Ri eur Electrochemistry Electrochemistry - | (Electrochemical Cells) BASICS Section - 1 Electrochemistry deals with the inter-conversion of electrical energy and chemical energy. This part of Electrochemistry will, ‘deal with the conversion of chemical energy int electrical energy (Electrochemical Cells). Electrochemical Cells : Consider the following redox reaction Znls) + Cu?*(aq) —> Culs)+Zn°*(ag) In the above reaction, Zn displaces copper ions (Cu®) from aqueous solution. This reaction can be achieved very easily in practice. Put a Zn rod into a solution of CuSO, (containing Cu®* ions). Itis observed that blue colour of CuSO, solution disappears after sometime. What happens actually ? Zn loses 2e°s per atom and Cu** ions in the solution accepts them. Cu® ions from solution in this manner are deposited out in form of solid Cu and Zn goes into the solution as Za (colourless). The reaction can well be understood in terms of two half reactions Oxidation Zn(s) —> Zn?*(ag) + 26° Reduction Cu! (ag) +2e° —> Cuts) Note: (In this reaction, Zn atoms are directly giving electrons to the copper ions. (ii) Another aspect of this reaction is that it is an exothermic reaction, This means decrease in energy of the reacting system takes place which appears as heat. Now, we can make the same reaction take place even if the copper ions and zine rod are notin direct contact. If we put the ‘Cu’ ions and Zn rod in two separate containers and connect the two by a conducting metallic wire and introduce an inverted U shape instrument (called as s:l-bridge), then electrons will stil be transferred through the connecting wires. “The electrons from Zn rod travel to Cu ions through the connecting wires and the same reaction takes place. current flow gunent flow = current flow @ Zn cu salt-bridge LHE RHE (Anode) (Cathode) Zo cL Kc Electrochemical Cel Self Study Course for IITJEE with Online Support 1Electrochemistry - | OCU 2 In such an arrangement, the solution does not get heated up. The loss in energy now appeats as the potential difference Which is used to do the work in transferring the electrons from Zn to Cu ions. Such an atrangement is called as lecirochemica cell or Galvanie cell or Voltaic ell. The potential difference which drives the electrons from Zi to Cu ions, is called as coc\romotve force (BME) of cel An clectrochemical cell (shown in diagram) mainly consists of two compartments : eft hand electrode (LHE) and right hand clectrode (RHE). In LHE, oxidation takes place andis called as anode. In RHE, reduction takes place and is called as cathode. “Anode is generally of that metal (or substance) which readily loses electrons (L., oxidised easily). A rod of that metal is prepared and put into one of its solution in LHE to get anode. In RHE, « rod of metal that loses electrons less easily as ‘compared to the metal of LHE (in the diagram, Zn is taken in LHE and Cu is taken in RHE) is prepared and putinto one of its solution to get cathode, LHE and RHE are also known as (wo half-cells. Now the electrons move from anode (LHE) to cathode (RHE) and hence a current flow is maintained in the external circuit, ‘The two half cells are connected by a inverted “U’ shaped tube called as sal-bridzc, The salt-bridge contains solution of song ionic salts ike NaCl, NaNO,, KNO, and KCI, etc, (salts of most reactive alkali metals) soaked in a colloidal solution ‘of agar-gel which allows only the