Unit Electrochemistry a ‘his Unt, you willbe able to: a0 in pmical col and serena between . cells; Sen and cece secaton for ctelating the emt of galvanic coll ee i alc cl 5 vraton beeen standard potential of e cl and bs + cl acon aes equi constant Ladner) conaucvty (and motarconductiy(N) nic solutions: + ratte ccanductvty, between ionic (electrolytic) and electronic -y ela corosion as an electro-chemical process; the variation of conductivity and molar conductivity of | sons nth change in their concentration end define, A° (molar ‘anducty at 70 concentration or infinite ciution ‘+ enndate Kobrausch law and leem its applications; + understand the quantitative aspects of electrolysis; i ‘nscibe the Gonstruction of some primary and secondary ‘teres and fue! cals. Eel INTRODUCTION It is a well known fact that energy menifests itself in different forms which are interconvertible into one another. Among different forms of energy, the electrical energy plays a very significant role in our daily life. Many chemical transformations and industrial processes are based on electrical energy and its relationship with chemical energy. There are large number of spontaneous redox reactions which form the basis of production of electrical energy. The device in which such chemical processes are carried outis called electrochemical cell or galvanic cell. For example, Daniell cell is based on the following redox reaction Cu2*(aq) + Zn(s) —— Culs) + in + Electrical Energy ‘At the same time many of the non-spontaneous redox reactions can be made to occur by the use of electrical energy. Some examples are: 2,00", Hy) +06) Electricity, 2A1,0,() ——> 4Al + 80, _——— een oma Scanned with CamScannerssociated witl transformation GALVANIC CELLS The process a rh such : is called ‘Electrolysis and the device used for electrolysis: is called ‘electrolytic cell. The device in which chemical, The branch of chemistry which deals with the into electrical energy is called ealvany atudy of relationship ‘petween electrical CneTEY and name of Luigi Calvan? or electroeh, a chemical enerey and interconversion of one form ol voltae el (al we the name of Alessang, ical a i re eiletry. — Babvamioes | a redox reaction is carried gat? Yin, energy into another 18 called .electrochen- galvanic the decrease i fi don Blectrochemistry is very caleand interdisciplinarY chemical na ne made to free ener ain, i finds tremendous mica’ Pl le to appear as elect Mi! branch of chemish which fn as i usm indirect redox reaction is such th ectriegh Be applications. Its study i8 VO" important as it helps in oxidation processes are ion is such tha rei development of ne technologies which are re nomical —norder tounderstand this Tenant SeParte it we shall focus the "in_-CuSO, reaction as the basis ort Su In its simple form, a zine strip ion : ipped jn ® f electrochemical cells, conductance and REDOX REACTIONS solving oxidation and called redox reactions. the process in which a Chemical reactions inv reduction processes are Oxidation may be defined as species (atom, molecule OF jon) increases oxidation riper by losing one or more of Teclnon ‘The substance rijengoing oxidation is called reducing agent. Reduction, on the other hands is ¢ process in which a species (atom, molecule oF jon) decreases oxidation rember by gaining one or more elector The species undergoing reduc! Neither oxidation nor reduction oP .s and occur side by ‘These are complementary processes side, Redox reaction can, thus, be termed as the chemical reaction involving transferrence of Slectrone from reducing agent t0 oxidising agent. Some examples of o dats) + Cu*(aq) —> Reducing idisi ‘agent redox reactions are aS follows: nt (ag) + Culs) agent ° os) os {00 + 10HNO J) —> 2HIOs + 10NOz + 4H,0 Reducing Oxidising ‘agent agent Redox reactions form cells and electrolytic cells which this chapter. he basis electrochemical are discussed later in x80, solution and a copper strip isd Ziution taken in soparate giribis dipped ints Strips which act as electrodes are conan? Bey senducting wires through a voltmeter. The toes grejoined by an inverted U-tube known asselne The U-tube is filled with the ‘solution ofsomecte™ The Uae KCI, KNO, or NH,ClI to which cht ch a has been added to convert it into sgalte paste, A sohematic diagram of this cell has been in Fig. 3.1. Shon ‘The deflection i tial difference .n voltmeter indicates that th js a potent .e between the two lectrdany has been found that the conventional CUITent fy has on the outer eirouit from copper (0 zine strip nities that the electrons flow occurs from zine top per strip. Let us now understand the working of the cell ) Zine undergoes oxidation to form zine ions Zn(s) —— Zn?