Electrochemistry for IIT-JAM|CSIR-UGC-NET/JRF|GATE TIFR| BARC | DRDO! SLET| NTPC | ONGC-GT | HPCL | Geo-Scientist | Ph.D. Entrance First Edition : June 2015 CAREER ENDEAVOUR PUBLICATIONS has taken due care in collecting the data and providing the solutions, before Publishing this book. laspite of ths, fany inaccuracy or printing erorsare there, CAREER ENDEAVOUR PUBLICATIONS owes no responsibilty. CAREER ENDEAVOUR PUBLICATIONS will be grateful # you could point out any such error. Your ‘suggestions willbe highly appreciated, © All right reserved by CAREER ENDEAVOUR PUBLICATIONS. No part of this book may be reproduced or utilized in any form without the writen permission from the publisher. ] Regd. Office: 28-A/11, Jia Sarai, New Delhi-16, Ph: 011-26851008, 26861009 E: publications@careerendeayour.com, W: www.careerendeavour.comCONTENTS PART-A (For IIT-JAM, CSIR-UGC-NET /JRF, GATE) Chapter 1: Electrolytic Conductance 01-20 Chapter 2: Electrochemical Cells 21-61 Chapter 3: lonic Equilibria 62-83 PART-B (For CSIR-UGC-NET/JRF, GATE) Chapter 4; Electroanalytical Methods 84-104 Chapter 5: Batteries 105-108Electrolytic Conductance Elecrolytic conductance: Resistance of any conductor (electronic or electrolytic) having length ‘? and area of cross-section ‘AVis given by é R maar ee ,P, = epeeific resistance ,} ] rasishy SL Unit ofRis‘Ohm’aidd F)'S-Ohmmeter",C.GS unit of Ris ‘Ohm’ and of pis Ohm For anclectrolytic solution, we generally use the teem feel constant” for \ The conductance (G) is the reciprocal of resistance, ie, \ je=t 4] w pel S.Lunit ofG is mho or Ohm™ or Siemen(S) ‘The specific conductance (i) of any conducting materials defined asthe reciprocal ofthe specifi resistance TT Saduckivity (2) [SL Unit of x= mho-m" or Siemen - m } From equation (1) and (2) - @) \ Equivalent conductances) For electrolytes itis convenient to define a quantity called equivalent conductance (A, ) representing “the conducting power (ie, conductance) ofall the ions produced by 1 equivalent ofelectrolyte ina given solution” Ven? 1 eq, of electrotyte lem Consider acell whose parallel electrodes are Lemapart and V cm’ of solution is containing leq. ofsolute A=Vonis /= TemElectrolytic Conductance Electre Conductance of this system, which is also equivalent conductance may be written ftomequation (3). as, v(om’) Ag = &{Siemen em!) ——* went ) (cm) a= YSiemen] 4) ‘Note: Jt must be remembered that equation (4) for determination of equivalence conductance is valid only when clectodes are unit distance a part (ic. !=1 em or m) and V is the volume of solution between the electrodes containing one equivalent of sofute in em or nt unit Ifeoncentration (c) of solution in equivalent per litres given, then we can write V (ex per equivalent) as, 1000 v= o Soln. Fromequation (4) and (5), [, _ «x1000) A, at [ham ¢ |) Siemen Where x in Siemen em unitand cin equitre” In. L. unit, «> Siemen m+, V—> m? pereqzand-¢ = eq-per. m* - pal fe “ef [ Nao= ZAe9, Jinee Ag =KV O) uy — ==) ! Molar conductance (A, Itis the conductance of } mole of solute If V,, is the volume in cm’ (or cc or ml) containing a mole of solite inside 2 cell of electrode seperation cm, then. in Where «= specific conductance of salute in Siemen em” unit & Vj, Siemen + ‘V,,=volume in em? per mole, Ifconcentration of solution isin terms of mole per litre unit, then A. can be written as [51000 Aw (9) InS. Unit: «> Siemen m7; V > m' per mole; c= mole per mv [Ay (10) Problema: For which of the following aqueous solution of a specific concentration the molar conductatice (A,,) and equivalent conductance (A, ) willbe same: (2) CaCl, solution (6) NaC} solution (<) MgSO, solution (d) K,[Fe(CN), | solution Soln, (b) For NaCIsolution concentration in terms of both normality (ie., no. ofeq)ltre) and molarity (i, no. ofimole/ litre) issame, ~ A,, =as lonly nthe as, lem, stance No. ne @ Soln. Experimental method for measurement of conductance: Let A, (or A.,) ofpuresolvent =x Siemenand A,, (or A,,) ofsolution ie. solute +solvent)= y Siemen A, (solute) = (yx) Siemen Similarly specific conductance or conductivity (k) of solute is found, Proble1 ek, The specific conductivity of a saturated solution of AgClat 25°Cis 3.41x10“Sca 0 sonton baa S. cu?. What isthe solubility of water is 1,60% 10° Sem". The molar conductivity at infinite dilution, vi AgClin water in moleflitre at 25°C. : cane | nn @ 13x10" (b) 115x107 (©) 1.15x10° @131x10° ee) The specific conductivity only due to Ag* and Cions (i.¢. only due to saturated AgCl)is, asp (Ase) = x(nectsa solution) (4,0) ] Koger: Ragulsa) =3.41x10 Sem —1.60x10 Sem" 81x10 Sem! Asthe solubility of AgClis very low. So, it can be assumed that, this small solubility (let C) sme as infinite diluted case.(°. Avy, agian = Agcl _1000%K Variation of condu: Fig: Equivalence conductance of electrolytes of different types Above graph shows that the conducting power ofions in one gram equivalent of any electrolyte increases with decreasing concentration. The figures approach a limiting value in very dilute solutions; this quantity is knowns the “equivalent condyc- tance at infinite dilution” and is represented by symbol A2,Soln, For strong electrolytes (rate of decrease of A., with increasing ‘e”) (i) uni-univalenat (eg. KC NaCl ete.) Stow (i) Uni- bivalent (K,SO,) and bi-uni (BaCl, ) Intermediate (ii) bi-bi(NiSO,) Fast So, as the valancy of the ons increases the falling of A, is more marked, Incase of weak electrolyte (eg. weak acids and weak bases). the behaviour of graph is much different wt strong electrolytes. Itis observed that at higher concentration, the A., is very low, which is characteristic of ‘weak electrolyte, but in more ditute solution the values rise with great rapidity. Relation between A, A’ and ‘c’ forstrong electrolyte (Koblrausch’s fav) for eid L oe Luntedfeyet Lot 1 Inanextensive series o( measurements Friedrich Kohlrausch showed that at low concentrations the molar ‘or equivalent conductivities of strong electrolytes vary linearly with the square root of the concentration, This variation is called Kohlarausch’s law, Where A? is limiting molar conductivity (Le., when ions are infinity apart and donot interact with one another): K+ Koldrausch constant (found to depend on the stoichiomerty of the electrolyte ie., whether itis of the form MA, or M,A, eto, than onite specific identity) Note: Kohlrausch’s law isnot valid for weak electrolytes, Problem: The limiting ionic molar conductivities of K* and Cl are 73.5 and 76.5 Son? mol", respectivley: If the motar conductivity of 0.1 M KCI solution is 130,0 S cm? mot", calculate the Kohlrausch’s constant for KClsolution, w Kohlrausch law for variation of A with conc (c). Aad -Ke Where \° =molarconductivity at infinite dilution K=Kohlrausch’s constant o(KCI 22° 429 A(KCl)=A), + ces A® =(73.5+76.5) Sem? mol! = 150.0 § cm® mot Given, A=130.055 cm? mol™ ‘Tra Ace tion The cati Tra Sir Par bec By De Hit anc Itf Ifee) cwaet, isticof e molar ion: nity is ofthe tivley. If stant for Ss Electrolytic Conductance pss a 20.1 M = 0.1 mote /1000 om? = 107+ MO aca om > => Fromegquation(1), Ae _ => Ket mmol te -150-K 107 Tra 130=150-Kv10 , 107 nol? om 32 yo = K=2000S em’ (mol) 2. Transport Number : According to Faraday’s fist faw of electrolysis, the number ofions discharged at an electrode is rOPO™ tional to the total quantity of electricity passed through the solution, hence it follows that Total quantity of electricity that cc sumn of the mobilities of the i passes through the sokation } cee ‘The quantity of electricity Na’ +CF +H1,0 + During the reaction highly conducting F{* are replaced by Na* which has auich ower conductance , so addition ofalkalito acid sofution is accompanied by a decrease of conductance.ance Electrolytic Conductance in 3 2 5 3 A é a pan nthe ‘i i nthe Vol. of alkali added > + When neutralisation is complete then the further addition of alkali results in an inctease of conductarice, since the sodium ion and hydroxyl ionare no longer used up in the chemical reaction. + At the neutral point the conductance of the system will have a minimum value. (b) Strong acid with weak base: When the strong acid is titrated witha weak base, e.g., an aqueous solution of NH,, the first part of the conductance titration curve representing the neutralisation of the acid and its replacement by a salt is very similar to previous case since both NaCland NH,Cl are strong electrolyte, however the conductance will remain almost constant when he end point is passed due to very low dissocition of NH,OH, (a! +l") +(NHj +OH") > NH; +Cl +H,0 ! 2 Ve i a aN | Vol of Weak bse —> (c) Weak acid with strong base: (CH,COOH + Na’ + OH" > CH,COO+Na‘ +H,0 + Weak acid (CH,COOH) has low conductance than its salt (CH,COONa), due to its lower dissocia- luce tion w.rt sal, so addition of base increases conductance (region ab in graph). ft + The reason fr initial decrease in conductance (region oa) is because smull addition of base leads to commion anion, ie., CH,COO> ion formation which represses the dissociation of CH,COOH which gives highly conducting H’ ions, ep + cia : 3 & ofa | Volume of tase added > 0 + After the end point there is higher rate of increase in conductance because Na* + OH" has higher conduc- tance than Na* +CH,COO* (region be in graph-1)(d) Weak acid with weak base: CH,COOH + NH,OH > CH,COO” + NH,’ +H,0 + Graph II, shows the titration of weak acid with weak base. + First two points of the explanation, is same as the above case. * The region p'c' of graphiis due to weak nature of base, so conductance remai addition of weak base after end-point, Note: (i) End point determination in case of weak acid with weak baseis easier than titration of weak acid with strong base because region ab and be of graph may have almost same slope (due to closeness in conductance value ofsalt of weak acid and conductance of strong base). (i Sometimes region oa an o'' are so small that itis not shown inthe graph. (©) Mixture of weak acid and strong acid with weak base: + [end-point is obtained when strong acid is consumed + 2» end-point is obtained when weak acid is consumed salmost constant with the Conductance —> S Volnt of weak base added—> () Mixture of weak acid and strong acid with strong base: Similar explanation asthe above case a. V : “ ‘Volo Song hase 0d —> Conductance —> (g) Precipitation reactions: . Type I: (a) titration of KCl with AgNO,: (kK #Cr')+(Ag* +NO;) > AgC! 4K" + NO; (b) titration of MgSO, with NaOH: Sola (Mg +SO{")+2(Na" +OH")— Mg(OH), ) +2Na° +80} + Inreaction (a) net result ig placement of Cl by NO;. Asboth Cl’ and NO; have almost same con- ductance so upto end point theres no change in conductance value, « Afier the end-point there is increase in conductance due to combined conductance of Ag*and NO; ionswith the ‘nd point 2akacid aaa Vola of titan AgNO, or Ni0H aed > + For reaction (b), same explanation as above ‘Type II: Ifboth products of the reaction are sparingly soluble. Example: Titration of MgSO, with Ba (OH), (Mg +SO7)+(Ba* +20H")-» Mg (OH), 4 +BaSO, 1 z cd pont Volm of B(OH) ed—> Here conductance of solution decreases right from the commencement, but increases after the end-point be- cause of the fie barium hydroxide, SOLVED PROBLEMS 1, Which one ofthe following conductometric titrations will show a linear increase of the conductance with volume of the titrant added up to the break point and an almost constant conductance afterwards. (a) Astrong acid witha strong base (b) Astrong acid with a weak base (c) A weak acid with a strong base (d) Aweak acid with a weak base. Soln, (a) 2. (a) The molar conductance of 0.012 mol dir? aqueous solution of chloroacetic acid is 100 9" em? mol The ion condiictance of chloroacetatgand HT ions are 50 Q°' cm? mol”! and 300.2"! em? mol", respec- tively. Calculate (i) degree of dissociation and pK, of chloroacetic acid, and (ii) H* ion concentration in the solution, (b) Sketch the conductivity versus concentration of base curves for the titration of aqueous solutions of acetic acid (i) with NaOH, and (ii) with NH,OH. Soln. (a) Concerntration of chloroacetic acid = 0.012 mol dx? ce = 100.07 cm? mol! : Dissociation of CH,CICOOH, CH,CICOOH —> H* +CH,CICOO™ Ay, = Conductance of Ht + conductance of CH,CICOO- = 50 + 309 = 350 07 em? mol!Electrolytic Conductance iectrol ‘Ag _ 100 Ac = 100.2" cm? mol!: “= y# ~ 359 286 Soin, §15x10~ 0.714 =13.74x10 log(13.74x10™ [log 13.74-4 log 10] =-[1.13—-4]=4~1.13 = 2.87 [it ]=ca.=0.0120.286=3.4x10" mol / dm? (b) (1) Weak acid with strong base: CH,COOH with NaOH 4 CH,COOH +Na* + OH" —>CH,COO” +Na" +H,0 . (i) Weak acid (CH,COOH) has low conductance than its salt (CH,COONa), Due to its lower dissociation ‘vert salt. So, addition of base increase conductance (region ab in praph) © Soln. a be end point Cone, of base (Gi) The reason for initial decrease in conductance (region(Oa)) is because small addition of base leads to ‘common anion ie. CH,COO™ ion farmation which represses the dissociation of CH, COOH which gives highly 5 conducting H' ions. . (iii) After the end point there is higher rate of increases in conductance becatise Na‘ +H” has higher con- dactance than Na + CH,COO™ (region be in graph). (2) Weak acid with weak base: CH,COOH + NH,OH—4CH,COO- + NH +H,0 Soln, (i) Weak acid (CH, COOH) has low conductance than its salt (CH,COONA). Dueto its lower dissociation Wart, salt. So, addition of base increase conductance (regia ab it graph). small addition of base leads to 1,COGH which gives highly (Gi) The reason for initial decrease in conductance (region(oa)) is becaus common anion i. CH,COO™ ion formation which represses the dissociation of condueting H' ions Cone. of base (ii) The region 'c* of graph is dueto weak nature of base. So, conductance remains almost constant with the addition of weak base after end point. ‘ The molar conductances at infinite dilution for BaCL,, KCl, K,SO, and Cl are 280, 150, 300 and 76 A" mmol" respectively. Calculate the transport number of Ba” in BaSO, solution at infinite dilution.ANCE Electrolytic Conductance Soln. Transport numberat infinite dilution for cation or anion is given by DATA An here,» =Stoichiometiccoecient ofion 2.= Toni conductivity. 0 i ; _ 1 _tfsincs=2her) Aner PA inner ner pat? = Mpsos Mien + e020 __BO=2x16__ 280152 _ 128 _g gsy 286+ 300 -2x15t 580-300 280 4. The mofarconductivity of 0.009 M aqueous solution ofa weak acid (HA) is 0,005 S mr? mot" and the limiting \ 7 inolar conductivity of HA80.05 S mf’ mol at 298 K. Assuming activity coefficients to be unity, the acid siation dissociation constant (K,) of HA at this temperature is: (@) Ix104 (ol (©) 9104 (@ 1.108 Soln. (a) \° =0.05 sm? mol! c= 0,009 m Ay = 0.005 sm?mol! Ay a="B=01 ate (0-1) 0.009 (1-0.1) shighly 5. Tf te transport number of Na” is 0.463 (dilute solution of NaClin methanol, the transport number of H” (Clute solution of HCLin methanol) s: . Forw k, =10" ir eak acid, ky “ee (Given, A® (NaCl in methanol) = 96.9 ohm? em? mot and A* (HCI in methaaol) = 192 ohn? em? mor) @ 027 ©) 0.46 (0.54 @ 0.73 Sol. (a), of Na* = 0.463 (dilute Solution 6f NaCl in CH,OH) baggy thu? 7 ziation es t, of H* (dilute solution of NaCl in CH,OH) =? seh ads to AP (NE 1) = 96.9 ohm“em“'mol highly ‘n (NaCl in CH,OH) wenn A‘, (HClin CH,OH) = 192 ohm ‘cm ‘mol’ t Nat = Ase") 463x96.9ohmem™mol AAG, (NaCl) Ag (HCI) — Az (NaCl) = (192-96 9) obm“em™ mol! =95.1ohm“tem'mol™ > AH’ <3 (Na" )=95100 Tem" Imol! > Ae 1H) =(95.1+0.46396.9) Oem ‘mot with - ee) (95.14 0.463%96.9)0"fem-'mol"! bed =—s7GC) onal = an ‘Az (HCI) 1920 'cm™'mol ——— - Correct answer is (d10 ‘Which ofthe following equations is correct? (2) Cond.=sp. cond. x cell constant (6) £q, cond.