CONSTANTIN MIHAILCIUC COCLEAS ALE XANDED 4 7 ELECTROCHEMISTRY editura universitatii din bucuresti® 2006Referenti stiintifici:_ Conf. univ. dr. Cezar Bendic Prof. univ. dr. Elena Volanschi — © editura universitatii din bucuresti” ‘Sos. Pandu:i, 90-92, Bucuresti ~ 050663; Telefon/Fax: 410.23.84 E-mail: editura@unibuc.r0 Internet: www.editura.unibue.ro eee [Descrierea CIP a Bibliotecii Nafionale a RomAniei /MIHAILCIUC, CONSTANTIN Electrochemistry / Constantin Mihaileiue, ~ Bucuresti: Editura Universitati din Bucuresti, 2006 Bibliogr. ISBN 973-737-133-X 544.6(075.8) Preface This course for chemistry students embraces the main topics in fundamental elerochemis. Inthe presentation of the materia eat imporance isp 0 the phenomenology’ of the electrode reaction, which isthe base for a modern undersnding of the electrochemistry. Obvious, desled proofs of main laws and formula of theoretical elecvechemisty are given together with ther meanings and the ways in which the theoretical electrochemistry may be applied Besides, the sty ofthe proofs helps lot in acpiring experience and provides prerequisites for further electrochemistry self-education, In studying electrochemistry great importance is atached to theoretical and numerical problems (termed in the book by Example) discussed in del starting from the fundamentals ‘ofthe involved fils. They aid in acquiring a profound and cative mastery ofthe theory. The purpose of the every Solution is to guide the student in a proper manner to become more Samitiar with the electrochemistry concepts inorder to master the general principles and the base rules of, 1 express my gratitude to Professor Dr. Nicolae Boncocs forthe quality ofthe ining he did many year in his restarch group also express my gratitude fo Professor Dr Elena Voanschi for valuable advices and comments on several subjects. 1 ilso thank tothe referee Assoc. Professor Dr, Cesar Bend for he rica eading ofthe mae 1 would ike to thank those students who conibuted in 8 way to the present version of the took either by writing some texts (Mariana Uriasu, Daniels Necula and Dina Mich) or by reading almost entirely and coret it (tila Bote. 1 hope tis book wil be a valuable experience forthe resders interested ina beter and coherent understanding ofthe electrochemistry at its basi level ‘Constantin MinaieiueCONTENTS 1, CONDUCTION IN ELECTROLYTIC SOLUTIONS .. 1.1 Conductivity, Molar conductivity and equivalent conductivity 9 12 Kohirauseh’s Laws 10 13 Electrochemical mobility 2 14 Ohm's law fr low elect Fe 8 1 Relations between the conductivity, molar conductivity and equivalent conductivity ann elecvochemical mobilities “ 116 Relation of the elecrochescal maby 15 16.1 The Einstein relation... 15 1.62 The Stokes-Ensteinrelaton. 16 1 Relation ofthe molar and euivlen condutiviy. 18 171 The Nemmst-Einstinrelaton 18 1.72 The Hitorff anspor munter. : 19 [8 Measurement of conductivity 2 18.1 The significance of conductivity data 21 118.2 Experimental arangemert and measurement of conductivity 24 1183 Experimental determination of transport number. 25, 1851 HitoeP= method 25, Toclecrodes occurs se clectode reaction 2s ‘To eleotodes occu diferent electeode reactions 28 1.83.2 Moving boundary method 31 118.33 Transport number from electric tension measurements of concentration cell with and without transference. I. THE ELECTRODE REACTION AND THE ELECTRODE... 1. The redox chemical reaction and the electrode reaction, TLL1 Companson 1.1.2 How to transform a redox chemical reaction into an overall cell reaction 1.2 Blecttode re80400 eo. 112.1 Fast (reversible) elecuove reativn 112.2 Slow imreversible) elecuode reaction. 1123 Comparison 113 The main notions and definitions 113.1 The electrode. 113.2 Electrode potential, reversible electrode potential, overvolage, polarization ....46 Il. POLARISATION CURVES AT THE ELECTRODE... 1IL1 Experimental setup.. 1IL2 Polarisation curves a the electrode 11.2.) In the eletrolyte solution there is only R 1L22 In the eletroyte solution there is only © 1L23 Fast (reversible) electrode reaction 5 11L24 Slow (ireversible) elecrode reaction 8 L255 Polarisation curves in water 39 M1126 Comparison between a fast (teversible) electrode reaction anda slow (irreversible) clectrode reaction : 03 The Nerst lav IV. ELECTROCHEMICAL SENSORS 1V.1 Ideal ~ polarined and ideal ~ nonpolrized electrodes 65 1V.2 Flectrical analogy. z 66 1V53 Classification ofthe electrodes according to thir function in wn cleciochemcal cell 67 Potentiometric electrodes. 6 1V.3.1 Reference electrodes o 13.11 Silver, silver chloride electrode (Ag, AgCI/ HIG 8M)) 68 1V3.1.2 Mercury, mereury () chloride electrode, He, Hi,Clp/KC3. 8M) an 1V.32 Working clesrodes ” V'3.2.1 Several kinds of working electrodes, z 74 ero kind eiectrodes ds First kind electrodes. n Second kind electrodes 7 Electrodes of n® kind : : : st 13.22 Gas dectrodes. : 83 The hydtogen electrode, : : 83 The oxygen electrode. nnn z 84 1V.32.3 Amalgam electrodes... 85 1V.3.3 Counter electrodes CELt ELECTRODE REACTION AND THE ELECTROCHEMICAL V1 Fundamental igs of elecrechemieal cele V.L.1 The galvanic cll ae as 7 V1.2 The electolyst.. om : 91 V.13 Synthesis E : 96, V2 The Nemst law for an electrochemical cel. aay VI ELECTROCHEMICAL CELLS WITH TWO ELECTRODES UNDER POLARIZATION VL Cals with wo polarizable crdes unr cosa V1.2 Celis with one polrzable le an electrical polrtenion . ; V13 Cels wit one parable cocwode and another no-jolaraic cessed saber “chemical polrizatn”. "Redox poteniometis tation VII, ELECTROCHEMICAL CONCENTRATION CELLS V1 Conceneation cls without wansterence (without gd junction VILLI Catone xt eee Vil Anion cat VILL Comparison : ¥i12 Concentration cis with ansterence wii junio Vila caiaue aie are enter i122 Anion al nna VIL3 Concentation cls with iminate iui jntion pote ViL3.1 Caine cl eee Vii3.2 Anion cel z a ae 133 VIL4 Comparison betwen concentration cll wi nd loa wares 4 108 VIL Comparison between concentration cell with liquid junction potential and with climinated liquid junetion potential... 13s VII. APPLICATIONS OF ELECTRODE POTENTIALS AND CELL VOLTAGES MEASUREMENTS sense 37 IIL Thermodynamics of galvanic cells 17 VIlL2 Determination of standard electrode potentials and mean ion activity coefficients 139 VIlL2.1 Determination of standard electrode potentials by redox potentiometric titration 139 \VIL2.2 Determination of standard electrode potentials by zero-curent potentiometry 142 \VH2.3 Determination of standard electrode potentials andof mean io activity coefficients, 145 VIII3 Determination of chemical constants M7 Vil13.1 Determination ofthe constant ofthe solubility product 107 VIL 3.2 Determination ofthe constant of stability for a conpiex 149 VIIL3.3 Determination ofthe constant of acidity 150 VIII3.4 Determination ofthe redox constant 153 VIL Individual overvoltages measurements 2 155 IX. ELECTRODE KINETICS. DY Intoduet0M com 137 1X11 Electron distribution in metal and inthe electrolyte solution. 137 1X12 Electrochemical energetic barer. Eyring model... 159 1X.1.3 Significance ofthe symmetry factor... 164 1X14 Electrode reaction ~ a complex assemble of charge tansfer step, mass transport by dlfusion step and chemical reaction step. 166 1X2 E, mechanism, : 168 12.1 Theory. : 168 1X.22 Half wave potential. Equation ofthe polarization curve by using the half-wave potential in 1X3 E, mechanism 7 PX3.1 Theory. 17 1X.3.2 Limiting laws ofthe overvalage : 179 1X.3.2.1 Equilibrium case. Kinetic dedvetion ofthe Nemst equation. 179 1X32. Very small overvoltages. The lov-overvoltage approximation 180 1.3.2.3 Very large overvoltages. The high overvoltage approximation, Tafel approximation. . : 183 ‘Anodic Tafel approximation. 183 1X. 3.3 Half-wave potential. Equation of the polarization curve by using the half wave potential 190 ‘Aodie ea. : 191 1X.3.4 Several dependences : : 195 1X.3.4.1 Influences of symmetry factor for a given stardard exchange current density so . : 195 1X.3.42 Influence of standard exchange current density fora given symmetry factor (here P=1/2) and for equal bulk activities 196 13.43 Influence of bulk activities of R and O (here taken equal) for given symmetry factor (here =1/2) and given standard exchange enent density eo... 197 13.44 Influence of WE area for a given standard exchange current density, given symmetry factor (here P=1/2), and forgiven bulk activities 197X. ELECTROCHEMICAL CORROSION. X.1 Introduction 2 199 X.2 Corrosion dielecrode unaffected by diffusion 200 X3 Corrosion diagrams. 206 X/3.1 Evans-Hoar diagram. = 206 X3.2 Evans diagram 206 Xe Factor influencing the corrosion process 208 X-41 Influence ofthe difference between the two reversible electrode potentials. 208 X42 Influence ofthe total resistance... X<4.3 Influence ofthe polarizability X-44 Influence ofthe stirring... X:4.5 Depolarization by I : X46 Depolarization by 03... XI. ELECTROCHEMICAL TECHNIQUES. XL1 Introduction. X12 Stationary electrochemical technique 215 X12.1 Inerpretation ofthe polarization curves obtained at stationary electrodes... 218 X12.2. Hydrodynamic electrochemical technique =e X1L22.1. Rotating dse electrode. Fast (reversible) electrode reaction. Slow (reversible) electrode reaction ‘The anodic ease, 12.22, Direct curent polarograpiy Fast (reversible) electrode reaction . 231 X13 Non-stationary electrochemical techniques Cyclic voltammety technique 235 X13.1 Fas (reversible) electrode reaction. 236 X13.2 Slow (reversible) electrode reaction. 238 References. 1. CONDUCTION IN ELECTROLYTIC SOLUTIONS 1.1 Conductivity. Molar conductivity and equivalent conductivity. ILE" or $ (Siemens) (1.1) and the reciprocal of the resitvty (specific resistance) is the conductivity (specifi conductance): "ax or Sm" 2) ton of ects ae second cls constr fr which he condi sa lnis stg, lie oye epee of secon, mor concentra. Thai te ‘ndutviy ofan eecreycslvion ves wilh he cnceination, To compar the conic itso to electro soins, they ust have the sme Ila concenrtcn andthe two eels mit have the sume valence pe 2 2. I they have deem molar concentration but the same valence type, one may compare txt molar candvtvies. The molrconduvites Ag is defined ste rato of condo othe Tg 02" mor a3) 1 they do not have the same valeee type andthe same molar concentration one may compare their equivalent conductivities. “The equivalent condvctvty A is defined as the rato of conductivity « tothe equivalent concentration Ae [nro'nteg! aa Between the molar and equivalen:concensation ther is simple relation: as)‘where zhas a known significance ‘A first siht, this above normalisation of the conductivity must remove the molar concentration ‘dependence of the molar conductivity and the equivalent concentration dependence of the equivalent conductivity In spite of this normalisation mode either on the concentration or on the concentration and the charge, both the molar conductivity and ‘equivalent conductivity vary with he concentration Kohirausch’s Laws From experimental data and for strong electrolytes, Kohlrausch established an linear reaionship between Ay and et? (the square rot lw) en a6, where Aly is the molar conductivity at infinite dition cy +0 (or limiting, molar jonductivty) and A is an empitial pasive constant, Both the intercepts A, and the slopes A ofthe Ay versus 4? line depend not so much on the particular electrolyte (whether itis KCI ‘oF Nar) as on the type of electrolyte (whether is 1:1 or 2:2 valent. ‘ly being obtained by extrapolation (For ey ->0) ofthe plot of the Ay versus Sh itisa significant quantity because it characterises the infinite dilution state where the ion ion interactions dipper, From the experimental data, for strong electrolytes having the same valence type and ‘onsiering the limiing molar conductivities, Kohtausch noticed thatthe differences AYN, = Alay —A8 jg “eons 2 variable an 818 = Nua Abn may variable on (anon, cation) are conan forthe same pir of cations but een ion an ‘especies, forthe sime pair of aio bit silent cations, This finding dconmed Kohlawch to concide tha each type of om brings its own patelarcoution ee limiting molar condusivity ofa salt. The essence ofthis conclusion isthe law a independent ‘migration ofthe fons infinite dition: nV Rina Ri as) where the strong electrolyte is Cy, A, ind I mole of Cy, Ay. gives rise tov, moles of Positive fons and v_ moles of negative ions; AS, and A. are the limiting nie molar ‘onductives for cation and anion. 