movement of ions of salts, not water. The role ofa salt-bridge is very important as it allows the continuous discharge of the cell (..,the supply of voltage from cell). The salt-bridge keeps the two solutions (ie. in LHE and RHE) electrically neutral to each other. Inthe Zn-CuSO, cell, in left hand cell as Zn loses electrons, excess of positive charge (in form of Zn2* ions) is collected near LE and as Cu* ions gets discharged (accepting electrons from Zn) in right hand cell, excess of negative charge (in form of SO} ions) is accumulated near RHE. Now the salt-bridge provides positive charge to RHE (in form of K*, Na* ions) and negative charge to LHE (in form of CT, NO,” ele) and thus bringing about the neutrality of two solutions. If this does not take place, a reverse potential difference is ereated in the two compartments and thus breaking the continuous supply of voltage (current), whichis the purpose of the cel ‘The efficiency of a cell is determined by the tendency of LHE to loose electrons and the tendency of RHE to accept electrons. A measure of cell efficiency is called as electromotive force (EME) or the voltage or the difference in potentials of two electrodes. EMF is defined as the difference in the potential across LHE and RHE due to which electrons from anode travel to cathode. EMF value of a cell made up of such two half-cells isa constant provided that the concentration of electrolyte, temperature land the pressure (if gases are involved) remains constant. It means that EMF values do change with concentration, temperature and pressure, EMF values are hence standardised at a temperature of 25°C (298 K), a pressure of | atm (if gases are involved) and at concentrations of 1.0 M for all solutes present as electrolytes. EMF value under these conditions is called as stanslascl EMP and is denoted as ©". EME of a cell is measured as the difference of potentials of anode and cathode. The potential of a half-cell or EMF of a hhalf-cell (Le., a cathode or anode) is called as electrode potential. It is defined as the tendency of an electrode either to get ‘oxidised of to get reduced ie., to loose ot gain electrons. Blectrode potentials ate of two types Oxidation Potential : Itis the tendency of an electrode to get oxidised, ic., to loose electrons Reduction Potential : Itis the tendency of an electrode to get reduced, ie, to accept electrons, Electrode potentials at standard conditions (1 atm, 298 K and 1.0 M) are called as standard electrode potentials set Study Course forIMJEE with Online SupporNie eum Electrochemistry - | Note: > > ‘Anode is the negatively charged electrode in electrochemical cell and positively charged in electrolytic cell (o be discussed later) but it will always be the oxidation electrode (electrode on which oxidation takes place) Cathode is the positively charged electrode in electrochemical cell and negatively charged in electrolytic cell (0 be discussed later) but it will always be the reduction electrode (electrode on which reduction takes place) We can also define cathode and anode electrodes as Anode: Blectrode at which current enters. Cathode : Electrode at which current leaves ‘An important property for an ionic salt to act as a salt bridge is that ionic mobility (ease with which ions move in solution) of both cations and anion should be similar Aso, it should not react withthe contents of ether anode or cathode. ‘Types of Electrodes : 1 Metal in contact with its ions : ‘Metal (M)in contact with its ion (M®")is represented as M/M™* when it acts as oxidation electrode(anode)and M""/M_ when it acts as reduction electrode (cathode). Whether a given electrode acts as anode or cathode depends upon the other electrode with which it forms an electrochemical cell. So it is necessary to define both oxidation and reduction potentials for an electrode. M/M is written as: M(s) —> M"™'@.0M)+ ne (oxidation electrode) and its potential is called as oxidation potential and at standard state is represented as E°(M/M"). Mi / Mis written as: M™ (LOM) + ne” —> M(s) (reduction electrode) and its potential is called as reduction potential and at standard state is represented as E"M™/M) Note : Symbol "7" denotes the phase seperation between the two substances. 2. Gaseous electrode : Gases like H,(g) ean loose electrons to form H’ ions and henee ean act as anode and also H jon can add up electrons to form H, (g) and hence can act as cathode. Similarly, gases lke Cl, (g) can add electrons to form CI-ions and CI-ions can loose electrons to form C1,(). The concentration of electrolytes isthe value for [HJ ions and we take pressure of gas in atm. A/bydrogen electrode is made by passing H, (g) at 1 atm near an electric conductor made up of platinum (for conduction of e°s) dipped in an aqueous solution containing H* ions (generally He) 1.0MIT (from Hci) HCI) as shown in figure. Electrode representation: Pt, HHI" ° Finely divided Pt coated . ‘on Platinum fll or HH, Pt Sc td Course for IIE with Onn Support 3Electrochemistry - | eeu Its electrode potentials are represented as EGH/H): HQ) 9H (a) + (oxidation potential) Bot): Waa) +" 5) {reduction potential) Bats): L1,dam)—s 1" aM) + —_(standaré oxdation potenti BTU /H): H'aM) +e” >} Hdatm (standard redutin potenti Similarly, CL/CY electrode is prepared by passing Cl, gas and taking HCI (aq) or KCI (aq) as electrolyte, 3. Redox Electrodes : In this type of electrode, an inert wire (c.g. Platinum) is placed in a solution (electrolyte) containing ions of an clement {in more than one oxidation states, e.g. Pt wire dipped in an electrolyte of Fe? and Fe"* ions, The electrode (inert material wire) acts as a source / sink for electrons, Electrode representation: —_Pt/Fe®*, Fe®* Electrode reaction: Ascathode:Fe!(ag.) +e" —> Fe (aq.) Asanode: Fe (ag) — Fe'*(ag)) +e ‘Another example PU/Mn0j, Mn, H* As cathode» MnO] (a9.) + 8H (aq.) + Se” —o Mn™* (aq.) + 4H,0(0, Redox electrodes can also be made using substances that exist in two different oxidation states. Quinhydrone is an equimolar mixture of benzoquinone (Q) and hydroquinone (HQ) O _ Chae ,Q) Q ‘Note: If¢wo substances are in same solution then in the cell or electrode representation, they are separated by comma ('") 4, Calomel Electrode : It consists of mercury covered with mercurous chloride (calomel) in contact witha solution of KCL Electrode representation : He/He,cl, /cr Electrode reaction: Ascathode:-Hg,Cl,(s)+2e~ == 2Hg@)+2Cr-Gq) Asanode: 2g @)+2Cl (ag) = He, Cl (9) +26" Most common calomel electrode isthe saturated calomel electrode (SCE) in which the concentration of KClis atts saturation (about3.5M). cq = 0.24V (vst SHE) 4 Set Study Cours for ITIEE with Online SupporNie ecu umcced Electrochemistry - | 5. Silver - Silver Chloride Electrode : consists ofa pure silver wire in a solution of KCI saturated with solid silver