=sp. cond. x cellconstant (6) Cond. =ea, cond. «cell constant (4) Cellconstant= sp. cond /oond. Which ofthe following solutions of KCL has the lowest value of equivalent conductance? @4M (0)0.1M (©)0.01M (0.001 M ‘Which ofthe following solutions of KCthas the lowest value of specific conductance? Ele @1M 01M (6) 0.01 M (@..001 M __ Under which of the following conditions, conductanee, sp. conductance and eq. condutance are all equal? (a) 1000 cc of the solution contains | eq. of electrolyte (b) 100cc of the solution contains I eq. ofthe electrolyte (©) 10cc of he solution contains | eq, ofthe electrofyte (@) 1 ecofthe solution contains 1 eq, ofthe electrolyte Which ofthe followings the nits, coductance?s @) mbo Wren eniy ee) ko err! (a) mho om? IF, the equation A= sp. cond. *V, is the volume in ce containing 1 eq. of the electrolyte, V for a ~~ solution will be (a) ee )100.ce (©) 1000. (2) 10000 ce At infinite dilation, the eq, conductances of CH,COONa Chand CH,COOH are 91, 426 and 391 mho end respectivelyat 25°C, The eq, conductance of NaCl at infinite dilation will be A (ay 126 (b) 209 (391 (w 908 Tonisation constant ofa weak acid (HA) interms of A and A, is CAz CAL ccagy? K mn OK, = = K,= ~ (4) Noneofthese ORG a5 OK aaa Oka Sasa ONmeottiow A dilute solution of KC! was placed between two Pt electrode 10. apart across which a potential Ov ‘volt was applied. Which is/are comrect statement nt (Given molarconductivity of K* at ditions 96.5 Sent?mtot") Which is/are correct statement ? (2) Ionic mobility of K* is 10 cm’ sec” volt” (b) The speed of K* is 10“ cmsec™ (c) Distance travelled by K* is5x10* sec isSem — (d) The potential gradient is 10 volt cry Equivalent conductivity of Fe, (SO, ), is related to molar conductivity by the expression @A,y (b) A, =A, /3 (0) Ay =3A,, SAA = Ag! 6 ANSWER KEY cammnena| Quests J 7 Sd 5 Option [| (a) @ | ib) Questions 6 7 & 10 Option | (a) (a) (b) (a)“hapter 2] Electrochemical Cells e Introduction: . Electrochemical cells can be broadly classified into two cates, ve, eet ica an ns Voltaic) ces Ip the former, a chemical reaction (more precisely a Me) cane 7 ae gat oe 4m electrical current, whereas in the latter an electrical current is produced as q "ay get ih os oes chemical reaction Me Sp Electrode and Half Cell: ra e tio narod (or plate} oCcanductor material is dipped in the aqueous solution of ap ee “1 e ous Solutj tholyte, called electrode or haf cell. For example: Cuplat® dipped in the aqueou on get Olvte, Thesystem is electrode, "SO, constitutes an nthe basisof chemical reaction electrodes are oftve °NpeS - Anode: The electrode on which oxidation oocuts telleg anode ma + Cathode: The electrode on which reduction occurs {Lie clectnde which doesnt participate in chemical reactions, buts only the heyy, "> exchangeot electrons '8 called inert electrode. a Electrode potenti ectrical d 'en a neetal plate is dipped into the solution ofits own iat decal doa “eis developed onthe (Odlact surface of metal and the solution, Due to the oa tential dference Pa poe at ifference Trae leped on the contact surface of metal and solution. This potent Seay electro le potenti tistepreseated as E Standard Electrode Potent 25°C, the poten ionof, was at 25°C, ti ena metalrod is clipped in the molar solution ot eee A reps Strface of metal and solution i called standard electrode p Factors ON, d ag eee on the contact Affecting Electrade Potential: Concentation, lature of Metal (2) Temperature oe 8 votental \Sfohaign the basis of chemical reaction occurring on electrode, 7 e. The electrode por,° tYpes ‘xidation Potential: [foxidation occurs on theelectrode. The Potgy SPE Potential “Alis called oxidation OR uh 7 ‘ s called oxidation potential. It represent, {‘tidency ofan electrode to lose eleetronsis called 0 ecto, theelectrode por bye, ) Reguetion Potential Ifrediction ovcuts on the electrode, feny Potentia), "alis called reduction OR 1 re ential E,.4) pitty ofan electrode to gain electrons is called reduction po Ered “tion potential = - oxidation potential, “Presentation of Electrode Potential: M‘+e7—9MElectrochemicalCelis Elect Electrode Potential: Eyaj = Byeyi Box = =E Bret = Engg Lox =Errigt acting? ox Note: Standard reduction potential is accepted as standard electrode potential by IUPAC system. Some Common Types of Reversible Electrodes: 1. Metal-Metal ion Electrodes: A metal rod dipped in the aqueous solution of its own ioas is called metal-metal ion electrode, Forexample Cu rod dipping in CuSO, ac Zu rod dipping in ZnSO, solution constitute metal-metal ion type electrode. For the general half cell reaction, +ne"—=M(8) The electrode is represented as: Mls M(S) or MOS) Mea Cathe Ade 2. Gas Electrodes Inthese electrodes, an unreactive metal (Pt or Au) isin contact witha gas and its corresponding jon in solution. Hydrogen Electrode: It consists of platinumelectrode immersed in solution of H’ ions. Hydrogen gas is bubbled over the electrode and passes into solution forming 1" ions and electrons. Hy 32H" 426° The electrode is reversible w.rt. H' ion, Since H, gasis non conducting, Pt or some other metal which is not attacked by the acid and easily comes in equilibrium with hydrogen is used for making electrical contact inthe circuit The electrode is represented as: Peg (g)|H* OR H’JH,(g)Pt ae) Standard Hydrogen Electrode: Itconsbsts of Pt clectodsimmasedina | msohition of Hons maining’ at 25°C and | bar pressure. Hydrogen gas is bubbled over the electrode and passes into solution forming H* ions and electrons. Hp —32H" +2e The emfcorresponding to this electrode is arbitrarily assigned the value of zero and this electrodeis used asa standard for other electrodes. (abasic at (( baetioo kPa) lie posse z| alr ons There are two conventions in common use, arid the student shoul be aware of both methods of procedure, The standard hydrogen electrode can be either the left hand or the right hand electrode. In the convention adopted by the International Union of Pure and Applied Chemistry (IUPAC) the hydrogen electrode is placeleCu ition. sis resin ained eH dasa dure. ation place een a onthe ieft-hand side, and the emfof the other electrode is taken to be that ofthe cell. Such emf values, under standard conditions, are known as standard electrode potentials or scartdard reduction potentials and are given the symbol B°. Alternatively the standard hydrogen electrode may be placed on the right-hand side. ‘The potential so obtained is known asthe standard oxidation potential. The later potentials are the standard electrode potentials with the signs reversed; the only difference is that the cetfs have been tured around, 3. Metal Insoluble Metal Salt Electrodes: These electrode consist of a metal and a sparingly soluble salt of the samme metal immersed in a solution ofa soluble salt having same anion. (a) Calomel Electrode: It consists of Hg, solid g,Cl, anda solution of KCL. This electrode is represented as,Hg, He,CL(s), KCI (solution) Mercury of high purity is placed at the bottom of glass tube having a side tube on each side. Mercuryis covered by a paste of calomel (Hg,Cl). Asolution of KClis introduced above the paste of calomel through the side tube on right. A Pt wire sealed into a glass tube serves as electrical contaet ofthe electrode in the circuit ‘The reaction occured in the electrode is shown below: Hg}iig) + 2e —> 2Hat) Reduction Hg;Cly(s) = Hedy + 2C1" (aq) Thus incase of calomel electrode, the electrode reaction may be represented as, Hg,Cl,(s) + 2e7 = 2Hg(N) + 2C (aq) (b) Siver-Silver chloride Electrode: A silver wire coated with a layer of AgClisimmersed in thesolution of KCl or HClofknown concentration. This electrode is represented as, Ag, AgCl(s)|CI (aq) ‘This electrode is reversible wat-t Cl ions. 4, Oxidation Reduction Electrodes: It consists of'a unattackable (say Pt) electrode immersed ina solution of substance in two different oxidation states. The potential at the electrode arises from the tendency of the ionsinone oxidation state to change into the other more stable oxidation state.Electrochemical Célls Fe (aq) +e” === Fe** fag) Sn* (ag) + 26° <== Sn™* (aa) Cef* (ag) + &° = Ce (ag), ‘The function ofthe Pt wire is to provide electrical contact in the circuit. 5.aGlass Electrode:, Ags electrode isa type ofion-selective electrode made ofa doped glass membraae that is sensitive to a specific ion. It is an important part of the instrumentation for chemical analysis and physico- chemical studies. In moder practice, widely used membranous ion-selective electrodes (ISE, including glasses) are part of @ galvanic cell, The electric potential ofthe electrode system in solution is sensitive to changes in the content of certain type of ions, which is reflected in the dependence of the electromotive force (EME) of galvanic element sate Seema concentrations ofthese ions. Here exchange of metal ions like Na’, Lit etc. take place instead of H* ions. Range of a pH glass electrode: (pH 2 to 12), Complete realization of general clectrode function, where dependence of potential on pH has linear behavior and within which such electrode really works as ion-selective electrode for pH. 2.308RT, E=E°- pH Sign Convension for Electrode Potential: Ifoxidation occurs at the electrode when it is connected with hydrogen-lectrode, electrode potential ofthe clectrode willbe negative. Ifreduction occurs at the electrode, when itis connected with hydrogen electrode, electrode potential ofthe electrode is positive. For Example: When copper electrode is connected with standard hydrogen electrode, reduction occurs at copper electrode and the electrode potential (Ec, c,) of capper electrode is positive. Cufty + 26° == cus) Hy (g) = 2H) +27 When Zn electrode is connected with standard hydrogen electrode (SHE), oxidation occursat Zn electrode and electrode potential of Za(E,,.,, ) ismegative. [ Electrevior ‘the fhe tsat ode Electrochemical Cells Tab] Half-cell reaction Lit +e =Li Kt+e=K Nat +e" =Na Mg?* +2" =Mg Hy +26” = Hy +2087 APY 436° = AL 2H,0+2e =H +20H™ Zn* +36" = Zn ca(ni i +2e7 =Ca+4NHG 20, +2" +207 = HyC204 Fe? +20" =Fe opt se =r ca?* 426° =Cd Ag(CN); +¢ = Ag+2Cn ))#2e° = Cu+ 20H" Agl+e” = Ag+! sn7* +2e" =Sn Pb? +2¢" =Pb Cu(NHs), +267 = Co+4NHy Felt 43e° =Fe 2H +2e" =Sn AgBr+e” = Ag+ Br cu +e" Cu" n't 425° =8n"* AgCive =Ag+CI HgCh +20 =2Hg+2Cl” Cut +20" =Cu E -3.045 ~2.925 -2.714 -237 2.25 1.66 0.828 -0.763 0.61 0.49 0.44 ~0.41 -0.40 -0.31 0.224 ~0.151 0.136 ~0.126 0.12 ~0.036 0.000 0.095 0.153, 0.15 0.222 0.267 0.337 a tandard Electrode (Reduction) Potentials, T= 25°C: Half-cell representation uit |li K*|K Na*|Na Mg”* |Mg | Hy |Pt APY | AL OH |Hy [Pt Zn” |2n Ca(NH);*, NH [Cd H,C,04,H* |CO, [Pt Fe™* |Fe crt, cr?" | Pt ca?" |Cad Ag(CN), .CN™ | Ag OH, Cu(OH), |Cu F | Agl| Ag Sn°* |Sn [Pb Cu NH jf”, NH |Cu Fe [Fe Ht | Hy [Pt Br | AgBr| Ag cu", Cut | Pt Sn**,Sn?* [Pt CI | AgCl| Ag CI” |Hg2Cl, | He (Pt) cu" Cues — ElectrochemicalGells Electro ‘Ag(NH3); +e" = Ag+2NH; 0.373 ‘Ag(NHG); , NHs | Ag ' 02 (g)+2H,0+4e" = 40H” 0.401 OH” \0, [Pt ' Cut +e" =Cu 0.521 cut | Cu b ed 0.535 : Fe be = Fe 0771 1 0.789 Hg3* | Hg(Pt) 0.799 Ag*|Ag Bry (¢)+2€> = 2Br- 1.086 Br, Bry |Pt 0) +4H* +4e° =2H,0 1.229 H* {02 |Pt (CnOF +14" + 607 1.33 cr0F, CO, HT) Pt $Ch (g)+e"=Cl 1.359 cr \Ch|Pt Colt 0" =Ce* 1.44 cot, Ce | Pt Aw +3e7 = Au 1.455 Au |Au MnO4 +8H* +5e” = Mn?* +4H,0 1.51 MnO4,Mn?*, H* | Pt Co 46° = Co 1.82 Co™, Co” |Pt systemin which: (i) Two electtodes are dipped into a solution, OR \ (ii) Two electrodes are dipped into two different solutions and are connected by one another: ‘Types of Cell: (I) Electrolyticcell (2) Electrochemical or Galvanic or Voltaic Cell (1) Electrolytic Cell: The cell in which chemical reaction occurs by passing of current from external source is called electrolytic cell For Example: On passing electticity inthe Molten NaC, Naand Cl, gasare obtained at cathode and anode respectively AtCathode: Nat +e —>Na (Reduction) AtAnode: — 2Cl —— Cl, + 2e (Oxidation) Anode or Positive Electrode: Oxidation occurs at this electrode. It is positive electrode. Cathode or Negative Electrode: Reduction occurs at this electrode. I! is a negative electrode, (2) Hlectrochemica} Cell or Galvanic Cell: An electrochemical cell also called a vottaic cell ora galvanic cellisa device in which a chemical reaction occurs with the production of an electric potential difference between two electrodes, Ifthe electrodes are connected to an external circuit there results a flow of current. Which can fead to the performance of mechanical work so that the electrochemical cell transforms chemical energy into mechanical work.[ als | Electrochemical Celis urce wode anic snee ent. tical In this cell two electrodes are immersed in one or more suitable electrolyte solutions. One end of these two electrodes are connected by a wite and other end is connected by a salt bridge through the solutions of electrolytes. ‘When both the electrodes are externally connected, oxidation occurs at one electrode and reduction occurs at the other electrode. ‘The electrode at which oxidation occurs is called as anode. It is a negative electrode. ‘The electrode at which reduction occurs is called cathode. It is positive electrode. The reaction occuring at each electrode, i called as halfcell reactions. Examples: Daniell Cell, Dry Cell ete. copper (cathode) or i2e vig s826V ia een te vazey AtAnode: Zn(3) — Zafihy + 26° (Oxidation) At Cathode: Cubty +26 = Culp) (Reduction) —~ Overall Reaction: — Zn(s) + Cufisy == Zn?hy+Culs) ~Salt Bridge: It is a U-shape tube in which a semi solid paste of inert electrolyte like KNO, or K,SO, or NH,NO, or KClor NH,Cl or KCI with agar-agar or gelatin. (1) It complete the circuit and participate inthe flow of current. {Fhe ions move from one half cello other through salt bridge, so it maintain the electrical neutrally of sofutions in two half cells. : Note: The electrolyte which do not participate in the redox reactions are called inert electrolyte. ‘Types of Electrochemical Cell: Ifthere isa net chemical change. Such electrochemical cells are classified as chemical cells. There ate also cells in which the driving force, instead of being a chemical reaction taking place between electrodes and solute ions, is adilution process, Such cells are known as concentration cells. The changes in concentration can occur either inthe eketrolyte or at the electrodes. Example of concentration changes atclectrodesare found with electrades made of amalgams or consisting of alloys and with gas electrodes (eg. the Pt, H, electrode) when there are different gas pressure atthe two electrodes. Following figure showsa clasificaton ofelectrochemical cells. A subclassification of chemical and concentration cells relates to whether or not there isa boundary between two solutions. [fthere isnot, asin the cell. PUHJHCKag)AgCls)|Aga eee! pee Electrochemical cells ie = t a « [ nee | th ¢ Chemical cells Concentration cals = — s | | a Without with Blectrolyte ‘Amalgam Gas T transference (I) transference (2) concentration or aley electrodes(?) cells electrodes(6) | e —L_— i | | al F Cells in which Redox. Without With the chemical cells (3) transference (4) transference (5) ¢ reaction involves the electrodes Wehaveacell without transference. Ifthere is a boundary, as in the Daniell cell. The cells is known as a cel! with transference. If there is a potential difference between the solutions which can be minimized by use ofa salt bridge —and there are irreversible changes in the two solutions as the cell is operated. Representation of Electrochemical Cell: According to IUPAC, Galvanic cell is represented as: Za(s)| Zn™* (C,) |} Cu* Cy}iCu Fey =? shalfcell Cathodic half ell (i) Anodic halfcell is represented on left and cathodic halfcelton right. 1 (ii) Theemfor cell potential ofthe cll is written on the right ofthe cell. Cell Potential (Ecell): ‘The difference between the electrode potential of two electrodes (cathode and anode) is called cell potential. Ezai = Reduction Potential of Cathode Reduction Potential of Anode Fea = Eeathode ~ anode = Evghe ~ Eien Feo = Eeahode ~ Banos = Big ~ Eee This may be illustrated for the standard cell IIH (1 bar) | "(2 m) [Cu (1m) | Cu For which the emf (E®) is 0.3419 V. cu 203419. V = Exattode ~Fogate #03419 -0= 0.3419 V ‘The overallreaction is Hy + Cu* —+ 28° +00Cella, acell seofa ential, Thermodynamics of Electrochemical Cells and Nernst equation: (Gibbs free energy change and equilibrium constant): In general, for any standard-cell reaction associated with the passage ofn electrons and an emf of E°, the change inGibbsenergyis Tao apes | a Since this Gibbs energy change is calculated from the £° value, which relates to a cell in which the molalities are unity, it is a standard Gibbs ‘energy change, as indicated by the superscript. The same argument applies to any cell; ifthe emf is , the Gibbs energy change is TAG =-nFE 7 (i) ‘The AG isthe change'iti Gibbs ‘when the reaction occurs with the concentrations having the values ‘employed in the cell. A positive £ means that the cell is operating spontaneously with the reactions oceurring in the forward dection (e.g,, H, + Cu" > 2H" + Cu), andthis requires AG to be negative For any reaction aA+DB > y¥ +22 Gibbs energy change is given by ac=ac® varo( We) (are? ’ =nFE = -aFE® + RT én (pve) (are ar ,[ 112") po 2SOSRT 9 XVI fro(aner) On Pe Faroe »_o0s, [y] [zy on apts? ‘This relationship is known as the Nernst equation, AL 25% 2303RT o=B'- logk nF 5) = 230RT og k = RT pak oF nF AL2s*C, oo a Ifthe problem had been to calculate the equilibrium constant k for the process Hh +Ee* —s Ht +Fe* The reactions would have been written as Wee ott, E'=0 Fe +e" > Fe” E*=0.71V. And E°=0.771V, Inthis case m = Land 0771 0.771 = 0.0257 én K or fn TT 30.01 0.0257 And therefore, K=1.1x10"Soln: Soln, iq eee SOLVED PROBLEMS i Catcutate the equilibrium constant for the reaction. Fe’? +. CoM! Fe + Ce Given: Bb s4jqg08 14 Vand Be py = 0680 0.059 Feat =~ Ioaie Ke Bfgy = 1-44-0.68= 0.76 V 0.76 Ko= © 0.059 Ko = 76x10! i2.set4 L089 Itshould be emphasized that emfis an intensive property, so that in making this calculation we must not multiply the value of E* when the whole reaction is multiplied by any number, but free energyis 4, an extensive property. Fe" +e" > Fe B =0.771V AG? =—1.FE* joln. ‘2Fe”* + 2¢° — 2Fe™* EP =0.771V AG! = -2F.E° = 2G) Show that the potentials are additive for the process in which half reactions are added to yield an overall reaction but they are not additive when added to yield a third half reaction? M,—>Mf" +mye AG} =n, EiF M3" 4 nge—>Mp, yn oa Soin: M,=Mi" Mi" +M,#{(n;—n,)e AG} = AG} +AG3 sf Ifn, #n, #1n,, then E®,, are not additives > =nsthen 15 fn, When two half reactions E? are added to give an overall reaction, and the number of moles of electrons involved in each half reaction and the overall reaction is same, Calculate 2° for the process Cul +e > Cu making use of the following E° values: Oc Asdifferent number ofelectrons are involved in reactions (i) and (i). So, simple substraction willnot give E®.y 0341V * he Cu £) = 0.153 (ii) Cu +2e° + Cu So, we will use 4G" based method to calculate EB, Solu. Cu +e > Cat AG} =-nE}F =-1x0.153xF J mol" Cu* + 20° + Cu AG} = -nE}F = -2x0.341«F Fmot™ a 1 It FiCells | electrochemicalCetls | The reaction Cu* +e" > It follows that, E°= 0.529 V, 4.\_--Given the following £° values involving both a one electron and a two electron process, Fe? +e > Fe™ Be =0.771V 1, +2e° > 21 B'=0.536V Find E°,, for the overall Reaction emust 2e" £20 > 2Fe* +1, 2y'S Soin, 2Fe™ +207» 2Re™ “CO 1426 Sar 2) Asnet cell reaction is obtained by substraction of equation (2) from (1) and also both equation (1)and (2) have same number of electrons involved. ver So, |B =0.771-0,536=0.235 V 5 If Ef is standard electrode poteittial for Fe/Fe!? and E3 for Fe"/Fe"? and E3 for Fe/Fe”. Derive a relation between, E}, BS and By Son: Fe—-sFe*? +2e ~AGj =2E(F (1) Fe’? 