0 For low concentration range, where the fon ~ ion intewctons are very sll, one can Also write that Nan hae 0 Obviously, the importance ofthe second Kohlrausch bv is that it consides the molar conductivity of an'elecolyie as a coligative propery allowing its specialisation from the slectolyte tothe ions formed by dissociation ‘The wo Kohirausch laws canbe wetten as wel in equivalent conductivities: as) as) as Example Lt Given that ‘Sabitanee 50, | Naliso, | NaGi RiGemteneq) | 2 [te | aes calculate te molar and equivalent conductivity at infinite dilution for the hydrochloric acid if each electrolyte is of 1:1-type. ‘Solution: If for an eleewolyte C,A., the equivalent conductivity is Reo thon but the molar conductivity is: fecet re ‘The relation between the two quanti i B= hy cre 4H gag CA cee +R, gig "CFC cre +he ara cache because €-z¢ #2 fq) (the eleeroneutaliy condition ‘Therefore inthe table the third row has the coresponding AS, (each electrolyte is considered |i-valent, ee the dissociation reaction below) Substance 380, | NaHS0, [NecT_] aeacae aa |_| 26s Ae en-wot) | A |_| aes] Obviously, one can wre 1,80, -+ 1" +80; Rasnso, “Bays + Masor NaliSO, ~+ Na* +1803 reso. ME aso5NaCI» Na? 4cr> and the final equations: Hh» Ht +c 1 results that in order to obtain the requested reaction it mst multiply the fist by +1, the second by | andthe third by +1, The same consideration applies onthe lation deserting the equivalent conductivities at infinite dition, “Therefore: Nene = Meansog Me anso, + Aeaucr = 402 — 10241265 Asconcers Aye; one ean write that: 26.5S-em* 09"? Nopaict © 426.58 em? mol! (End of Staion) 3 Electrochemical mobility no field acts in an electrolyte solution (this being in thermodynamic equa state) the particles move in all possible diretions with equal probability performing andor ‘movement. Particles (ions and molecules are engaged in the so-called thermal mation whch ie Ihily Violen. This random movement remains asa background motion even ifa field is applied. ‘The applied field creates ales random movement inthe field direction (a preferred merion) ‘This migation sin fact, a very slow di of ions superimposed on their much more rapid The cause of the migration is the existence of an eleetrc field (or of an elestie potential gradient) E=-ndo (10) tons fee the electri field differently, ther response being a function of charge, mass Sexsenain, coi, te. they wll havea velciy whi pends pone sg oF ‘The drift velocity under a unit electri field strength (under a certain force excited by (his unit electric Feld is called electrochemical mobility withthe symbot 5) Taking ino account the somewhat unigue physical transport mechanism operating on allthe fons, one expects as all the mobilities tobe small ina given solvent. Looking ata lst of ‘onic mobiles in water, one can see that, excepting the mobilities of HyO" and HO™ ll the cother ions have small and close mobiles. The two mentioned ions have extremely high ‘mobilities, The transport mechanism operating inthis case is very different from the physica transport mechanism mentioned above ay Protons are exchanged Seween neighbouring solvent molecules producing movement of charge and causing continvows destruction and reformation of the species. The “iceberg” structure of water plays te essetial role 1.4 Ohm's law for low electric field The conventions O's ave over] ay eigen! hl al of A (ptt iene aco he ese solution) to d (distance across the electrolyte solution on which potentil difference acts) is the stength ofthe electric il: 413) and thatthe current i the product between j (ihe current density through the cross section of the electrolyte solution) and A (the area ofthe cross section ofthe electrolyte solution): 1eia as) I iferene - erent relation, one has finally and substiting. AY and 1 in he poten as) a Ra Considering the definition ofthe conductivity ¢ andthe significance of the resistivity (9-14 oe as tds ron: Z A a6) benween the strength of the elestrc field F and the current density j. Thus, a electrolytic solution obeys Ohm's law foe swall fields, and can be represented in an equivalent electrical circuit by a resistance that increases withthe length oF the conductor and decreases with the ‘Therefore, the total curent density under the presence ofa smal electric fed isthe {otal conductivity times the strength of the elec Fla er anLS Relations between the conductivity, molar conductivity and equivalent ‘conductivity and electrochemical mobilities, ‘The equivalent of Ohm's lain electrolytic solution allows the connection of the conductivity with the electrochemical mobilities. Lets conser astrong lett C,, A, for which 1 mole of Cy,Ay_ gives rise to v, moles of postive ions and.» moles of negative ins. The fx density 1, of ionic species is given by relationship ‘ ci) =emi (us) nd the ind curent density of fone species by 322), a9) ere, obviously, the individual conductivity Meas = vee = Req) =Foyuy, i andthe total conductiviy i obtained by summing ove j [Fens = lem; azn Fey ju) =Fequ, Taking account the definition ofthe molar conductivity one has: Dobbs ves (2) Dew ‘here molar ionic conductivity is given by: do bslPay (22) ‘and, in an analogue way, for the equivalent conductivity one has: he=FEN =D (2) ‘where equivalent ionic conductivity i given by dey ay 123 In all Eqs, (122}(.23') the dependence ofthe molar and equivalent conductivities on the concentration does not appear but itis known that the electrochemical mobiles are ‘concenration- dependent ‘Obviously, the Eqs. (1.22)(.2") can be writen by means of limiting elecvoehemical mobilities to: a2 a2 25) L6 Relation of the electrochemical mobility. 1.6.1 The Einstein relation ‘The diffusion process results fom the random walk of fons unde a chemical potential gradient (or concentration gradient) b) ‘The migration proces results from the drift velocity of ions when they experience @ force created by an electri il: i (126) b).-emi azn ‘But this dit of ions is superimposed on their random walk and, therefore, the dit and the random walk must be intimately ike, ‘Both diffusion and migration are non-equilibrium (irreversible) processes and they do ‘ot obey the equilibrium thermodynamics or equlbriom sail mechenics, Ivis possible however Io imagine a situation where the (wo processes oppose and balance each oer and a “pscudo-equlirium’” is obtained, In this steadyestate:Gd Bike 128) te even (22.422 my eg =) Ske cuf-0 aa» Dv thea ston oe may Blinn dbo tw ere ‘the concentration of ion species j ¢(x), ata point x where the applied potential is x) in terms of concentration ¢? at 4x)“ Bn eoecte th «30 Differentiating this expression, one obtains: 2/0) oF aren) Besse (P52) wo sn ivodcing he (31) in Eg, (128) on a the nln elation a wx pap, 03 RTT ‘ich shows he ima ak ete he migaton ros ane isn process In at {this intimate link is an atomistic point of view. - cee = 162 The Stokes-Einsten relation Duct the Einstein relation, the diffusion eoeicient can be linked up tothe viscosity. A particle engaged in its random walk is subject tothe viscous force excited by ils {ulrnment. The on sees jis ner she non of an “india ional ees” 33) ‘andin its drift motion the ion experiences the ation ofthe viscous fre given by Stokes law: Ey =6mrnv, (134) When steady-state is reached: 35) HS Grey 1.36) aeons (136) aan) (38) hich shows tht, due to the Stokes viscous fore, the electrochemical mobility of an ion depend onthe radius ofthe solvate ion andthe viscosity ofthe medium. ‘One ean dedvce from the Einstein and Stokes-Enstein relations the dependence between the electrochemical mobilty and medium viscosity, radius of the solvated ion and charge ofthe ion. Using the Eq, (138) imo the Eq, (132) one obtains 2A __ 2 39) Garatig Gary Win the Ba (1.39) one inicduces the Eg, (124°) ane obains oF 2, n= = const, 1.40 a Gary a ‘the Walden rule which means that ihe result ofthe multiplication of the limiting ionic molat conductivity by the limiting viscesty ofthe solvent fora particular eiecirelyte should be a Constant (a certain temperature). This relation holds only ifthe radius of the moving (kinetic) temtty ean be considered the same in solvents of various viscosities. Looking critically atthe Eg (1.40), the following relation may be considered a core: 2p aan ae nn ons; GmNa because one should expect diferences inthe solvation of in in dferent solvent1.7 Relation of ihe molar and equivalent conductivity. LT The Nernst. Hinstein relation ve oe inn relat, the dilision coef ca eink up with the mor and equivalent conditvity mate dens By mvdring te expreson fh cletocenicl mails, ven by he isin rretation (1.32) into the first equality (1.22), one has: picid Pa dagger ie and into the first equity (1.23), ome as Ebb, i hich pais the calculi of molar and eqalem conti ‘coefficients of the individual ions. “ ae bv the ionic molr and esvalent conductivity cane in orn ea tity ca be inked to he fn {om the ditfasion oF er Ps (4) oF == 10,-2% 2p, «Fy, Sof ,D,= Fa (4s) Trae serra aspect of the Neri Elsen ein which nit alii Firstly, a requirement for the Nemnst-Einstcin relation to hold is that the species involved in fson mast also be involved i conduction Ihe on poses in ees ae in iin oi omton un aise frm eee fa of ne a ison bu conaicton forthe eal pr an tee, the mal eae eye Sitsion coi nt equa to he moby aclaed fom he equals eden) the Nemst=Einsin lation docs ot al, Secondly, inthe lero olan ia which te ion on interactions cannot hep tes ntncons ae he fon secon a he Sse seas sire and the above relation doa ol. Bute NemscEieis ction eee, increasing) valid rece sauion with neato 1.722 The Hittorff transport number Suppose an electrolyte solution in which the only acting fed isthe electric Feld. The iret and logical result is that all present on species moves as flows the cations moves inthe direction ofthe electric fed the anions moves inthe opposite direction ofthe electric fehd Each ion species fels the influence of the electric field as funtion ofits charg, radius and fof the viscosity ofthe solvent. As a consequence: some fons respond 10 the action of the tlectric field by migrating more than others; in ether words the cary the current diferent because not ony ther charge and radius (Le, ther electrochemical mobility) could be different hut even thet concentration could be diferent The curtent density, which an ion species caries, is give by’ iy =2,Feaamil 046) and the cal curentdersitycartied by all ion species is piven by: Dhl-HiZlkees aan ‘To measure quantaively the exten to which each ini species tranepots the tos current one can define the transport number as a action ofthe teal eurent density carried by ‘the particular ion species alas) Example 12 Calculate the transport mamber fr the fons in 8 2°10" M. solution of KMg(SOg)s Hf me knows the following data Yon «| Me” | sor Rem ea) | 88 [| 93 | cousdering Tat the given coneenraton belongs to# domain in which the conductivity foes not depend upon the concentration, Ue for ealulting both me conductivity. Solution: “To calculate the transpor number the following eatons are necessary in ionic molar conductTa of couse, the fink between then hg, =f ey enous 1-2 75595000 © “Tagasssae OM 393 295 Swe RON ty eS OBS 950m Me Tass 2sosea wo 8” 0 2.40 ot “FEST Tay 03% gp = en a76 SerrEOxs) sot" 27a sea. 9502 (End of Slton) ° ‘The above defnition requires two properties of he transport numbers: ‘+ ifan on species j aries current oer + thesum ofthe anspor numberof lhe on spies mast he ui: ww-Ls Ss In order 10 get better definition for the Hitortf transport number itis useful to ‘consider that the ionic species j, endowed both with charge and with mas, gives rise Lo two possible anspor mods: a migration fx and a sion fh, the sum of wich mus Bethe 6): =O))m do (a9) ‘Tacking into account that: (10) and oS yo =D) asi iteesults that & doa = (152) “Two observations are impcrtant + even if #0, itis sill possible to have 8 Hux of the ion species j, obviously that is & Aifasion ax of pwat =O))o ass) ony ey + if te chemi potemial ain is 220 (E20) Gin which ese SE 0) he fon species j does not participate in the diffusion grocess but does participate inthe migration proces: You = Oar ass) “Therefore, the Hitorf transport number must be associated only with the migration ‘ux, i with tha portion of the ttl fax produce! hy an electri il 20). eae a ass) Lees "Yor Yoc ‘A remar is neesar: te anspor munber fa pail onic mpl can end 0 zero (1,2) Bu atthe Sametime is sho Mx can be ite and fre from 2 “Thisisimpran in decronayicl hemi to. one desea an aay on species o move toe clectouc nea tyson ly thon he rere to sang ois on zur wnspr ruber. This is ered by ang some inet tae na peal exc Thine elecoltin a elo does no ives to an eleode reaction But kes over whole he conduction eure 1.8 Measurement of conductivity 14.1 The significance of conductivity data ‘Conductivity data permit: = quantitative study ofthe effects of interior Forces on the degre of dissociation and on the Jom pair formation; the determination ofthe physical quantities such as solubility, slubiity product, ionie ‘product ofsl-ionising solvents, dissociation constants of weak aids and bases: = the determination ofthe amount of cerain electrolyte by conduct metric titration method 2Example 13 Knowing tat fer the formic acid = 350S-cm?-gaeq"! and Bycoo: "85S-em!-g-eq"! and Ky 1-76-10" mL", caeulate the molar and ‘auivaentconductivity's fora solation in which 0.092 ¢ of HCOOH was dsolved at 280 mt, final solution. Calculate alse the conductivity ofthe given soaton, Solio: ‘The molar concertation ofthe solution is «y= 0% My, 46-025, 10°M The molar conductivity infinite dilation is fant * Macao: Fora weak acid one can write: eee |_ = 3504 $5=4058-em? mot"! therefore from the following equation: ey +K,a-K, ‘one obtains the disociaton degree a we Ret VRE aR 2 2176x104 + YO.T6x10-4) +49. 76H10 BO 2x10 ee Considering the expression ofc one gets the molar condetivity atthe conenttion cy = 8-107M Amscoon=@-ASysicoon = 0.1375 «405 = $8.69 -em? mol! (nd of Soin) Example Lt ‘The constant of the solubility product for BaSO, i Ky =1-10"" mol?-t-? and Mya O61 Sem? peg? and Hy = 798104 S-m?-gmeq”. Find the conductivity for BaSO : ‘Solution: From the constant of solbilty product Ky, (a? SOF] and det the et that tees Saturated solion of BaSO, one ean wite Ky =? ({Bs?