Introduction “E ctrochemistry defined as the branch of chemistry which deals with inter- conversion of chemical energy to electrical energy and vice versa”. For example, in a battery, chemical energy is converted to electrical energy whereas in electroplating / electrolysis electrical energy is converted to chemical energy. Gaivanie cell Chemical energy is converted into electrical energy by Galvanic cell. These cells are known as electrochemical cells or voltaic cells. The best example of galvanic cell is j Daniel cell. This cell is formed by combination of two half cells. One is oxidation half} cell or anodic half cell and other one is reduction half cell or catholic half cell. The \ oxidation half cell consists of ‘Zn’ electrode dipped in ZnSOs solution and reduction half cell consists of ‘Cu” electrode dipped in CuSOs solution, Both the half cells are \ externally connected by metallic wire and internally connected by ‘salt bridge’. Salt | bridge is a U shaped tube containing solution of K2SO., KNO3, KCI or NHsNO; in agar-agar gel contained porous site. It maintains the electrical neutrality between two solutions. i + ay wwon Bh tty ret mo mao.) [eos ‘The following reactions take place in the cell. At cathode: Zn — Zw? 12e (oxidation) At cathode: Cu? +e > Cu (Reduction) The movement of electrons from Zn electrode to Cu electrode produces a current in reverse direction. The overall cell reaction is: Zn +Cu? — Zn? +Cu The galvanic cell can be represented by a eng enn eS neta ReZn + CuSO, + ZNSO4 + Cu Presentation of palvanie cell ZalZn* (qy| Cu2* (CajICU Electrode potential! smigie eivetrode potential: In galvanic cell, two electrodes are presented; at one electrode oxidation takes place and at other electrode reduction takes place. “The tendency of an electrode (M) to get oxidized or reduced when it is contact with its own ionic (M") solution, known as single electrode potential”. It is represented by Eaam™) or Bum. If metal rod or electrode (M) loses electrons and change into metal ions (M™) then metal get oxidized (oxidation potential, Eaam"). \ M ——*> M"+ne™ (Oxidation) Ifmetal ions (M"*), on collection with metal rod by gain electrons and change into metal atom (M), then metal ions get reduced (Reduction potential, Equ™/ x) Meine ee M (Redis During oxidation negative charge developed on the metal electrode and during reduction positive charge develops on the metal electrode, Standard electrode potential: If the metal electrode is suspénded in a ionic solution of 1M (molar) concentration or unit activity and temperature is kept at 25°C under latm pressure, then potential develop between electrode and ionic solution is known as standard electrode potential. It is represented by E°. The standard electrode potential of two half cell are represented by E% um) or E%at"/ a. Factors affecting electrode potential: i Ability of an clement to lose or gain an electron depends on it properties like | ionization energy, electro affinity, size etc. For example, the oxidation potential of Li atom is higher than Na, therefore it release electron easily and get oxidized.Concentration of io solution Hconcentration of ions is increase the equilibrium shift towards the metal site MM ne In this case, metal have lower tendency to lose electron (Oxidation potential) temperature ‘The equilibrium between ions and the pure metal is also affected by the temperature. If reaction is exothermic then an increase in the temperature will make the equilibrium move more to the left hand side making the electrode potential more negative. If reaction is endothermic then an increasing in the temperature makes the electrode potential more positive. Eiectrochenfical series Scries in which elements are arranged in increasing order of their standard electrode potential is known as electrochemical series. Electrode Half cell reaction | E°volts (standard reduction potential Lali Lite =i I KK 29 i caica caste ca. || -28 i Nene Nate Na i Mg@/Mg. Mg?42¢ -Me 23 | Zn7/Zn Zi*+2e-Zn | -0.76 ' Fe"/Fe Fe? +2e Fe 04 | | Hage W+esit, +0 | owen cu? +2e—Cu | 40.15 Ag/Ag Ag +e —Ag +07 | prclycr’ cht2e—2er | +13 | PLE F)+2e—-2F" 728Applica ion af Electrochemical series BX Comparison of retativ , J r i The greater the reduction potent greater the tendency af the element or ions to get reduce, For example, the reduction potential of Fe* (-0.41 V) is higher than the Li* (-3.04 V), therefore Fe?* ion is easily reduce and Li” ion is easily oxidized. Relative reacti y of metals: Greater the oxidation potential of the element, greater will be the tendency to lose electrons (greater tendency to get oxidized). A metal with higher oxidation potential can displace the metal with lower oxidation potential. For example, the oxidation potential of Zn** (-0.76 V) is higher than Cu?