4 Fe¥ +e (2) Fe—FeF43e a0} =265F B) Susbstracting equation (1) from (3) Fe 5 Pe +e -AG} = AG} - AG} (4) ESF =3E3F-26;F 2Ej + 3 ectrons 385 =267 +E} / Calculate the emfof the cell, gen told de Co | Co” |j Ni*|Ni Uyet dae oe tl Ifthe concentrations are : (a) [N@*]=1.0m and [Co] =0.10 m (b) [N#"]=0.010 m and [Co*}=1.0.m ve Bi, Given that, Byy2ejyq=-0257 V and Bo,2r4¢5 =-0.280V Soin, The cellreaction is Co +Ni** > Co 4Ni Halfcell reactions areSoln: AB. Soln: Soln. ie) ee ee Nit 42e° Ni BP = 0.257 V Co 420° Ni BP 0.280 ‘The standard emf (E°) is thus ~0.257 - (0.280) = 0.023 V, and n=2. The cell emfat the first concentrations species (a) is ~00n3 °F go 10= 0073+ 0630-00053 V ams, 10 E 23 -———In~ Soin: nb, 0 TO o10 0.023 - 0.059 = -0,036 V We see that the celf operates in opposite directions in the two cases, AL2S°C, the free energy of formation of H,0(1) is -56700 cal mot" with that ofits ionisation to (H* + OH) is 19050 cal mot". What is the reversible emf of the cell at 25°C? Hi, (1 atm)| H" |] 0, (g)(Latm) |OH i +40,- 3,0 [)) AG, 56700 cal/mo} 7 H,0-—+H" +OH- AG, = 19050 calmot Addition ofabove two reactions gives, net cell reaction Heb 2 ), 3H +O AG =~$6700 + 19050 = —37650 cal mol"! = -158130 Joule mol’! AG= AG _ 158130. =o gigy nF 296500 Aine electrode is dipped in. 0.1 M solution of Zi$O, at 25°C, Assuming that salts dissociated to 20% at this dilution. Calculate the electrode potential. £7.22, =~0-76V Zn Za" 4 20 Concentation of (2n'2} = 21% 20g s 100 0.059 oct oe olen") Soln. 0.039, 0.120 0.059 (0,76) ~ 2952 joy 0120 «9 75 0059), oy 00 eae Caleulate the emfofthe fatlowing cell at 25°C Pt|Br—(0.01 M) | Br, (1 atm) j) H* (0.03 M)] H, (J atm) | Pt 2. 7 + é ‘ Given: ye = 1.08 VE , ‘ Cellreactio 2B +2Ht —> By tH, Eon = Eeuts ~Elas Ee Bliyogen 7 €1 Soin: =0-1.08 V=~1.08V[ cae letotomlal Cot © 0.059, Pay Px, Batt = Bee ——— log 2 Be Pury ations a = 1.08". jog _1__ = 1.03 -0. 208-1288 A 2" 0.03)" (0.017 10 gi the emfofeell UL Pt|H,( aim) | CHyCOOH (0.1 M)|| NH,OH (0.01 M)| Hp (i atm)| Pt K, for CH,COOH = 1.8 « 10%, K, for NHOH = 1.8 x 10% 2 Soln: AtL.H.S, (CHyCOOH——> CH;COO™ +H” ba teh ny Ky 5 5 3 -1 (Hela) CS = YRC = 810° 0.1 1.342107 mol ie -OH) ACRES. NH,OH NH] +OH Hoa cK = fe= eos 3 “1 e eof KyC = 1.8% 107 «0.01 = 0.4210 mol litre (HoH ]=10"* jet 1 4 [Ht ]= = 235910 mol litre 8a2x10 Now, forcell, AtLHE Gin +e AtRHE Hereby Been Bay og ee. (H ene ee 0.059, 134x109 0058 jgg LM 107 9457 vote 1 2.35x10" 11° Forthecell Mg(s)/ Mais) Il Agfiq) | Ag(s), calculate the equilibrium constant at 25°C and maximum work that can be obtained during operation of cell, ‘MgiMe vt = 42.3 7V and EY. 9 = 40.80 Given: & etig Son. Mg+2Agt—>Mp”* + 2Ag Beal = Ey 0 oo . ier’? * Eagtiag = 237 +080=3.17 V Wyax = AG? =—nE°F = 23.17 96500 = 6.1 «10° Joule =-6.11%10? KI 12, Consider the reaction: 24g + Cd —> 24g + Cd", The standard reduction potential of Ag'—Agand Cd” Ci couples are +0,80 and -0.40 volts respectively (a) Whats the standard cell emfE°? (b) Will the total emf ofthe reaction be mole +e or ~ve, it cone. of Cd is 0.10 M rather than } M? Ely =0.80~(-0.40)=1.2V Soln: (a) For 2Ag*+Cd—>2Ag+Cd >(b) Eee he 7 Ifconcentration of [CJ isreduced, the value of E, will increase, So it witl become more positive. Cases of electrolysis Electrolysis of Aqueous sodium chloride solution : ‘Two oxidation and two reduction half reaction must be considered. Oxidation: (A) 2C/)- —+Cl,(g)+2e", -B° =-1.36V 2H,0(£)—»0, (g)+ 4H" +4e" -E° =1.23V Reduction: (C) — 2Na* +2e° —42Na(s), =-27iV (D) — 2H,O(¢)+2e° —+H3(g)+20H" E’=-0.83V + Electrode potentials of (A) and (b) are quite similar + Exact values depend on {CH in (A) and [H" in (B), in concentrated NaCl solution. (A) is favoured. Ifitis quite dilute, (B) is favoured, + The observed product at the anode, however is Cl,, not O, because of overvoltage. Experiments indicate thatthe applied voltage required is always required i always greater than the voltage calculated from the standard oxidation and reduction potentials. The additional voltage required is the overvoltage. + By E° values of (C) and (D) it appears that reduction of water may take place much more readily than that of Na’. However, if liquid mecury is used as a cathode, reaction (C) is favoured due to the solubility of sodium metal in liquid mercury and due to the high overpotential of hydrogen on mercury Electrolysis of water (acidified): Dilute H,S (0, is added to water to increase conductance. Attheanode : 2H,0(£)—+4H,0(¢)—>4H" (aq) +0, (g) +4e" At the cathode 4H,0(€)+4e° — 40H” (aq)+2H, (zg) Electrolysis of aqueous CuSO, solution: (a) With inert electrode (Platinum) Soin: Atthe anode : 2H,0(€)—+0,(g)+4H"(ag)+4e" BY =-1.23V At the cathode 2Cu* (aq) +4e” —>2Cu(s) +0337 Net electrolysis reaction is 2Cu" (aq)+2H,0(¢)—> 2Cu(s)+4H" (aq)+02(g) Eley = -0.89V + This the principle of clectrocyplating. Copper metal is berated is at cathode, + Due to electrolysis, blue colour ofthe solution gradually fades, ElectrochemicalCells Electroc (i omi | ile | i (b) With copper electrodes: Attheanode Cu(s)—>Cu* (aq) +2¢" At the cathode Cu?* (aq) +2e" —>Cu(s) ‘The net electrolysis reaction is Cu(s)—Cu(s) anode cao + Onlya very slight voltage is required for this electrolysis for every Cu atom that enters the solution at the anode, a Cu’* ion deposites as a Cu atom at the cathode. + All tha happens is that copper is transformed from the anode to the cathode (as Cu through the solution). The solution concentration remains unchanged. + This makes the basis of purification of metals called refining (by electrolysis) + Inmany cases the voltage necessary to bring about a particular electrode reaction may exceed, We calculate theoretically, interaction called polarisation may occur between the electrode surface and the species involved in an electrode reaction. An over potential is voltage in excess of that calculated to electrolyse, ee Faraday's Law of Electroly ont Faraday's Ist Law of Electrolysis: ‘The mass of'a substance altered at an electrode during electrolysis is ml directly proportional o the quantity of electricity transferred. that clectrode. Quantity ofelectrcity refers to : : the quantity of electrical charge, typically measured in coulomb, s th Faraday's 2nd Law of Electrolysis: For a given quantity of electricity (electric charge), the mass of an othan elemental materialaltered at an electrode: directly proportional a the element's equivalent weight. The equivalent o the weight of substance is its molar mass divided by an integer that depends on the reaction undergoneby the reury. watetial Soln: ‘The following galvanic cell was a|20NOs)2 |Cucno; aa} ca 100 oni 00 ml, IM operated as an electrolytic cell using Cu as anode and Zn as cathode. A current of 0.48 Amp was passed for 10 hourand then the cell was allowed to function as galvanic cell, What would be the emfof the col at 25°C? Assume that only electrode reaction occurring were those involving Cu/Cu and Zn/Zn", cuioe ota Initially electrolytic reaction wil take place, which is reverse of spontaneous cell reaction, Given E; = +034 and BS, 22, =—0.76V W _ 0.48 106060 E 96500 Mole of Cu”? formed = Moke of Zn"? deposited= 0.09 =0.18 or milli mole of Cu formed = milli mole of Zn” deposited= 90 auilli mole of Zn” left= 100 x 1-90 = 10 milli mole of Cu” left= 100 1+90 = 190 Both are present in 100 ml solution of each, Reaction after ten hours, Zn(s) + Cu"? (aq) —>Cu(s)+ Zn (aq,) ° " 0.059, (cw 0.059, 190 4 137 vol Beat =E para? +E gyticy tg P80 gy = 07640344 Slo .0 Fy =1.137 voltElectrochemical Cells Electrochem Relationship between Electrical Energy and Enthalpy of Cell Reaction: " nd From Gibbs Helmholtz equation te Relati AG=-aF Bay Ifeot =nF By = AH 7[ Pa Ifeon ar lp eon eon ° wont Equat! Or, Activi ‘Temperature Coefficient ofa Cell emf and relation with AS, AHand Cp. Cons From themodynamic relationship Bylt aG = VadP Sat At constant P dG =~SaT Or, and. Or The enthalpy change, AH = AG+TAS Or, JAH = —nFE egy + ver| | a , iT Cor 14, The emf ofthe cell Cd, CaCI, 25 H,0 saturated || ACIG), Ag in which the cell reaction is Cals) + 2AgCUGs) + 0g ——+ CAC, 52H O(sat) + 2Ag(sp is 0.6753 volt at 25°C and 0.6915 volt at °C. Let Calculate the free energy change (AG ), Emhalpy change (AH) and entropy change (AS) for the cell reaction at 25°C, The Soln: Free energy (4G) = -niBP = -2 96500 0,6753 = -130.33 KJ ro We have, cha Me (2) -{ 95195V~0.6753V) __6 ogg6s VK! a)p 0-25K 4 Or 0.6735= 4, 298-0.00065) 296500 re AH = -167717 Joule = -167.72 KIsella Electrochemical Cells HH And AS= =1238 5K" T Relation between activity, activity coefficient and concentration terms: Ifeoncentration isin terms of mole fraction (x) WX @ concentration is in terms of molarity (¢) a= Tee Q If concentration is in terms of molality (mi) Aq = Ym mM @) Equation (3) is the most common way to express activity. A ity Coefficients of Electrolyte: Consider the dissociation of auni-univalent electrolyte , M4—*M* +4 By kaw of chemical equilibrium. 2) aya = activity ofelectrolyte MA 4,0 = activity of Mion tivity of Aion ‘Theactivity is related to molalityas a= ym yg = YMA Matte Aye Vag Myer Oye VM --Q) Or G) Activity and Mean lonic Activity of an Electrolyte: Consider the dissociation of uni-univalent electrolyte MA MA== M*+A 10°C Let activity ofcation (M’) vation a. = activity ofanion (4) The activity ‘a’ of an elctrolyte is givenby a Activities of cation and anion is indeterminable. Since it is not possible to have ions exclusively ofone charge present in the solution. Hence mean ionic activity and activity coefficient are to be considered. ‘Meanionic activity = (aya)? (2 a=@)\@_)! =(,)") or Baaana Foranelectrolyte 44,I Electrochemical Celle Electn MyAy SPM” 4 yA” a=(a,(a_)” If m=mohility ofelectrolyte. Therefore, Molality of cations (m,) = xm Molality ofanion (m_)= ym but a= ym_=y_ym a= (yan) (ym ary raY mye Here, (yy =," Example: (i) K80,—>x=2,y=1 a= xt x(ygm) t= 4 (yemy (2) KCL—sx=1,y=1 et a=1 x1! x(yem) mi) (3) BaCl, —>x=1,y=2 2 aol! x2? x(ygm)h? =4 (ram)? (A) Al,(80,),—>x=2,y ? 333 x (yg) 108 (ym)? Note: The activity coefficient ofeach electrolyte at infinite dilution is taken as unity For dilute solutions, concentrations are taken as activity. Tonic Strength (1): The ionic strength ofa solution is a measure of the electrical intensity due to the presence of ions in the solution. It isgivenby 2 mp2? + mz? myzh mg 23 + Mz ton Where mg, m..... ate molalities and 2;,29, 2..... are the charges of variows ions inthe solution. for asingle electrolyte, For example NaCl, totfm zh m2 2 Where m’ and nr are molalities and z,,2_ are the valencies of Na* and Ct-respectively. 1s, For K,SO, solution of molality m, Soln m,=2m, m_=m (Ky, —> 2K" +807) mad sn [2me2 + m22|Interionic Attraction: The ionic atmosphere: Debye-Huckel Limiting Law (DHL) The possibilty that the attractive forces between ions might have some influence on electrolytic conductance, especially with strong electrolytes, was considered by Debye and Huckel. The essential postulate of the Debye-Huckel theory is that every ion may be considered as being surrounded by anionic atmosphere of opposite sign. ‘The thickness of the ionic atmosphere is given by Debye-Length (4p): ( 4 (ege, kT 1) oS 2 x IN 1 Where, €, = dielectric constant ofthe medium. €y =permivity of free space. e=charge on electron. k, =Boltzmann constant lo I=lIonie strength ofeletolyte solution =3,5 CZ (Where C, “oncenttation of ion in molality unit and charge on ion.) Mean activity coefficient is given by | log(y,) =—-A|z,z_|I" lution. at 25°C, A=+0.509 (for water) log(y;)=~0.509| 2,2. |? 15. Calculate the ionic strength of () 0.15 molal KCI solution (ii) 0.25 molal K,SO, solution (iii) 0.2 molal BaC, solution and (iv) a solution whichis 0.1 molal in KCland 0.2 molal in KSO,, Soln. (i) In0.15 molal KCI solution, the molality of each ion=0.15, Hence, im, =0.15,m_=0.15 and z,=1, =.=! £=20.15x2 40.1501) 015Soln. ElectrochemicalCélls | electroc (ii) Since K,$O, produces two K* jons and one SO?” ion, hence the molalities of theons in this case would | beas follows: | im, =2x0.25=0.50,m_ =0.25 and z, =I, 2.=2 { 1H (0S«1? +0.25%24) =0.75 i Gi) For 0.2 molar BaCl, solution, m,=0.2,m_=2x0.2=04; 2, =2, 2.= 4022? 041") 06 (iv) Ina solution which is 0.1 molal in KCl and 0.2 moll in K,SO,, the total molality of K* ions, m =0.142«0.2=05 Molality of CI ions, m, = 0.1 and molality of SOF ion, m5 = 6.2 Also in this case, 4 =1,2)=h2,=2 Hence, T=} Sef 40.be1? 60224) 07 Calculate the mean activity coefficient of (i) NaClat a molality 90.0! (ii) Na.SO, at a molality of0.001 in aqueous solutionat 25°, (i) Mean Activity Coefficient of 0.01 Molal NaCl The ionic strength (J) of 0.01 molal solution of NaClis given by 1 hint sm Hoo1x? +0011?) $0.01 (For auni-univalent electrolyte, the iouic strength is, evidently, equal to its molality) ‘The mean activity coefficient («is given by the equation logy =-Az, 2.NE For waterat 25°C, the constant A =0.509. logy, =-0.509x1x1x J@dT =-0.509 On, y,=0.889 (i) Mean Activity Coetiicient 00.001 Molal Na,SO The ion strength (1) of 0.001 molal Na,SO, solution is given by 1S +m Z)= * (0.0021? +0.001x2")=0.003 Ax, 217 =-9.509x1x2x 0.003 =-0.0558 log Ye The Extended Debye-Huckel law: ‘When the ionic strength of a solution is too high for the Debye-Hiicke! Hinting law to be valid (ie. the molality of the solution is too high), the mean activity coefficient may be estimated from the extended Debye-Hickel baw ~Alz,Z.\1" logs = +l 1sBI® * Where B and C are dimensionless constants.id | Debye Huckel eo | t Jimsiting kaw a \ ley Extended Debye | Huckel law viz Applications of emf Measurements: 1. pH Determinations: Sine tte eufofa cell depends on the hydrogen ion concentration, pH values can be determined by dipping | hydrogen cleetrodes ito solutions and measuring the emf with reference to another. Incommercial pHmeters theelectrode immersed in the unknown solutionis often glass electrode, and the other electrode may be the { silver-silver chloride or the cafome! electrode. in accordance with the Nerast equation the em¢ varies \ logarithmically withthe hydrogen-ion concentration and therefore vaves linearly withthe pH1. Commercial instruments are calibrated 50s to give a direct reading of the pH, | 2. Activity Coefficients: a Upto now we have expressed the Gibbs energy changes and emf values of cells in terms of molalitis. This is an approximation and the errors become more sovious as concentrationsare increased. For acomect Bymmvation, activities must be employed, and the emfmeasurements over a range of concentrations lead to values for the activity coefficients, Consider the coll i Pt, H, (1 bar) HCI (aq) | AgCl(s) |Ag The overall process is i My FARO) > Ag +H +c and the Gibbs energy changeis AG = AG*+RTnfa,a_} Where a, and a_ are the activities of the Hand Cl fons, and AG? is the standard Gibbs energy change, when the activities ae unity. The emis since n= 1 -_ go AT ; E=E = In{a,a. F (a,a_f Since each ofthe activities isthe molality m multiplied by the activity coefficient we can write ee Lat? ay We. BE yy en, Where #e, equal to J¥,¥-. isthe mean activity coefficient. This equation can be written as, Be ame? 2 iy, lity F F kel and if is measured over a range of molalities of HCl, the quantity onthe left-hand side can be caleulatedat various molalities, [fhe quantity is plotted against mas shown schematically in following figure, the value extraploted to zero m gives E°, since at zero m the activity coefficient is unity so that the final ter vanishes. At 2RT any molality the ordinate minus ° then yields -287 iq, (which is +ve because 7, i Consider the following cell: Ag(s)|Ag” (a = 0.001m) || Ag* (c= 0.1m,a unknown), Ag(s)m Ifan EMF at 25° Cis +0.1110V. (a) Write the cell reaction and (6) calculate the activity coefficient ofthe Ag’ ion in 0.1m solution. (a) The cell reaction is, Ag" (c= 0.1 m,a=say,x) —> Ag” (a= 0.001m) Isis concentration cell with no net reaction so that E°= 0. Hence E = 0,059] log (0.001/ x) log x = log 0.001 + 1.878 = =1.122 Taking antilog, x= 0.076 Thus ,a~0,076, Hence, the activity coefficient y=a/c=0.076/0.1=0.76 EMF of the cell Ca(s), CaCI, (2 0.02) |AgCI\s), Ag(s) is found to be 0.780 V at 25°C. Using the standard potentials, viz., Egy, cy =~ 0403 V and Bsc, 4g" + 0.222V, calculate the mean ionic activity coefficient of ACI, at this temperature. The half-cell reactions are: RHE: "AAgCl (9)+26° = 2Ag ()+2C"; Evgct, dg = 0220V LHE. Cals) == Ca?* (ag) + 2€°5 ag =~ OMY 19, Hence, for the overall reaction Ca (s) + 2AgCl (5) = Cd”* (ag) +2Ag(s) +2CI (aq) ' on, E iy — Bj = 0.222-(- 0.403) = 0.625V CACI, ionises in solutionas CdCl, (ag) = Ca” (ag) +2C1- (ag) Thus, the number of ions produced on ionization of CdCl, =3 with x =1 and y=2. Hence, aeact, (0a)? (aC Ii a 4m, =TymEeT — CX=H) a_=y_m_=y_my=2y_m C 2) eae, = (06) =(ay )Ca.)* = (74m) x02)? = ACY)? =ACr) 0.0591 3 — ‘The EMF of the cells given by B= £2" oga,a? = B25 Hoslag)* at 25°C ir ells | Electrochemical Cells Or 0,780 = 0.625 — 0.0295 log [4(y,)3m?) 4 yg)? = O08 5 9545.2 5154 log 4 (¥4) nips 5.2546 = 6. ‘Taking antilog, Alyg)Pm? = 5,57 x 10% ‘ us ya (ssrx10" _(557x10Y Claremore Am (0.02) 3. Determination of the Solubility Products: The Solubility product of sparingly soluble salt is a kind of equilibrium constant. Consider the salt MX in equilibrium with its ions ina saturatedsolution. MX(s) = M*(ag)+X-(aq) Ag dard tof Soln, The Solubility product ofthe salt is given by Ky = a,y+ ay- =(M*JIX"], assuming an ideal solution so that activities equal concentrations. The above reaction is the cell reaction for the fotlowing cel! ‘M|MX(satd. soln.) | MX (s), M- The half-cell reactions are RHE. MX (ste = M4X™ LHE: M = MM(ag)+e" Overall reaction: MX(s) = M*(ag)+X"(aq).