}= (80% ) and therefore: » “The molar conductivity at this concentration is given by Ay = ©, but due to the very low aS, concentration in the solution, the molar concentration isin fc the molar conductivity at infinite dition aor Therefore one ean write = shy = 8th =10°? MO 286.8-10°4S sm? mol = 2.868: 10°* Sm im because Nah aoe Po aaa HH go = 2868-1074 Son? mot! (En of Salton) Example Ls In the fable Delow are given values of the molar conductivity of HCOOH at diferent ‘molar concentrations. By an appropriate graphical procedare obtain an approximate value ofthe dissociation constant ofthe methanole aid (Ceo © | Owoor | @o00 | wwor | woos | oaT | [Risxememon) | OS) 7 re [ere | ‘Solution: Combining the Ostwald law Ky =SS! and the definition of the disci mn dearee A, Aw ene obtains the equation K, = ak ~ An) ow Figure having the slope K, ‘The following table is necessan ‘hat canbe rearanged inthe form: A ‘one ebitns the straight fine in Poting non = 0] BcoOT | OGG | TOOT | THOS | OOF a (mol Ap(Sx em? x mol™)| Ts | Os | Ore | omss | OTS r <5] 3008 Toa | B00 | Toroun! fo soe! wae wo Vey(motert) Fire Example (End of Solution) ee 1.82 Experimental arrangement and measurement of conductivity Experinentlh, the condita ei mesurenent is made with te aid of 2 condvimete ands ‘senctace eel. The posi quay ale mes i ie To have acess o conduits messy to knw the ewes cx ‘and the distance between them, f fe know the es oe Two major lites per and mast be Fira verame. Fest, oe cannot apy a direct tension across the electrodes becat ‘hand, it is i eae on one hand i's prety to eae leas ands on the ter han, is probably forte elecodes to became plaid The choses ates the composition ofthe salon andthe plarzton of he cecwoes acco ne fhe resi that is measured (eeu on two polation esances cos apres ‘To vercome hs frie, teen oe an sein ee es 9 ‘ht no sgn anol fess psa cre oon lee she hanes osuring in on aye se evd inthe ont haley) There Oe testo mst ear api in oro hve sal cage tense poet ee ‘ecu tis est the eleceoe are made fm pina ih coating of face tended Platinum elestodeosied on ti surfaces. Te Back painum curs fey feed coakae peri, which gs sie to high sandr exchange eure Sie Seen fe Sit 6 mes te es he se le Sane Se hy ih To overcome his second duly one eemines cel onan which she ri the dsance between the lesodes othe commonsrencfthen nn sais eran 2m (156) by using a solution of accurately known conductivity for erin temperature, One measures the conductance ofthis standard electrolyte solution and the rato of known 6 to the measured Lis the cell constant k ast [ Xnoving the eel] constant it is posible to determine the conductivity of certain clectolye solution fits conductance is measured by using the same above formuls For maximum sensitivity inmetsuring a ‘+ high conductivity a hign cell constant is required (small electrodes separated by a large distance) + small conductivity @ small cel constant is requiee (large electrodes separated by smal distance) or maximum sensitivity nmeasuring a 4+ high conductivity (ie, « high concentrated soition) an alerting current with igh Frequency is required: ‘+ small conductivity (Le, a low concentrated solution) an altemating curent with lo Frequency is required 1s also of maximum impcrtance that the electrode reactions to be #0 rapid that they ean be in phase with the applied allerating tension. Otherwise, i is posible for a diffusion polarization resistance to appear as aresult of a delayed diffusion proces. {3 Experimental determination of transport number L831 HittorfPs method ‘The anode, the cathode and the bulk of the electolyte solution are physically separated between them and the solutions contained within them (anolyte, catholyte and entra) are analysed after controlled electrolysis (known current, known period of time). Suppose thatthe cletrodesare made ofthe same metal whose cations are thse ofthe electrolyte in solution and thatthe etal and is eatons participate athe electrode reactions. “To understand the process aking plae atthe electrodes, nto the anolyte, into the catholyte and im the central portion (the bulk) of the solution see Fig 11 ‘Suppose QC of positive charge are passed from the left 1 the right, in the electric field direction “To cary this postive current, atthe left electrode occurs un anodic electrode reaction (an oxidation: anode: MoM 4207 ss)in which Q/.,F moles of M are oxidised (dissolve) passing in Q/2,F moles of M®*. The Jef elecvode behaves as an anode, Simultneoisly, at the right electrode occurs a cathodic electrode reaction (a reduction). cathode: MP 422" 9M (sey) in which Q/ 24 moles of MP are reduced (deposited) pasipg in Q/2,F moles of M. The Fight electrode behaves as a cathode. anolyte | featholye Oe Gee | ne Om wore gaa] [Tet oa mosnettes| loca, a, of MA, : : 'Srpoies AF Figure 1. The diagram ofthe faxes of diffasion and migration in the case ofa same electrode reaction occuring tthe two identical electrodes. snl a of lsicty @ C mast be cared Urge aot, he uk nthe {in the bulk tere is only electric field and therefore the Q C of postive charge are ‘wansported by migraton ofthe cation M®* and anion A> as follows 128 pole es : 1 les move inthe desion: andes) as) EF (mole. A? move inthe direction: eathode-vanode). as) 26 In the anolyte and the catholyte, in each moment of time afer the electrolysis star, tere is both an electric field, which causes migration, and a difsional field, which causes and of t_Qifp_|F moles of A® in anolyte: PEAR 1-8 anoles of Mé* inside the anol SPO EF (oes of ME inside he analyte) (160) imoles MP + = (motes A* )=1:8 (moles inde the anole (moles mE oes A=) Plmes MA, inet nay) 60") ‘The existence of this “net gain” explains why the diffsion Muxes appear. A ‘concenation gradient is setup between the anode and the bulk (in the anolyte region) and 1.Q/2,F moles of M,_A,_ pass from the anode tothe bulk Consider the catholte. Q/2,F moles of M"* disappear asa result ofthe cathodic ectrode reaction. OF these Q/2,F moles only 1.Q/2,F moles of M! migrate in the direction of th field ({fom the bulk to the cathode). Simutanesusy, +_Qip_|F moles of [AT migrate in the opposite direction of the electric fed (from the eathode fo the bulk) results a “net loss" of ~(1~1,)Q/2,P=-12,F moles of MP and of t_Q _|F moles of AT in catholye © (oles of M+ inside the catholyte) (1.61) moles Mi y+ t= 2 (motes A be side the catholyte). (161°) 7“The existence ofthis “net loss” explains why the diffusion axes appear. A concentration on radient i set up between the bulk and the ethode (nthe catholyte region) and —1.Q fa_fF ‘moles of M,,.A,_ Pas from the bulk othe cathe Now, one can understand why itis said that the anion is in a thermodynamic «ultram: the migration flux and the diffusion flux compensate eath oer both in anolyte and in catholyte. ‘One can also understand why its sad that the liffusion completes the migration in ‘he case ofthe cation. The diffusion fux inthe anolyte removes the excess of 1.2, F moles oF M™ andin necting ack the 1.0/2, F moles ean be en tht both the nt ain an hess depend pn he anspor number ofthe anon whch dos not partate in te aos sn exo clesre ean, ‘Suppose that the intial concentration of M,_A,_. i ca the volume ofthe anolyte ‘and the volume ofthe eatholyte V;. Suppose tha tthe end ofthe eletralyis, afer the sage of @Cofpstve charge the final concetration of MA, in anlye is cy and in catholyte isc, The rlation between the inal and intl concentration: (182) (oer) ‘fom where one ges the transport number ofthe anion 1 REM a6 4163) and then forthe cation: ue (164 To electrodes occur differen electrode reactions ‘Suppose that athe anode the anion participates in the snodic electrode reaction: node: AY Ash fem (8s) and atthe cathode the cation participates inthe cathodic electrode eatin: cathode M® 42,07 9M (166) ‘e2cheletroe being chosen accordingly tits own electrode reaction, ig. MOAT oT PONS charge PSs om he ef othe ight inthe ele eld dreton, see Fig 2 ‘+ atthe left electrode occurs a anode (oxidaton electrode reaction AM ase (165) (the lef electrode behaving as anods) ‘atthe right electrode occurs aeahodic (redvetion) electrode reaction: Mé +z 9M (166) ‘the right electrode behaving as catode). In the anolyte region, as a result of the anole electrode reaction, (2 |F moles of {AT are consumed. The migration process brings +.Qi|F moles of A" srom the bulk to {he anode and removes 1.Q/2,F moles of M" fom te anode othe blk )0f2-|P=-L.Qlp.F moles of AY and of 1 results 2 “net loss” of = -1,0/2,F moles of Min anole: ae 2 ot motes M+! oles Im anolyte) (16 {2 tes Ay EB mole Mis eB ame M, A, namie) (6 ‘The existence of this “net loss" explains why the diffusion Muxes appear. A. ‘concentration gradient is set up between the bulk end the anode (inthe anolyte region) end “U.Q/2.F molesof M,, A, pas from the blk the anode In the catholyte region, as @ result ofthe cathodic eletode reaction, Q/2,F moles cof M¥ are consumed. The migration process brings 1,0/2,F moles of M™ fom dhe bulk tothe cathode and removes t.Q/e.|F moles of A from the cathode to the bulk Tk results a ‘net les” of —1.Q/pfF moles of A and of O=1,9Q/2,F=-1.0/2,F moks of MP in anolyte: 9 ae 3p 2a 8c, A, ine ec 4) ‘The existence of this “net loss” eeplains why the diffusion Muxes appear. A concentration _watient is setup between the bulk and the cathode (in the catholyte region) and —t_Qz_|F moles of M,_A,,_ pass Frm the bulk othe cathode. 29anodet+) catost) an yp, t : t dd Pree] roneras] Pastor] Was] Moa. | | mown | | Men, 1Q of M.A, 1.) a et Er laied Figure 12. The diagram ofthe Muxes of ffuson and migration inthe ease of two diferent elestrde reactions occuring atthe two diferent electrodes ‘Supposing he same notation as below one has: (1697) and then 70) |zJPlee ~co)Ve o By introducing these results fr transport number nto equation (64) one has: 2oFlea eo Vu, BMee coe @ o snd then iz. Fley “co )Va +E-|Fle~co)Vel Finally we can write; 20 2.decVa ee un + Ties +e [Bee oe fe JoeeVe i. any Tae eee whee os am aecneeneo (U2) “Therefore, in anolyte the net fss depends ypon the transport number of the cation “which does not participate in the anodic electrode reaction, in eatolyte the met loss depends Upon the transport number of the anion which does no participa in the cathodie electrode Experimental determination of transport number by the Hittorff method requires 3 three-compartment cell ands covlometer. current of 10-20 mA i passed for 1-2 hours. Aer the electrolysis is stopped, samples of solution from anolyte, cathljte and bulk are analysed. 18.3.2 Moving boundary method (Obviously the transport number can be writen by means of drift velocity of the ions lune the influence ofan applied ele Hel : $5 Eke) Esfnsss ay Moving boundary method is based on the observed drift velocity ofthe ions under the influence ofan electric field generated by an applied elecic tension, Ths ionie dit velocity is Substinted by the direct measurement of the rate of movement cf a sharp boundary formed between two different electrolyte solution having either an anion ara cation in common. The sharp boundary results either from the diferent celour of the two electrolyte solutions othe difference inthe refractive indices ofthe electrolyte solutions. "To have a sharp boundary and to Keep i during the measurements itis necessary for {the rato between the tv concentrations o be around a certain vale, In order fo have the effect af movement of the bouncary it is necessary for the lectrochemical mobilities ofthe uncommon ions tobe different, asa consequence their rates ‘of movement are different "Experimental principle for the determination ofthe wansport number of a cation Is shown schematically in Fig. 13. For ation transport number two electrolytes with @ common anion are used. IF the transport umber ofthe Mj cation is required then itis necessary asthe following condition tobe fulfil, 5

Mn? + 44,0 (€nd of Sottion) : Example 112 _ Consider the redox chemical reaction involving the following redox couples MnOj/MaO; (acting as oxidising agent) and CNO™ /CN- (acting as reducing agent), ‘This redox chemical reaction involves HO” too. 4) Trying to write the equation of the redox chemical reaction decide in which side HO™ has to beadded. Why? 1) quate the redox chemical reaction considering the redox procedure, Solution 8) Obviowsly, the reaction may be writen a MnO; +CN" > Mn, + CNO Considering the conservation principe ofthe number ofthe atoms for C of N we ean sc that in each side of reacion equation itis necessary to have the sme number of CN" and CNO™ ions. As consequence, to eset the pincipl of charge conservation fora chemical reson, Streaks thatthe HO" ions must be ade inthe ih side 1) Considering the oxidation degree of manganese in MnO; (Mn) and in MnO, (Ma**) tnd respectively in CN" (N*) and in CNO™ CN") one can wrt: Ma" sata" fea NOt fs Ad, ill one geste balanced equation: 2Mn0; +3CN + H,0 2Mn0, +3CNO +2110" (End ofSluion) For red shomaleacton he lowing note fees can be remember "the rein pares mist ealide With ome atte in oer Tee tro Conds ms ule he ener cndon and ke pxmetc non the eleron ase kes ae ny whan te fact piles approach one ‘another closely; : pie brea of this lose vent of the rang pres he path which the ‘electrons have to travel is very small; fe = the clin may ceca ny oi of he reaction space, and uc oth thermal (hat motion, he coe geome poston oie in my Seslon OF the pce wih ea prob at oeucn he eon al tet 8 ‘may oceur in any direction in space with equal probability: because ofits leer charge, the elcizon carries an electric cument, suming over all directions it esuls thatthe total currents ze. ‘A eedox chemical reaction tay be regarded as the algebraic sum of two electrode reactions follows Oy 426° Ry AG, =-2FE aay 03426 OR; G3 =-23FEy aus) 2aR) +2403. 