chloride. Electrode representation AgiAgcvcr” Flectrode reaction: Ascathode: — AgCKS) +e" <= AE()+ CG) ER acon =0.222V Asanode: ——Ag(s)+CT (ag) == AgCls) +e" Insaturated KC sution, Ejay Become 0.197V (wt SHE) 6. Mercury - Mercurous Sulphate Electrode Inthis electrode, the metal is mercury the sparingly soluble compound is mercurous sulphate (Hg,S0,) and the source of 80,2 anions is H,SO, or K,SO,, Itrepresented as Electrode representation He /He,S0, /S0, Electrode reaction: Aseathode: Hg,S0,s)+2e" —> 2Ha(4)+S0,> (aq) FO scuon =0.616V (wrt SHE) Asanode: — 2Hgt#) +S02-(ag.) —> He,S06) +26 ‘Note: [1] Calomel electrodes, Silver - Silver chloride electrodes and Mercury - Mercurous Sulphate electrodes are secondary reference electrodes. Silver - Silver chlorides electrodes and calomel electrodes are the most commonly used. (practically) as a reference electrode rather than SHE/NHE due to practical difficulties associated with its (SHE) use and maintenance, [2] ‘The potential of metal-metal ion electrode and metal-metal insoluble salt-salt anion electrode is same while their standard potentials are not same, Standard potential are related by the following equation. 2303RT iat ge PEK a0 [Referexample-4] 7. Amalgam electrodes : ‘This is the modified version of Metal / Metal - ion electrode in which metal strip is replaced by metal amalgam. eg. Na in Hg atc, M)/Na* (¢,M) Electrode Potentials : Itis impossible co measure the absolute EMF's (electrode potentials) for half electrodes. This is done by arbitrarily selecting cone half cell and setting its electrode potential as ‘0" volts. The electrode potentials of other half cells can then be measured by combining them with the standard reference electrodes in a cell arrangement ‘The reference electrode against which all other half cells are generally measuted is the hydrogen electrode half-cell at a ‘concentration of I” ions equal to 1.0 M and H,(g) at 1 atm pressure kept at 25°C (298 K). Itis also known as SHE. (standard hydrogen electrode) or NHE (normal hydrogen electrode). Its potential is taken as ‘0 volts. 9d, /H") =0=E°UN 1) Self Study Course for IEE with Online Support UES” sElectrochemistry - | CYCIACUS LRG Now other half cells can be divided into two categories : One which will act as anode and other which wall act as cathode in ‘cell arrangement with SHE. Each type of cell arrangement will give an EME value which will be actually the EMF value of known electrode as EMF value of SHE is 'zer0" volts (whether SHE acts as anode or cathode). For example : Cu electrode (half cell) acts as cathode with SHE, i.e, as cu (eu Cu** (aq) (.0M) +2e7 —> Cuts) ‘The experimental measurement of EME value for this cell arrangement give 0.34 volts, Since Cu electrode shows reduction ‘with SHE, the given value of EMF represents the reduction potential of Cu half-cell 9 (Cu*/ Cu) = 0.34 volts ‘The oxidation potential of Cu half-cell is just the negative of this value. 