* (0.34 V), therefore Zn replace Cu from its salt solution. Zn CuSO4 9 ZnSOy+ Cv Spontaneity ot reaction: ICEMF of the cell is positive then redox reaction is spontaneous and if EMF of the cell is negative then redox reaction is non-spontaneous. Electromotive force (EMF) The force which causes the flow of electrons from one electrode to another electrode and thus results in the flow of current from electrode at higher potential to electrode at lower potential is called electromotive force. Carcuiauion oF baie oF une cet: Standard EMF of the cell = [standard reduction potential of R.HLS. electrode] — [Standard reduction potential of L.H.S. electrode] Peet = E%cathag Ovidation potential = ~ reduction potential Question 1 Write the half cell and net cell reactions for the following cell, Zn ZnSO, (aq) // CuSO (aq) / Cu. Calculate the standard emf of the cell given, | | le 1 \ \ | | | |0.76 v and E%¢u"?;cu= + 0.34 V Solution Half cell reactions Atanode: /n — Zn? +20 At cathode: Cu - ecu Net cell reaction = eu eCu 0 c Cu Az ZNACU 5 22g E*cett = E®eatmode = E%anode =E%ev" cu - E°zn an = 0.34 ~ (0.76) =v In determination of F on concentration oF a) Using Hydrogen electrode: of selution b) Using Quinehydrone electrode: ° EQ- Ecatomai ~ Eceu 0.0591 pH= EX~npnst Pquation Vets us consider a hypothetical cell reaction BA 4 ihe mom C4 dD Applying Van't Hot? reaction isotherm AG =A AT INQ. (Qin the renetion co-efMicien) ser cn nb RT WCE IPE [-AG = nF} “ TARO? Both side is divided by —nF* ep? wey ICR IDI Bao Boar REIN Trig pep crpr Fen Boe 2QOMRT Noy = Poa ART A Re 8.314 JK mol! Pm 298K, P96, 500 C [cr ipr vet O,0591 tog n tay? Where, Ever single electrode potential F2,= Standard reduction electrode potential ! The above equations are the form of Nernst equation Question 2 | \ 1 | Consider a cell Ni/Ni* (0,01M) |] Cu? @.SMYCu, The standard reduction potential of Ni and Cu are -0.25 and 0.34 V, respectively, Calculate the EMF of the cell, Solution Atanode, Ni ——> NE+2c¢ Bw?" =0.25V_ {oxi. Pot. = - red, pot) Atcathode, Cu +2e° ——+» Cu Per cn 34.V ————————— um —‘The net cell reaction is Ni+Cu ——+ Cu + Ni* (0.SM) (001M) = Brce"Bcu - Eni ini ' = 0.34 -(-0.25) \ =0.59V 1 EMF of the cell can be written as | " Fug Eon asaitog OI \ n [cu] \ Fea 039 9.0591 10g 29! | ” {05} ' =o6ty i \ i Battery, | A battery is a device in which number of electrochemical cell are connected in a series. It transformed chemical energy into electrical energy. i) Primary battery ii) Secondary battery iii) Fuel cell i) Primary batteri Primary batteries are those in which only one redox reaction occurs an battery become dead after some time. These are non rechargeable and ce reaction are irreversible. For example: fithium cell, dry cell, mercury cell k ii) Secondary batteries: Secondary batteries are those which recharge when electric current pa through the cell. These are rechargeable and cell reactions are reversib rr—_———- “qq therefore they can be use aga ad storage battery (lead acid battery), Ni-Cd battery. Fuel cell is a device, which produce electricity by the combustion of fuel. ' 1b oxidation y ' Lead Storage Battery x Anode: spongy metallic lead Cathode: Lead dioxide | f | ' Electrolyte: dil, H2SO4 Construction: A number of spongy lead plates (anode) and a number of lead dioxide (PbO2) plates (cathode) are connected in parallel. The spongy lead plates are fit alternatively between lead dioxide plates. All the plates are separated from adjacent plates by insulators like wood strips, glass fiber etc. The entire combination is | immersed in approximately 38 % dil. H2SO; of specific gravity 1.2 to 1.3 g/em* solution. Anode Cathode iS ow) Pb plate = 38% H2SO4 packe. |x Acid proof wi container Pb plate packed Lead Storage Battery with Discharging: Battery is said to be discharge when used for production of electrical energy. In this process the lead electrode loses electron and get oxidized into Pb’? which react with 503- and form PbSOs. The released electrons from anode are used up by cathode to reduce PbO; into Pb'? which react with $03~ and form PbSOy. In this process PbSO, |} deposited on both the electrode and cell stop working. ] At anode: Pb ——* Pb”? + 2e" Pb'? + SO} ———» PbSO,, At cathode: PbO? + 4H* + 2e° ——+Pb"? + 21,0 Pb’? + 503- ——+ PbSO; | The net reactionsi a a, eo ee ese Pb + PbO2 + 4H” + 2502- + 2PbSO, + 2,0 + energy A battery needs charging when the specific gravity of H2SOs falls below 1.2 g/cm’. This can be achieved by applying external direct current so as to reverse the cell reaction. PbSO, + 2e-———+ Pb + S0}- PbSO, +2H,O ——+PbO, + 4H" + SOR" + 2c" The net reaction 2PbSO, + 2H20 + energy + PbO; + 4H* + 25037 + Pb i | | | |