230,42 er en) For the redox chemical reaction which could be an overall cell reaction if AG, <0 (or Eg %0), the redox chemical rection occurs spontaneously inthe forward direction (>); + if Gyqy 20 (OF Eg 0) the redox chemical reaction does not oscur inthe forwatd direction (~»), but occurs spontaneuusl inthe backward direction (-); if AG “0 (or Fgh “0) the redox chemical eaton is at eauilbcium, Suppose thatthe overall cell reaction occurs in an elecuochemical cell I isto said thatthe oxidation electrode reaction (3) could oceur at an electroce, namely at anode, andthe reduction a eathode. in a separated way from spatial viewpoin For an electrode reaction the following noteworthy fetes canbe enumerated: thre is no direct contact between the reacting paicles, they do not collide: instesd each of the reactants is brought into contact withthe electrede isl in ‘other word it collides withthe electrode; = the eleczons must travel a sufficiently Jong path from the anode wiere the ‘oxidition occurs othe cathode where the redvtion accu ifthe overall eation| takes place in a galvanic cell; the electrons travel fom Ry to O» though an ‘wire which connects the two electrodes; + the electron tranafers from R. to anode and from eahode 19 O (fora galvanic ‘cel, sit was mentioned) occur ony in one direction in single definite dretion the path travelled is great as compare tothe sizeof acta Example 13 Knowing the standard clectrode potentials of the following redox couples Fe®* /Fe* (Ef) =0:771V) and Fe!" /Re (EY = -0.036V) caleutate the standard electrode potentiat (€$) ofthe Fe*/e redon coupe Sali ‘Wing he electrode reactions andthe coresponding relations between AG*and E° forgiven redox couples, we have: FOS FE NOP ae =F pe FEE Fe OO Inthe same way the required eleewode reaction:FGI Fe AGN [Considering the Hess aw one can write forthe 3, el re W050 155 B05 ype ofthe ast rection: 0%. and replacing he each AG" by the coresponding - 2FE® meaning one aes = SFE’, ~PFE se IPE ae jpg nd finaly (End of Soltion) 11.1.2 How to transform a redox chemical reaction into an overall cell reaction ‘To transform a redox chemical reaction into i eel i 4 overall ell reaction (ie, ino two distint ectrode reartons occuring each a a distinct electrode) iis necessary to (se Fig 1} external creat Kcr sal ig > z Pm Figure I. The hema dlazam of x consisting of v0 halls joined together bridge and a corresponding exterisil circult. i tinea Sine in syce each esting pil, he 0,7 couple in ll and the Ry coil in antral * mar an elec contact een the vo hel by means of sk ew Slows te low of nas, pang othe etic ens | ine in ech ace ofa tae metic phase which allows the echnge of theless withthe eacing parses this mc psp cot wie (VR coupe or wih Oo R sir ony andi an lato, oeg Oe couldcseris hoy as cede; shut the electric circuit between the metallic phases by metalic conductors (wires) ‘and suitable apparatus; tis called the externa iru Often to ensure a high conductivity of the solution containing O/ couple or only ‘one of the two forms of the redox coupe, I is necessary to add an indifferent electrolyte in reat excess this must be a strong electrolyte in order to dissociate completely. example 14 Consider the following redox couples Ce"/Ce"" (Ba, j.3+ =161 V) and Fe Fe OATLY). Choose the necessary species (you have all species at your b). an electroyser Put in the external circuit the necessary clectric devices choosing from the list: voltmeter, ammeter, power souree. (Use Pt electrodes and sot bridge. a) (=) PRET Het |PCH) Inthe external citeuit one can use vellmeter and ammeter. ©) (= )PtIBe™ Oe" PEC) Inthe enteral circuit its compulsory to use power source, (End of Solution) Il. 2 Electrode reaction [An electoce reaction is very’ complex notion. In this couse an electrode rection is regarded aba two step ensemble, bath compulsory. ‘The former is the charge (elecvon) wansfer step (els) occurring atthe electrode imerface. This means electrodie which s the major, the main par of electrochemistry “The later is the mass trmport of the eleceoastive species through the eleetolytie Solution: to the electrode and fom the electrode “The mass transport processcan be made in thee diferent wayslmodes. I there is 4 diference im the concentration of ons in ctferent repions of the clectrolye, the resulting concentration gradient produces a diffusion process. & ay & Sy Hh 20) = (yp =D) #0 as) 0 we B20) > yp Biro as) & ( Oe +0) aus) there are differences inthe electrostatic potential at various poins inthe electrolyte solution, then the resulting electric Feld produces a migration or conduction processas ain) I there is a difference of pressure or density or temperature in various parts ofthe dtc son bebe emery whee tine nee Ser nsieatlcoma toes enbesane ho) cr rs a & All these three modes of ionic transport are encountered in the experimental clestochemisty, bul a5 @ general rule only one or two of them are important. In all experiments one of ke transpert modes coud play a key role acting a a variable and the other ‘could be arranged in ch a manner wo not play the role ofa variable. Suppose sucha two-step electrode reaction in which the mass transport ofthe © and R species is made ty diffusion only (ic, the whole process is made bythe ions oxiginating {rom the indifferent decteoyte which is aded in great exces) For simpliciy, let us assume that the two activites ofthe O and R. species are equal: so = an. Let us not he activites ofthe O and R. species onthe electrode surface by By and 3p. In the case of equilibrium the current is zero, overvoltage is also zero, no electrode reaction occurs. Therefore sy and the diffasion layer does not appear, the bulk stains the electrode surface/extends 10 the electrode sucfae (see Fig. 1.2, midale case) Ian oxidation elecrode rection (see Fig.l, left case) takes place a the electrode surface (in outer Helmholtz plane: OHP Ore CR aus) then an anodic current passes through the electrode under an anodic overvoltage (7) > 0) end the R activity in OAP decreases (R., being a reactant, is consumed) and the O activity in COMP increases (© being a produc, is produced): i080 ia 0 | » nae Leathodic, > 0 + theresa diffusion = there is no| + there ia difusion bayer, {fusion layer, layer + bulk extends to the + bulkextends 10 + butk extends tothe | Aifuson ayer, the OP: Sifasion layer; + petanodie there is no net + net cathodic ‘letrode reaction ectrode eation ‘ectrode action 20 +a" R tao | ©. R 0. © | Figure 2. Te linear profiles of the concentration nthe dfason lye for equlbrium (mile), anodic non-equilibrium (let) and eathodie non-equilibrium (ight) cases, [As the cathodic electrode reaction curs a diffusion layer appears near the electrode ‘due to the difference in concentration between the OHP and the bulk. There are 160 onoentation gradients: one of O shih determines, O's movement to the elecirode surface; the ether of R which determines R's movement rom the electrode surface. 112.1 Fast (reversible) electrode reaction ‘Such an electrode reaction ofthe same two step type consists ofa very fast charge transfer step aise tn be tested as 8 gre-equiibrium reaction and avery show diffusion step which plays the role ofa ate determining step (rs). "The diffusion layer appears and has an important rolehe Coup +2654 Rowe fst (re-eqilirium) k va || 7 | >, eo = kee =P ap “his PE slow rate determining 3 | ka slow (ate determining sep) Ova Rou 2 Slow (irreversible) electrode reaction Such an electrode reaction ofthe same two-step type consists of avery slow charge ransfer Step which pays the role of arate determining step anda very fas fusion step which canbe ‘weaed as a post-equiirium sep. The isin layer des not appear but the difsion exis ke Coup +24 — Rowe ‘slow (rate determining step) eT «|| I. yg =DR ——fast(postequilitciu) 3 an hy = Orit Roun 1123 Comparison ‘Let us think atthe diffasion process as diving on a road and the charge transfer as, crossing a bridge, For fast (reversible) electrode reaction the picture is: thee is only one road which does nt allow to drive quickly and a very large bridge which allows crossing it immediately. ‘The speed with which one can travel is determined bythe speed that can be developed on the road. Driving to an from te ridge is rs For siow (reversible) electrode reaction the pete is: there are many roads wich do allow to drive very quickly anda narrow bridge which allows crossing it very slow. The speed with which one can tnvel ie determined by the epeed with which the bridge ean be ome Crossing the bridge i 11.3 The main notions and definitions 113.1 The electrode ‘The electrode isan ensemble of two conductive phases in direct conac (one being & firs class conductor andthe other a second class conductr) and endowed with an electrode ‘easton for which the essential step isthe charge transfer between the two phases. ‘The elctrodic interface isthe iterphasic region which hat its own spec ferent from those ofthe two pure phases in direct conc. lectonic Ionic conducting | conducting “6 hase phase properties, ‘The electron conductive shase could be: + an inactive, inert meta + anactive metal, semiconductor: a the ionic conducting pase can be: 1an electrolytic soluonin water or in an organic solvent, ‘molten salt at high temperature, =a metallic oxide at high temperatre = polymer. Panicles exchanged through the electric interface could be: = electrons tan interface ike PR OUR cations st Me/ Me™ electrode; anions at Nem /Nem* electrode electrons ard holes at Semiconductor /O/R. electrode. Single-electrode ‘When only one electrode action ocurs atthe electro interface, the elestode is called single-electrode, Muli-electrode ‘When a least wo eloewode reactions occur simultaneously atthe electrode interface, the electrode is called mlti-electrod ‘Anode-cathode, conventions The anode isthe electrodes which a net oxidation electrode resction gees Dez eR ns) oo ne ‘This electrode reaction is also called anodic electrode rection or d-electronaton “The cathode the electrode at which nine reductioneletode reaction oocure Daze” 9R any Ore Ga OR aur “This electrode reaction is also ealled cathodic electrode reaction o eletronation Te anode works under an anode over oie that is always taken as positive: n> 0 ‘The cathode works under a cathodic overvoltage that is always taken as negative: n <0 The anode always works under an electrode potential hat is moee anode or mote positive than ‘the reversible electrode potenti: 45E> Ey a.) ‘The cathode always works under an electrode potential which is more cathodic oF more negative than the everdble electrode potential BE aus one an stan lth noe is negatively charged and the etd postive charged me alas his: ‘ 0, <0, aus) In.anelectrolyer, the anodic curent is postive and the cathode negatively charged, ‘One aways has: e _ 0,20, (16) nan galvanic el, the anodic current is postive and the cathodic curent is negative: In>0 ho aun Iman electrolyer, the anodic current is negative and the cathodic currents positive <0 I> (us) 113.2 Electrode potental, reversible electrode potential, overvolige, polarization ‘The difference between the inner (Galvani) electric potential of the metalic phase (Mand of the elecrolsc phase (8), under a non-zero current, i caled electrode potent: E=E yo “(Oy - Os reo ais) ‘Asa general rule, the electrode potential is intimately inked with the current ‘The difference between the inner (Galvanic) elect potential of the metalic phase () and of the electric phase (S), under a zero current i called reversible elecrode Potential only ithe eleczode at sa single-elecrode: Ep Ey (Oy -Os)i.o 120) ‘The deviation of the electrode potential when a non-zero current passes through the electrode fiom the reversible elecvode potential when zero cient passes through the lecirode, inthe ease of singe-lecrode is called overvolige: 46 aun If this fference is positive, the overvoltage is also positive; he avervoliage is anodic and the electrode behaves as an anode. IT this difference is negative, the overvolage is also negative; the overvoltage Is Ey; jy moti a6 Fy <0 if Eq O50 i anodic 130 E> Ey Figure 1L3. The linear profiles of the inner (Galvani) electric potential in the compact layer and the dt layer for equilibrium (right) and ‘anode non-equilibrium (left) cases for a very fat electrode reaction, r4m0 | Prtne0 svn 5¥q D0 . i anodic n>0 E>Epey Figure 14, The liner profiles of the inner (Galvani) eletrc potential in the compact layer and the diffusion layer for equilibrium (right) and ‘anodic non-equilibrium (left) cases fora vey slow electrode reaction, 48 Example 1.5 Draw the picture describing the linear profile of inner (Galvani) electric potential of an clectrode operating. as cathode beth for a fast (reversible) and slow (irreversible) ‘ectrode reaction ‘Solution: Pictures illustrating the electrode furetion as cathode (cathodic non-equlitxium) for a fast ‘fectrode reaction (et) and Tor a law eectode reaction are shawn in Figure Example I. nso} une nc ° Oyo — . Ce neo | + eahate i eathotic neo no B0 oR ovr, 1 a vy mised e EP) OFye = / 0, 4¢° qt g, ne ev. - P>o any Teoyim Foye, Figure IS b. The individual polarisation curves atthe di-letrode for each electrode reation and the mixed polarisation curve inthe eae of P> 0 or E> Epiged «when the net current \hrough the d-elestrode isan anodic eurent 1, each electrode reaction being ou ofits own eaulibeium state. III. POLARISATION CURVES AT THE ELECTRODE, IIL.1 Experimental setup ‘The polarisation curve atthe electrode isa curve that links the curent (oF curent density passing cross the electrode and te electrode potential or the overvoliage under which the electrode reaction occurs. Sech a poarsition curve could be obtained experimentally with the aid ofthe sexup presentes in Fig IILI, by using en electrochemical cell withthe electrodes (or ith 8x0 ‘ecirodes) in which the electrolyte solution i tire. ay Figure IIL. The experimental setup used to obtain the poirisation curve atthe eleewode in the picntostatic procedure. P: potemtiostal,C:electochemical cell, R standard resistance, mV: milivolimete, X-Y: recorder, WE : working electrode, RE. reference electrode, CE : counter electrode ‘There are wo electri circuits having differen oes: ‘+a polarization circuit which consists of the P, the WE and the CE ; by means ofthis one apple an overvotage on the WE ; the overvoltage is thermodynamic Force; +a moritoring circuit which consists ofthe P, the WE andthe RE ; by means of this one measures the electrode potential ofthe WE ; the current is a thermodynamic x Let us focus on the action of the eletonic circuits of the P on the call, precisely on the clectrodes. Initially, when no eurrent passes through the cell, measuring the electric tension between the WE and the RE one has Use ne-RE = EE Ere RE any and between the WE and the CE one hs: User we-ce = Ere ~ErencE a2) 3In order to apply a known controled overvltge atthe WE , it is necessary that no curent pases through the RE (he P ensures this condition using a very high input resistance) and thatthe CE i not a polarizableelectrodic interface (the CE can have slrge enough size ‘compared to that of the WE ). To madiy the eletrode potential ofthe WE its necessary to tse the polarisation circuit and apply a polarisation between the WE. andthe REE Uwe-ce=Urewe-ce +P amy 204 aking nto acon the equation reversible sion Write ow dhe ofthe CE, one has a peas Uwe-ce = Ewv.we~Erexce +P Frey We *P~ Enyce cay er WE WE ~ Er. ce (because the nce 0). Therefore the P and the nyg have the same sign and the same magnitude, we aus) andthe whole pplied polarisation