£° = ER Bi, The values of Egand Fare taken from Table. knowing the value of ° for the cell under concentration and using the reactions AG? = ~nE® and “AG? =2.303 RT log Kyp,we get nFE® 8K» = 3503 RF 2,303 RT ie, B= a Nog Kay = Pog ky 25°C Thus K,p can be calculated for the sal! MX in water at 25°C. Calculate the solubility product of AgBr in water at 25°C fom the cell AglAg’ Br (sata. soln) | AgBr (5), Ag ‘The standard potentials are Eaghrag =0.071Vs Egjqg=0.799V. The electrode reactions are: RHE. ‘AgBr(s)te" <= Ag(s) + Br“ (aq): Ey =0.0071V LHE: Ag(s) = Ag*(ag) +e Ej, =0.799V Hence, forthe overall reaction: AgBr(s) = Ag*(ag)+Br° (aq), E° = Ep —Ej, =-0.728V S ae tog[]az* [or Tow = 0.0591 log Kyy E0728 .0591 0.0591” log K,, Hence Ky = 481x109Soln. 2. Soin: S = ElectrochemicalCells | glgctre = fF ‘The EMF of the cell: | ‘gl AgClin 0.1 M KCI|j Sat. NH,NO, ||0.1 MAgNOJAg | #8 0.45 volt at 25°C. Calculate (i) the solubility product and (i) the solubility of AgCI. 0.) M KCLis 85% | dissociated and 0.1 MAgNO, is 82% dissociated. Here the salt bridge has NH,NO, , Since at 25°C, 0.1 M AgNO, is 82 per cent dissociated, hence, the Ag” ion | concentration (c,) on the AgNO, side~0.1 * 82/300 = 0.082 mol dar’, Let o; be the concentration of Ag’ ions on the AgCl side due to the solubility of AgCL. Then, assuming that activity coefficients are each equalto unity, the EMF of the cells given by £205 oy (ar rseC) ng Substituting the value of 2= 0.45 V, n= 1 andc, = 0.082 mol dm’, we get 0.082 mot dm 045 V=0.0591 Vlog 2082 mold 4 Hence, ¢, = 2,008 * 10 mol d Since at 25°C, 0.1 MKClis 85 per cent dissociated, hience the CF ion concentration is given by cr) -2285 0.085 mot dm” Kg of AgC1=[Ag'] {CI} = 2.008 x 10°? mol dm « 0.085 mol dar? =1,7068 10-” mok dns Solubility of AgCl = /Sotubitity product of AgCl = 1.2068 « 10° mo! dm“ = 1,308 x 10° mol dm = 1.308 « 10° mol dav? x 143.5 g mol = 1.875 «107 g dav ‘The EMF ofcelf Ag | Agl(s)|0.05 MT || 0.05 MAgNO, | Ag is 0.0788 V. Calculate solubility product of Agr. 0.059, TAs" Iex e ro hB0 iu [As" Ikxs { 0.788 = 29%? jog O05) 1 “Tae hus [Ag* Jus =2.203x10715 Kgp of Ag =[Ag* 0” ]= [2.203% 10"'5)(0,05]= 1.10 «107™6 2. Concentration Cell: Inthe case of galvanic cells the electrical energy arises from the chemical reactions which take place in the cells. There is, however, another category of cells in which the EMF arises not due to any chemical reaction but due to transfer of matter fiom one half-cellto the other because ofa difference in the concentrationsofthe species qin, involved. These are called concentration cells. Concentration cells are of two types, viz., (1) Electrode-Concentration Cellsand (2) Electrolyte-Concentration Cells. 1. Electrode-Concentration Cells: In these cells, two like electrodes at different concentrations are dipping in the same solution, Two hydrogen electrodes at unequal gas pressures immersed in the same solution ofhydrogen ions constitute an efectrode- concentration cel, This may be represented as follows: Pt|H,(p,) | solution of H* ions, say, HCI | H,(p,)| Pti 85% tion stat FAgl reells, at due gecies rogen trode- Se Electrochemical Cells 22, Soln. The reactions occurring ae: RH. 2H +2e° == Hy(p,) (Reduction) LH.E. Hy(p}) — 2H" +20 (Oxidation) Overall reaction: 15.) —* Ha(p,) This reaction isevidently independent of the concentration of the electrolyte. At moderate pressure, H, can be considered to be an ideal gas so that the ratio of the activities can be considered to be equal to the ratio of the gas pressures. Hence, the Nemst equation may be writtenas 0.059) 2 ogtpa/) at25°C Since, by definition, E°= 0, we have =-0.02955 log (p,/p,) = 0.02955 log (p/p,) ‘When ?2

the EMFis positive so that the whole process is spontaneous, being equivalent to the expansion of H, gas. Another example ofthe electrode-concentration cellis that of an amalgam with two different concentrations of the same metal : . Hg—Pb (c,), PbSO, (concentration =c), Hg—Pb(c,) ‘The electrode reactions are: RHE. Pb2* +2" > Pb(cy) (Reduction) LHLE: Ph(c,) == Pb +2e~ (Oxidation) Overall reaction: PD(qy) =" Pb(c2) The EMF of the cllisgiven by wer fee. 20591 2) fpr 00891, a, E=E,-E, -( Haves ke ele [Free aoe = 20591 op“ + 0.02955 lop“ a 2 Here, t00, if (@,); Substituting activities (a, ); and (a, }p by molalities m, and m,, we have RT, Yam Soln. QF yim cit Where 11 andy are activity coefficients of the electrolytes inthe two solutions. Consider another similar concentration cell represented by Pr[Hp(g)/H" (a, jl] H” (a, )2 |a(e)| Pe Vain teen In this case, both the electrodes are hydrogen gas electrodes which are in contact with hydrogen ions of different activites. The two soiutions which are generally solutions of hydrochloric acid, are separated by a salt heidne| ons meal be | are ible de m4, Soln, sof | asalt | iS The following processes take place at the two electrodes: RHE: LEE Overall reaction: = 1/2H3(g) (Reduction) (Oxidation) HY(a,y +e V2Hp(g) © HY (a,)p 3 Hay) 2H (a) em ‘The reduction potentials of the two electrodes san the a ofthe cell are given as follows: ( T \ EaEe-E, a gy, #7 e~Fy=( Ba = “ay c EG) RT @, Fh For E to be positive (a,), should be greater than (a, }. Consider another electrolyte concentration cell: PtH, |HCK(a,)| AgCXs)| Ag|| Ag, AgC\(s)|HCl(a,)| H,IPt ‘The electrode reaction a RHE: Ag+ H (a9) + Cay) # a= 212 Hy (1m) #ARCIG) _ (Reduction) LUE. WOH (atny + AgCI) —= Ag+ HMCa)+ Celadee (Oxidation) Overall reaction: H*(a;) + CI (ay) —=* HG) + CI-(a)) Thus, the overall reaction involves no chemical change. It consists only ofthe transfer of HClfiomsdtution of activity a, to solution of activity a, The EMF ofthe cellis given by = OiBdiag 222 we 25%C Fw " @) Where (a); and (a,), are the mean ionic activites of the HCI solutions inthe two cells Here, too, we see that when a, > a,, £ is positive so that the process is spontaneous from right to left and consist in the dilution of HCl ftom activity, c activity a, eventhough the two solutions arenot incontact with each other. Calculate the EME of the concentration cell consisting of zinc electrodes, one immersed in asolution of0.01 molality (number of moles dissolved per kg of the solvent) anc the other ina solution of 0.1 molality at 25°C. The two solutions are separated by a salt bridge. The mean activity coefficient of the electrolyte may be assumed to be unity. ‘The cell maybe represented as Znl Zn** (mm, = 0.01) | Zn?" (m, = 0.1)Zn The EMF of the cell, £ is nam ym RE, (a)p _ 2.303RT = ae OK F"@y oF 0.0591, 0.1 7 ot to 2 = 0.0295 volt, at 25°C G nena)25. Find the potential difference between the hydrogen electrodes in the cell | | Electrochemical Cells | Electroct PUFE,(@)| HCL |ABCKS), AB I Ag, ABCKS)| HCI, | HaC@)|Pt a Van me010 oem at 25°C. The activity coefficients of 0.01 m and 0.10 m solutions are €.95 and 6.85, respectively. Soln. The potential difference (£) between the two hydrogen electrodes is given by RT, (@.)a _ 2.303 RP a Gay nF 00591 0.10 x85 oN yg ONES 050 . TB pornos 225°C = 0.05624 volt 2. (b) Concentration cell with transference: Cell in which electrodes are reversible with respect to cation c Example: consider the cell, Pt| H, (Ibar)| HCI(a,):HCI(a, )) H, (Ibar)| Pt In Anode Cathode H, |HCI(c,) HCI(c, ))H;, : Hite ott; Sip He {fone Faraday of electricity is withdrawn from the cel, then changes taking place are (i Electrode reaction at anode , (Ibar) > H* (a, )(1eq.) +e (i) Electrode reaction at Cathode K (e,)te> 5H, (1 ba( len) (ii) Transfer of t, mole H from right to left UH (a) > tH" (a,) (iv) Transfer of t_ mole of CI- formright to left t.CI (a,) tC (a,) Addition of equation from (i) to (iv) gives, HY (a,)+t,H" (a)+ CCL (a,) SH (a, ) +t," (a,)+t.CF (a)) i leg. Leg. 1} Or, H*(a,)(1-t,)+t_CV (a,) oH (a,)(1-t,)+t.Cl" (a,) Or, LH? (a,)+t. Cr (a,) > H*(a,}+CL (a,) 1 Thus the net reaction is traisfer of t_mole of HCL fiom solution of activity a, to that of activity a, ‘Therefore, total five energy reaction chenge ofthe net cell reaction is, AG =t_[p, (a,) + HCI (a,)~p,. (a.)-HCr (a,)} AG =t [fu +RTAn(ay}yef+{ul, +RTEn(a,),,}-ful, + RTE (a,)e} fe, +RTén(a,)..}]3 | Electrochemical Cells pl deltider |g (aa(HC) AGst_ cra (ea)ex | AG=t_ ari 2 ARE a (wei) = acrtin | oe + Bay (WG) w | So for spontaneous functioning ofcel, (2.2), >( Cell without liquid junction potential: ) {this case only reaction (i) and (ii{as stated above) will tke place, | net cell reaction without liquid junction potential (wal) is H” (a,) > H* (a,) | cellpotentialis Ey (wod}) =? = én (ade | F(a) E.,,(woéj) =0 RE py (Ghoe Jes cy Ea wos) (vi) Liquid junction potential, Eig) = Eas (WH) Ea (Wo8)) RT py (adhe: , RE py abs =-2t (aa), 7 OTE Gada Fade c wan RE pg Hoi 7 FY (2)s0 i \ RT Buc | on (i-t)= ina gE) (ao (vil) From equation(v) and (vi) we can write, Bu (Wj) = 24. (wod)) Form equatin(vi} we can predict the sign (positive or negative) of liquid junction potential<] eletrechemclCole ‘Anode Cathode Anode Cathode: eae c 7 ‘ / -i+ a | al+ a c -1+ atts atta, ina xt fo 1 iF He t+ $e ‘ Ifa,>a, and t_ >t, Ifa, > aand <1, then, (J) is + ve and then E(i) is -ve and Equi (WE}) > Ena, (woe) Ey (WE}) > Equi (wod}) r 2) Cellin which electrodes are reversible wrt, anions: | Example: Consider the cell . | L Ag| AgCl|HCI(a, ): HCI(a,)| AgC!| Ag | When 1 Faraday ofeleticiyis s withdrawn from the cell | Anode : Cathode c Seo Ag|AgCl|HCI(a,) cr HCI(a,)| AgCl| Ag mee c Changes taking place are () Blectrode reaction at anode Ag(s} Cr (a,) > AeCl(s) +e (ij) Blectrode reaction at cathode F AgCl(s) +e° —>Ag(8)+CI(a;) J i) Migration of H ions | t,H"(a,) tH (a,) | (iv) Migration of CI” ions, tcl (a,)—t_Cr'(2,) | Net effect of reaction from (i) to (iv) is tH (a,)+t,C1 (a) 9H (a,)+t,Cr (a,) ) Thus the net cell reaction is to transfer t, mole of HCI from the solution ofactivity a, to that of activity | ay. beg ‘The free energy change of net is reaction, AG =t.[ ty. (85) + Hoy (22) By (2) “Her (®)] Soln, Or, LF Ea (wei) = (RTE lta fee (Using p,.(a) =n, +RTEn a] hy (ayCelle — | Electrochemical Cells Or, ~FBen(wéi)=2t,RT tn Cur)oa Or, (vi) Therefore, for spontaneous functioning ofcell (a), > (212 yor Cell without transference: Fromequation (i and (i) cr (a,)—er (a,) (vi) 5) = ORT py (@rdox RT p, (222) Egy (WOE|) = fn 200 = py i Ae ae Fake 7 ‘Liquid junction potential, Ey = Bea (wAl) “Beal wot)” bp =o, Malta or, B= é : Fhe init wy (2, ne a Fae = a> mitt Rote Ee tivity tH)» EuW08) an g(t) < Eg) |26. Forthe given cell Ag] AgCl(s)|KC1(0.01mol Kg",y, = 0.90): KCI(0.01mol Ke, y, = 0.90) Ag| AgCl(s)|Ag (a) Write the net cellreaction (b) Calculate the emf of the cell at 298 K. Given = 0.60 Soln, (a)Let one furaday of lectrivtyis withdrawn from the cell Anode Cathode — Ag(s)+CI (a,)—>AgCiis\+e" ver RoC ile) —_s Aaled cern laElectrochemicalCells| Electroc Net cellreaction a 1 tK*(a,)+t,Cr-(a,) tk" (a,)+t.Cr (a) u (©) Since, weknow that, AG =, [tty (22)+ Hoy (22)-Hye (a) He: (1) ' F ) h FE = 2t,] aril =e ad a )eer d 14, BL gg Bate fa ca = Fe Gas { a Bay =—2(1~0,6) 2242298 pq 010-80 yoy, i an 96500 0.01«0.96 iW =-0.045 Volt. A The above cell is non- spontaneous ,s0 the net cell reaction will procced in the backward direction. 2 SOME LIMITATIONS TO THE USES OF STANDARD ELECTRODE POTENTIAL 1, Substitution of concentration for activi To illustrate the standard electrode potential forthe half-reaction, XM Fe” +e" = Fe" is +0.771 volt (ie: Bl s,q2 =0.771 Volt) ‘When a platinum electrode immersed ina solution containing 1 moll eatkst e* and Fe" ions in addition to | moV/L perchloric acid is expected to have a potential + 0.771 Volt wart, standard hydrogen electrode, bul the observed experimental potential is +0.732 volt. 1 F The reason for the discrepency is seen if we write the Nemst equation in activity terms, 0 B=E! 0.0591 log bs [te sc oO Yow FE] + Where tp and y,,5 are respective acivity coefficients Theactivity oveffivients ofthe two species are les ‘than one inthis system because ofthe high ionic strength imparted by the perchloric acid and ironsalts. gag. c is less than Y_.0 5 ‘ From equation (1), E islessthan E°, Here discrepency is because activity and concentration are identical only in dilute solution. 2. Effect of other equitibria : a ‘The application of standard electrode potentials is further complicated by the occurance of solvation, dissoci# tion, association and complex formation reactions involving the species of interest. = Example: Forhatfcellreaction, Fe"? +e" = Fe” i c Er Value Solution having equimolar Fe"? and Fe"? a +0.BV IMHCIO, iE +0.70V 1M HCI @ +0.60V IMH,PO, (@ Soln. Ss:| | | | | dition! le, but peer ia ‘These differences arise because iron ({It) forms more stable complexes with chloride and phosphate fons than does iron( {1}. Asa result, the actual concentration of uncomplexed ironilII) in such solutionés less than that of uncomplexed iron (I1) and the net effect isa shit inthe observed potential. Formal potentials: In order to compensate partially for activity effects and errors resulting from side reactions, suchas those described above. Swift proposed substituting a quantity called the formal potential g inplace ofthe stan- dard electrode potential B? in oxidation reduction calculations. “The formal potential ofa systems the potential ofthe half-cell wrt, the standard hydrogen elec trode when the concentrations of reactants and products are 1M and the concentration: ofany other constitu- ents ofthe solution areclearly specified”. Example: The formal potential for the reduction ofiron (111) is + .732V in IM HCIO, and + 0.700 V in | MHCL Use of these values in place of the standard electrode potential in the Nernst equation wilyield better agreement between calculated and experimental potentials, provided the elecrolyte concentration ofthe solu- tion approximates that for which the formal potential was measured. For halfcell reaction Oxidized species (O) + ne” ——* Reduced species(R) RT, [R] ty “GE [0] in IMsolvent X”, Modified Nernst Equation: OLVED PROBLEMS, From the data of half-cell reactions [GATE 2003] AgCl(s) +e” — > Ag(s)+CI° (aq) Bo =40.22V Ag’ (aq)+e" —>Ag(s) 8 =+0.80V ‘The solubility product of AgCl at 298K is, caleuiated to be. (a) 1.5x10°? (b) 2-1x10? (©) 3.0x10° (@) 1.2x10% Soin, Since, we know that, 0.0591 = 022-0801" Hoek, (- 2503RT _ 6.0591 at oom temperature) 0.58 logK,, =-~ eee 90591 = RK,=bsao? Correct option is (a) 2. The solubility product of silver sulphate at 298K is 1.010-. Ifthe standard reduction potential ofthe half-cell Ag’ +e"——>Ag is 0.80V, the standard reduction potential of the half cell Ag,SO, +2e° —>2Ag+SO2" is [GATE 2004] (@)0.15V (0)0.22V (0) 0.65V ()0.95V \ Soln. Since, we know thatElectrochemical Cells | Elects " ap), 205M iopK Frot-wesoase ~Eaethe’ °K 0.0591 5 0.0591 oe 0 = + She ———x(-5)=' — = = Brot ansouas 75° tog (Ixt0 j= 0.804 (-5)=0.80-0.15 =0.65 Correct option is (c) 3. _ Given the standard potential for the following half-celf reaction at 298K, | Cu* (aq) +e" —+Cu(s) By =0.52V | _ Cu** (ag) +e” —> Cu" (aq) £) =0.16V 5. Calculate the AG® (kJ) for the reaction, IGATE 2006) 2Cu*(aq)-—+ Cur(s)+ Cu” | Soln. (a) 34.740 (b) -65.720 (©)-69.480 (6) 131.440 Soln. Given, 5 (LCut (aq) +e" —+Cu(s) =0.52V (2) Cu* (aq) +e" —> Cu" (aq) By =0.16V From(1) and (2), we get (3) 2Cut —>Cu** +Cu(s) Fromequation (1), we get AG, =-nFE, = -1xF(0.16V) =-0.16FV From equation (2), we get AG, =-nFE, = -1xFx0.52V=~0.52FV AG=~0.52FV+0.16FV = AG =-0.36FV =-036x96500KI = AG=-34.740KI * Correct option is (a) aoe creaiat Ey (Fe™ Fe) =-0.04V and Ep (Fe, Fe) =~0-44V, the value of E, (Fe™, Fe") is 6 eo 036v (b)-0.40V (90.16 ()040V [GATE 2007] Soln. Given, B, (Fe Fe) ~0.04V and Ey (Fe"*, Fe) =~0.44V (1) Fe*+3e"=Fe, AG, =—nFE,(Fe™,Fe) Soln. ©) Fe 42¢=Fe, AG) =-nFB?(Fe”* Fe} ‘From equation (1) and (2), we get "Fe! 4e—4 Fe", AGnay =-nFB,(Fe™, Fe™} AG, =-nFE (Fe ,Fe) = ~3xFx(~0.04V) =0.12FVr Electrochemical Cells Soln, Soln, And AG, =~nFEg (Fe Fe) =-2xF(-0.44V) =-0.88FV AG gat =#0.12F -0.88 0.16FV = —tFE, (Fe Fe )= —0.76EV = ~1XFE9(Fe*, Fe?) =-0.76FV = B,(Fe™,Fe*) Correct options (a) 0.76 According to the Debye-Huckel limiting low, the mean activity coefficient of5%10 mol kg-t aqueous solution of CaCl, at 25°C is (the Debye-Huckel constant ‘A’ can be taken to be 0.509). (a) 0.63 (b) 0.72 (c) 0.80 (0.91 [GATE 2008] Given, concentration of CaCl, (m) = 5x10 molkg" and A= 0.509. 1 Since we know that, =3[nz +m,Z;] For CaCl, —9Ca*4201- 1-2 [e107 x44 2x5x10] 1 gf107] T=15x10% logy, =~0.509|2.2. |i logy. = -0.509|(2)(-1)|Visx10% logy, = 0.509215 x10 7,=0.913~091 So, correct optiow is (d) According to the Dubye-Huckel initng au ifthe concentration of dilute aqueous solation of KClisin- creased 4-fold, the value of Iny, (y, isthe motalmean ionic activity coefficient) will (GATE2009] (a) decrease bya factor of 2 (b) increase by a factor 2 (0) decrease bya factor of 4 (4) increase by factor of4 For KCL—>+k* +CI tog y, = -A\Z,Z_|VI aG& Soln. Soln. iS => (logy,)=-Allx(-1)vi i = (logy,), =-A -Q) Ifconcentration is of ions is increased four times, then 1a (ay +4x(-1)"] I=4 From equation (1), we get (logy) =-Allx(-1)}V4 (logy), =-2A @) From equation (2) and (3), we get (logy. }, =42(logy..), Correct option is (b) The standard potential at 298K forthe single electrodes are given below Electrode Electrode potential (volt) Mg** /Mg -2.34 Zn” (Zn -0.76 Fe?" /Fe 70.44 From this we can infer that Electrochemical Cells [GATE 2010} (a) Zn can seduce both Mg” and Fe* (b) Fecan reduce both Mg” and Zn* (c) Mg can reduce both Zn’ and Fe** (d) Mg can reduce Zn®* bist not Fe Metal with lower standard reduction potential ean displace the metal with higher standard reduction potential from their solutions. Mg with lower standard reduction potential (2.34) can reduce both Ziv (-0.76) and Fe" (0.44), Correct option is (c) Ifthe ratio of composit correct potential difference willbe (bp = 2RT nF RT oF (@) For oxidation reduction hal-cell (© B-B” Oxidized species (0) + ne” =—* Reduced species(R) Frommodified Nemst equation (in terms of formal potential E” ) pane 22 (8) nF [0] 2RT E-E"=+ ae nF IR] n of oxidised and reduced species in electrochemical cell is given as 0] =e the [NET June 2011} | Elect 9. Soln. 10. Soln. i. Solnells ee & @ 9. Soln. 10. Soln. ul Soin. Fora I molal aqueous NaCl solution, the mean ionic activity coefficient (y.