9 (Cu/Cu) =- 0.34 volts [Note: , eduction ~~ Bosdainl Note: Reduction potential is taken as a standard potential i. if electrode potential is given (and nothing is mentioned whether itis oxidation or reduction), itis taken as the reduction potential, by default Rules for assi ing sign (+ve or -ve) to electrode potentials : 1. The oxidation potential of half-cel (or an electrode) is given a positive sign ifthe given electrode acts as anode ina cell arrangement with SHE and its reduction potential is given a negative sign with the same magnitude. For example : oxidation potential of active metals like Na, Mg, Al, Zn, Fe etc is given a positive sign. 2. The reduction potential of half-cell (or an electrode) is given positive sign if the given electrode acts as cathode in acell arrangement with SHE and its oxidation potential is given a negative sign with the same magnitude. For example : eduction potential of less active metals like Cu, Ag ete is given a positive sign, Note: Electrode potentials measured in this manner are called as standard hydrogen scale potentials Standard EMF of a Cell (E°,,) : 2, can be defined in wo ways 38 (By = {standard reduction potential ~ standard reduction potential of cathode of anode 0 Brett note Erato sou ~ i) Bly = fstandard oxidation potential ~ standard oxidation potential of anode of cathode Blan =(Boaiain aga ~ (Postatin ose ni Self Study Course for IITJEE with Online SupportRie ecucumccr Electrochemistry - | Construction of a cell and writing cell representation cis clear that an electrochemical cell will be developed by two half-cells, If you arbitrarily select two half-cells for the purpose of constructing a galvanic cell, then always actin following manner ‘Compare the reduction potentials of two electrodes. The electrode whose reduction potential has greater positive value is rade the cathode and the other electrode is made the anode, * (i) Constructing the cell in this manner will always give a positive EMF otherwise sometimes if an electrode is chosen ‘wrongly, the EMF comes out to be negative. In that case, you should reverse the electrodes ie., make anode the cathode and vice-versa, Gi) Tis now standardised to use the definition of EMF in terms of standard reduction potential lat = (Ends Cell Representation : ‘The cell representation ofa cell is written as LHEIIRHE, I: represents salt-bridge In general, iftwo electrodes at standard conditions are MIM" and NIN? and let B%(M"* /M) NOs) [reduction] Overall Reaction = yM(s)-+xN°* (¢)M)—+M"* (M426) {Balance the number of e°s transfered at Cathode and Anode] Self Study Course for IITJEE with Online SupportElectrochemistry - | eur ace Electrochemical Series : In this series, the standard reduction potential measured on hydrogen scale are arranged in increasing order. Half cell Electrode reaction Reduction Potentials (volts) Lirti Lir(aq) +e — Li) -308 KK K (ag) 4° —9 KG) =295 ceca Cx(aq)) 2° — Cal) -287 Ne'/Na Ne’ (a9) 4° —+ Nats) -271 Me*/Me Mg (aq) +26" —> Mets) -237 Pont Hi, (@) +2° —> 21T aq) -225 APIAL AD (aq) #3e"—> Ale) =1.6 nent Mi?* (aq) #26 9 Malo -o |g 2 own, rt 20,0) +2e — HY@+201r@a) 083 | E : 20" Za Zn°* (aq.) +26 —> Zs) 07% 5 z oetyer Cx (aq.)+ 3° —> Cris) -0.74 i S Fev /Fe Fe (aq) 2° —> Fe(s) -om |E ceycespt ce* (aq) +e° —> Cran) -041 care Ca? (aq) +2e° —> Cale) =0.40 co*/Co Co (aq) #2 —+ Cols) 028 Nv Ni*(ag) 426° —> Nits) =025 TVAgl/Ag Aglis) +e° — Agts) +Taa) =01s sa Sn Sn’*(a9,)+2°—> Sn(s) -014 Pot Pb Po (aq,)+2e°—> PO(s) -013 Fe) Fe Fe? (aq) +3e°— Fes) =0.08 w/t, Pe 211 (ag) 426° Hyg) aw Br-/AgBr/ Ag AgBr(s) +e" —> Agts) +Brtea) a0 cu / Cot Pe Cu (ag.) +e" — Curaa,) a6 Sot Sn, Pe Sn'* (ag) +20" —+ Sn™(0a)) ais SOZMSO, $0-(ag)+41"@g) He $0, (ag) +400 047 CTIARCI/Ag AgCl(s) +e” —> Ag(s)# CT(aa) ox CIM, Heh) —He,CIy) +2e° — 2H!) +2CT 9) ox owen CuP*(ag)+2e° — Cuts) 08 PLO/OH” 06g) +2H,0(0) +46" —+ 4 OFF (aa) ao ‘ set Study Course for MJEE with Onine SupporMC CIuCU Sees Electrochemistry - | owen Cut (ag) +e" —> Cus) 052 arp 1s) +e" —> Fag) 054 PL.0,/1,0, 0,(g)+ 2H (ag) +2e" —> 1,0, (9) 068 Fe! /Fe%, PL Fe! (ag) +e" —> Fe* (ag) on He,2*/He (PO 12H," (aq) +e" —> He) 079 Agt/Ag Ag’ (ag.) +6" —> gts) 080 Hg? / He? 2HHg® (aq) +2e” —> Ha,**(aq) 09 NO,-/NO, Pt NO, +4H"(ag.)