*(aq) + 2e- (Oxidation) ring oxidation ae trons liberated dw ecting wires (i) The ele igh the conn pushed throu; copper strip. (iii) Copper ions mo up the electrons, atoms which are d Cu**(aq) + 2° ——> Cu re electrode at which oxidation occu? and that at which reduction occurs is cathode. above cll, sine tip is anode and the copper striP ® cathode, Duo "Wo the nxidation process occurring at te oo eee ‘a source of electrons and acquites® ee the cell. Similarly, due to reduction ee eae at the cathode it acquires positiv® ctaresiend beomnee aoc of the electrons. Thus i® negative ery cell, anode electrode acts seeeize eeecina oa (entmoaa electrode acts Is copper strip, rit ‘and get reduced to Capps leposited at the copper st (s) (Reduction) s anode Inthe ve toward: Scanned with CamScannergolt Bridge and its Functions. Salt Bridge is a sauped tube containing a semi-solid paste of some inert Usbitae like KCl, KNOs, NH,Cl, ete., in agar-agar and strl inert electrolyte is one which: (@) does not react chemically with the solution in either of the compartment. (@) does not interfere with the net cell reaction. Function of Salt Bridge. In the electrochemical cell asalt bridge serves two very important functions: (lt allows the flow of current by completing the circuit. (i It maintains electrical neutrality, ‘The transference of electrons from anode to cathode leads to a net positive charge around the anode due to increase in the concentration of cations and a net negative charge ‘ound the cathode due to excess of anions in solution. The psitive charge around the anode will prevent electrons to flow ‘out from it and the negative charge around the cathode will prevent the inflow of electrons at it. The reaction would thus, ‘stop and no current will flow. The salt bridge comes to aid and restores the electroneutrality of the solutions in the two compartments. It contains a concentrated solution of an inert ectrolyte the ions of which are not involved in electrochemical Teactions. The anions of the electrolyte in the salt bridge ‘Rigrate to the anode compartment and cations to the cathode ‘cimpartment, Thus, the salt bridge prevents the accumulation charges and maintains the flow of current. In the ‘trochemieal cell, the salt bridge can be replaced by the Porous partition which allows the migration of ions but does ‘tallow mixing of the two solutions, Fig. 8.1, Electrochemical cell, REPRESENTATION OF GALVANIC CELL Galvanic cell is a combination of two half cells, namely; . ation of twohalf cells, namely; oxidation half cell ana reduction half cell. If M represents the symbol of the element and M' represents its cation (ce. its ‘oxidised state) in solution, then Oxidation half cell is represented as M/M™*(c) ‘Reduction half cell is represented as M™(c)/M. In both the notations C refers to the molar concentration of the ions in solution. Conventionally, a cell is represented by writing the cathode on the right hand side and anode on the left hand side. The two vertical lines are put between the two half cells which indicate salt bridge. ‘Sometimes the formula of the electrolyte used in the salt bridge is also written below the vertical lines. For example, zine-copper sulphate cell is represented as follows: [rece =T\ Pr Besson ew] zaven(1M) \ \ ANODE (-ve) CATHODE (+ve) ( cP (QM) icu Scanned with CamScanner118 ae Remember — ——_—_$_$_$__—— Th order to avoid confusion about the nomenclature of the electrodes and the process occurring on them, remember the word LOAN. Here, Li(leo; 0 (Oxidation); A anode; N Nesativd) ‘Thisimplis that lero represented on ef hand side involves oxidation acts a anode andis~ve termina of the electochemiea! cell. Onc this is known, the nomenclature and process cccurring on the other Legs arb ene la alee Keoukedge Plus —___— ‘VARIOUS TYPES OF ELECTRODES Some important types of electrodes which are frequently used in electrochemical cells are described 1s follows 1. Metal-metal Ion Electrode. Such type of clectrodes