Ps ek only bythe WE as an overvolage Typ | the polarisation Pis postive then the WE is anode and the electrode reaction taking plac is anodic. P50 = nye >0= anode electrode reaction at WE ifthe polarisation P is negative then the WE is cathode and the electrode reaction taking place is cathodic: PO => nye <0'=> cathodic electrode reaction at WE ‘To know the overvoltge My the monitoring cteuit measures the eletial tension between the WE and the RE hich is: Uwe-ne = Ewe ~Ere ans) ‘By subtracting from this equation the equation oF the reversible electrical tension U, ‘one as en ~ Us ERE =Frex We + MWE~ Ere ~ (Ere, WE Ere) au =e 2 ‘Therefore the applied polarisation P, imposed with the sid of the polarisation czcuit ets as covervoltage at the WE and that overvoliage can be known by two readings 10 the milivoketer ‘Also, by reading the curtent with the amperometer one has a pair of values (I, n) or (.E) or (in) or (i, B) (ifthe rea ofthe WE is also known). For another Pon has another pat and so on. Having these pairs of vals one hes, in foc, the polarisation curve obtained By 2 point by point metho. To obtain a polarisation curve itis posible to sweep the electrode potential in postive rection or in negative direton instead of wsing a point by point method ‘The right direction of sweep is chosen depending on the species present into the electrolyte solution. One condition must be fulfilled: the potetat sweep must be very slow in ‘order net to disturb the statorary condition (the time-independent concentration andthe time independent curren’ 1112 Polarisation curves at the electrode 1112.1 Inthe electrolyte solution there i only R ‘The K species sable to giv rte only tan oxidation (andi) electrode reason: Ove OR ans) and, therefore, itis necessary to sweep the electrode potential in anodic (positive) direton. ‘Let us start the potential scan at an electrode potetsl at which no electrode reaction ‘occurs. This cestode potential must be very negative. Then one sens in positive direction, At 1 cerain clecvode potential, namely E,.cq., the anodic current stars to increase due tothe beginning ofthe anodic electrode reaston (See Fi. 11.2). The current will increase ntl it wil ‘each a limiting vlu= known as anodic difusion plateau region (to reach tis current all the R species in OHP give rise to the elecrode reaction and therefore the concentration of Kin the ‘OHP i zero), The electrode is very reactive for chosen R species in this region of potenti. Ove R anodic branch au there is only R Figure 2 Polarisation cure at letrode in the case when inside the solution ‘oer is only R species. 111.22 In the electrolyte solution there is only O The © species i ble to give rise only toa redetion (cathode) electrode rection:Ose +R aus) si, therefore, it is necesaryto sweep the electrode potential in cathodic (negative) direction Let ws start the potential sean at an electrode potential at which no electrode reaction ‘ceurs. This eletrode penal must be very positive. Then one scans in negative direction. At 8 certain electrode potential, namely Eg, the cathodic curent stato increase due to the beginning of the cathodic electrode reaction (see Fig IL3). The current will inctease uni it ‘will reach a limiting valte known a cathodic diffusion plateau reign (to reach this erent all the © species in OHP give rise to the electrode reaction and therefor the concentration of O in ‘OFP is zero), The electrode is very reactive for chosen O species inthis region of potentials, eon ae ‘cathode branch there i only O Ove — R Figure 1.3. Polarisation curve at electrode inthe case when inside the solution there is only O species. ‘The problem of he pertrtation-esponse relation ‘to know that a pensation applied to an elecrode reaction works you must observe an cect, a response, moreover you must beable to measure the response, 1+ fr fast elecizode reations a small perturbation produces large response; the eason i the very high standard exchinge curent density i"; therefore to noice and measure a response the needed perturbation i very small, * or slow electrode reactions unly a large perturbation produces a measurable respon; the reason i the very smal slope of the polrisaton curve (geometrically speaking) or the very small standard exchange current density 1°; therefore to noice and measure a response the ‘nceded perturbation has ibe very large The problem of reversibiliy-reversibility: ‘+ fone applies a conszant perturbation toa sytem being in an equilibrium state, then the system moves inthe dren in which the perturbation is reduced (Le Chitlier principle) ‘for reversible elecede reaction, the pemurbation being small it maintains the system in ‘he coexistence region ofthe two partial electrode reactions; when the perturbation is cancelles ‘the system retuns tothe nial position because there i vehicle to bring it back; + far imeversible eleczode reaction, the perturbation being large, the System i sent outside the “coexistence” region, in the iteversiblity region and when the perturbation cancelsends, {he system ean nt retunto the intial positon because thee is no vehicle to bring it back; co 1112.3 Fast (reversible) electrode reaction Such an electrode reaction has a very fast charge transfer step and avery slow Aisfosion tp, 1Winitially there is only R one has the partial anodic polarisation curve (se Fig, 1.4). theres only O one has the arial cathode polarisation eure (se Fig, I.) IT inially thee are both Rand O one hs the mixed poarisaion curve which can also be obtained ty adding the two partial polarisation curves (see Fig.l), iii Figure IL. Polarisation curve at electrode inthe ase when aside the solution there are both © and R species, inte case o very fat elerode reaction Feanres 1 Always Exen Ezcq there is oly oxidation. 4. The Ey exits is well-defined, settles down quickly. In tis pon, the Nemst aw holds 1112.4 Stow (reversible) electrode reaction Such an electrode reaction has & very slow charge transer step and a very fast Aitfuson tp, iniially there is only Rone has the paral anodic polarisation curve (se Fi 1 iniiay there i only © one has the parialeatboic polarisation curse (se Fig. I). IT nally there are both R snd O one has the mixed polarssion curve which can be slso obtained by adding the two partial polarisation curves (see Fig. I), ts). F 1. Always Eee “Fae 3s2. The current increases very slowly, the polarisation curve practically being almost horizons; the stone OY is very smal 3. For E en there is oxidation only, For Ecen n,,). 4. EWE, -P (where Pcn,;) b) Write the electrode reactions occurring tothe di-slectrode in the above points. Note: Ey, isthe mixed electrode potential, O,/Rj redox couple 0; /Rz redox couple 56 Solution: a) L E=Eg—m) Eye) = Eq 8 cathodic being generated only by the reduction of O, (the O, +26" <2 Ry, being a equilibrium, 1, = 0), 1= 1p 2, Beam eras! i8 anodic being generated only by the oxidation of Ry, (the Oy +2,€" 6 Ry being a equilisium,|y = 0), 3 E=Eq-P (where P>n,y) represens a point situated (0 the left of Eyys (E< Eggs) therefore 1= 1,41, sith both of them cathodic (0) is reduced as well as aE nF =P (where P Ey) therefore | BL Orne OR, 0, 42507 © Ry 2 OFA SR, 0, 4236 Ry 3. O42 Ry 1, is cathodic 0, 426° ORs 1, Iseathodic 4 O42 OR, 1 isanodie 0:46 OR, 1, is anodic (End of Solution) Example 1112 ‘Consider triclectrode consisting of thre electrode reactions which polarisation curves, fare sketched in the figure forthe same potential range as being independent one from cach other. The bulk redox chemical reactions, even if some of them favourable ‘hermodynamically, are very vey slow from the kinetic viewpoint. 712) Order the electrode reactions after their increasing rate. 'v) Indieate the rs (rate determining step) in each case (conskdering them as belonging tothe pattern case). ©) Indicate an E atwhich all of them work om the anodie diffusion plateau, icate the E ai which each redox couple, in turn, does not work. diate the E at which two of them work anodically while the other works cathodically. Solution: 8) Electrode reaction 2« electrode reaction 3< electrode rection 1 1b) Electrode reaction I: rds the mass wanspor by difusion sep electrode reaction 2: rs the charge transfer step, ©) At the mixed electrode potential Eq the electrode regtion 1 occurs under an anodic overvolage, the electrode reaction 2 oecurs under a cathodic overvoliage andthe electrode reaction 3 occurs under a cathodic overvoage, 4) For E greater than E all the electrode rections occur on the anode iffsion platen ©) For E=Ejgyy the electrode reaction | is at his equlitrium state, for E=Eyey the electrode reaction 2 at his equilibrium state and for E™= Fg th electode reaction 3 6 this equilibrate. 1) For Ejey2 H+ 2H0" ES =-0828V 0.000 EP = 1.229 =0401V ‘These anodic and cathodic electrode reactions at which the species of water panicipatein function ofthe pi ofthe electrolyte solution, determine the so-alled “potential ‘Window" which isthe range of elecvode potential in which cne may study an clecvode reaction without having the undesirable interference ofthe electde reaction of the species of ‘water (Se Fig. 11.) 03 +4H + 4e-9 28,0 regions of redox + Ti Sabi for 2H,0+ 26° 9 4280" F m0.nt ado! 1 L Figure 11.5. Polarisation curves at electrodes in water lke solvet in the thre cases of acid, reutal and alkaline solutions. 9Ouiside these “potential windows” it is not possible to study electochemically a redox couple, an elecrode reaction. Observations: ‘The water concentration is very high compared withthe concentration of HyO" and HO” For water molecules iffsion Imitation do not appear. 2. The H,O* and HO™ ions ae in slow concenration, even in acidic or alkaline solution and, hence, for these ions diffsion limitations appear and the polarisation curves have tathodic or anodic difusion plateaux 1112.6 Comparison between a fast (reversible) electrode reaction and a slow (reversible) clectrode react Fast (reversible) ‘Slow (irreversible) charge transfer step fast slow (1d) Alifasion step slow (ds) fast (pure diffoson (pure charge transfer overvolage) overvolage) slope age. igh slow effect of 1 slow = Thigh ‘large = I small reversible electrode potential, Ee, well-defined i-defined settles down quickly settles down slowly Nernst law holds does not holds (Wo see if perturbati cts you must observe response) small perturbation 8 large perturbation ‘ofthe equilibrium, keeps ofthe equilibrium, ‘the equilibrium inthe sends the equilibrium reversibility region, when inthe ieversibiliy the perturbation vanishes region when the Perturbation vanish ‘the equlibeium resens to the intl position he equi dane ot return tothe Initial position polarisability less more slectrode reaction yes Es I1L3 The Nernst law For an ionic species (2, #0), the condition of thermodynamic equilibrium requires ‘he equality of the elecrochemical potential ofthe Ionic species ino the two phases in which it is dstebuted at equilibrium: Co | a.19) ‘The electrochemical potemial is given by the sum of the chemical potential and the clerical work: AP = uP + 2,60" aun) ‘where © isthe internal (Galvani elect potential oF the phase @, The chemical potential is _iven by the well-known relation: oe +RTIne? a2) Considering the electrode PL/O/R at which the following electrode reaction occurs: VoOFRip + 20h <> VaR Ep m3) here the charge conservation law is Voto -2* Yaz amas) nd supposing that this electrode restion sat equilibrium, one can write: Voll +2 = alia any corby the above relations for he elstrochemical and chemical potentials, one has YoU +RTInag +29F5)+ 264. -FO\)= va(uk #RTInag +29FOs) (1.15) 2P\ ~(Voz0- Yate IOS =Yokb +24, YR +RTIn“Z-—(UH.16) ‘oF considering the charge conservation: (Oy Os) = Youd +24. ~ Yah + RTD au.a7y Dividing his relation by 2F one ha: vou +a. — reek Rr ale uu.) 3 ae ae Dy -Os = and replacing the difference of the nwo internal (Galvani eletre potential under a zero current (Geeause ofthe condition of equlitrum) by the reversible electrode potenti 6Ew «ui one has: E, 7 “¢ 20) IF in this last equation one considers a standard state for the activities of R and O (ag = aq =1) then one gets: BP= Ep ag-an-| ana the expression forthe standard electrode potential, Coming back othe expression ofthe Ej, and replacing the fr: term ofthe second sie ofthe equation by its thermodynamical meaning, one obtains RT, ae mi2a) the Nemst law fora fast (reversible) electrode reaction, for which one can discuss about an authentic equilibrium, Discussion: 1. If =0 then E=Eygy and 1=0, the electode reaction is at equlibsium. The Nerst equation holds hee 2. If #0 then E+ Ejay and 1 0, and writing the expression for Eand for Ejy By B+ RE jg f. 2 and making the difference one has EE gy = ETigtotn Fane and: 50.520 and the electrode reaction iy ay ‘occurs in atodie direction given by Eq (19), R being reacint and © product (Bg 49) + if E> Eyes (> 0) it results that a + if Ea ) Example 113, sven redox couple solved in the same solvent but reacting on diferent ‘made of different metal Pt, Au, Ag ett) the standard electrode ‘potential is different. Solution: : ot ta va F nature ofthe metal ofthe electodic interface determines the vlue of E® by means of, ‘which depend upon the nature ofthe metal (End of Salton) shows thatthe ‘The expression of the standard electrode potential E* Example IL For the fast electrode reaction 0+2¢" e> 2R establish the equation desribing the Nernst law. Solution: “The thermodynamic equilibrium condition is Tig +2R,. = 2 and he charge conservation conditions is 222% where Zo and 24 ar the charge ofthe © and specie. Developing the themadsnamic equa condition by using ie above procedure (Severe inthe theory) and the charge conservation cndton, one clans the expresso: yy w+ ET Ig a oF at we 42m, = 20% ae where B® (End of Sotsion) Example IS Calculate the shift in the reversible electrode potential of the electrode Pt/Ma0j,Ma"* Imacidie solution ifthe pHl ofthe solution 1) doubles; by decreases with 3 units. ‘Comment the varition of the oxidation strength? 