+ 36" — NO(g) +2H,00%) 097 PL Br, /Br Br,(Q+26° —> 2Br(ag) 109 Mn0, /Mn?* MnO,(s) +4H"(aq)+2e" —> Mni(ag.)+2H,0() 123 HY/0,/Pt Og) + 4H"(aq,) +4e° —> 21,09 13 c,0+/C8* €x,0,> (aq) + 14H (ag.) +66" 9 2Ce* (aq) +7H,O(0) 133 ayrer 12C1, (@) +e" —> Creag) 136 Au /Au ‘Au (aq) +3e° > Ants) 140 MnO,/Mn™*,HMPt_— Mn0,~(ag.) + 8H*(aq))+5e° —> Mn?*(aq)+4H,0(0 151 Col Co, PE Cel*(aq te” —> CoM(ag,) in H,0,/1,0 HO, (+ 2H" (aq) +20" —> 21,00) 178 CoM / Co, Pe CoM(ag) +e" —> Co* (ag) 181 0,10, O,(g) +2H" (aq) +2" —> 0,9)+H,009 2.07 PLR IF F,@) +2 —> 2F (aq) 287 > Lower the reduction potential, higher will be the tendeney of forming positive ions. This is related to reactivity of metals. The order of reactivity of metals is: Li> K > Ca>Na>Mg>AL > Inthis series oxidising character increases and reducing character decreases, eg., the reducing character follow the order : Na> Mg > Zn > Fe>Ni> Cu>Ag CEE) 7 agg) = 08 V and (H*IH,) = 0 V, in a cell arrangement using these two electrodes, which will act as anode and cathode ? Also find the Ey (©) Construct a cell using given electrodes at 25°C. Find its standard EMF. EP (Zn®*12n) = -0.16 V and E° (Cu*/Cu) = 0.34 V SOLUTION : (a) Note that reduction potentials are given. Comparing PL. H, (J atm)/H’ (1.0M) Ag* (LOMV/Ag(s) the two values, clatly J. (e ENGL) < BXAg*/Ag) ee rte at = Hydrogen electrode will acts as anode and Ely =0.8-0=0.8V silver electrode wil act as cathode, The cell representation ofthe cll willbe Self Stuy Cours for IEE with One Suppor 3Electrochemistry - | TOC (b) Note that E°CZn*/Zn) < E%Cu* /Cu) = Zinc electrode will act as anode and Copper electrode will act as cathode. Fe) =0.34-(-0.76)=11V (hans ata a ‘The cell representation of the cell is ‘Zos)fZae* (10M) lICu** (10M) / Cuts) The dry cell flash light battery) used to power flashlights, clocks, radios etc. follows following reaction: Zn(s) +2 MnO,{s) +8 NH,’ —> Zr* + 2Mn™* + 8.NH, +4 11,0 (@) Write anode and cathode reactions. (6) Calculate the Eo. of the dry cell if the electrode potential of cathode (Eduction) Varies between + 0.49 Vand 4+ 0.74 Vand of anode (Ereducion) #8 ~0.76 V. SOLUTION : Anode Zn(s) —> Zn*(1,0M)+2c~ ; EXeuciion =—0.76V cathode 2Mn0,(s)+ 8NH,* (aq.) +26" —> 2Mn'*(aq.) +8NH, (g) +4100) E® sucuon of eathode varies between +0.49 to +0.74V For 49--0.76)=1.25V Foe F2y2074-(0.76)=150¥ > Ey varies bereen 1.25 Vio 1.50. Note A given electrode potential isto be taken as Reduction Potential [as reduction potential is tobe considered, “by default” ] KEELE) For cach ofthe following ces (a) Write the equation for cell process. (b) Find E* for each cell. (©) Explain the significance of any negative answers in part (>). 1, FelFe(NO,), (1.0M) Il Zn?*(1.0 MylZn(s) 2. PLCl(g) / KCI.OM) 11 KCI. OM/Hg,Cl,(sVHg@) 3. Gd/Cd?*(1.0M) W AgNO,.OM)/Ag(s) EXFe"IFe)=-0A1 VV; EXCd™ICd)=-0.40V ; — E'Zn*IZn) =-0.76 V ECTICL)=-136V ; —E%Ag)=+0.80V E° (Hg | Hg,Cl,) =+021V 10 Self Study Course for IITJEE with Online SupportMC CUCU MSE SOLUTION: se: Bla = (Beaton) agpr Feo) ae Anode: Fe(s) —> Fe®(1.0M) +2e~ Cathode: Zn**(1.0M)+2e° —> Zn(s) Cell Reaction :Fe(s)+Zn?