit Oa oye re if C79 ae we | PUR ENES U=o ] Poa AE Ven eas a)8.4 Reference Electrode (Standard Hydrogen Electrode, SHE or NHE) The potential of an individual half-cell cannot be measured but the diflerence in the potential of two hal-clls can be measuted experimentally It is therefore, necessary to couple the electrodes with another electrode whose potential is known, Ths electrode is termed as reference electrode lke standard hydrogen electrode (SHE). Which 's standard electrode potential considered zero, | Figure 172: Representation of reference electrode ‘The hydrogen electrode thus obtained forms one of two halt cells ofa voltaic el. A voltaic cell is created when this half-cllis connected with any other half cel. The hydragen electrode can act as cathode or anode with respect to other electrode, SHE half reaction Electrode potential Hy 92H 426 0.0 (Anode) 2H +26e@ —H, (0.0 V (Cathode)CeO RG ON NM Ceo cocoa) a me) (an Bs tn() a Cees a a — RT tn On) ne ke a Ce ° Mn a CW Eom = Eye, |e n (ate) an 7) Fy ee a ae ; ( Retomter)F Ean = Ents, — RE My (4m) + RE tnayt re F Se, = Rith(@,) ata (hae are ae cr F lacy, ° Eyton, ~ a In (Fe) ts (log cw") ii} ad RT In (Ain) — 2303 RT Py Tewa BE A aac = Oo. (S59) eer Ce oo ae areas OS ores. C45/sne) Cae i ia a ee8.5 Some other Reference Electrodes ( Calomel Electrode: > Saturated Ch solton FL Ha,0, ane Figure 17.3: Representation of calomel electrode Reaction when electrode acta cathode: 2Hg,Cl, + €=—=tHg +Cl 6 Silversilver chloride electrode: Ths i another widely used reference electrode. It is reversible and stable land can be combined with cells containing chlorides without inserting liquid junction, Silver chloride is deposited electrolytically ona sver or platinum wire and itis then immersed in a solution Containing chloride ions. its standard electrode potential with respect to the standard hydrogen electrode (0.2224 V at 298 K. The electrode is represented as: Ag | AgCI | C The electrode reaction is: AgCI+€° —»Ag +Irey = a ale vas oy T_ a Q h| 2u Re aaa —— ey rau kpc mS A See Q + oR> — Bom, oa Hyd Hy Ss : LS Coes > (our) ~ Cr GS Ee re ot eM x ( 2) Een = a . C a Ft R sty (ow) re io ae et eeoum ceeeC CCA) DESIGNATE 5S CCC CMO EL annie preers Ccotnode)3 i Se orl + 2e —— (an oO a Ohne iy doquinone) (quinn) =y Bes Eg = Ex’- 2302RT } __ we ) ze = Eg °— DPA (my & a 5 &g= O.4V — 0.059 PH A a ee 0054p H ) — (9.2415 )rr! PLease 3 | PH = o4s8l— Eee 0.084} Pr on ‘ ad (Se ea ce rate 8 A aL (ow) Cz a3 Eau Ede (Ee ~~ Cell Assembly pe ie ree’ oor Oo. a pe on A eat Cig Pann V= Ee- Ea ee Ee V = Ee EaHeat of reaction (AH) in electrochemical cell AG = AH TAS dG = VdP ~ SdT For chemical reaction; d(AG) = AVdP — ASaT At constant Pressure dP = 0 d(AG) = -ASdT 4 AG Gp AG) = (AS) -d ar as=nr(#) a), as —nFE) Entropy change in electrochemical cell: (3), - ee ao ~ Atl Tas ag = aH -T-nr( aT nt of cell.5 Rd eae reir ad The electrical work done in a galvanic cell is the electricity (charge) passed multiplied by the cell potential. Electrical work = amount of charge * cell potential Charge of one mole electrons is F coulombs. For the cell reaction involving n moles of electrons, Charge passed = nF coulombs Hence, electrical work = nFE ce Electrical work done in a galvanic cell is equal to the decrease in Gibbs energy, ~ AG, of cell reaction. It then follows that Electrical work done =~ AG Therefore, ~AG = nFE ey of AG =~ nFE eq, Under standard state conditious-we write AG? = —nFE?8.6 Nernst Equation Nernst Equation: Suppose, for example, that we reduce the concentration of Zn in the Zn/Cu cell fom its unit ‘activity value of around 0.5 M to a much smaller value: Zs) [2n**(0.001M0 || Cu I] Cus) This wll reduce the value of Q forthe cell action Zn(s)+Cu* ——».Zn?