6Solution: ‘The electrode rection is MnO; + 8H” + Se" <> Mn? + 41,0 and the Nemst expression for the reversible elecrode potential can be writen in two equivalent sways: ands on 23082 pH oF svhere, of course, pH =—Ieay. 8) When the pl is doubled oe has: 3 , RT, Shao aRT Egg = E+ EincMOt 2 5038°T SF age op PH and the variation ofthe reversible electrode potential is given by: SRT ser AE ea * va Ene #-2:303 57 (ptt pt) = 2.5085 pl ‘This shit in the value of reversible electrode potential is negative and it results that the ‘oxidation strength decreases by increasing the pH (ie, by dereasng the H concentration. 1b) When the pH decreases with 3 unis, one has aRT, 2303887 ip 303 (H-3) B, and the variation ofthe reversible electrode potential i given by: aRT, aR. AB gay = Emu ~Eme © 2303882 pes 3 —(oprayp= 2.303%38RE, es En Se OH -3- Cpt} = 2303.98 ‘This shift inthe value of reversible electrode potential is positive and i results thatthe ‘oxidation strength inereases by dereasing the pH (ie, by increasing the H” concentration), (End of Solution) IV, ELECTROCHEMICAL SENSORS 1V.1 Ideal — polarized and ideal — nonpotarized electrodes 1 on an eletrodic interface one operates with a perturbation 1 (which is a thermodynamic force) then it respond bya eurten density i (whieh isa thermodynamie ux). Considering the magnitude of the perturbation and of the response, the electrode can be slasified in wo types: . polrizable—the limiting ease being ideal-polarzabe; . ‘on ~ polarizatie~ the limiting case being ideal-nonpolarizable. ‘The idea! non-polarized elecode is one that allows free and unhindered/unimpeded charge transfer across the electrodicintefie. Only avery, very small overvoliage is necessary 10 be used fora very, very large curentcensiy o pass. Infact, such an electrode does not change its cleetode potential fom the reversible value when a small curent density crosses the electrodic Interface. Such an elecrode is encowed wih a infinitely fast (reversible electrode reaction. ‘The polarization curve obtained at this kind of electrode i almost vertical ‘The ideal polarized electrode is one that allows no charge wansfer across the electodic interface, The charge transfer is completely hindered/impeded. Very small, small and even large current densities cannot eros the electrode inerface without using a very, Very large lovervolige. In fct, such an elerode changes its electrode potential from the supposed reversible value tothe imposed valve at will Such an electrode is endowed with a infiitely slow (imeversibl) electrode reaction. The polarization curve obtained at this kind of electrode is almost horizontal 1 1 a b Figure V.1. The polarization curves for ‘deal non- polarized electrode (3) and ideal polarized electode () Excepting the two limiting cases discussed above, every electrode isin some extent poarizable and in some extent non ~polaizale (in sme extent it opposes othe polarization and in some ‘extent allows the polarization). 65‘The main features and ferences between the two limiting eases are presented below ‘deal non-potarizable sleetrodie interface eal polarizable electrodie interface electrode reaction infinitely fast infinitely slow exits does not exist, charge transfer infinitely fast infinitely sow Aistesion infinitely slow Ininiely fast exchange ‘current density Poe Poo standard exchange ‘current density Poe 0 standard rate constant oe Boo charge transfer resistance Ry 4 0 Rye equilibrium of the electrode reaction ‘well defined ot — wel defined attained instantaneously tained harly| escrbed by the Nernst law not described by the [Nemst law in its usual form perturbation = response relationship ‘ery small n produces very large n produces ‘ery large | current-density nature i les ign + peo nature ofthe process {aradaic process non faadaic process 1 double layer charging Gouble layer charging process process 1V.2 Electrical analogy 11s usual to consider an electrical analogy ofthe electro interface. “The charge transfer step means the passage ofa current through the electrode interface which ‘opposes to it a cern electrical resistance. ‘The electrochemical double layer charging occurring at the electradic ineface (which siructure means, in fat the electrochemical double layer structure) is tread as a condenser charging, 66 onabacoanecsnueny i ‘The simplest electrical mode! of an elecvodic interface consists ofa charge wansfer resistance coupled in parallel with an electrochemical dooble layer condenser ca Ca 1} if Rao Rave Figure 2, Blectieal analogy for a very fast electrode reaction or an ideal non-polarzable electrode Figure 3. Electrical analogy for a very slow electrode reaction or an ideal nompolarizable clectode IV3 Clas ion of the electrodes according to their function in an electrochemical cell Potentiometric electrodes 1.31 Reference electrodes A reference electrode is made up of conducting phase: having constant chemical ‘composition and because of this it exhibits a knovn constant electrode potential (hich is independent on the nature and the on the activity of the eletwoctive species which is the analyte, but is dependent on the nature and chemical composition ofthe matrix), Obviously, there isnot an universal reference electrode, ‘To work in tis way its necessary for the RE to bean deal non-polarized interface tras clase as posible to such a behaviour. That means thatthe elecrode potential does not ‘move from it reversible value even ifa very small curent passes trough it Tis customary for no curen or, betters, «very small corent o pass throug it. ‘A.good RE must uli the following requests + reversibility, + reproducibility, = stability The reversibility means thatthe direction ofthe eletrade reaction can be changed (moliied) by changing the polarity ofthe electrode (when n changes to ~ then i becomes ~ i). ‘The reproducibility is expressed as the standard deviation of the electrode potential at conseettive measurements ina Soltion of given concentration ‘The stability is discussed in terms of deft in Mowing solutions and the residual standard Agel «way for which one can write the equilibrium condition sonemstoe cotter | Figge tiie “Finger avs) ‘rom which one has: ave) where avy avs) By introducing this activity into equation of the reversible electrode potential one has successively avs = Frey AgclAgcr where the standard electrode potentials are linked by: RT. ° En Kspagct v.10) Buectiagcr Pegs rag * pt Renee 222V 25°C), (One knows thar EB .,20799V and Eo the chloride activity is very high, them the reversible electrode potential is constant because the a, could not be changed 2y the occurence of the electrode reaction when only very small currents pass across the elearode ‘ia small anodic current pases, then the electrode reaction and the chemical reaction occur as follows: °Agee @=t Ae a Agtecr Go aged avay andthe electrode reaction producing Ag” increases a, andthe chemical reaction consumes |Agé as reactant (he eld phase increses), + fa small cathodic curent passes, then the electrode reaction and the chemical reaction ‘occur as follows Agi te Ag avr agtecr «2 agcit aver and the electrode reason consuming Ag* decreases a. and the chemical reaction ae produces Ag” as product (the slid phase decreases) ‘As a consequence, the silverlsiver chloride electrgde works as reference electrode ‘only if the component phases (the solution phase saturated in KCI andthe precipitate phase) preserve ther existence ‘The small magnitude of the Kyp age is of maximum importance for the occurrence of the RE, When the a, is modified by the occurence of the electode reaction, the chemical equltrum is involved only in avery smal extent, n order to satisfy the value of the constant ofthe solbilty product (and, of course, the activity ofthe chorie fons could be changed without altering the chemical composition ofthe two phases ina dramatic way), ‘Therefore, when 2, is modified by the elsiode reaction progress, the chemical reaton works to keep the oni product + {is modifed oo, but very litle if one considers the concentration of the KCI inthe saturated Solution, As result the concentration ofthe KCI inthe solution remains 3,8 M because some KCl dissociates to remake the equilibrium. tis noteworthy thatthe equlibum: constant, whichis in fact the Kp, ager- TRE Bey. kK’ scr oka ava is alo involved and has its important role: if small anodic current passes, then the elestode reaction andthe chemical retin occur a8 follows: Keser 2 ket av. ran tne an i i i ira small anodic curent passes, then the electrode reaction andthe chemical rection cccur as follows keg ee ret ce That means that a, i kept constant and therefore the reversible elesrode potential of this RE is alo constant 1V.3.1.2 Mercury, mercury (1) lorie electrode, Hg, He,Cl, /KCIG.8M) “This RE clectrode includes a platinum wire immersed in a paste of mercury and mercury (I) ehoride placed ina lass tube. Te interna illngsoltion is potassium chloride of Known concentration, saturated with mercury (I) chloride. This reference electrode is well known a8 SCE (Saturated calomel electrode) Features ‘+ there is «commercial hal-cell ‘itis very used becase itis easy to prepares {the presence of KCl crystals guarantes is constant solution concentration; 4+ can be used as RE at temperatures below 75°C: 1 there ate both single and double junction mercury, mercury i) chlorie, being used in funtion ofthe chemical composition of the solation in which s immersed on short flee reason Haft #26 © ae ava i + 2h. = 2a v.13) Byyp tH =e nig +201 ¢ HagCls ova ava Kosieachr (V.16) Kostexchy avait Kiser e Kel avay nreversible electrode potenti: E, nee Heh 284207 “Fic 20” ° RT, RT Fagevane SDinag- (vrs) where ° Rr e BP ay 1 REMK hiejol/ane 20> ~ Pha vate” OFX patesctr ov.l9) Ba ay, MOTHR, ES - (he rae Tia /anezcr ~0288 Example V1 Considering the SCE indicate which of the pure phases must Keep » constant chemical ‘composition (in other words must be present in the electrode composition in order to assure a good running of i) ifthrough the electrode passes anodic current; » ‘cathodic current. rium involved in euch ease, 8) Hg and KCI are the phases which must keep a constant composition inorder ta have a ood SCE under sal aoe cure pasng ars Te glib invoved work 5 He} «207 2He Hg}! 42cr SS He,c, Kiser ga kel 1) HgsCl; iste phase which must keep a constant composition in order to have a good SCE under a small cathodic current passing across it. The equilibria involved work a follows: Hg} 42° > ae ngisrcr 42 ect (end Soon kscr GE Ket n acon mei ebanenet Nc ‘ i 5 i i i; { i 1V82 Working electrodes [An working electrode is made of conducting phases not having constant chemical composition and because ofthis itexhbis a known variable electrode potential this electrode potential cepends upon the nate and the activity of the electractive species which isthe [nalyeand, of cours, upon the mare and chemical composition ofthe mai. The reversible electrode potential is desribed bythe Nernst ls for fst (eversibe) electrode reaction and by an extension of the Nemst law for slow (irreversible) electrode reactions. 'AS a general rule, its important that the working elecwode to be a single-electron this ear, is reversible electrode potential isa fuetion of the elestoastive species activities “The electrode potentials reversible with respect to elecoactve species. "The chemical nature of te eectonie conducting phase, as well a its surface slate, can influence on the oceurtence of the electrode reaction (see for thatthe expession of the Standard electrode penta n the Nernst law), The chemical sips could also be influenced by the chemical nature ofthe WE. "The geometry of the eictronic conducting phase, as well asthe geometry of the ectrchermical ell can influence the diffusion process. For example, for aspherical electrode there is 2 difusion process of spherical symmetry, for cylindrical electrode thee is a diffusion process of eylindrisl symmetry, for a planar electrode there is a difusion process of, ‘planar symmety. “The WE is an electro terface that could have any behaviour between an ideal non- polarized interface and an ideal polarized interface, from a very fast eletrode reaction to a ‘very sl electrode reaction. "The WE is used to allow the occurence of an electrode reaction in order to study it For a certain electrode reaction a suitable working electrode is chose. The working electrode -must expose a very larg potential window both in anodic direction and in eahodie direction to “low the study ofthe electrode retin and to avoid the interference ofthe electrode materia “The physi! form of the working electrode, slong wi the cell design, plas aso an important rol. Jor microelectrode ‘+ may be used in small volume of electrolytic solution; ‘+ inay be used both in vivo and in vio conditions; “shows asmall obmic drop beeause it draws ony small curets; + could be used in media with high resistance and without indifferent ‘leciolyte (which being in large excess, introduces impurities which could interfere in the electrochemical response), very high sweep rtes may be used inthe CV experiments, ‘ensures an enhanced diffusion process; ‘enhances faradaic to double yer charging curren aio; needing only small curents it can be used in a two-electrode configuration cell with @ conventional ference electrode; afor usual electrode ‘+ may be used only in large volume of elecireyt solution; ‘+ the ohmic drop could be large, especially in the absence ofa large excess of an indifferent electrolyte; draws large currets ‘+ could be used only in media with small resistance in which a large excess of an indifferen: electrolyte is added (the impurities eoncentation could be comparable with that ofthe eletroactive species and therefore an interference coud sppear if the impurities a also eleceoactve), + allows only small sweep sates; ‘+ anordinary diffusion process takes place; + ismecessary to use a thre-electrode configuration cell. ‘The usual classification on the working electrodes is + classical electrodes of er ype; first ype; sezond ype; a ype; as electrodes; ‘+ amalgam electrodes; ion seleaive electrodes; + chemiealy modified eletrodes. 