°) and the Debye-Huckel limiting low constant (A) are related as (GATE 2011] () logy, =V2A logy, =-V2A (e) 1y=10* (ad) He =10* For NaCl—+Na*+Cl- 1 2 ts 5[ mai +m,23 = [capex] ot 2 logy, =-AlZ,Z_|vI => logy, =-A((t)<(-1fvi A => bey, => =e" So, correct option is(a) At298K, the BME of the cell, {GATE 2012] Pt|H, (I bar) | H* (solution) | Cl” |Hg,Cl, | Hg is 0.7530V. The standard potential ofthe calomel electrode is 0.2802V. Ifthe liquid function potential is zer0, the pH ofthe solution is (a)47 74 (8.0 @127 Given, Pt|H, (1 bar)| H* (solution) | CI” |Hg,Cl, |Hg 0.7530V, Baad = 0: Ey —Ecaioma 0.0591 pry = 07530-02802 0.0591 pH=8.00 Correct option is (¢) Statement for Linked Answer Q. Land Q. 12: ‘The standard half-cell reduction potential of Fe™ (aq)|Fe is— 0.036 V and that of OH (aq) [Fe(OH),(S) Fe is- 0.786 V For the determination of solubility product (K,,) of Fe(OH), the appropriate cell representation and its cemfare, respectively. [GATE 2013] (a) (Fe|Fe(OH), (s)|OH" (aq)Fe™ (aq)|Fe), -0.750V (b) (Fe| Fe (aq) OH" (aq)| Fe(OH), ), (8) Fe), 0.750V (©) (Fe| Fe(OH), (s) OH (2q)Fe" (aq)|Fe), 40.750V (a) (Fe) Fe™* (29) OW" (aq) Fe(OH. ), (s) Fe), 0.822V Fe(OH), +3e°—+Fe+30H (reduction)Soln, Soln. Electrochemical Calls Fe —>Fe*’ +3¢ (oxidation) Fe|Fe**,OH (aq) | Fe(OH), | Fe Ei = E auction ~ E° =-0.786V -(~0.036V) E Eidtin E? =-0.750V Correct option is (b) The value of toge(K,,) for Fe(OH), at 298 Kis (GATE 2013} (a) -38.2 (b) +87.6 (96.0 (a) 87.6 Since we know that, 0.0591 a E=E'+ log. Key 0.0591 = 0.786 = -0.036+ log. K, P log, K. Correct option is (4) Given the E® values for the following reaction séquence. Mn®* 128 ngs 28V" pte 0960" vgn 3t 5 gett the compound value of for Mn > Mn?* (in volts) is (GATE 2015] Latimer diagram, Mino? 128-5, ManS+ 29 gt? 0960 yp Mat —228V0 pig BV Spe O96V SV ae [oo 46 Mn*6 +4e” —+Mn™ AG=—nFE (4G) pi =—4FxE, Mn*6—> Mn‘ AG, = -nFE = -1F x{.28=~1.28F Mn 25. Mae4 AG, =-Fx2.9=~2.9F Mn" 225 Ma"? AG, =-Fx0.9 =-0.9F 14, Soln. Is. Soln,Tr Ee Electrochemical Cell < le = Mn“? ——> Mn** AG =-Fx1.5=-1.5F (AG) na = AG, FAG, +AG; + AG, ~4FE) =-1.28F -2.9F~0.9F-1.5F 4B, =-1.28-2.9-0.9-15 AE, =~6.58 #,=1.66V 14. The solubility product of AgBr(s) is 5x10"? at 298K. Ifthe standard reduction potential of the half-cell. EF yagndsyer 18 0.07V, the standard reduction potential E44 (invots) is [GATE 2025] Soln. Given, solubility product K, = 5x10 and Eig: pe OOTY | Since, we know that, | Pe - eB, 42S ok, ‘nage aehAs ° =p? 5 : | 0.07 = Brigg 0.0591 (log 5 13]ogl0) =F = \ 0.07 = Bi agg 10.0591(0.70-13) 0.07=E° , +0.0591(-12.30) \ Agtte i | 0.07=E° , —0,72693 | aatAg i E° , =0.72693+0.07 = 0.79693 = 0.796 V 1 | ae : | 15. Themeanionic activity coefficient of0,001 molal ZnSO,(aq) at 298K according to the Debye-Huckel limiting, law is (Debye-Huckel constant is 0.509 molat!) [GATE 2015] Soin, Since, we know that, i i AlZ,2_|vi (2 A=0.509} | 0.509|z,Z_ JI Given, ZnSO, — Zn** +SO7 | Ir 2 \ m,Z} +m,Z}| [Given, m, =m, = 0.001] [0 001(2)° +0.01(-2) [0.004 +0.004] = 0.004 Therefore, mean ionic activity coefficient, logy, = -0.509(+2)(-2)|v0.004 = ~2.036,/0.004 = -2.036x 0.9632 logy, = 0.1287 = -0.129 4, =10° = 0.743iS ElectrochemicatOetls | plectroc PRACTICE SET aT A L. Activity coefficients calculated using Debye-Huckel law are always (@)Lessthanzero —_()Greaterthanone (c)Equaltoone (4) Less thanone (@ 2, Thestandard cell potential for the reaction, Zn(s) + Cu** (aq) + Zn** +Cu(s) ,at 25°C is 0.5 V. The c standard free energy (in) is: 0. TI (a)-24.1 (b)~48.25 (©)-96.5, (@)-193.0 3. Standard reduction potential at 25°C ate: Culte =Cusl (B°=-0.17V); Zn 4207 = Zn(B" =-0.760 The voltage ofthe cell Zn} Zn** (IM) (1M) } Cul is: (042Vv )059V O135V (a) Lasv @ - nT 4, standard emfofthe cell, Cu| Cu?* (ag)|i[,Cu(NH), Jaq. NH {Cu | - { is 0.35, then stability constant of the formation cupric amine complex is: w (a) 1.01077 (b) 8.4x10° (©)7,0x10" (@) 43x10" ¢ a 5. Thespecific conductivity of'a saturated solution of ACL at 25°C is 3.41 10-4S.can! and that of water is 1,60%10~ Sm”. The molar conductivity at infinite ditution is 138.3 S. cm, What is the solubility ofAgClin _ water in moles/| at 25°C, (a) 13x10% (b) 1.15103 ( Lasxi08 (@ 131x10° | a 3 @ 6. For the process, Fe" (aq.)+¢" > Fe* (eq) E=0.771V no ek Therefore, E for the process; 3Fe™ (aq.) +3e" - 3Fe** (¢q.) will be: ( a . @)3 0.771 W)UBXOINV — ()OIV @-0771V | “4. Tt 7. Forthe processes, Cu" (aq.) ke" > Cu* (aq.)E=0,15V. is (a Cu (aq.}-+2e° + Cu(s) B= 0.336V bod ‘Therefore, F for the process, Cu (ag.) +e" > Cu(s) Zz willbe E, (a)0.486V (6) 0.186 V ©6522 @-0.522V 8. Foranaqueous solution at 25°C, the Debye-Huckel limiting law is given by [NET Sune 2011] ( (b) logy, = 0.509|2,2_|u. (@ logy, = -0.509|Z,2Z. |?ris y seins @ a 9. I uy 15, The overall reaction for the passage of 1.0 faraday of charge in the following cell Ag(s)-AgCl(s)|KCI(a,)|KCI(a,)| AgCl(s)~Ag (s) is given by (t denotes the transport numbers) (a) t. KCI(a,) > t+ KCI(a,) (b) t- KCI(a,) >t. KCI(a,) [NET Dec. 2011] (©) t-KCl(a,) > t-KCl(a,) (d) t-KCl(a,) > t-KCl(a,) ‘The correct value of E°, ofa half cell in the following graph of vslog m(molality) is: [NET June 2012} © | oem (2) CCyAC’ (b) AB’ (© BB @cc The correct Nernst equation for the concentration cell: [NET June 2012] Pe|HL(p)IHCI(a,} [ARCI(S)IAR-ABLARCILA) ICH.) A, (p)|Pe without liquid junction would be art, (a), RT, (a), (a) fn (b) Bae F(a), F(a) 2RT , (ax), RT, (ai). y B= ARE py eee E=se fn Or a) OR a The potential in Debye-Huckel theory is proportional to [NET Dee. 2012] (a) tr (b) exp[-xr] (©) exp[-xr]/r (@ Tithe concentration (c)is increased to 4 times its orignal value (c), the change in molar conductivity for strong electrolytes i (where bis Kohirausch constant) [NET June 2013] (0 (b) bve (©) 2bve (@) 4bve Thecal vltageot Dariel cal [Zn] Zn80, (aq) | CuSO, (aq) | Cur] i 1.07 V.Ifreduced potential of Cu"Ca is 0.34V, the reduction potential of Zn?"[Zn is [NET Dee. 2013] (a) L.141V ()-141V ()0.3V (90.3 Consider the cell: [NET Dee. 2013] Zn|Zn"* (a =0.01)|| Fe™* (a =0.001), Fe™* (a =0.01)| Pt B,,= 1.71Vat 25°C for the above cell. The equilibrium constant for the reaction: Zn+2Fe* == Zn +2Fe™ at 25°C would be close to (a) 10” (b) 10 (c) 10 (@ 10% ANSWER KEY Questions: 1 2 3 4 5 Option td) ©) (ey d @ Questions 6 7 8 9 10 | Option @ @ @ (a) (by Questions 1 2 13 14 iB [option @ (co) () @) |lonictg lonic Equilibria Tonic Equilibrium: + When an electrolyte is dissolved in a solvent it spontaneously dissociates into positive and negative ions and the total positive charge remains equal to the total negative charge i. the solution remains neutral. + The degree of ionisation is defined as the ratio of number of molecules undergoing dissociation upon total number of molecules. Number of molecules undergoing dissociation Total number of molecules + For diluted solution 0, =1, For concentrated solution a <<1 In deciding colligative properties, the ions behaves like molecules Soln. Ostwald’s Dilution Law: For Weak Electrolytes: Equilibrium exists between weak electrolytes and its ions at constant temperature. ABO AY OBE t=0 1 ° 0 t = eg. l-o a a iro a « v v Molar concentration, ~~ {AB} _ C/V) /v) xe [AB) fi-% Vow = Tay Porwork electrolyte 1a = 1) =a) 2 : a K-F 2 kV=@ 2 a= MV = [ol Degree of dissociation is directly proportional to the dilution.| J ons ral. pon sure, lonie Equilibria Soln. Limitation: () This Jaw isnot applicable for strong electrolytes Ct dilution and dissociation does not occur on dilution. (i) This law is not applicable for concentrated solution since a and molar concentration (m) are different for concentrated solution. ABO OS AY + OB ic o 0 C-€a Ca Ca , strong electrolytes dissociates completely at all uct) Cw ae Cea > K* & Weak clectrolyte(1~a)=1, K CH,COOH) == CH,COO- + Ht 0.016 0 9 0.016 ~ 0.016 = 0.04 6.04%0.06 —0.06%0.04 © Factors Affecting Degree of Dissociation («.): (@ Nature of electrolyte: Weak electroiyte a < Strong electrolyte & igher the dielectric constant (Solvation power) of the solvent, the higher will be Gi) Nature of solvent: o: and vice-versa, (ii) Temperature: On increasing T, «increasing (iv) Dilution: On increasing dilution, « increasing for (weak electrolyte) (v) Common Jon Effect: The dissociation of a weak electrolyte decreases in the presence of a strong electrofyte having common ions. This effect is called common ion effect. eg. CH,COOH == CH,COO- +H", HCL == H+ Cr «a. decreasing with common ion effect, K x 10° ~ Weak Electrolyte K> 10% - Strong Electrolytea @ wares |e Problem-2, Determine the concentration of hydroxyl ions (OH?) in 0.4M NH, OH solation having (I) No |p NH,Cl (2) 5.35g NH,Cl, Kyacgon = £8 » 10% 2 Soin, (1) NHOH == NH,’ + OH- } ood 0.4 0 0 ‘soln. p 04-040 040 04a, x Co 0402 P ao? a) PB 18x 105~ 1.8 x 1050 = 04a 04a? + 18 x 1054 - 18 x 105=0 P Ko fissio joasxio : SOT Og PON 940 = [ a= 1075 @ ~ 06787 x 102 - Be Ga FXO a = 04 [OH"] = 0.44 = [OH] = 0.26 x 10% = [OH] = 2.6 « 10% 5.35g NH,Cl « 0.1M NH,C! INH," JOH 7 [ x ~ NEAT J x= lon A [NH,OH] 04 7 [OW] = 7.2 « 105 it If Problem-3. Nicotinic Acid (K, = 1.4 » 10) is represented by the formule H Nic. Calculate the percentage : dissociation of H Ni,c at equilibrium which contains 0.1 mole of HNie per litre of solution. a Soin, HNic —> Ht + Nic € 0.05 a 6 Sola, pt 0.05~0.05a 6.05a 0.05a = 0.0507 ¢ leo) For weak electrolyte, : tt 0 => @ 2167x107 Pp Percentage o, = 16.7 x 10° x 100 = 1.67% Son, H Tonic Product of Water: HO <= HY+OH- e @ = HOH). Koy = ary ore [Ky=i OHI] = K, = 10a ac & wo THONo wntage °C onic Equilibria Soln, Soln. q it Problem-4, The K,, for water for the following equilibrium, 2H,0 == HOt + OF changes from 107 at 25°C to 9.62 x 10 at 60°C, Calculate the pH and nature at 60°C. pH =-log("], K, = [H'] [OH], 9.62 10=x? x= 962x107 = x = 3.18 x 107 pH = -log[3.18 x 107] pH= 6.51 pH value: Negative logrithm of H’ ion concentration. pH=—log[H’ ] ct [i] (#" [on ]=K, pH=—log pH+pOH=pK, at 25°C, K, log k= log 104 = -14=> pK, = -log K, = 14 At 25°C IfpH =7, solution is neutral, fp <7, solution is acidic If pH > 7, solution is basic Problem-S. Calculate the pH for (1) 5» 10M Ca(OH), 200m! H,0 (3) Decinormal solution of CH,COOH having 1.3% dissociation, pOH = -log(10 x 10°°]=> pOH = -log{10~]=> pOH = 4 = pH=4-4=10 36.5x10% (2) pH= see S| => pH = -log{l0*]= pH=3 (3) Decinormal = 0.1 BY] = Gq =01 x 2 ptt = ogl tt) 100 Problem-6, What is the pH of 5 x 10N HCP HCI=H'+Cr — and--H,O= HY + OF 5x 10% x x (H*] [OH] = 10°"* (Acid + water) [5 x 10+ x] [x] = 10-4 (2) 73 * 107g HCI dissolved inSoles. Soln. Soln. Soln, & ee x49 * 10% — 104 = 0 => x= 7.8 x 10% Soln. pH =~log [x + 5 * 10°] = pH = 6.95 Problem-7. What is the pH of 5 x 10%M NaOH {H'] (OY = 10 base + water x5 * 108 +x) = 104 = x= 7.8 x 10% PH = -log(H*]=> pH = -log(7.8 * 10) => pH = 7.8 Probjem-8. Calculate the percentage decrease in the concentration of H* ions of water in the presence ol M HCL for the following two cases (i) when K, = 10"! (ii) Kw = 10-4. Soln, 9.910% ty S100 = 9.5 (1) Percentage decreasing ~ ——~ 1 (2) fH] [OH] = 10" Acid + water (x + 10)x = 10M x2 + 107K — 10-4 = 0 x= 6.1 108 107 6.110% Percentage decreasing = mas S100 = 38.19% (1) {H"] [OH] = 107 (x + 107%)x = 10° x? + 107 ~ 10°” = 0 x= 9.9 x 10% 1 9x10-% Percentage decreasing = ——S 93 — = 0.5 Problem-9, Formic acid 4.5% dissociated in 0.1M solution at 20°C, Calculate dissociation constant (K,) 0.1% (4.5/100)* * 1-(4.5/ 100) Problem-10, The dissociation constant of a weak acid (K, = 4.9 x 10). Calculate the pH and OH concentration in decinormal solution. => K,=212 x 104 poke {49x10 Vo°V a1 2 = DUO 49» 10? Ia Ola? 44.9107 44,9 x10 =0 => a=0.49 fH] = Ca = 0.1 x 0.49 pH = -log(0.1 * 0.49) => pH= 13 pOH = 14~ 13 = 12.7 te O99 = atitnerl 17 Ths (ORF = 10-27 —nee of Soln. t(K) dOH & w Problem-11. What is the pH of IM HCN (K, = 4.8 * 10-4)? IK, _ [4.8x10-! ‘ a= foe = J 10" Yo VOY * Here, a <<1 pH =-log(VKC] = pHi = -log [4.8107 x1) =>pH = log¢7 « 10) pH = -log? + 6= pH = 0.8 + 6=>pH = 5.2 Problem-12. pH of the solution which contains 100ml of 0.1M HCI and 9.9ml of 1M NaOH will be M C= => M=CV v HCl +NaOH > NaCl +H, 1099 0 0 01 0 0.1 milimoles of [H"] ol TE) T0499 PH = og[H"] => pH = Relative Strength of Weak Acids and Bas ‘The relative strength of two weak acids is equal to the ratio of their concentration of H’ ions liberated by thom. Let HA, and HA, be any two weak acids. HA, == Ho+ A c 0 0 C\(l-ay) Ca, Cay HA, ea G 0 0 C,(1-a) Ca, C0 Relative strength of Acid (1) wart. Acid (2), ed from HA, Cia, [H*Jions furnished fromHA, ~ C202 (For weak acids, a cak acids, a= |X ee Vea J lonic Equilibria, Ionic E Problem-14, Find the relative strength of X watt. Y wheve X and Y are tivo week acids having same initid concentration of 0.0(M and dissociation constant: K,, = 1.02 « 107, K, = 11S x 10%. Soln, Relative Strength = Soin. . 02%107 Relative Strength = => Relative Strength = 2.978 Viasxio pH of the Mixtures: (1) Mixture of a Weak Acid and Strong Acid: Problem-15, Calculate the pH! of a mixture of 10-°M acetic acid having 4% degree of dissociation with 10? M HCl, Soln... Let we have two acids HA (weak acid) and HIB (strong acid) HA KB Concentration iG c, Degree of dissociation a , HA == Ww & ci 0 0 C\(-a,) Ca) Ca (H) =C,o, HB. eee + B ie o 0 0 cs oy (CO, HB is a strong acid) (H=C, Now, | (H"}, = Cyoy +C, | when o is given [Kr fH, = GJ-t+c, TYG (H*Jp = YK,C, +C, | when K is given and pH = -log[H'], Problem-16. What concentration of formate ion is present in a solution of 0.015M HCOOH and 0.02 M HCl, K, HCOOH) = 1.8 * 10“. Soln, Direct formula is not used CO, in equation common ions effect is not incfuded. HCOOH = HCOO- + Ht __ [COO "}{H"} 4, [HCOO7}x0.02 2° “THcoony > SIO is [wiceinitial Problem-17. Calculate the concentration of H' ions in a solution containing 0.IM HCOOH and 0.1M HOCN. a ve | cs = a = vba 3x10 = 33x10 = 1) = 5.09 « 107 2 | [Ht] = Cyay+Cyay = (0.1 * 4.12) « 10 + (0.1 x 5.09) x 10? sn with) Here in question common ion effect is not included CO, ,K, and K,, are given for separate solutions and not for mixture therefore direct formula can not be applied. HCOOH === + = HCOO™ | Ol 0 0 O1-x (x+y) x HOCN == HY + OCN Ol 0 0 y (x+y) y (The concentration of common ion will be constant =x + y) COOH] x(x+y) 1 a = eTACOOnIES =18%10 K,= “THcoony) ~ o1-x 18" => x(x + y) = 18 «104% 0.1 = 18 x 10% 0) and similarly {OCNTIHY]_yox+y) 4 HOON oy 33x10 =33 x 105 . % [HOCN) ~ O.1-y % yx + y) = 3.3 * 10 Q Dividing (1) by @) x(x+y)_18x05 x_ 18 rs ~ x= 0,545: yoary) 330057 y 33 > : Putting the value of in equation (1) 0.545y(0.545y + y) = 1.8 x 10-5=50.545y(1.545y) = 1.8 * \0%= 0.842 y= 1.8 x 10% 0.02 — = y= 4.62 « 107 x= 0.545 x 462 x 107=2.519 x 107 (H], = x4 y=213« 109MSoln. Soln. + HA 0 c(-a,) (Ca + CHa) Coy HAY ie + ow Cay (1-049) (Coa, + Ca) Cay + ap 2) Soln. K,= [HWA] _ (Co, + Coy, )(Coyag) [HA] Cay (1~a) pH =—loglH"}, pH = -logiCoy + Coy ag] Problem-18. The molar concentration of H*, HCO,” and CO,2> in a 0.01M solution of carbonic acid having pH of 4.18 will be? K, = 4.45 x 107, K, = 4.69 « 10! H,CO, HCO, + #F 0.01 0 0 0.01(1 - 0) 0.01a, 0.01 a) HC = fey + CO, 0.0Lay 0 0 0.01.04(1 ~ a) 0.01 4 ty 0.01.04 a _ COS HR (H"ICO;™) HCO) > 2 THcoy] pH =-log(H"] => (H’] = 107 = 6.61 x 105 6.61x10°)(ACOs” >, 661x107 {HCO,~ 6.6110" (COs Daas x 107 = pel eI OaTEcOseles [HCO,"] = 6.73 x 10% 0.01 0.01 (661x107 jCO;*"} 61x10 [CO] © 67x10 Problem-19. | litre of an acidic solution of pH = 2 is mixed with 2 litre of other acidic solution of pH = 3. Calculate the pH of the resulting mixture. pH =2 => [H*] = 107 pH =3 => (H*]= 10% my, + m,¥, = Mg Vp => 4.69 x 10th = => [CO] = 4.78 x 101! lonic Equilibria jonicEqu M Mp acid ion of 10? x 1+ 107 2=M,x3 M, = 4 * 107 (H'}, = 4% 107 pH = -log[H"],=> pH = 2.39 Problem-20. A solution of HCI has a pH = 5, iff Im of this solution is diluted to 1 litre then pHi of the resulting solution will be? MY, = MN, 10°S x Iml = Mg x 1000ml [Hg = 109M, [Hue = 107, FAI ggig = 10% pH = -log(0"? + 10°). pH =—log(107 +10") (1 HH =—log 10” wt) 10 pH =~[logl.1-71og10] pH =-[0.0413-7] = pH=69 Conjugate Acid-Base Pair: Conjugate acid of a Base = Base + Addition of H’, Conjugate base of an Acid = Acid — H* Conjugate Base and Acid differ by I-Proton HX —F + & K (PC) Ky o= (Acidityconstants) [HX] (ly X + HO —=HX+ OH [HX] [OH] K yy ww (2) (easciyeonnay— EX] @ Multiplying (1) and (2), we get HTVIXT) [HXJIOH K> k= THX] oy K, « K, = [") (OH) K,xK, =K, => log, + log K, = log K, ~(log K,) + (log K,) = Clog K,) uSoln. Soln, aS eee => pK, +pK,=pK, = (pK, pK, =14 | Note: For any conjugate acid-base pair the lesser the p® value, the stronger will be the acid and hence (yy weaker will be its conjugate base. Problem-21. The pH of pure water at 25°C and 35°C are 786 respectively. The heat of formation of water will be? aa 2) RUD) At 25°C HO —= H+ OH 1H) [OH] = [H']= 107 K, = 107 x 107 = 10° AH by ti] 2ealK™! mole| TT, | AH [308-298 2cal mole!