include a metal rod dipped in the solution of its own ions. Some examples are Zn/Zn*(aq), Aw/Ag*(ag), Cu/Cu*(ag) ete. 2, Amalgam Electrodes. These are similar to metal-metal ion electrodes, but here the metal is used in the form ofits amalgam with Hg. Amalgam is formed to modify the activity of metal. (Zn-Hg)/Zn**(aq) is one of the common example of this type. 3. Gas Electrodes. Such electrodes involve inert metal such as platinum dipped inthe solution containing } Comprchensioe Cus, 4 solution of KCL The concentration of Ag*j the tration of poet XC | tons contzlled bythe concentration ot Cl solt can be calculated from the knowledge of K,. op. follows. Kyp of ACI _ Kyp of AgCl (sl=—“Tory OKC ‘The electrode reactions are: Ag(o)+ OM(aq)—> ACL + Orda, AgOl(o) +e" —> Ae) + OG2) Redut, Another important example ofthis typeof 4, trois calomel electrode: He HesCh(SVIECH ag) yee electrode reactions are: aig() + 2CH(0a) — He,Cl0)+ 26 Orie Hg,Cl,(6) + 2e° ——> 2He() + 2C(ag) Reducin| 5. Redox Electrodes. These electrodes include, | platinum wire dipped in a solution of a mixture of yy | salts ofthe same metal having different oxidation statey ‘Some common examples are as follows: Pt, Fe#*/Fe™ Fe ——> Fe + e- or Feit +e" Fe* Pt, Sn*/Sn* Sn*——> Sn'* + e~ or Sn'* +2e-——> Sn**. eg ELECTRODE POTENTIAL When a strip of metal (M) is brought in conta {ons of the gaseous element. The arrangement is made in such a manner that gas and its ions are brought in contact at the surface ofthe inert metal. Some examples along with their electrode reactions are as follows: with the solution containing its own ions (M"), the either ofthe following three possible processes can ak place: Hydrogen electrode: Pt, H,(g)/H*(aq) H,— 2H" + 20 or 2H°+2e-—> H, + Pt, Ch¢gyCr(aq) 20r— Cl, + 20° or Cl, +2e-—s 2C- 4. Metal-Metal Insoluble Salt-Salt Anion. In ‘such electrodes, the metal and some sparingly soluble salt of metal is dipped in the aqueous solution of some other soluble salt whose anion is same as that of sparingly soluble salt of the metal. One of the common example is Ag-AgCl(s)/KCl(aq). Here, silver and sparingly soluble salt of Ag, ic, AgCl is put in aqueous Chlorine electrode () The metal ion M"* may collide with the metallic strip and bounce back without ay change. (i) The metal ion M% may collide with the sti gain n electrons and get converted into met! atom, i.e., the ion is reduced. M** +ne-—> M (ii) The metal atom on the strip may lose * electrons and enter the solution as M"™ iom ie., metal is oxidised. MM" + ne“ | The above changes have been shown in Fig. 82 | | } Scanned with CamScannerigi 32. Electrode equilibrium, © sox ifthe metal has a relatively high ter ee tre woul a aie ee pst i positive ions and pass into the solution. nto Pioat accumulate in the metal strip and ae rrodeveloP negative charge. The negative charge ti the strip does nt allow motal atoms to fe losing electrons but it would reattract the ions from the solution in an attempt to neutralise ele mately, stato of equilibrium will be uaara between the metal and ite Sons at the wate ete (etal str) (Solution) Gn metal strip) Sinilarly, ifthe metal ions have relatively greater tndency 10 get ‘reduced, they will accept electrons at fbestip from the metal atoms and consequently, a net sre charge is developed on the metal strip. ‘Ulti- Piely, asimilar equilibrium is established between the etal ions and the metal atoms at the interface. yer + new — iM (Golution) (From metal strip) (Metal) The development of ‘negative and positive charges cathe metal strip has been shown in Fig. 3.3 (a) and en: Negative charge con stip ‘Heita:@ pevetopment of ve charge on metal strip. 118) 3 ° 2° or 2 0°} O° 9S estes games coma ees (by De FT equiting ha cae, the separation of charge a She Aifference between te metal andthe aol potential and ie reratmenn the metal and the slusion fit fons ‘The exact poter aa Potential. depend ert tential difference atthe equilibrium depend on, the nature of metal its ions, the s Acordngtathe prevent UPAC convo half roastons are always writin as zoductiog ‘halt Tesetions and thir potentials represented by ent . It may be noted that: (@ Reduction potential (tendency to gain electrons) and oxidation potential (tendency to lose electrons) of an electrode are numerically, equal but have opposite signs. (ii) Reduction potential