* + Cus) The free energy change AG more negative than AG, so than E would be more positive than ° The relation between the actual ell potential E and the standard potential E® is developed inthe following way. ‘According to cell potential and Gibb’ fee energy change: AG = ~nE*F; AG = -nEF These expressions can then be substituted into the relation AG = AG® + RTIn Q This is Nemst Equation, which relates the cell potential to the standard potential Ef Qis unity then at 25°C Nernst Equation will be E= 22959 }ogq ‘And fora general electrochemical reaction ofthe type aAvb8cC+dD RT, (CIO! oF areNO , (oa RN seek) — fame @ ces Bs eis [Reactors roe ON A ae olpoe ve oa NERS rae ey BF [TRG = RTInG > veh 5 SCE ) at CO oe SECS) =) al ek ATC, anak elaiv elae a= vi om Ce oe PiDiscuss the physicochemical principle involved in the measurement of pH of ~af aqueous solution by using a hydrogen electrode. (WBUT 2006, 2014(0DD), 2014(0DD), 2016(EVEN)) OR, Derive the pH of an electrochemical cell with the help of Nemst equation. [WBUT 2012(EVEN)| ‘Answer:= [Producti/Reactant Since there i only one hydrogen atom present, [H/ Therefore, Hydrogen's standard electrode potential (Es taken to be zero volts at all temperatures, tha is, 1 simplified Nernst equation E = €° ~ 00591 Vin logi@) = E0591 Vit tog fH] Since a =1 and pt +, we get2.4. What is calomel electrode? How can we measure the pH of a solution usin, calomel electrode? [WBUT 2012(0DD), 2017(EVENy,‘A measurement: The experimental solution whose pH isto be measured is taken ina eaker. A pinch of quinhydrone (which is equimolar mixture of compound quinone CH,O, and Hydroguinone C,H,(OH), are held together by hydrogen bonding Consequently there is decrease in ¢o-associaton) is added to it, with stirring to ensure saturation. Then a bright Pt wire (or foil) is suspended in the solution. In solution {uinhydrone breaks up to equimolecular proportion of quinone and hydroquinone such that A =a, ‘Thus we have both quinine (Q) and reduction product of hydroquinone (HQ) prsext together in solution, containing H* ions. Consequently the following oxidation and reduction leading to occur, = Qrartae This indeed a red-ox system, so the immersed Pt wire records a potential. Evidertly # red-ox half cell known as quinhydrone half cell is set up, Pr | quinhydrone, H” of experimental solution. Thus H,Q electrode is then coupled with a saturated calomel electrode, so as to be a complete cel. The liquid junction potential is eliminated bY means of a suitable salt bridge. In this combination 11,Q acts as the @ve electrode Hence the complete cel is represented as Hg|HgCl,(s)| saturated KC! solution] Q, HQ (Saturated) experimental solution|Pt ‘As reduetion takes place at eathode hence, Q42H" +20 3H,02.2. What is reference electrode? Explain the working principle of one reference electrode, (WBUT 2010(EVEN), 2011(EVEN)] Answer:2.8. Derive the relation of EMF of cell with AG and AH. [WBUT 2018(0DD)] [NG eden toe pa Bee? — [verre Lae =ite short notes on the following: e slectrode potential [WBUT 2007, 2014(EVEN), 2016(0DD), 2017(0DD), 2019(EVEN}] n6l electrode [WBUT 2009, 2011(ODD), 2015(EVEN), 2016(0DD)] c) Reference electrode [WBUT 2010(0DD), 2014(0DD)]a) Explain the term chemical potent b) Derive the relation of EMF of cell with AG and A2.11, Write the Nernst equation for the cell reaction in Daniel cell. How will the Ecay effected when the concentration of Zn™ is increased? {WBUT 2022(0DD)] Answer:jon of EMF of cull with AG and AH. b) What type of storage cell is used in your mobile cell? [WBUT 2018(0DD)] Answer: oe : Perchlorate doped poly acetylene lithium system is used in the mobile cell. 2.40, Write the Nemst equation for the cell reaction in the Daniel cell. How will the Em effected when the concentration of 2n™ is increased? {WBUT 2019(0DD)]