| ass In(l0?) = AH = 84.551K cal mot! ‘Therefore, AH formation = —AH (negative of the heat of dissociation) = ~84.551 K cal mol! Problem-22. The pH of a solution obtained by mixing 10m! of 0.1M HCl and 40ml of 0.2M H,SO, will be? mv, + mv, = MVq O.1 x 107 + 0.2 x4 x 107=M, x5 « 107 17x10 17x10! _ 17 po I My = PIO = EP = 034 5x10 5 (H"], = 0.34, pH =—log(H1"],, pH =—log(0.34), pH = 0.68 Salt-Hydrolysis: Salts are strong electrolytes when dissolved in water they dissociates completely g BAS= BY + A Ifcation reacts with water, the resulting solution is acidic and it is called cationic hydrolysis. BY + HO == BOH + Ht Ifanion reacts with water, the resulting solution is alkali A + HO ==HA +0 ing cations and anions. and H is called anionic hydrolysislonic Equilibria nce ater will ons, a The phenomenon of the interaction of cation or anior of the saft with water producing acidic or alkaline solution is called salt Aydrolysis. Salt Hydrolysis of Salts of Strong acid and Weak Base: NH,Cl +H,0 —= HCl + NH,OH Salt Strong Acid Weak base ‘NU,’ + Cr +H,0 == H*+ Cr +NH,OH NH,’ +H,0 == H' + NH,OH (H"] [NH,OH) Ki . M " (yeep onsen) [NHA"] ay Other equilibrium constants, HO == H* + OH Kw = [H"] [OH] Q) and NHOH == NH, + OHD (NH,*][OH™] [NH,OH} ~ G) ‘Multiplying equation (1) and (3), we get [H"] [NH,OH. NH,*][OH”] =[H JOH ]=Ky Kk, [NH,*] [NH,OH] —. = Kae Le Use of K,: NH,’ + HO — WH + NHOH ic 0 0 cU-h) Ch ch [H'}=Ch Ch _ cr? — =H0-h=1n h=bria lonic Equilibria [OH] = Ch= ope = VKyC = [0H] = loglOH} [logk, -logK, + loge] 1 => log [OH] = ql log Ky —(-logK,)~loge] pow 1 1 plPKe—PKs - loge] 5 | POH => [PK —PK, 1 + pOH =14 = pH = 14—~[pK, ~pK, —loge] > plt= Sek, +0K, roe] Using pK, =14 (pK, + loge) = | pH=7+4 Salt hydrolysis of salt of weak acid and weak base: CH,COONH, + H,0 CHCOOH = + NH,OH Weak Base Weak acid 00° + NH, + HO <= CH,COOH + NH,OH [CH,COOH][NH,OH] . K, = [CH,COO”][NH,"] a) #0 — H+ 0H K, = [H) [08] -Q) CH,COOH = CH,COO- + Ht [CH,COO7][H*] [CH,COOH) -G) NH,OH == NH,’ + OH H4" [OH] K NH,OH] ~~ @) Multiplying (1) (3) and (4) we get [CHyCOOHJENE OH}, [CH COO” IH], [NH,* LOH") kK, 7 K i K, © TECOO UNE TCH.COQHT TNH. i w®76 lonic Equilibria | tonic Eq 1 aor 1 x *K = (Ht K, * K, * K, = (HT [OH | ; CH,COO- + NH,’ +H,O === CH,COOH + NH,OH | @ ic 0 0 1 ch) cn) ch ch ( € ( i e ( a kKy=W a h= f= =e \ F : = LKR | ( Now, CH,COOH <== CH,COO™ + Ht In the presence of salt the above process wil be in reverse direction CO, salt ako gives CH,COO" ions. 0 Cc E ch cay =f") (H) Si es k= Slee ch ny ) - : LK, a (KukKs [1] =Kh >[H*]=K, VK xK, 2 Kea) ft losft¥] = HlosKy +o, -logk] 1 og{H'] = 5[-loeKy logK, ~(-logKy)} _———— pH=—[pK, —pk, PK] 4, Salt Hydrolysis of Salt of Strong Acid and Strong Base: NaCl+H,O == HCI + NaOH Strong Acid Strong Base Net + cr +H,O == Ht+Ch+ Nat + OH * HO ==+H'+OH Such salts do not undergo salt hydrolysis 2 Bria —_lonic Equilibria Buffer Solutions: The solution which opposes the change in their pH value on addition of small amount of strong acid or strong base. pH of buffer solution are reversed. \ ‘Type of Buffer solution | (a) Acidic Buffer : Mixture of weak acid and its salts with strong base e.g, CH,COOH + CH,COONa ; HCN + NaCN (b) Basic Buffer : Mixture of weak base and its salt with strong acid. e.g. NHOH +NH,Cl, NH,OH + NH.NO, (©) Simple Buffer: NaH,PO,, Na,HPO,. pH of Buffer Solutio (a) Acidic Buffer: CH,COOH +CH,COONa CH,COOH == CH,COO" +H" CH,COONa —=CH,COO" + Na* Bylaw of chemical equilibria, kK _[ex,coo” |[H"] “~ [CH,COOH] [e] ats {c,coon] {.CH,Coo™ | ‘Taking log both ses, we obtain that 7 [cH,cooH] tog} H* |= ent log[ H" | leak, #8 C00" -logl H*]=-logk, — fog HCOOH] «(A }=-tog +l cH,coo | eat cH,COO"} ee +198 cH,COOH] where, K,= dissociation constant ofacid CH,COO™ | = initial concentration of salt, [CH,COOH] = initial concentration ofacid. 2. Basic Buffer: NH,OH + NH,OH™ NH,OH == NH; +OH™lonic Equilibria) !on'eE Soln, NH,Cl==NHj +c By law ofchemical equilibrium, [por] ~[NH,OB} 2 4 _K,[NH.OH] bse] taking log both sides, we obtain that log[ OH” =logK, +1og{NH,OH]-log{ NH; } = [oH [NH,OH] [Nu] ~log[ OH” ]=—logk, + log Problem-23, The pH of buffer solution containing 410° and 0.4 moles of acidic acid (pK, sodium acetate respectively will be (2) 6.76 (b) 4.76 (©)2.% (6) 0.76 We know that [sate] [acid] [oa] HH = 4.76 log — f : "Tax 0 a pH =4.76 + log 10° pH=4.76-+2 fog 10 }.76 + 2.00 log, 10=1 16 (log ,10= 1] ae pH=pK, +log Correct answer is (a) Problem-24. One mole of each HCO, NaHCO, and Na,CO, are added to value to prepare | litre solution. ‘The pH ofsolution. (Given: pKa, = 6.37 and pKa, (2)6.37 (6/831 (6) 10.25 (a7 H,CO, =H" +HCO; pK, =6.37 HCO; =H" +C0; pK,, =10.25 0 NaHCO, — Na” +HCO; Na,CO, —>2Na* +CO; According to equation (i), _ [a] fae * [H,CO,]onic Equilibria (w]- a uillibria Since, given that, pK, = 637 and pK,, =10.25 K, =10°" and K,, =10"* K,, [HCO;] Since, eeondtem, “gg neelected becasel 0" is very low than 10”, 76) and - [1,00] A] =- log [w'],=-bex, -rel L pH= pk, ~log7 pH =637-0 pH=6.37 Correct answers (a) Problem-25, A certain buffer solution contains equal concentration of A- and HA. The K, for Avis L0"". The pH ofbufferis @7 (b) 10 (4 @i4 Soln. At25°C, K,xK, =10" solution ~logK, -logK, =14 pk, +pK, = 14 @ Since, @ Fromequation(j) and (i) pk, +10=14 pK, =14-10=4 Correct answers (c)aS a ae Stability Product (K,): At constant temperature and in saturated solution of sparingly soluble electrolyte, undissolved soli, dis- } solved solid and ts ions remains in equilibrium with one another, eg. AgCl(s)*AgCl(aq)——=Ag'Cl- ae'I[a j because, was AgCl(aq) = Ag’Cl er] fac] [ae [ag jer] cy [PS [aecit 1G] , [where KK, = K] = [Agci(s)}«K=(Ag"][cr'] K, [ae'Jer]], where fK, ABCs) x K] So, we say that, at constant temperature and in a saturated solution, the product of concentration of constant ofa soluble electroyte remains constant and this constant is called solubility product. Ag,CrO, 2g + C10, «, <[oe Toor] eg A,By===xA" +yB™ Relationship between solubility and solubility product: Solubility: Concentration ofsaturated solution at constant temperature or minimum amount of solutes dissolve inone litre of solution at constant temperature. eg. (i) AgCl—=Ag’Cl smolelit ss 9 [Ag ]fcr] — lonic (i @ Gi aEe] (i) AgCr0, = 2Ag" + Cr smolefit 2s [GATE] K, =[Ag" ] [cror] K,=(25)'(s) \ For general equation: | AB, ==xA | smoleflit xs ys Solubility product and ionic product: «stant (i If ionieproduct> K,, —> precipitation — (super saturated solution) (iit iovicproduct No precipitation — (unsaturated solution) (i Ion product = Ky — saturated solution issolvelonic PRACTICE SET B. 1. The following equilibriumis established for an aqueousacetic acid solution CH,COOH @2 CH,COO-+1® Upon addition of 2.0 g of solid sodium chloride to 20 ml of IN solution of acetic acid, (2) The pH ofthesolution doesnot change —_(b) The pH of the solution decreases (©) The pH of the solution increases (d) The pH of the solution is 7 2. The ionization constant of formic acid, which ionizes to an extent of 4.2% in 0, 1 Maqueous solutions “ (a) 0,92 * 107 (b) 1.84x107 (©) 184x104 (d) 092x107 3. The pH ofa buffer solution containing 4 x 10° and 0.4 moles of acetic acid (PK, =4.76) and sodiumacetate respectively willbe 15, (6.76 (b) 4.76 (2.76 (0.76 4, Given K, for NH, as 1.85% 10°, the pH of 0.2 N NH,Cl solutionis (a)4.98 (b) 5.02 (5.13 (6.87 5. Thedissociation constant ofa weak acid Ha is 2.5 x 10%at 25°C. The degree of hydrolysis of 0.01 Mofits sodium salt NaA wil be approximately, (a)2* 10" (b) 110" (00.02 (2104 6. A 10 mL of 0.1 M ofan acid (K, =10*) is titrated with 0.05 M NaOH solution, After adding 40 mL of NaOH solution, pH! ofresulting solution is (a) 123 (11.0 (92 (50 7. Solubility product of AgClis 1.6%10" at 25°C. The maximum concentration of Ag" ions in a 0.1 M solution of NaClat 25° Cis: @ 16x10°M (b) 1.265x10° M_—(©)1.6x10""M (@) 1.26510’ 8. One ml ofa solution of pH.6 is diluted to 1000 mL. The pH of the resulting solution isnearly equal to (a)7 (0) 6.5 (9 (d)7.5 9. K,, values for Cu, FeS, PbS and ZnS are 8.510“, 6,310", 3.4x10 and 1.6%10* respectively. If HS gas is passed through a solution containing these ions with same molar concentration, the ion that will precipitate first is: (@) Pb 6) zn © Fe (a) Cu 10. Onmixing 120 ml of 0.05 M CH,COOH and 40 ml of 0,05 M of NaOH, the pH of the solution is (pk, =-logk,) (a) pKa+0.69 (b) pKa +0301 (©) pKa (@) pKa-0.69 IL Strontium sulphate (StSO,) precipitates when aqueous sodium sulphate solution is added toa strontium nitrate solution, What will be the strontium ion, Sr, concentration remaining after 30.0 mL of 0.10 MNa.$0, is added to 70.0 mL of 0.20 M Sr(NO,), solution? (04M (b) 0.15 M (011M (4) 0.20M 12. The dissociation constant ofa weak acid HX at a given temperature is 2.5%10°. The pH of 0.01 MNaX al this temperature is (a)73 (b)7.7 (8.3 @8.7bria | onic Equilibria 13. Forthe reaction A, 2A ina closed container, the relation between the degree of dissociation («1) and the equilibrium constant K, ata fixed temperature is given by a a @ a=[K,/(K, +49) (©) a=[K,/(K, +40) /* (9 a=[(K, +40)/k, ] @ a-[(K,+40)/«, 72 14, 10 mlof0.02 MNaOH is added to 10 ml of 0.02 M acetic acid (pK, =4.75). The pH of the solution will be closest to state (7.0 (b) 8.4 (5.6 (a9. | 15. Anaqueous solution contains 0.300 mole L' of KH,PO, and 0.0150 mole L~' of KMPO,. Which of the | following statement(s)sfare true about this solution ? (TIPR: 2015] | (a) Itcan act as a buffer solution around pH= 7.0 (b) Itcan act as a buffer solution around pH = 12 | (6) Its pH will approximately equalto 6.9 ofits (@ Both (a) and (c) ANSWER KEY Questions 1 2 3 4 S Lof Option aj @ fl (a) (@) | Questions 6 _7 8 9 10 \ Option (a) {a) (a) (@) (c) | Questions i 2 3B 1 15 ution Option © @ ) (b) a) \ \ aly. If will ritrate 30, i) aXalElectr Chapter 4 Electroanalytical Methods Electrolytic polarisation: Z ‘Whatever potential measurement, we did in the previous chapter, was the E.M.Fs of reversible cells Under the reversible conditions either there is no net flow of current or the magnitude of the current passing isso minute that tte electrodes are not sensibly disturbed fiom their equilibrium condition. Ifthe conditions are such that there is an actual passage of current, the electrode is disturbed from its equilibrium condition; this disturbance ofequiirium associated with the flow of current is called electrolytic polarisation and the disturbed electrode is said to be polarised. ‘The type ofpolarisation dependson the nature ofslow process, Polarised electrodes are often said to behave ireversibly and the phenomenon associated with palarisation are often referred as irreversible electrode phenomenon. Concentration polarisation: This ype of polarisation is due to changes inthe vicinity of the electrode. The concentration ofthe cations in che immeadiate vicinity of anode willbe greater than in thebulk ofthe solution (due to slow diffusion of cations w. r,t. cation generation), Similarly concentration of cations in contact with the cathode i fess than the bulk ofthe solution Concentration polavisation can be reduced by increasing temperature or agitating the electrolyte Concentration polarisation at cathode due slow ionic diffusion : Activity > © Distance from Cathode Due to the relative slowness ofudiffusion the concentration and activity ofthe ions at the electrode surface differs from that in the bulk ofthe solution. Actual extention of concentration gradient is from K toM Forgeneral practice, we can assume that concentration is varying linearly from K to N. Accordingto Fick’s Jaw, the rate of diffusion of a particular ionic species per unit exposed area of electrode (i.e; aumiser ofions diffusing per unit area per sec.) across the layer KN is given by, dS @ -2ee-a) a here E a iffusion coefficient of the ions, 5 =thickness of hypothetical diffusion layer = activity in solution side i.e, in the bulkectromatialMethos ia a activity at the electrode suface L Let n= no, ofelectrons involved in the discharge process ¥ Inet current density (current/arca) at electrode ' cathode —_ = netrate of discharge of ion per unit area tun nF uit, } D(a), Rew, i = rate of discharge per unit area due to transference | LJ _ 5 (a—a,) = rate of discharge per unit area due to diffusion. tl J jee Tnder ar me (ea) omits lytic: (a-a,) 2) a here t= 1-t, , represents the sum of the transference numbers in the diffusion layer of all the ions other than the one being discharged. DnF Let k GB) a fiom equation (2), T=k(a-a,) 4) (5) Determination of concentration polarisation (AE) : For the reversible reaction at cathode M" +ne"-—> M wo RT, 1 E, = E?-—_In a, = activity of M'*near cathode | (6) If there would have no concentration gradient then activity of M’* near electode would have same value wurface asin the bulk ie., ‘a’ corresponding potential E =E? +. a Ina (7) Fick’s nF ofions concentration poarisation (AE) or, AB=RT yy * , AE From equation(4) a, : nF a,iS Eteceromnalvtoalcthode| Sect Rivals AE =——h nF ka—T & ‘When concentration or activity of ions in the bulk ofthe solution is high then for a given current density (1) theextent ofconcentration polarisation is small DaF AE can also be decreased fora given I, via increase in value of k (ic es } and this can be achieved either by decreasing the thickness (5) ofdifflusion layer (Le., by agitating the solution), or by increasing the diffusion coefficient “D’ of the ions e.g., by raising the temperature, The Limiting current density (L,): Fromequation (7) A 2 é 5 6 0 3 05 Applied potential (V) ‘ ae= y= Tuoi] oF yl oF ka) ia (fae Por sma alee For small value of I, ( Bleue f , a=RT ifs 1) 2503EE gl z oF \ ka nF ka 2303RT(I PY nF (ka 2k?a? As Lis small so neglecting higher order terms ( 2308) AE=) (nF ka {AE a I] (for small value of 1) So upto AB region of graph can be explained by above analysis Half-Wave potential : The half-wave potential, E,, is characteristic of the electroactive material. Consider the reversible and rapid half-cell reaction at the microelectrode. Ox +ne—>Red where Ox is the substance being reduced and Red stands for the product. The constituents of the thinlayer in the film surrounding the microelectrode are in instantaneous equilibrium with the electrode surface. Hence, the¥O either | Fusion xd rapid ilayerin nee, the electrode potential is given by the Nernst equation. Accordingly, 0.0591, [Red] 0.0591, lo "fox, = () where the zero subscripts denote that the concentrations apply only to the film surroundig the DME which acts as cathode. The applied potential is given by Ecppted = Fostede + Eonode ~@Q) The anode is the saturated calomel electrode (SCE). Hence, we can write E, cathode 0 0.0591, [Red] Exppieg = E n log: [ox 1 +E sce GB) 0.0591, [Red] Ecppiiea ~Esce —— log: Tox], (A) lo Suppose the beginning, the solution at the electrode surface consists only ofthe oxidized form, When the applied voltage is sufficiently large to reduce some of the oxidant, the oxidant concentration at the electrode surface starts decreasing. Some ions move towards the surface of the micraeiectrode from the bulk ofthe solution building up a concentration gradient, Thus, at the applied voltage, the observed current is given by i=K ([Ox]-[Or],} 6) where K stands for the capillary characteristics and other cosntants of the IIkovie equation. At the diffusion current plateau, the concentration of the oxidant at the electrode surface is virtually zero so that diffwsion current is given by i, = K[Ox] © Subtracting equation (6) from equation (5), we get fOr}, =(i.