1V.32.1 Several kinds of working electrodes For a general electrode reaction To, +2" oS vpR) v2) hich ecu the estriol condones Sov, +2, oF vin evan the charg coneritin aw xing Svzo, +, Ty, wary ™ eeciasa sine oe aca ested al Developing the thermodynamic equilibrium condition by taking into account the definition ofthe electrochemical potential and of the chemical pent one has, ily, the NNemst lw RT poets SE p, WV, at ava) av23) Obviowsly, ata given temperature and at a given pressure, the reversible electrode potential is detemmned by the standard electrode potential E® and by the activites of the Substances taking pat in the electrode reaction (reactant and prods), The standard electrode potential isa constant that is specific Tor each electrode interface (by ‘means ofthe standard chemical ptentials ofall substances taking part and aleo by means of the chemical potential ofthe metalic phase which is speifc to i). Their activities are variables depending on the concentrations and, of course, on the ionic strength ofthe medium. There are many cases in which these activites can be modified by 2 ‘chemical reaction oeurrng inthe medium ar by fone association, Zero kind electrodes Zero kind electrodes, also known as redox electrodes, tave an inert metallic phase whose material doesnot paricipae tothe electrode reaction, This metal is immersed into the lectolye solution serving only a5 electon wansporer as a soure of electrons in cathode lectrode reaction ora a sink of electrons in an anode electrode tion, “There are simple redox elecuodes Puork VOOM VR Ey E+ in“ av24 ‘here the hydrogen fon or/and hydroxyl ion do not ake part There ae also multiple redox electrode PUOIRM’ or HO” oO pH” +e” 6 va +gH,0 oro + P+ M1) 2 vR2R Ese eta avasy 6ez the hydrogen in orand hydroxyl fondo takepart, being potentia-etermining fon, Example V2 For the quinhirone electrode Pt/C.H.03,C,H,0,,1"* » ‘Write the electrode reation » ‘Write the expression of the Nerast low. ‘Which in the shift of the reversible electrode potential ithe pH of the sol ° Increases with an unity. a Decreases with an unity? Solution 2) These mtn eaioy4a¥" +26 © 04 ©) Thee ton salen : Sy Load 1668602 ~ tenon 086m FF Fcmaoas 1668602 ™ ©) Obviously AE ge = E, -S9.2mY at 298K 8) Obviously AE ag = Ena (Ene of Sion) 12382 sean a 29K. Example V3 Consider the following electrochemical call Pt/Fe?*(5.6mg),Fe®*(28.0mg)//SCE_ in ‘which the electrolyte solution has 0.5L. a ‘Which is the reversible electrode potential ofthe WE? » Calculate the WE reversible eleetrode potential after the addition of 1 rmmole Ce" to the solution Solution: » ‘The necessary mola concentration ae: yoy 2 5.60107 ary = 2810? _ 16, Fe SSI? aortas Fe 10°M (rend S605 tre S505 therefore: By B+ Tin FEA) - 0.71 0.025980 212 F pe] 10 » “The number of moles the iron ions are: wpe" = 10 moles, vj,” = 5*10™ moles 6 | i i i i Considering that Ce! reves completely, it results that afler redox chemical reactions so moles and the (nd of Solution) First kind electrodes “There are meal elestodes(M/M™* ): RT. eect OM B, zen, 1v26 ee MPM ee and metalloi electrodes ( Me/ Me™) e seine BEM | » wan Eset Me the metallic cation and the non-meallie anion being potntaldetermining ins TRovas considered thatthe setivity of a pure solid ata given temperature is constant and it was assumed to be equal to unity. ‘Meta electrodes of the fist king ate of greater practical importance and are easier to construct than non-metal electrodes, In he latter ease, measurements of the elestrode potential usually requires insertion of an iner metal conductor (elecrochemically end chemically) into the system consisting of a non-metal and its fons. ‘Second kind electrodes Electrodes of the second kind are hal-ells consisting of « meta covered dy one ofits sparingly soluble compounds (sl oxide oF hydroxide), immersed in a solution having the Same anion asthe sparingly soluble compound ofthe meta: MMII 1X2 ava) the electrode reaction can be writen either as two-step mechanism MO 4 ae" eM v9) mM 1K OF MaXy v2) coras one-step mechanism (thie step being the sum ofthe two steps) nMpX gg #2ME" OM) © MM yy) +20% 5) avo) am(-t)= xz ava) ‘Let us consid this electrode rection al equilibrium when one ean write Fayre +20 © mig + Nyay v2) Im the Known way, ene can obtain the following expresion for the reversible electrode potential RT. g, . BT AM se nM EA, ment Yak Oa avs) a hich can be impli: ° Rr, gE, ax 2 — Egat rev Maka (mM aK Na, ant me aK ee) because the actives of pure phases ar taken nity yy = 1 and ayyqx, <1. The significance ‘of the standard electrode potential is Higa MH, oh +H og) ° aks 7 My Sox ae mtx cn ei) lone considers the standard cestode pte forthe met lecwode (st pin the two- Step mechanism), one a . ws tye : apy et . ee Hage X, CRA + XS tm Xx mF (v.37) gO + ay) RT Rr nF and frally, beeuse gg, =1 and Kepaagx, =A, ese he OME Be * B oo Rn read ener PR ae am = Rina 2%, ovr) nen ee = Links, ‘nk "Koons From the equilibrium condition applied to the chemical action of precipitation one hes igen 4 4M © Heyy avas) Ae ag) Konatgns =© wy way ‘Therefore one can calculate the constant of solubity product knowing the corresponding standard electrode potential TE go ranant Phat? = a wavy Kpatare “The values forthe reversible electrode potential ofthe second kind electrodes are stable and realy reproducible, These elecodes are often employed as standard hal-cells or ‘ference electrode with respect to whieh the electrode potentials of other electrodes are measured "As commercial half.clls, they could develop junction potentials atthe junction formed between the immersed RE and the studied solution. 1 the ling electrolyte solution is KC! then this liquid junction potenlals are insigatican; they may be ignored in many cases The explanation is that the electrochemical mobilities for potassium ion and chloride are alimst equal Example 1V.4 Let us consider the mercury-mercurie oxide electrode Hg, 1Hg0/HO™ 18) Write the two mechanisms describing its behaviour. b) Write the two Nernst equations describing the dependence between reversible clectrode potential and the concentration ofthe eestroactive species. ©) Determine the relation between the two E°*s. 4) Get the expression showing thatthe Eye, depends on the a, Solution 2) The electrode reactions and the chemical reactions involved into the mechanism: MechanismFgh 426° He He? + 2HO" © HgO+ #0 Mechanism I gO +H,0+26" e> Hg +2HO™ 'b) The Nemat law equations expressing each mechanism: (governed by the equilibrium constant K ) Mehran tint in OF a Considine expen ofthe equim constant K.fthe hei acto oe Ben Bite because ayyo = 1, one has Mechanism I ecause ty = dyyo “1 ©) Comparing the two expressions ofthe reversible electrode potentials, obtained above, one has Et REIN =E* he” OF Worm 14) Taking into account that the ion product of waters BB = Ke and replacing the hydroxy! ion activity inthe Nerst aw equation one gts the researched ‘expression of the reversible electrode potential ‘Mechanism | 80 saminda Mechanism I (End ofSotion, lecrodes of i hind The following electrode of ith hind Za,2nC04,A8C,04,A8CLTICUT avany ‘Actsas a reversible electrode wih spet othe activity of 11" butalb wih respect fo zante 2n,Z0C 304100 ZZ 304,ABC204/ AB" nin sO4,ARCO4,AgCV CT the standard electrode potential being in each case diferent. smple VS 44) What i the kind of the following electrode Zn,ZnC04,CaC,04/Ca"* 1b) Indicate the electroactive species with respect to which the electrode works, ¢) Establish the expression ofthe Nernst law in each case. Solution: ab) Third kinds Reversible with respect 10 Za* zni2n** Reversible with respect to: Zn and C,0%° Zn. 2nC04!C,0% Reversible with respect to: Zn**, C,0}° and Ca?* : Zn,ZnC;04,CaC,04/Ca"* an 422° © Zn Ink + C0," 29 Z0C,0, ca +C,0/° © CACO, forthe fst one aos the Nemst law equation: PE and forthe sw ast nes act the expressions ofthe constants sui prac: 82 WC,07} cs HC,0F 1 Using the procedure knewn fom Second kind erodes on as ues: Beatty, EEaa ee, «Habeas a aE 2 ot RT, Stina op MK mayo, — 3p Reso! & EL ie,07 cui2n 208 ~ 3p OOD and then: Rr, Lee eran tap OR 200304 9p MCOF ] + Linkgaco, ernie arn ag mmc ZBI Kyo 24 Rr Keaton , RT ica) wera OF Ryecaioy aK pcx teeonie.C0t OF =F eee neu 206288 feo, 10,08 (dof Solan) Example 1V.6 Considering the foloving electrode of third kind Zn, ZnO, expressions of ls standard electrode potent Solon “Taking from Example V5 the expression ofthe necessary Ey RT ee wet +EDian?y-e° EE ig(c,0% Peer eee one hs: ar, pea Elst eae ap Kwanci0e and cesposively ij one has: Kuzeo, ee RT, Kmzscioe Kymco, 4 RT be pouien 08 OF (nd ofSctution) 1.3.22 Gas electrodes ‘A gas electrode is « hal-cell consisting of «metalic conductor in simultaneous contact with the corresponding gas and the solution containing its iors. ‘Therole ofthe metalic conductor is + to crete an elecircal contact berween the gas and he solution containing its to acelerate the attainment of equilibrium state to the electrode (the metal acts as catalyst forthe electrode reaction); + tobe independentvinert with respect to other posible electrode reactions + to provide an interface as large as possible, om which the reversible electrode reaction converting the gas othe nie state could procee. Such an elecrode is Pt tha ulils best all these requirements. To havea large surface area, tbe Platinum is created by electrolysis with finely divided black platinum, this resulting In so- ‘alld platnied platinum, ‘The hydogen electrode Thisclestrde is epresented Puta ova the comesponding electrode ration bin: 2H 426° @ Hy van and the corresponding reversible electrode potetal being: 9 BT, 2 FO, Ene vas) ‘Asi could be seen, the reversible electrode potemial depends not only upon the hydrogen fon activity, but also upon the partial hydrogen gas pressure For this electrode, its standard electrode potential is convertinally taken as zero at all lempeatures and therefore one can write the simplified expression 8ae was’ ap avasy E, the hydrogen gas pressure is eld at at then the expression ean be simplified Ey = Stina, vas" b= 22005, - ava =a "Eng ‘he hydrogen reversible electrode potential becoming, under definite conditions, « measure of the pl If, in addition, the hydrogen ion activity is unity, the electrode becomes the well- known and the so-called standard hydrogen electrode (SHE) having s zero reversible electrode potential This elecuode isthe primary reference electrode whose reversible electrode potential 4s well a its standard electrode potential ao taken to be equal to zero it pays the role ofthe origin ofthe hydrogen seal in which the hydrogen electrode is considered a a unit hydrogen jon concentration and at a hydrogen pressure of one atmosphere (inthe Nernst hydrogen sale luni activity and unit fugacity are chosen in place of unit concentration and unit pressure). The oxygen letrode “This electrode is represented as P03,08 vas) the corresponding eletrode reaction being 03+ 21,046" 69 440" «was ad the coresponing reversible clcctrode potential being Ep = 8° + Lip POR a van) 0 [Asi is seen, the reversible electrode potential depends not only on the hydroxy in activity, but also on the partial pressure of oxygen Bas, a sich abana seal sn ct For this electrode, i stardard electrode potential is 0401 V. At po, «1 the reversible electrode potentials gvenby RT Rr, BEng, «0401-23038 ga, ee eer: Egy #0401 avary =0401+ 23032 por 401230382 (ok. ~ nal) 128°C and with Ky the reversible electrode potential becomes Ee 229-0.0892p,H ass) ‘Bur, in practice the experimentally reasured value ofthe reversible eleesrode potential ofthe ‘onygen electrode usually does not ecineide with theory. Part ofthe oxygen gas can be reduced ithe pltinum in different way by a different eletrode reaction (0, +30 +26" €3 HO; +HO™ vas) siving rise to hydrogen peroxide ions rater than 1o water ions, the corresponding reversible ‘letrde potential being eB Tine v.50) Sno" *woz sind showing another dependence on he oxygen pressure and even onthe hydroxy ion activity “Therefor, the behaviour othe oxygen cectode isa least hat ofa dielectrode but, in addition, the surface itself ofthe painum can be changed by oxde films formation affecting its behaviour, These all manifest in the way the reversible eleerode potential responds to the ‘cnygen gs presnure or evento the hydroxy ion activity 1.323 Amalgam electrodes “These are halt-els in whieh 18 astnes beiaviouss cou be met + fest gM! ME «sty for which the cecrode ection is poh tame © MeFi) vs) the mercury serving only as an inet mem in wich the metal Mis disolve the metalic cations playing the role of potentia-determining fons 8s(vss) Hg.MyHg, /M vss) i the mercury ret wth the metal withthe formation ofan ntrmetalic compound soluble in mercury: the electrode reaction AME 3207+ yg © MyHe (He) avs) the reversible clectrde potential being i eee (v.56) (bere aig compound activity being potential-dtermining )the ions oF metal being potental-detenaining ions and the intermetallic 1.3.3 Counter electrodes ‘The function of the counter electrode isto complete the electrical circuit and to allow the ‘current to flow between it andthe working electrode (ith the id ofthe polarization circuit). ‘The siz, geome, placement and nature ofthe counter electrode ‘+ ae cia in small volume of cleevolyte solution andlor in electoyte solution ‘with arg concentration of electoactive species: + ae not sitical in large volume of elecioyte soltion andlor in electrolyte ‘solution with small concentration of electractve species. In small call the placement of the CE becomes closer tothe WE and more possiblities of interference could appear, The cE: “+ must have a large surface area, at least $0 times greater than the WE; inthis way the ‘current density will be small the oozurence of the electrode reaction it will be less important land its electrode potertial wil shift very Title from the reversible value: ‘mist be as