increases with the increase in the concentration of ions and dect- ‘eases with the decrease in the concentration of the ions in solution. ‘The reduction potential of electrode when the concentration of the ions in solution is 1 mol i and: temperature is 298 Kis called standard seduction potential (E2,) or simply standard electrode potential *)- In case of gas electrode, the standard conditions chosen are 1 bar pressure and 298 K along with 1M concentration ofionsin solution. (jv) The absolute value of B® cannot be determined because once equilibrium is. yeached between the electrode and the solution ina half cell, no further displacement Sr charges can occur unless and until it is Connected to another half cell with different Cfeotrode potential. Tia difficulty is overcome by finding the electrode potentials of variou: electrodes relative to some: reference electrod whose electrode ‘potential is arbitrarily fixe Scanned with CamScannerEee oe ‘The common reference electrode used for this purpose is standard hydrogen electrode (SHE) ‘whose electrode potential is arbitrality taken to be zero. 3.4.1. CELL POTENTIAL OR EMF OF THE CELL ‘The electrochemical cell consists of two half cells. The electrodes in these halfcells have different electrode potentials. When the circuit is completed the loss of electrons occurs at the electrode having lower reduction potential whereas the gain of electrons occurs at the electrode with higher reduction potential. The difference in the electrode potentials of the two electrodes of the cell is termed as electromotive force (abbreviat EMF or emf or cell voltage (E,qi)- Mathematically, it can be expressed as ; EMF = E,,, (Cathode) — Eyqq (Anode) or simply as Eee = Ecathode ~ Panoae Since in the representation of a cell, the cathode is written on right hand side and the anode on left hand side, therefore, EMF of a cell is also sometimes written ated as, EMF = Epigut ~ Even = Ex Ey, EMF of the cell may be defined as the potential difference between the two terminals of the cell when either no current is drawn from it. It is measured with the help of potentiometer or vacuum tube voltmeter. ‘The EMF of the cell depends on nature of the reactants, concentration of the solutions in the two half cells, and the temperature. The EMF of the cell at the standard state conditions is called standard EMF and ‘can be calculated from the standard electrode potentials of the two half cells. FEn= Faas ~ Phote 4.4.2. STANDARD HYDROGEN ELECTRODE (SHE) Standard hydrogen electrode (Fig. 3.4) consists of. platinum wire sealed into a glass tube and carrying a platinum foil at one end. The platinum foil is coated with finely divided platinum, The electrode is placed in beaker containing an aqueous solution of some acid having one molar concentration of H* ions. ‘Hydrogen gas at 1 bar pressure is continuously bubbled through the solution at a temperature of 298 K. The oxidation or reduction in the SHE takes place at platinum foil. Hence, it can act as anode as well as cathode and may be represented as: sical ite H, at298 K and 1 bar pressure {1M HCI Pt. foil coated with, platinum black Fig. 3.4, Standard hydrogen electrode (SHE), Pt, $H, (1 bar)/H*(. M) or H‘( M)/4H, (1 bar), Pt respectively, If SHE acts as anode then oxidation will tate place at it as He) > 2H°(aq) + 2 If SHE acts as cathode then reduction will tai place at it as (8) 3.4.3, MEASUREMENT OF STANDARD ELECTRODE POTENTIALS In order to determine the standard electrode potential of an electrode, the electrode in standard conditions is connected to standard hydrogen electrode (SHE) to constitute a cell. If the electrode forms the negative terminal of the cell it is allotted negative value of electrode potential and if it forms the positive terminal of the cell, it is allotted a positive value of electrode potential. The potential difference between the electrodes is determined with the help of potentiometer or vacuum tube voltmeter. At the same time, the direction of flow of conventional current in the external circuit is also noticed with the help of galvanometer. This helps us to know the positive and negative terminalsdf the cell because conventional current in the externil circuit flows from +ve terminal to ~ve terminal. Nov, the direction of the flow of electrons is opposite to that of conventional