—#) ik o Agaii, the concentration of the product Red at the electrode surface, provided its soluble, italso given by i=K'[Red], (8) where, K *is another constant analogous to K. Or, [Red], =WK* (9) Substituting equation (7) and (8) into equation (4), we obtain, po 0.0591 tog: i n 0.0591, A i Bo Rewriting, + nS oe (10) By defintion, when =i /2, Bapied = Evra (ty Substituting in equation (10), we get po Bo 20 og K oa make(sa) Electroanalytical Methods t 5 +1 ++ A0 05 0 105 +10 lool] + Graphics representation of equation rte polarographic wave. Determination of We see from equation (12) that the hal wave potential is a constant which depends on the standard potential ofthe redox system and is independent ofthe concentration of the electroactive substance. Substituting equa- tion (12) in equation (10), we obtain, 0.0591, i log osy (13) = By plied Equation (13) isthe equation of the polarographic wave. A plot ofF,,,¥et5¥s (j, 1) sivesastraght line ) 0.0591 ‘rom the slope, the value of n, viz, the number of electrons gained by the with slope equal to ~ reductant, can be determined. From the plot , E,, can also be determined. From the plot, E,, can also be i (a-i) By means ofthe polarographic technique, concentrations in the range of 10° to 10+ M, and some- times as low as 10-°M, can be determined. The polarographic method is seldom used for qualitative of substances because several substances give the same value of half-wave potentials and hence are not easily distinguishable from one another. BC Region of Graph: From point “B’ onwards as the value of ls increased AE incteases very rapidly. Fromequation (7), we can determined. It is the potential at which theterm log. =0,ie. when f= say that this will occur when I -> ka and infict when I is equal to ka, the concentration polarisation should theoretically, increase to infinity. Actually of course, a finite increase of potential (by X-axis distance BC) occures, as shown in figure until the discharge of another cation begins (.e., region CD), The current density at which the rapid increase of potential is observed is called the limiting current density ({,), because it represents the limiting (maximum) rate at which the particular ions can be dischargedumnder the given experimental conditions. The magnitude ofthe limiting current density (C:D)is given by equating ka to DnF 1, and inserting —— for k, thus DnF (9) Since, Lg o bulk activity (a) Comparision of equation (2) and (8) shows that, when the limiting C.D is reached, the concentrationor activity (a,) of ions at the electrode has fallen tozera, therefore, the rate of diffusion ofions to the electrode must be then a maximum. | Blectrrds tial qua- line y the vo be veof sasily ecan vould :BC) nsity erthe kato stivity ast be peecewe ere a Ifka term in equation (8) is replaced by I,, the result is, Concentration Polarisation |E = (10) Ymportance of using supporting electrolyte and diffusion current: Usually inthe solution, we introduce an excess ofan indifferent electrolyte (also called supporting electrolyte) which carries the whole ofthe current. So, under this condition t=1. So equation (9) becomes DaF a a=k ane All) Limiting current as given by equation is often called the diffusion current, since tis a measure of maximum. rate at which the charged ions can be brought up to the electrode by diffusion alone. From equation(1) it follow that, Diffusion current ‘Thickness of diffusion layer Relation between diffusion coeff. (D) and molar ionic conductance (2.,,) ofion : LRT Nernst-Einstein equation |D ZF (13) Z=charge onion, Relation between 5 and i, From eq (12) and (13) 2,RT na Zp |, | em (ormeter) (14) Overpotential (1) + . ‘The difference between the potential of the electrode when gas evolution was actually observed and the theo- retical reversible value for the same solution was called overvoltage or overpotential. The point at which there is visible evolution of hydrogen or oxygen gas in the form of bubbles has no theoretical significance, although the potential corresponds approximately to that where appreciable current begins to flow (point D in figure) nevertheless t Current density DS Call Voliage —> the results are of practical interest in connection with the possiblity of hydrogen evolution as analternate proccess in electrolytic reduction and metal depesition. Note: Over potentialis also know with the name “minimumovervoltage” or “bubble overvoltage”. Overpotential (1) always reduces the theoretical cell potential when current is flowing.Electroanalytical Methods Electr cis) overpotential means that in order to stant the redox reaction we willhave to apply a potential greater by value 1} (overpotential) on equilibrium potential (obtained from Nernst equation), Voltametry: Study of electrode processes (oxidation, reduction, rate ofteaction, ete) through the current whilst potential is varied. On the basis of potential function applied across the working electrode and the type of material used as working electrode, the voltametry can be classified into 4 -types:- (2) Linear sweep and eyelic voltametry ()Hytrodynamic voltmetry (©) pulse methods (@ polarography ret Ei (a) Linear sweep voltametry (LSV) and cyclic voltmetry (C.V) : Inlinear sweep, the potential is varied linearly in one direction, and the electrode used is stationary electrode. ig + ve y i aa time ~> (Triangular potential function in C.V;) Incyclic Vokametry triangular potential wave is applied. \. (b) Hydrodynamic voltametry: Inthis case different methods can be employed (stirring the electrolyte solution while keeping the electrode fixed or (ii) rotatate the electrode at a very high constant speed in the electroyte. This technique is known as rotating dise voltametry, Here the working electrode potential is solwly swept back and froth across the formal potential ofanalyte, (© Pulse methods: Different types of wave forms (of potential) are applied ondropping mercury electrode (OME) or stationary electrodes. The main aim js to reduce the capacitative currents and oise in current response. y t 1 1 Potential Vv v pt — tine > pat eae eee Dilfecental Pulse Vollammetey) (Sweep Wve voltae (Normal Pulse Voltammetry) Fy) (Sweep Wave volinmety (@) Polarography: An clectrochemical method of analysis particularly suitable for dilute solution of sub stances which are susceptible to electrolytic reduction (or oxidation) ata mercury cathode, | + Current (i) is plotted against voltage (V), generally using a clean surface such as dropping mercury elec | trode (DME), although Pt electrodes can be used. |tods value rent ad as rode, wnas iss the strode urrent of sub- yelec- cannes @ om + ivsV plot is said to be polarogram + Polarogram showsa step for each reducible species present in solution + This step is ofcharacteristic potential (E,,) and of height proportional to the cocentration of component and number ofelectron in the process. t i | —— step Height ae —___ yo Polerogram (each step is for specific ion) * This method is particularly usefull for determination of trace amounts of metal and for investigation of complexes in solution and for studies in non-aqueous solvents ‘The dropping mercury cathode: This polarographic technique was developed by Heyrovsky. [tis based on the principle ofthe limiting or diffusion current Fig: Dropping mercury cathode. Air in vessel and the dissolved oxygen in the test solution are driven out by an inert gas like N, bubbling through the solution, before taking readings. If O, is not removed then it will be reduced to HO, and then HG and the redox system O, / HO, will givea polarogram, y+ 2H'+4e" = H,0, 0 04 08 12 16 20 Applied potential, V vs SCE (Polarogram due to oxygen, if present in test soltion}iS cectombatNetiode | He Let the test solution has Cu”, Pb”, Cd", Zn”, Mn”, Ba®?, Ca” and the’supporting electrolyte KCl (let0.1M). The concentration of supporting electrolyte is very high compared to concentration of reducible ions, The polarograph wil look as Current 02 06 #10 14 18 22 Potential > I Figure: Polarographic waves General Polarograph: Total current (I) = residual current + migration current + diffusion current { E> Residual current and Migration ewcrent(region AB): Residual current is due to minute concentration of impurities ike heavy metalions and also dissolved oxygen. This region also includes migration current due to transport of supporting electrolyte under the iafiuence of potential gradient, so if KClis the supporting electrolyte, then K” move toward the cathode ‘The supporting electrolyte isnt discharged, but forms a cloud close to the electrode, This positively charged cloud (due to K’) will attract the Cl ion, which forma layer, alittle farther away from the electrode, Thus an eletrical double layer results and some current is required to charge the double layer (which acts like a condenser) and maintain the layer this current known ascondenser current, Diffusion current (1,): Thisis duc to active species (ie. the reducible species). Tis only the active species that move to the electrode surface and get discharged there, by diffusion . Thus inthe current-voltage curve, the migration current is practically not included. Thus in portion BC in the curve corresponds to the current flow by diflusion, Point C conrespondsto the limiting current, since at this point, the diffusion is maximum, that is the current flow is maximum. Note: Region BC and DE in graph is said to be polaropgraphic curve wave. L(max) ‘The height ofthe wave shown in above figure is know as the diffusion current, |ods Iyte The from layer recies urve wrent » that Quantitaye treatment: The Mkovie equation: For dropping Hg-cathode, the (average) sion current is given as, [1,(avg.) = 607% mr 607n m’? tp”? C| es 9) 1, (max.}=706n m* Cc] “an Term Cone. af analyte (6) Meaurement Unit milli moles / liter l, Microampere ‘Number of charge on reducible ion (n) eg, for Cu”,n=2, for Ag*,n=1 Diffusion coeff. (D) om’ sec" Mass of Hg dropping per see ng avg time per drop seo Dependence of diffusion current (I,): £81.) «capillary characteristic or constant(m?” @(H)a. concentration (c) of reducible ion Gio n (charge on reducible cation) (iv) other factors (eg. siattire and composition of supporting electrolyte, pressure on the dropping Hg (which “affects drop time) besides temperature and viscosity of medium. Concept of Half Wave Potential: From concentration polarisation study at cathode due to slow ionic difusion, we have current density from equation (4). ()=K(a-a.) Where a=activity ofion in the bulk of solution and a, activity ofthe ion at the cathode For convenience replacing activity (a) by concentration (c) I=k(c-e,) Therefore, forthe half cell reaction Ox+ne>R Considering oxidised species (Ox): [Ox} = concentration of oxidising species in the bulk solution [Ox], = concentration of oxidising species at the cathode Tk, ([Ox]-[0x],) (18) Form equation (10), we can write 1, =Ko,[Ox] (19) Substituting [Ox] from equation (2) in equation (1) 20)Electroanalytical Methods Electr Considering Reduced species (R): [R],= concentration of reduced species at the cathode‘ [R] = concentration of reduced species in the bulk solution = 0 ‘We can write Tk RL [Lesa = I R]_=- Ray Ql) For the helfcell reaction (considering the reversible condition at cathode) In. i (22) Form equation (20) and (21) substituting [Ox], and [R}, in equation (22), av gp 20, alts) The help wave potential is defined as that potentialat which the current ‘Tis half the diffusion current ly. ie, [=1,/2 atE=E,, From equation (23) (24) ly ‘Where 6 isthe standard redox potential for Ow/R system From equation (23) and (24) Soln. (25) As ko, and ky ate constant and characteristic of the oxidised and reduced ions. ‘Therefore, farm equation (24). 2a» Soin, (Fig: graph depicting independence of Eyy warst.concentration of electroactive species)rods. oe | Electroanalytical Methods Note: (i) If ka, = Kg; then from equation(24) °, Ey, ie, half wave potential is the characteristic of the nature of the reducible species and is independent of concentration of electroactive species. (i) Ifany complexing agent makes acomplex with either Ror Ox, then it will disturb ionic concestration of R and Ox near the electrode. So acomplexing agent will affect E,,. (iil) Half wave potential is also dependent on concentration of supporting electrolyte Advantage and disadvantage of dropping mercury electrode (DME) ‘The advantages and disadvantages that this electrode has compared to other microclectrodes: (a) A fresh, smooth, reproducible drop is produced at regular intervais. This limits the effects ofcontamina- tion or poisoning of the electrode surface, (b) Many metals are reversibly reduced to amalgams. the surface. high ov ‘mercury electrode. This means that a number of mgtals withhigh ion potentials can stillbe reduced at thé Surface without reduction of water interfering withthe experiment. In suitable electrolyte solutions thé electrode may be used at negative potentials (relative to the SCE) of up to -2.6V before hydrogen is produced. The positive potential that may be used is limited to about 0.4¥ since at this value mercury is oxidised to H(). (4) The surface area of the drops can be calculated from the weight of the drops. These ae alladvantages ofthe dropping mercury electrode, but there are some disadvantagees too, mainly elated to the fact that, in the apparatus as shown, the size of teh drop changes with time and this complicates the electrochemistry. Most moder apparatus reduces these limitations by using a series of hanging drops (or even a single hanging drop) rather than a continuous streamof drops. i SOLVED PROBLEMS 1. _/“A substance undergoes a two electron reversible reduction at dropping mercury electrode and gives adiffusion at current of7.5 HA , When the potential at the dropping mercury electrode is -0.615Y, the current is 1.5 A The B,, (involt) will be (a)-0.683 (b) -0.674 (©)-0.652 (4) 0,633 | Soln. (a) From equation (8) we have \ Ty ae E=E,q-—In—— - | OF a7 1 [T=298k] | 0.615 =By, — 2959 tog! 2° 75-15 | = 0,615 =F, oO og 4 | 2 74 og 4 = 0615-9992 .240301- 0.633 volt. CalGulate the diffusion current using the polarographic equation using the following data for Cd reduc- tion [Ca] =3x10°M, D=0.72x10%cm? s“'; drop time =4s; mass of Hg falling persee= 3mg, Soln. Form Ikovic equation (in fixed units); 1, = 607q m™ t' D' C, here given, C=3 milli mole/lit Amp = 607 x32 6 e(0.7210)" BARE = 25.6110" APP _ 95.61 ya Jom?/ Electroanalytical Methods Electr Inaparticular polarographic analysis of copper | Cu"* |= 10M and the corresponding diffusion current =17.5 g.. With the same experimental set up, with Cu” ofunknown concentration, I,is 27.9 pA. Caleu- late the unknown cone. of Cu??? 10) 1,(2) ¢,' 299° 1.5 10% 115 10" ee P22 04 =1.50x10°M, 5 ‘Why asmall amount of freshly prepared gelatin are add to the electroactive species in polarographic analysis? “Under certain conditions the diffusion current at a point suckdenly shoots up (instead of being constant) at a particular potential. This is possible due to adsorption ofcapillary active impurities atthe surface ofthe drop . This shooting is cut down by using surface active substance like geletin, dyes etc Cyclic Voltametry: Cyele voltametry is one of the most widely used technique for acquiring qualitative information about electro- chemical reactions. It offers a rapid location of redox potentials ofthe electroactive species. Working: Current response of stationary working electrodes obtained against a triangular eyelic potential waveform. {In rianguiar (input) potential wave formwr.t, SCE: Switching potential: The potentials at which reversal takes place. Here in the figure + 0.8 and -0.2V are called switching potential <—H-Cycle——> 40 2 time > ‘ig. Tiangular Potential wave Forward Scan: A scan inthe direction of more negative potential is termed as forward scan. Reverse Sean: A scan in the direction of increasing (ie., more +ve) potential is termed as reverse scan, Scam rate: The rate at which potential is increased or decreased wir. time in reverse or forward scan (Its slope of reverse or forward scaneg, let 50 mV/s). Cyclic Voltammgram for 2 reversible redox process: Foraredox couple, Ox+ne==R It is assumed that initially only the oxidised form Ox is persent. So when forward scan (i.e., negative going scan} isapplied for the first helf- cycle, then initially there is no current is observed because potential is low «enough to cause the start of above half cell reaction, ‘When the potential becomes somewhat low, a cathodic current develops (Point B) due to start ofreduction of OxtoR.: ‘A rapid increase in current occures inthe region ofB to D as the surface concentration of Ox becomes smaller ren and smaller, aeu- < PA MY 1408 Potential (¥ v= Ag/AgCl) ctro- At0.3V, scan direction is switched (i.e., from forward to reverse). The current however contimues to be cathodic even though the scan is toward, more +ve potential because the potentials are still negative enough to.cause reduction of Ox’ form. Once the potential becomes +ve enough so that reduction of ‘Ox’ can no longer occur, the current rose to | zero and then becomes anodic, Vare | The anodic current peaks then decreases as the accumulated “R” js used up by the anodic reaction, Reversible cycle with single reactive species has the following characteristics: (i Anodic and cathode peak current are approximately equal in absolute value, but opposite in sign. 26) (ii) The voltage seperation between the anodic peak potential (Ep, ) and cathode peak potential 0059 ott at 298K. n | 21) (iil) The peak current is given by the relation ip = (2.69 10°) n°? (28) an ats ‘Where, n=no. ofelectrons x A= clectrode area (in cm*) cone. (in mol/en) v = potential sean rate (in V/s) iffusion coefficient (in cm? sec") going| So, peak current (i, )c.,/Scan rate(v) is low | (iv) AE, permits the determination of the half wave potential of the measured redox reactions. tionof| on (29)eS Electroanalytical Methods | Electro (v) The positions of peak voltage donot alter asa function of voltage scan ate. 5. ep j | Sala, Curront.uA Irreversuble case: Features: + Charge transfer is very slow + Depending on the potential only one of the cathodic or anodic reaction has a measurable rate, ie., no inverse peak appears on inversing the scan directions. One obtains only the continuation of current decay. | | | E> . [Voltammogram for an irreversible system] O+ne—>R For multi component system: Miattiple characteristic peaks are obtained which gives qualitative information about the eleetochemical process and type of ions,See ee 5. Fora redox reaction Cd" +2e” Cd, the (E,)yuic SV24 im cyclic voltametry at hanging mercury drop electrode is -650 mV vs SCE. The expected valve FOr (E) sie 8 (a)-708 mV (0) -679 mv (c) -650mV (@) -621mv A 0.0592 Soln, (6) weave, (Br)enia “(Es )ausc Volt 0.0592 n 0.0592 (Endemic (Erlang ng Be = BASOV ye 0.6796 volt =~ 679.6 m volt Amperometry orampereometric titration: A method of analysis in which current flowing through a cell is plotted against added titrant volume, There are sharp breaks 2 the curves atthe end-points Amperometryisthe polarographic analogue of conductomessictittation and it uses diffsion cureat (I,) measurements to locate the end point of a titration. \ 4, measurement is done at constant potential vs SCE at the indicator electrode. —_ Le Vv Constant potential (V;) Constant potential (V,) Cons, Potential end-point 4] end-point vol. of titant > ——. > vontat poles) sale volume oftirant > Soe ae cay. ced eagenilitan se! (fat constant poenis\(¥, agasse# (if at constant potential (Vv), both retieg not seduced by reagent is reduced) _feage ang analyte ae reduced). Examples: titrant) solution; ) Titration of Viatofcroe)~ . Fig: constant potential at indicator electrode is— 0.75 V (vs SCE) Here at this potential both Pb” and CrO?- give 1, - \ Pb? +Cro?