*(1.0M) —> Fe™(1.0M) +Zats) Hy =-076-04 03sV ‘Negative EMF value means that the cell will not work in the manner shown ie,, Fe as anode and Zn as cath- ode, So reversing (interchanging) the anode and cath- ode ic., making Zn as anode and Fe as cathode, can ‘make the cell work. Anode: 2C (0M) —> Cl, (1.Oatm) +2 Electrochemistry - 1 Cell Reaction: Hg,CL(s) —> C1(1.0 atm) +2H9¢6) 0 Bea Negative EMF value means that the cell will not work in the manner shown i.e., CI/CI, as anode and Hg, Cl, as cathode. So reversing (interchanging) the anode and cathode ie., making Hg,Cl, (ie., He/Hg,Cl,) as, anode and C1,/CI”as cathode can make the cell work. Anode: Cd(s) —> C42*(1.0M) +27 Cathode: Ag*(LOM) +e" —> Ag(s) Cell Reaction Ca) +2Ag'(L,0M) —> Ca*C.0M) +2Ag66) 8-(-04)=120V EME value is positive, hence cell will function with Cathode: Hg,Cl,) + 2° —> Cd as anode and Ag as Cathode, 2Hg(+2Cr.0M) MDL oi secon of Ny oni agus van, 096 Was of forme mos ee gen Bow V* (aq) + 2e° —> Vo) Au’*(ag) + 3° —> Au) E°=-119V .. (i) Fe*(ag)+3e —>Fe@) E°=004V il) B= 140V ill) Hg(ag) +2 —> Hg) E°=+086V iv) The pair(s) of metals that is oxidized by NO in aqueous solution is (are) (AX) VandHg — (B) Hgand Fe = (©) Feand Au (D) SOLUTION : (ABD) Fe and V NOF+e° 3? FRegetion =0.96V Fe ucion OF (i), (ii) and (iv) is lesser than Check the reduction potential of the given metals and Ee aucion fOr NOF compare it with that of NOJ reduction. So, NOF will beable o oxidise V, Fe and Hg. So, pairs are V and Fe, V and Hg, Fe and Hg, [DEES ih ting ccrcstonict cts been oop Pt (1) | Fe** , Fe?* (a = 1)|| Ce**, Ce** (a = 1) | Pr (2) Ee A ECT STE TINT -61V 5 EP ay par = 0.77V) a@ increase or decrease with time? (E° 4s yo,3+ Seti study Course for HEE wih Onne Support TOT 1:Electrochemistry - | CCCUR mcd SOLUTION: Forthe electrochemical cll Since E%gis positive, the cell reaction will be PU (1) |Fe**, Fe** (a= 1) 11Ce*, Ce (a= 1) 1 Pt(2) spontaneous. ‘The clectode reactions ares follows: The curent in the circuit wil owe fom P 2) (hie serves as cathode) to Pt (1), which serves as anode. Right half cell: Ce +e" —> Ce (Reduction) ‘With the passage of time, EMF ofthe cell will decrease Lefthalf cell: Fe"*—— Fe** + e7 (oxidation) ‘and so is the current in the circuit Celleaction: Cet + Fe* —> Col + Fe ‘Note: Current in an electrochemical cell lows from cathode to anode where as the electrons flow from anode to ‘The net cell potential is pee Efe = (Bjedution atade ~ (Exeduton node =161V-0.77V=084V NERNST EQUATION Section - 2 Effect of concentration on EMF of half-cells and on EMF of a cell (a) Foran electrode M(s)/M™ (cM) —_€ concentration of electrolyte It acts as oxidation electrode (i.e, as anode) ; M(s) —+ M"* (c M) + ne-, then its oxidation potential E(M/M™ at 25°Cis given as 2.303 RT E(M/M"*) Log10 Qoridation 1059 A tosio Qoidnion (28°C) Es(M/M™* @ (a1: numberof e(s) transferred & F= charge on 1 mole electrons = 96500C) Where Quay! Faction coefficient of oxidation half reaction and is given as | gga aM oxidation where [ ] denotes concentration ; ‘a’ denotes activity (ii) If it acts as reduction electrode (i.e., as cathode) : M™* (¢ M)+ ne~ —+ MG), then its reduction potential E(M™/M) at 25°C is given as E (MM) = B(M™/M) ~F— Logyo Qredecton 0089 F180 Qe (225°C) E (MP /M) = E°aM" /M) ete gan #0cton coefficient of edution bat ration andi given as ow 1M) er Me] ‘We can see that E(MP"/M) =-F(MIM™) zy ST Qeedation