current. Since electron flow in exte! circuit occurs from anode to cathode it helps us to matt anode and cathode electrodes of the cell. a ee Knowing the E°, ,, and electrode potential of of the electrodes (SHE) a calculated, (SHE), that of the other ca! 2H*(aq) + 26 == Scanned with CamScanner# order to find o1 HePiT of zine electrode, ne electeode til gntration of Zn** ions connected the vcimrater reading shows the potential si Be ‘£0.76 volts. The electron flow is found 00 ine )etrode to SHE. From this it follows ne gnode while SHE acts 08 cathode. The gs acts 28 8 spat 2 Regction 18 st ay ‘+ a) —* Zn**(aq) + Hye) Be Ee 2 B2nt (pity ~ E°znt/2n, 0.76 te ~ E°anode 20 - E%ze? ito tits =~ 0-76 8OltS. sinilarly, whe? standard copper electrode is ia igE the voltmeter reading shows a co irene (E°,q) of 0.94 volts. The electron paemtound 2 OCCU From SHE towards copper Bo de, TberetOre, ‘SHBin this cell acts as anode and er 1et7O8e ores as cathode. The cell reaction is cnt (aq) + Hye) —— Cu(s) + 2H*(a9) Eqn = B°cathode EB snode = E®cot/cu - B°H* Hs 0.34 = Ercu/cu 0 equtrica = 0-84 volts- SHE as @ owing difficulties: Unity o js difficult to be maintained, 4 bar pressure of H, gas cannot be maintained uniformly, «The hydrogen electrode gets poisoned even if traces of impurities are present oe Thee difficulties some other electrodes ‘ealomel electrode or silver-silver chloride “dectrode, are used as reference electrodes: Calomel electrode. It is represented aS “ig Heyl aa) To ceca is eres swith | respect to Cl- ions and its electrode potential varies s atration of Clr ions or KCi(ad). At ® M tion of CI- ions its E° value is 0.2422 V- ver chloride electrode. Jeisrepresented = AgC\(s)/KCK(aq). It is also reversible w+. jeoncentration. At 1 M concentration of CIions ELECTROCHEMI We have seen combinations eee a different metal/metal potentials. The vari ferent values of electrode Pabelapeap nee ious Cie can be arranged in order of inerensing or deroasing values of thei ct tt i oe ar reducll order of increasing values of standard The Sia earial iscalled electrochemics Feomasel ‘ical series, also called activity series ‘ing of some electrodes alc 3 reduction reactions has oor rie vietle aan : en given in Table 3.1. APPLICATIONS ‘SERIES oF ELECTROCHEMICAL Some of the important applicati . nt ay ,tions of electro- chemical series are discussed eows! ag Bea 1. Comparing the Relative Oxidising and yong ‘Powers of Various Substances.’ ‘Substance “igher reduction potential have greater ‘tendency to undergo reduction. For example, F, has highest reduction potential which means it is most easily reduced to F- ions. In other words, F, is best oxidising agent. Li* ion, on the other hand, had lowest reduction potential. Hence Lit is weakest reducing agent OF conversely Li metal is best ‘reducing agent. Thus, itcan be concluded that substances with higher reduction potentials are strong ‘oxidising agents while Se with lower reduction potentials are strong reducing agents. 2. Calculation of Standard EMF of the Cell Eee) Standard EMF of the cell can be calculated by applying the formula BP, = B® (cathode) ~B° (anode) ‘The electrode with. higher electrode: potential «e) act as cathode ‘while that with Jower electrode ‘potential will act as anode. 3, Predicting the Feasibility of Redox Reaction. Blectrochemical series help to predict the feasibility of the redox reacti jn in a given direction. Im the species undergoing ely higher B° value than Jet us predict whether the reaction ‘gn + Gu* is feasible or not reaction Zn? ions are getting reduced oxidit This process will be feasible greater than Evcu*icu ‘put in fact, ‘V) isless than. E? cucu (0.34 V). Hence + (20 © annot oxidise Ou atoms: ‘Thus, the given Scanned with CamScannerComprehensive CHEMISTRY a, & 12 Mt + nex > M enst equation can be written in two ways. 4, Predicting the Capability of Meta) 10 Displace H, Gas from Acid. The chemioa! reve between metal M and acid to liberate Hy & represented by the reaction n M + nH*(aqg) —> M™ (aa) + He For the above reaction to occur, the E°ar't should be smaller than E°x i... Thus, all metals wing above hydrogen in electrochemical series can Libord Hi, gas by reaction with acids. On the other hanes mutal lying below hydrogen in the electrochemical so cannot undergo such a reaction. ® rasaledge Plus ——_——— {B