-—->PbCr0, 4 (rot) So initially upto end point no I, due to PbC1O, . So, I, will fill after ‘end-point I, willincrease due to Cro; (i) Titration of Pb* solution (analyte) with CrO> (titrant) solution je metco> Fig: Constant potential of indictor electrode is O volt (vs SCE) i Here at this potential only C102 isreducibleso, i, is due to CrO% not dueto Pb™cecroaneMertede | 8 Here Pb® consumption has no effect on I,. After end-point, I, increases due fo CrO? (ii Titration of Pb* with SO; where Pb’*is reducible at experimental potential, but not SOS ———— { (iv) Titration of SO}> with Pb and experimental potential is such that a Pb” is reducible but not $0} - vl nso | Volume of Pb* Coulometry: Analytical technique involving the measurement of quantities of electricity Constant current coulometry can be used for coulometri titrations Example: | (@ Br, canbe prepared electrically and used for oxidation (¢.g. of olefnes (alkenes) instu and the end point | \) detected spectrophotometrcaly, (i Ag* canbe generated and used to titrate CY | Incontrolled (constant) potential coulometry one species may be oxidised or reduced and tis determined | at aspeciie potental Electrode in coulometry or voltametry: Usually3- electrode cellarangement consisting reference electrode (RE), working electrode (WE) (sation- ary lectrode) and a counter electrode (or auniliary electrode) (AE) is used aged — Powniosat FR sear £4) iy i Ra ae Wi {Schematic experimental setup) [RE reference clesrode (usually standard calomel electrode(SCE) i wed) WB = Working electode AE ~auniliay electrode (counter electrode) If WE is cathode then AB will be anode and vice-versa Applied potential (E())= Eg, +E yp [Exe = E(t) Eq So reference eletrode is used to get WE potential ‘The function of the reftence electrode in coulometric analysis is to (a) control the potential of the cothode (b) control the potential of the anode (c) Enable the meaurement of potential of the auxiliary electrode (d) Enable the measurement of the potential of the working electrode. Son. (@)lS reds Electroanalytical Methoda gS | POTENTIOMETRIC TITRATIONS Principle Underlying Potentiometric Titrations: The potential measurements provide one of the most important analytical techniques for carying out acid-base, redox and precipitation titrations, Theequivalence point of titrations can be determined accurately without making use of any visual indicators. The principal underlying the potentialmetric titration Nerust equation according to which the potential ofan clectrode de- pends upon the activigies of reduced and oxidized forms of the involved redox couple. During titration, the activities ofthese species vary, which in tur, varies the potential ofthe electrode. The variation in potential is zradualin the begining but becomes fsteras the equivalence point isreached, The variation ismaximumat the equivalence point and becomes lesser and lesser beyond the equivalence point, Thus atthe equivalence point, ‘one observes a point of inflecxion. Pa = 0 at equivalence point. ue (an | . 3 point on, he Fig: A pict potentiometric Fig: A peal fet deivative graph ned | tion. | bemeer tig: Atypical second denvalive gant (vaty? nat 5) ion: | (a) Titration of Ferrous ions versus Ceric ions: Let 50 em*of0.1 MFe* be titrated against 0.1 M Ce" in a medium 0.5 M with respect to H,SO,, The values at 25°C inthis medium.ean be taken as 1459 V and 0.700 V, respectively. The redox reaction is ay Fe* +Ce" Degree of conversion of Fe’ to Fe" at the equivalence point, Before computing te potential of indicator electrode at various tages of titration, its worthwhile to explore the degree of conversion of Fe®* to Fe™ at the equivalence point. This may be done as follows. ‘The equilibrium constant of the above redox reactions given by sonar (OO9EN102 Electroanalytical Methods | E Or, = Lott? 0V0099 1928 _ 6 919! (2) i At the equivalence point, we willhave | [Fe ]=[Ce*] and [Fe ]=[Ce™] 8) With these equation (2) gives | Fe" Fe fey 9x10" of 1 satot @ [Fe*] { Since the volume of the sofution at the equivalence point will be twice as the original volume of reactant, we will | have | [re ]+[ Fe] =21™M _ 005m 5 [Fe }+[Fe]= ’ 3) From equation (4) and (5), we get [Fe™ J=1.9.00* M Thus, the concentration of Fe is reduced from 0.1 Mito 1.9%10-*M indicating that the conversions practi- cally complete Potential at the equivalence point: ‘The two halfcell potentials are given by . a RT Feet soins Ee coin pO (6) nr, [ce] ont “Bosom pCa] 1 Adding equation (6) and (7) we get, Tre] . 0 rr, [Fe J Eero * Bose corn = Bee corn * Bee one Toe ~@) As indicated earlier, the two half-cell potentials will be identical at any stage of titration, Thus equation (8) becomes. y ip, [Fe* [co] ma te Peer] © Now at the equivalence point, equation (3) will also hold good. With these, equation(9) becomes, 1 Bern =] Bee pom Beetcorn | (10) (b) Titration of Ferrous ions versus Dichromate ions: Let 50 cm’ ofan acid solution (pH = 0) of 0.1 M Fe** be titrated against (0.1 M/6), ie. 0.1 N dichromate solution. The two half-cell reduction reactions are: Cr,O}" + 14H" + 6e" = 2Cr* +7H,0 Fe +e" =Fe™*rm eee ees a and E®, The value of E2.s. pp, 0% c°" ary AFC 0.770V and 1.330V, respectively. 56 = 5 9 K = 10° =3.1x10 ASK, is very large. So, at equilibrium we can assure that cell reaction is almost complete, Potential at the equivalence point: The two haif-cell potentials are given by : RT ope ~ Ere sor (1) , er, [ce'} cxoh cowry = Exot co mtin ge ey @ 12) seh ct arm = Foshan Ge TE OT] ( ‘Mutiplying equation (12) by 6 and then adding to it equation (11), we get Fe* [Cr Err 2 wer = Brecon + SE oo sent le] (13) ‘The two half-cell potentials will be identical at any stage of titration. Thus, equation (13) becomes ( 2 Tepe ; 1RT [rev|ce'y | sete t or co ae [5p | oe (14) - {[Fe* ][cn07 J[H"]") Now at equivalence point, we will also have 6[cx0+ ] and [Fe ]=3[ cr ] (15) Substituting these in equation (14), we get eS 4 LRT io ease one EELS] 06 2. Precipitation Titrations: In precipatations, the concentration of reactant decreases as a result of formation ofa precipitate with the titrant, [fan electrode reversible with the reactant is dipped into the solution, its potential will vary during the course of titration. Hence precipitation titration can be carried out potentiometrically ‘Titration of chloride ions versus silver ions: Let 50 cm of 0.1 M Ct be titrated against 0.1 M Ag’. The silver-silver chloride electrode can be employed as the employed as the indicator electrode. This electrode is reversible with chloride jons according to the following reaction AgCl(s) +e = Ag(s)+Cr Potentials given by the expression ‘ RT a Fenwacne “Eerie pL | Oy with E2, =0.222VSoln: @ Etctroanaytal Methode Potential at the equivalence point: ‘The concentration of CF ions at the equivalent point may be calculated from the solubility product of silver chloride. At 25°C, the latter has a value of 1.56%10" (mol dm)’, Since at equivalence point, the (CI is identical to [Ag'] itis obvious that [oP] pin VK (ARCH) = V1 56510" ME =1.24x10 M ‘The above concentration can be substituted inequation (17) to get the potential vaue at the equivalent point. A'50 mL 0.05 M solution of Fe(II) is titrated with 0.05 M solution of Ce(IV) in the presence of dilute H,SO, at 25°C. Calculate the equivalence point potential and the equilibrium constant K in terms of log K. Esty? .75V, BP Fett ) 40.7! Vs yatl4sv cea Fe( if) +Ce( IV) == Fe(II) +Ce( i!) Atequivaient point, — [Fe( 11) ]=[Ce(111)] and | Fe(1)]=[Ce(IV)]} For reaching equivalence point 50 ml of 0,05 mCe(LV) solutionis being used, op ° Ban = E ost sogt8 — Baye? 1.45-0.75 =0.70 From Nernst cell equation, at 25°C ws eau log [Q-> reaction quotient] ” Atequilirium, Q=k heren=1,and Ey =0 => — 0=0.70-0.059 logk togt = 9 _ 11.86 0.059 0 1 L,, = (0.754 $.45}=—(2.20) =1.10 J 3.45)=5(220) 1 0 - eau po. retingt TE prcoll ll ewis er is Batteries Chapter Primary Cell Batteries: (1) Dry-Cell Battery: The common household batteries used as power sources for flashlights, portable radios, and tape recorders use the dry cell, or Leclanche cell. Adry-cell battery has a zinc metal can, which serves as the anode, and an inert graphite rod surrounded by a paste of solid manganese dioxide (MnO, and carbon black, which functions as the cathode Surrounding the MnO, containing paste is the electrolyte, a moist paste of ammonium chloride (NH,CiJand zinc chloride (ZnC1,) instarch. The dry cellis not completely dry but gets its name fromthe fact that the electrolytes a viscous, aqueous paste rather than quid solution. The eiectrode reactions, which are rather complicated, can be represented in simplified form by the following equations: Anode: 2n(s) —> Zn?* (ag) + 2e~ Cathode: > s4n0(6) +2 NHG (ag) + 26° —>Mn.03(s) +2 NH (ag) +H,0(0) This cell provides a potential ofabout 1.5 V, but the potential deteriorates to about 0.8 V as thecell is used. ‘The alkaline dry cell is a modified version of the Leclanche cell in which the acide efectrolyte (NH,C1) ofthe Leclanche cell is replaced by an alkaline (basic) electrolyte, either NaOH or KOH. As in the Leclanche cell, the electrode reactions involve oxidation ofzinc and reduction of manganese dioxide, but the oxidation product is zine oxide, as is appropriate to the basic conditions: Anode: Zn(s) + 20H” (aq)—> Zn0(6) + HOG} + 2 Cathode: 2. MaiO(s) + HyO(I) + 2e° —~>Mn03(s) +2 OH (ag) Corrosion of the zine anode is a significant side reaction under acidic conditions because zine reacts with H(ag) to give Zn*(aq) and H,(g). Under basic conditions, hiowever, the cell has a longer life because zine corrodes more slowly. The alkaline cell also produces higher power and more stable current and voltage because of more efficient ion transport inthe alkaline electrolyte. (2) Mercury Battery Often used in watches, heart pacemakers, and other devices where a battery of small size is required. The anode of the mercury battery is zinc, as inthe alkaline dry cell, but thecathode is steel in contact with mercury (11) oxide (HgO) in an alkaline medium of KOH and Zn(OW),. Zine & oxidized at the anode, and HgO is reduced at the cathode: Anode: Za(s) + 20H” (aq) —> Zn0{s) + HO() +2.€° Cathode: Hg0(s) + Hy0(0) +2 e” —+ Hg(!) +2 OH” (aq) Even though mercury batteries can be made very stnall, they still produce a stable potential (about 1.3 V) for long periods of time. When possible, used mercury batteries should be recycled to recover the mercury because ofits toxicity.@ — Secondary Cell Batteries: Lead Storage Battery: The lead storage battery s perhaps the most familiar ofa! galvanic cells because it has been used as a reliable source of power for starting zutomobiles for more than three-quarters ofa century. Atypical 12 V battery consists of six cells connected in series, each cell providing a potential ofabout 2 V.The anode, a series of lead grids packed with spongy lead and the cathode a second sesies of grids packed with lead dioxide, dip into the electrolyte, an aqueous solution of sulfuric avid (38% by weight). When the cell is discharging (providing current), the electrade falfreaetions and the overall cell reaction are: Anode: Pb(s) + HS05 (ag)—> PbSO4(s) +H" (ag) + 267 Cathode: Pb0,(6) +34 (ag) + 8505 (ag) + 26° —» POSO4(s) +2400) F=1.628V Overall: pb(s) +PbOg(6) + 2H" (og) +2 HSO4(aq) —> 2 POSO,(5) +2100) -E'=1.924V (These equations contain sO; ions because s03- is protonated in strongly acidic solutions.) Lead is oxidized to fead sulfate atthe anode, and lead dioxide is reduced to lead sulfate atthe cathode, There isno need for the cel to have separate anode and cathode compartments because the oxidizing and reducing agents are both solids (PbO, and Pb) that are kept away from coming incontact by the presence of insulating spacers between the grids, Because the reaction product (solid PbS@,) adheres to the surface of the electrodes, “run-down lead storage battery can be recharged by using an extemal source of direct current to drive the cell reaction in the reverse, non-spontaneous direction. In an automobile the battery is continuously recharged bya device called an alternator, which is driven by the engine. Previously the charging process inthese batteries vwas accompanied by appreciable evolution of gaseous hydrogen and oxygen, owing to electrolysis of water. Not only did that electrolysis necessitate periodic water replacement, the accompanying gas evolution tended to loosen the Pb, PbO, and PSO, from the electrode surfaces, thus shortening the life of the battery. The “maintenaave- tree” batteries we tise now have electrodes made froma calcium-containing lead alloy that inhibits the electrolytic decomposition of water, These batteries are sealed because no openingis,needed for escape of gases or addition of water. NiekelCadmium Batteries: Nickel-cadmium, ot “ni-cad,” batteries are popular for use in calculators and portable power tools because, unlike most other dry-cell batteries, they are rechargeable. The anode of a ni-cad battery is cadmium metal, and the cathode is the nickel(111) compound NiO(OH) supported onnickel metal. The electrode reactions are Anod CA(s) + 2 OH™ (ag) —>Cd (OH), (5) + 2€7 Cathode: NiQ{OH\(s) + H,0(0) +” —+ NOH), (8) + OH (ag) Combining these two gives the overall ceitreaction dis Ca(s) + 2NIO(OH) (5) + 24,0 ee Ni-cad batteries ean be recharged many times because the solid products ofthe electrode teactions adhere tothe surface of te electrodes 2Ni(OH)2(s) + Ca(OH) (8) Lithium ion Batteries: Rechargeable lithium batteries riay prove to be the batteries ofthe fature because of their ight weight and high voltage (about 3.0 V). Lithium has a higher standard oxidation potential than any other metal, and only 6.94 g of lithium is needed to provide 1 molofelectrons. Lithiurn batteries consist ofa lithiurn metal anode, ametal oxide or metal sulfide cathode that can incorporate Li’ ions, and an electrolyte that containsa lithium. Anode: Li(s) Li? +e" Cathode: MnO, (5) + Li* + » LiMn02(s) Solr18 cit wy. Che: vith His ere ing ‘ing iss, the ged. ter. ded The that for ase, stal, are vere eof any ofa that Sola. @) Lithium batteriesare now used in calculators, waéches, cameras and cellular phones. Fuel Cells: ‘A fei cellis a galvanic cell in which one of the reactants is 2 traditional fuel such as hydrocarbon or hydrogen. ‘A fitel cel differs ftom an ordinary battery in that the reactants are not contained within the cellbut instead are continuously supplied from an external reservoir. Perhaps the best-known example is the hydrogen-oxygen fuel cell, which is used as a source of electric power in space vehicles. This cell contains porous earbon electrodes impregnated with metallic catalysts and an electrolyte consisting of hot aqueous KOH or NaOH. The fuel (gaseous H,} and the oxidizing agent (gaseous O,) don’t react direetly but instead flow into separate cell compartments where H, is oxidized at the anode and ©, is reduced atthe cathode. The overall cell reactionis simply the conversion ofhydrogen and oxygento water: Anode: 2 Hy (g) +4 OH” (ag) —>4 H,0(0) + 4e7 Big = 0.8279 V Cathode: 03 (g} +2 H,0 (I) + 4e” —> 40H (ag) E2, = 0.4009 V Overall: 2 Hy(g) + 0,(¢)—> 2H,0(), Boy, =1.2288 V Ho oF rT Paras aiton ee arade nos po ecto Fea26 Note: A highly devetoped hytirogen-oxygen fuel cell contains a phosphoric acid as acc electrolyte. Problem: Calculate the potential of pentane-oxygen fuel cell, having net reaction as, C,H), (g)+80, (2) SCO, (g)+6H,0(¢) The standard ftee energy of formation (in kY/moi) at 298 K are -8.2, -237.2 and -394.2 for pentane, H,0(4) and CO, (g) respectively. CHa (g)+ 803 () —95C02 (8) +611,0(¢) ‘Here number ofelectrons involved in cell-reaction (1) is equal to change in oxidation umber for eiher C,H, (here oxidation of carbon is only changing) or 8O, (here reduction of oxygen). As 16 oxygen atoms are going from oxidation state 0 to~2. So, net change in oxidation number a(OS)=16x2=32 n=32 4G° (reaction) = 5AG? (Product) - ZAG" (reactant) = -nte=(586%o, +6869,.0]-(a6 Ey, +8868, } > 32x 96500 B° = (6x -237.245x-394.2) -(-8.2+8%0) KI. E°=+1.096 volt.Batteries CORROSION ‘Atan anode region, iron is oxidized to Fe” ions Fe(s) —+ Fe**(ag) +20" E° = 0.45 V While at a cathode region, oxygen is reduced to water: Oy(g) + 4H" (ag) + 4e° —> 2H, 0(/) E°=123V ‘The actual potential for the reduction half-reaction is jess than the standard potential (1,23 V) because the ‘water droplet is not 1 M in 1" ions. (In act, the water is only slightly acidic because the main source of Hons is the reaction of water with dissolved atmospheric carbon dioxide.) Even at pH 7, however, the potential for the reduction half-reaction is 0.81 V, which means that the cell potential is highly positive, indicative ofa spontaneous reaction, ‘The electrons required for reduction of O, atthe cathode region are supplied by a current that flows through, the metal fromthe more easily oxidized anode region. The electrical circuit is completed by migration ofons in the water droplet. When Fe” ions migrate away fiom the pitted, anode region, they come in contact with O, (dissolved in the surface portion of the water droplet) and are further oxidized to Fe ions: 4 Fe?" (ag) +O, (g) + 4H" (aq) —- 4 Fe*" (aq) +2 HOW) Iron( II?) formsa very insoluble hydrated oxide even in moderately acidic solutio as the familiar red-brown material that we call rust; and the iron({I) is deposited 2Fe™* (ag) +4 HO) —> FeyQ3 -H20%s) + 6 H*(ag) Rast Anelecttochemical mechanism for cortosion also explains nicely why, automobiles rust more rapidly in parts of the country where road salt (NaCl or CaC) is used to melt snow and ice. Dissolved salts in the water droplet greatly increase the conductivity of the electrolyte, thus aecelerating the pace of corrosion,