Values and Thermal Stability of Metal Oxides ‘The knowledge of E® values of metals can help in’ predicting the thermal stability of metal oxides. A metal ‘with lower B® value (or higher oxidation potential) has relatively higher tendency of oxidation, which implies that it has more electropositive character and consequently; its oxide is relatively more stable. Example, E° values of Ba, Ca®*, Na’, Mg”, Alo are -2.90, -2.87, -2.71, -2.87 and ~1.66V respectively. ‘Thus, theiroxides are stable towards heat. The E° values of Ag’ and He are high, 0.80 and 0.86V respectively. Hence, their oxides are not stable and decompose on heating. Ba0, ease Het, No Decomposition Hg0 (6) B85 2Hg() + 0,(@) A019 Hes 2As(0)+ £0,@) NERNST EQUATION seer EQUATION FOR SINGLE ELECTRODE {thas been pointed out earlier of metal to lose electron or tendency ofitsione aaa electrons depends upon the concentration. of the ions sin solution. At the same time, the tendency to lose or aia Seohns is expressed in terms of electrode potentials, je value af electrode potential, therefore, changes with the variation in the concentration of the ions, Th quantitative relationship between the conventration ions and electrode potentials is given by N enor squation. For a general electrode reaction; the Ne RT nt eaten +e 1 Byerno = Baran +p} RT (M) = BPornn - FE or Beran "EO a In the present béok, only the first form ya used in the further discussion. Converting yyy tt logarithm (In) to logo in the first expression, we an 2.303 RT (Me) Ont we ee! ay Byers where; Eyyee;q = Blectrode potential Bryne = Standard electrode potential yy reference to SHE when con tration of M** is 1 mol 171 R=8.314 JK mol; T= Temperature [M"*] = Molar concentration of ions*; Number of electrons gained F = Faraday constant 96500 C mot [M] = Concentration of metal Substituting these values in equation (31) we get in) 2.303 x 8314 x 298 + log (M) n x 96500 (M"'] (M1 In general, for any electrode, 0.059 log [Oxidised state] SB [Reduced state] Jt may be noted that while using the Nem eauation, the concentrations of solids, ice., [solid] chen a unity while concentration of gases ressed in terms of thei rit po ‘ir respective pa Bygeeg = E°asiat 0.059 = Eee yg + log Brea =E*,.4t lB ee Gctivities of various species should be used its respects eee activity ofa gas is assumed to bee! falay Gee a Partial pressures and that of aqueous i its molar concentration per litre. The deta! ‘ussion of th ratio book, ‘© concept of activity is beyond the scope of Scanned with CamScannerTnerease (@) Tendency for oxidation to occur (®) Power as reducing agent Oxidised Form +ne- —_, a EP, qq(volts) li Liad+e cagneed Form K Req) +e, Km) Ba Ba?*(aq) + 20° —_, age) Ca (Ca?*(ag) + 26- — caw, Na Na*(aq) +> —s Nas) Mg Mg*(aq) + 2e~ Mgt Al Al*(aq) + 8e- ——5 Ale Zn Zn*(aq) + 2e- ——+ 2n(s) cr Gr**(aq) +8e- — cri) Fe Fe™(aq) +2e- ——5 Fe(s) H,00 +e" ——> J Hy@) + O(a) ca Ca?*(aq) + 2e- ——> Ca(e) ' Pb PbSO,(6) + 26° ——> Pb(6) +S0,2-(aq) ce Co Co*(aq) + 2e- ——+ Co(s) EY Ni Ni?*(aq) + 20° ——> Nils) ae Sno Sn**(aq) + 2e° ——> Sni6) q 3 Pb ‘Pb?*(aq) + Ze" ——+ Pb(s) 33 a2 [ Hy 2H +26 ——> H,(@) (Standard electrode) 0.00] § 5 z Cu Cu*(aq) + 2° —> Culs) +034 & & L I, +2e° —> 21a) +054 > Fe Fe (aq) +e" ——> Fe*(ag) +017 Hg He,?* (aq) + 22° —> 2He() oe Ag Ag*(ag) +e" ——> As) * ‘ e He Hg?*(aq) + 2e° ——> Het her N, NO,-+4H* +3e" ——> NOW) + 2H1,0 08 Br, Br,(aq) +2e° > 2Br(aa) * = +128 - 1,0 0, 0,(g) + 2H,0*(aq) + 2e° ——> 3Hs! 2 cats tae 20r%* + 7H,0 +133 Cr Cr,0,2° + 14H + ——? ney a, Clg) + 26° —— 2ci(aq) nae - Au(s) ” ‘Au*(aq) + 3° —— : ‘ . > Mn?*(ag) + 128,00 een Mn MnO, (aq) + 8H,0*(eq) + 5¢ +287 : (+200 > Fao Scanned with CamScannerd Problems Base Electrode Potential Pantene Le EY = Events anole or =E%q, (cathode) + Egg (anode) 2, For any electrode, Eya=— Bes ‘3, Foran electrode reaction at 298K Mer + ne M, The Nearnst equation is 0059 1,5 [Mt BeBe tomre il If EP, for copper electrode is + 0.34 V. ‘How will you caleulate its electrode potential when it isin con- tact with 0.1 M Cu** ions? How does electrode potential change ‘concentration of Cu** in solution is decreased? (A.L CBSE 2000) ; seyeg = EPeate rg 4 2059 joy [Cu] Solution. E°¢u/cu = E°cu**/cu + —>— log. [Cal [Cu] = 1; {Cu} =0.1M 2 Breaten) = Bat 100 + 2952 tog (cu?) = 0.34 +P t0¢ 0.1 = 0.3105 V. 2 If the concentration of Cu’? ion, (Cu**] is decreased, the value of electrode potential will further decrease. Calculate the E,,. of the following trode : Pt, Cl, (1.5 bar)/2 Cl- (0.01 M); Given that Feu jocr = 1.86 V. tion. The electrode reaction is Cl@) + 2e°-—— 2c" = poy 2059, {Cla} Boks") oe icre 0.059 Po, wr SP tog Pte 1.36 + 0.0295 x 4.1761 1,36 + 0.1231 = 1.483 Vv, TET OU ES NCERT INTEXT QUESTIONS -oo How would you determine 1, ‘electrode potential of the aystem Mg/Mgi"? Yo, Solution. The system MeME” ayo i consttuteg Mg rod in 1 molar aqueous solution of magnesiyn’ ‘The Mg/Mg* is then connected to standard hydrogens {H,(1 bax)/H*(1 MD} through vacuum tube = (or potentiometer) to observe the standard eng g yo (B? y= +2.87 V). ~ ‘The cell reaction is Mg(e) + 2H"(aq)—> Me™(aq) + 4) Bree = Eon, ~ E'Mg Mig ————— UFO or Bg /atg = (E°at tt, ~ E°cet) =-0-237 =~, Can you store copper sulphate solutin, zine pot? Solution. As E°zn**/zn (0.76 V) is lower than E°o,, (+ 0.34 V), therefore, Cu? ions can oxidise Zn to Zn ins, Cut(aq) + Zn(s) —> Zn**(aq) + Cu(s). Hence, Cus), solution cannot be stored in zine pot. Consult Table 3.1 and suggest thee substances that can oxidise ferrous ions under sti conditions. Solution. Ege is 0.77 V. Ions having B°ret vals higher than 0.77 V can cause Fe” to oxidise to Fe™ ion, To three such species are, Cr,0,2-/H*, Br,(aq) and Ag"(aq)- Calculate the potential of hydros electrode in contact with solution whose pH is 10. Solution. The reduction half reaction for hydrogen electro 2Ht(aq) + 2e°-— Hg) Applying Nernst equation, E= By one Jog (HP = 0+0.059 log [H*] PH=10 + —log(H]=10 or log {Hl E=0.059 10) =-0.59V. Scanned with CamScanner- L ‘ 5. Caleulate the 6 The standard electr 1. Atwhat pHT of HCI solution will 177 4 The standard reduction pote! dard electrode potential in vo ig? ation FeriFo =—04Vi Tome oat een? {Minin =+1.50 Memento relative stability of + 2 ana Cora stat of ion and Mi ~ © ice to meta is more casi omnia ly oxidised 1 reduction potentials of 1" yndatd Tag are respectively. 3.05 Vs + jucing capacity? : = 0.54 V; E°ro Fe) Pics isat) 201V nln, ood PPatn0y HIM?) od ct stones rida and reductant ‘oxidant and reductant ip Select weakest ig Which one of following is spontaneous? (oat + 2Fe* ——> ‘Sn®* + 2Fe™* fet" + Ip 2Fe®* +20" ga‘ +2 So" + Ip gait + Iz——> Sa +E nich ofthe following vessel! M solution ofiron (sulphate be stored? (9 Cu vessel Gin Alvessel pe they Cu? Wu, Btn Ton BP anal te OAV, +034 V,-0.70V.~ 1.6657 respectively. eduction potential of zine-7inc fon tleetrode in which the zine ion activity is 0.001 M. Given that B?2n2 zn =— 0-76 V- o @ (ii) Zn vessel Pogtt ou=0.34 V. At what concentra fins the value of electrode potential De zero? show a potential of -0.1 ‘Vv at 298 K, 1 ba pressure. No, + 2H" +" —— NO; (Calculate the eduction potential in 8 solution, (i) What will be the reduction potential cell ina neutral solution? Assume other species to be at unit Two half cell reactions of electrochemical fiven below MnO; (aq) + 8H* (aq) + 5° ——? Mn** (a) * aos =* 18 0.15 V concentratio Su? (aq) ——+ Sni* + 25 E9=* Se (A.L CBSE 1999) ‘ode potential of copper tion of copper tnydrogen electrode intial for the half cell ig) + 10 is 0-78 Mi rt of the half a. cell are Vv vo, nn ‘Soa inthe . Caleulate in he Catt porn fh ctr cel containing JOM Kcr, Wag. The hat ah oes oman LO m20F (aq) + 14 Haq) +e he neni in dete pi 1. Fe(tl > Feat, Mri (Mn ), Mn(II) > Mn(II1) 2 Li 3. (MnO; Sn*; (il) Sn**, BMn™; 4. Only in copper vessel. . hake 5. 0.848. 6. 2.98 101? M. 8. (@ 0.886V; (if) ~ 0.046 V. 9. E2y= 1.66 V. Formation of products is favoured. 10, 0.783 AWORK “OF LAXMI PUBLICATIONS | LTD. CALCULATION OF CELL POTENTIAL USING NERNST EQUATION Let us apply equation (3.2) cell potential of some galvanic cells 7. pH=30. for the calculation of 1 Zn/En* (aq) \\ Cou Cell potential = Eygthode ~ Pande = Et ica Batt it Ai) ‘Using Nernst equation for copper electrode =Pot 1059 jpg Eytrico = ‘cu? Co 2 Toa) similarly, for 2ine electrode ; aBPat 589g Bem fas +98 (dal substituting these values in @s ential Cell pot we cam 2 stro QP (Cad 959, (nt) erate al Scanned with CamScanner126 2+ = Bc? 1u ~ Bante an + 2982 tog (CH Wz] Beate icy ~ Etat an + 18 icgtzn} Since concentration of solids is taken to be unity [2n] = [Cu] = 1 {Cu} (an?) In general, for a redox cell reaction involving the transference of n electrons aA +bB—— eC +dD cge a ET jy (ARIBP Eon =E’n* ap" (cy IDI? Equation (3.3) can be simplified by substituting the values of R (8.314 JK“ mol"), T (298 K) and F (96500 coulombs) as follows: ye, 0.059 Cell potential = E%oy + 222? tog (8.3) 2.303 «8.314 x298 , (AI" (BI > 4 2.803 x8.314 x298 j,5 (AN (BT Fea = Bean yx 96500 (CI (DIF 0.059 5, [AI*EBI> Been = E'een tS 8 tet 3.4) While using equation (3.4), the following points must be kept in mind: (® Concentration of solids (metals) is taken to be unity. (ii) Concentrations of ionic species are taken in mol L-, (iii) Concentrations of gases are expressed in terms of their respective partial pressures in bar. The values of n, a, b, ¢, d are obtained from the balanced cell reaction. For example, let us consider the cell, Zn/Zn® || Ag*/Ag The balanced cell reaction is 2Ag"(ag) + Zn(s) —> 2Ag(s) + Zn?*(aq) Here, n=2 0.059, (Ag*}? (Zn) Een = E°, aa =.=. eat = Eee * 9 18 Age [Ag] = [Zn] = 1 Similarly, for the cell, AVAI* || Ni?*/Ni, the cell reaction is 2Al(e) + 3Ni2*(ag) —— 3Ni(s) + 2A5*(aq) Here, n = 6 269 (AT? Eon P (aly [Ni] = [Al] = 1. Comporchansive ree, <2 MY Kualedge Plus CERSERERTON Gas ‘The galvanic cells in which electrodes otal but they are immersed in the qa, different concentrations in two half cel concentration cells. The difforencs "* “le; concentrations of electrolytes in the two p,°7 ‘te creates potential difference across the tmy ct ‘The electrode which is placed in electrolyte gf f° concentration acts as cathode or + terminal, tte electrode which is placed in electrolyte gp concentration acts as anode or-ve ters 2" example, the copper ion concentration cell hee shown in Fig. 3.5. ye IT 6 Cy Imes Cu Rod, oe Porous barter Cu ion concentration cell. Fig. 9.5. ‘The cell can be represented as CwCuSO, (0.01 M) Ii CuSO, (1 MyCu ce simply as ‘CwCu* (0.01 M) | Cu (1 M)/Cu. Similarly, hydrogen ion concentration cell cas be constituted by connecting hydrogen electrodes lace! | in hydrochloric acid solutions of different concentration | It can be represented as Pt, H, (1 bar)/H* (0.01 M) jj H* (1 M)/H, (1 bar) Pe Bq, OF CONCENTRATION CELL Consider the concentration cel ofthe type MAN, (C)) IM*(C,/M. Since standard electrode potential | the two electrodes cancel each othe, the emf ofthe! can be written on the basis of Nernst equation a 3) Scanned with CamScannerProblems Baseq) lation of Cell Po : ee es pe cell reaction, For A+ bB—— cC + aD ving transfor of electrons, Bsroqstion a 208 canbe writen gg 0.059 jg (AP IB 2B gt ga Pont Crt ition of pure solids, liquids, oe stan to be unity ‘and gas at bay A voltaic cell is set up at 25% Decls,Ae*(0.001M)/Ae and Cu ‘oon, the write soltage ofthis cell. B° Cu, ‘t= 046 V are jon The given cell is ae atin cut" (0.10 80) IAs" (0.001 M/Ag (anode) (Cathode) sue at call reaction is ul) + 288"(aq) ——> 2AR(6) + CuP*(ag) ves the transfer of 2 electrons, Thus n = 2, ‘Nernst equation for the above cell reaction is te 059) (CultAg*?? Baa Beat ye Ga age Now [Ag] = [Cu] = 1 being solids. Aso Bq = 0.46 V substituting the value of E°,.y in (3.5), 0059 |, (Ag*? 46V + log 46+ Woe ie apitio the Ban 0.059 ,,,, (0.00117 0059 1, {0.0011" 2 010 6 46 + 2.959 jog 1x10 2 0.10 0.059 =0.46+ = 046+ log (1 x 10°) 1.46 - 0.1475 = 0.3125 V. ‘Agalvanie cell is constructed with Ag" /A& ‘Re elecrodes, Find the concentration of Ag” at which Seenff the cell is zero at equimolar concentrations of Fe" Fo iong, 1.77 V). (Bag iag = 0.80 V: EP eRe or 0.5086) = 0.5102 M. SOR INTER QUESTIONS Cateutae Teaction takes e iat the emf ofthe eli which the Nie) + 24g, i 002 M$ ne Glen hat aN seo Ht) Solution. The cell reaction is Ni + 288" (ag. 3 Here, NUN? elodrods ante tnd the hoe incatnelcT® NUN electrodes node and AA lcirode Applying Nerast equation to above system we have Hea Bg 088 f a agP INE .05 V5 (Ni) = [Ae] 002 M; [Ni*]=0.160 8, wi Here, Byy Be’) n=? 0.059, (0.0027 s Bay = 105 V+ 9 tog = 2 (a0) =094V. Represent the cell in which following reaction takes place Mg (6) +244" (0.0001 A) —> Ma** (0.180 0 + 2Ag (6) Calculate its By if Ean 217 V- Solution. As pet the given cell reaction, oxidation occurs at the MgiMe™™ ‘electrode. Hence, it ‘acts as anode, hares .duction occurs at yde. Hence it acts as cathode reduc the cells therefore, Me/Me" tL Agr/Ag electro represented a5 {0.130 MAK” (0.00001 MOAR Scanned with CamScanner