non-poarized interface ax possible to allow the cutens to pass very near to its reversible electrode penta; + must be separated in a different hal-ell fits eleewode reaction products interfere with those ofthe WE reaction. The material employe forthe CE is als important ~ usually Pr oC, “The shape for the CE is usally simple fil or grids 86 | Y. THE ELECTRODE REACTION AND THE ELECTROCHEMICAL CELL. V1 Fundamental types of electrochemical cells ‘There are two fundamental types of electrochemical els: + galvanic cells, these are energy producer devices, in which the chemical energy is spontaneously transformed inc eleccal energy by means of two electrode reactions; the sum of which gives the overall ell reaction; = there are primary balteris which produce yield electrical energy and can not be recharged they should be regarded as converers of energy; + there are secondary bateries which produce/yield electrical energy and ean be recharged, they should be regarded as stores of energy; they store the ‘nergy as chemical energy the unstable substances being the Storrs that is ‘why they must be separated; + clearolysis ells these are substance producer deviees, in which the electrical energy from an extemal power soure is transformed into chemical energy by means of to ‘lectrode reactions the sum of which eves the oveal cel reaction: = these electrochemical cell are extemaly driven and this sa specific way of commanding the couse of chemical reactions VoL The galvanic eet “The galvanic cell is an clctrochemical cell having so-called electromotive force (tension which is positive and therefore the device can supply cret ino a suitable external cireut. To the two eletrode, Wo spontaneous electrode reacties take plac, therefore the ‘overall ell eaction itself occurs spontaneously. ‘Suppose the folowing electrochemical cel PUR 1/03 /P wy consisting of two inert electrodes of platinum, a half-cell with an electrolyte solution of Ry, another half-cell with an eleatolyte solution of Oy (each of them containing an initferent clectrolyie too), a salt bridge between the two hal-cells, an extemal resistance, an lamperometer anda volumeter. 2aR + 0, Seen He ead iron cs ‘Suppose thatthe Ry species could only give rise to an oxidation process and thatthe Op species could only give rise toa reduction process Ry > Op+2e° wa) 0p #23€° > Ra ws) a‘he overall ell eaction being the sum ofthe two electrode reactions: 23 +40; 9 230,42Ry way and having, of course, the Gibbs energy change negative and the electromotive tension positive: ac0 a) Pf z Pt ‘sotation | —* | sotuion of Ry of O; Ota RO, 4296 CR cxidation reduction anode () cathode (+) Prisreduced ——Phisoxidized Figure V.1. The phenomenological scheme of a galvanic cel |ASit was said the Ry can only oxidise spontaneously. As a result of this, the Oy species and the 26° appear. The } appears in OHP and difises into solution but the ye Jump to the Tet side Pt which is reduced. Thin Becomes an anode being charges negatively. ‘The Og can ony reduce spontaneously. To happen this electrode reaction, the 736° Jump out of the right-side Pt on the Op particles in OHP, Asa result, the R species appears in OHP and diffuses into solution. The PL is oxidised becoming a cathode. It is charged Positively. Therefor, trough the extemal circuit the eletron lows from the anode to the tathode, ‘To close the circuit, in the sl bridge the cations of K* move toward the right-side half-cell and the anions of C1” move toward the left-side haf-ell ‘results thatthe correct formula forthe galvanic ellis PUR O/C) ws) rs 11 is also possible to taceldraw the polerisation curves at each electrode of the galvanic cel, 0p + 23¢7 cathode(+) Figure V.2. The poarstion curves atthe two electrodes in a galvanic eel [At the left-hand electrode, aba result ofthe oxidation eletrode reaction, inaly there js only the anodic branch of the overall polarization curve, Being negatively charged, is electrode potentials also negative, Ey is onthe let onthe E-xis. [At the righthand eletrode, a a result of the reduction electrode reaction, iislly there is only the eathodie branch ofthe overall polarisation curve. Being positively charged, is 0 and Ey = Ey <0, and, therefore one has E'= Ef ~B; >0 fore galvanic cll ‘The decay ofthe current supplied by the galvanic cell could be understood in close ‘connection with the ime-oceurtense happening ofthe electrode reaction, 'Att=O, the maximum curen J, result fom the galvanic eel if no kinetic reasons act sgsinsvoppose. The electrode reactions gocur at thei mavimum speed. The Ejay must be zero because ofthe formula (V.6). 89At any tt, the current decays when t increases. For example, in order to have an snodie curent through he anode an anodic overvatage n, must operate. Because ofthe serial connestion of thet electrodes, a eurent has to ow through the eathode under a eathodie ‘overvoltage ne operating on i ‘The By is now: = Elje0 tng ~ (Ea ico +Ma) way 1-0-P where P isthe cell polristion, » postive quantity tension of the galvanic ex, elation V6) and Ejeg isthe zero-curent electrical Peng-ne way Therefore, for» cel in operation the following condition is always fulfilled (during the passage of a curent,the tension is lesser as compared with the “reversible” or zro-curent tension: Ey 0 (taken as a9 anodic current in a galvanic eel), therefore the complete relation benseen E) and Eo becomes no -P~Fr, wary [As the galvanic call operates, the concentrations of Ry and O; decrease, the concentrations of ©} ard R. increase andthe formula of the cll becomes: IPLIRy,0, 1103.82 / PL in each compartment ofthe cell being present both redox species of the corresponding redox couple. “Thre important consequences result rom the occurence ofthe overall cell reaction i + the anodic (a) and eathodic (¢3} branches of the polarization curves become lesser and lesser, + the complimentary cathodic () and anodic (a2) tranches of the polarisation curves appear and grow vp; ‘+ the Ez eletode potential shifts toward negative potential becase of the decreasing ratio [O21R:} snd Ez eletrode potential shifts toward positive potenti becouse of the increasing rato [0,)/IR]; the two electrode potentials approach one another, for beter understanding, remember the Nemst law! ‘The current decays and then vanishes. The galvanic cell is endif the overall cell reaction isnot reversible. Example V1 ‘Consider the following redox couples Ce"*/Ce™* ( 61V) and Fe*/Be* (Ehejpn © O.TTLV). Choose the necessary species (you have all species at your Aisposal to define» galvanic cell. Describe from a phenomenological point of view its way of working. Soluion: (OF the vo redox chemical reactions that can be imagined Fo 4a! Fe" 4Ce" nly theft has AG <0 (or E>0) being thermodynamically posible. To have » galvanic Gell ts compulsory athe overal cell reactonto oocur sportarenisly. Therefore the formula for he galvanic cll consisting of sluion of Fe*™ anda solution of Ce is ()PUIFE het |PLC+) where the elctode reactions ae: (anode: Fe 4" Fe (eathode; Cet 46° 5 e™ nd he overall cel reaeion is Fe acolo Fel 4 Ce" (nd of Solon) Vi12 The eectralyser “The elestolyer is an electrochemical cell having a so-iled countr-leciromotive force (fension) which is negative and therefore the device can not supply a curent Into a suitable externa iui. “The two expected electrode reactions as well asthe expected overall cell reaction ‘self, donot ooeur spontaneously. ‘Suppose Following electrochemical ce PLO, /7R/PL was) ooconsisting of two inert electrodes of platinum, a hal-ell with an electrolyte solution of another haf el with an electrolyte solution of Ry (each of them containing an indifferent ‘lectrolyt too), salt bridge between the two half-cells, a power source, an amperometer and a volimeter (lo watch the electrical parameters of the eleewolyses; in Figure V.3 they are missing) OF2°—=R Op 4248" Ry reduction oxidation cathode-()pole anode) pole Pris oxidized Pris eduved Figure V3. The phenomenological scheme ofan eletrolyse. For the overall ell reaction to ozcur itis necessary as an energstic condition to allow its occurence, The energetic condition refers othe electrochemical Gibbs energy, AG , which has tobe negative: aG0 2 4G <0 one uses the electrical energy 2\29FE with a negative E applied between the left-hand electrode and the right-hand electrode 2006+ 22,FE was) ‘To los the circuit, nthe salt bridge the cations of K* move toward the left-side half-ell and ‘the anions of CI move toward the right-side half-cel 11 is also possible to trace/draw the polarisation curves at each electrode of the clectrolyser 2 seuss alta beth emer realatecanaaanee posas Suppose that the © species could give size only to @ reduction process only if 8 power source pumps electrons int the left-hand elestode. Obviously, the Ry spevies could five size only to an oxidation process only if a power source exrats electrons fom the right- hand electrode: Oy + me" +R, was) Rp 9 Ona 220) 4248p > 28) +240 wary having. of course, the Gibts energy change positive and the counter-clectromotive tension negative ac>0 (vis) Eo vs) (CE for counter electromotive fore or counter electromotive tension). One Ry cathodet-) Figure V4. The polrition curves atthe two clostrodes in an clestrolyaer. [At he lef-hand electrode, asa result ofthe reduction electrode reaction, initially there is only the eathodie branch of the overall polvisation curve. Being negatively charged, its clectode potential is also negative, Ez is onthe let on the E-asis (see the Figure V4). [At the righchand electrode, a a result ofthe oxidation electrode reaction, initially there is only the anodic branch ofthe overall polarisation curve. Being positively charge, is electrode potentials also positive, Fj is onthe ight onthe axis (see the Figure V4), ‘The behaviour of the two elecirodes, as cathode (the lets electrode) because of the ‘existence of the O, only in its halcll, and as anode (the rah side electrode) because ofthe aexistence ofthe Rp oly in its hall, i obviously determined by the application of an clecrieal tension so that each electrode is charged with an appropriate charge. In this case the el is riven from outside, Considering the recommended “way o express the clectic tension of an clectrochemical el: E=E-Fy oy) forthe case ofan eletrayser when no curtent lows leads to: Eno; yo <0 (v.20) ‘which is smaller than zero being the eounter increase. Three important consequences result from the forced ‘occurrence ofthe electrode reactions ‘© the cathodic (c;) and anodic (a) branches ofthe polaris and lesser: + the complimentary anodic (2) and cathodic (e3) branches of te polarisation curves ppeat and grow up (inthis electrical way the chemical energy i stored) + the E> electrode poten! shifts toward negative potential because ofthe decreasing ratio (Q,J[R}] and the ES elestode potential shifts toward positive potential because f the increasing ratiofO,/1R]; the to electrede potentials become more distant from each other. Remember the Nerst law! curves became lesser ‘This way, ifthe overall el reaction i a reversible chemical ation, an intially charged galvanic cell could be discharged to supply electrical energy becoming an electrolyser, the ‘letrolyser could be recharged becoming apain a galvanic eel, and 0 on. Observations: 1. Ina galvanic eek Ef refers to [02]/1R] redox couple (3 exits in the beginning); Ej refers o {0;1/1R) redox couple (Ry exists in the beginning). 2. Iman elecwolyser: Ef refers to [0,}/1R3] redox couple (Ry eniss inthe beginning); Ef refers to [0,}/1R_] redox couple ( exists in the beginning). Example V.2 Consider the following redox couples Ce"*/Ce"* (Et gue #161 V) and Re? /e™ (Eta. yas =O7TV). Choose the necessary species (you have all speces at your Aisposad) to define way of working. ‘ectrolyser. Describe from 4 phenomenological point of view its Saluton: ‘Of the to redox chemical reactions that canbe imagined 95Fel sce Fe Ce > ‘only the second has AG >0 (or E<(0) being thermodynamically impossible. To have an tlectrolyser it is compulsory asthe overall cll reaction 10 occur. To perform this overall cel Feaction it is necessry to supply from an extemal power source the necessary electrical energy in order 10 pass from AG>0 0 AG Eren.0)/R wan In each halfcel an indifferent electrolyte ensures the transport ofthe eurent by migration and te link between the two half-cels is made bya suitable salt bridge “The polarisation curve ofeach electrode is shown i the Figure V5. ‘Atequltrum shen no caren lowe throigh the el, the reversible electrical tension ofthe cell is piven by Eng * Breve ~ Eva Eres “Ere 28) Eyer /Ra “Evy ee If we want to pass en anodic eurent (I") through the fechand electrode the corresponding electrode reaction must work anodcally, namely under an anodic (positive) ‘vervoltage. Because the two electrodes are conmected in series, x eathodic curent (-I') posses through the eathode under a eahodic (negative) overvolage. "The occurrence of the anodic electrode reaction to the anode shits the anode reversible electrode potential a mote positive electrode potential 96 0 EP = Em oy'e) #18 (v.29) (the upper index holds fr the left hand electrode designated as (1)) and the occurrence ofthe cathodic eleciode reaction othe ethode shits the cathode reversible lecrode potential 1 2 ‘more negative electrode potent: BL = Brew oy 82 7 (v0) (Qhe upper index holds forthe left hand electrode designated a (2). o E af a cathodic reo Ry Osa Ry Ope — Re eee eae Ban pe Bvt Figure V5. Ac orig asc wth he imposed exes politi ars, “Therefore the cletcal tension of he cll wil be (ifthe ohmic drop could be neglected): wan where: Eee = Br 0212 ~ Eve. 0)/) 32) ”(33) ‘he cell polarisation * teing negative. I results thatthe eletric tension under which te cell Works, generating electode reactions in the supposed manner, is smaller than the initial, reversible electrical ension PE py was) asthe two arrons show. In the same way iis possible to analyse the opposite siuation in which we want to pass a cathodic current (1") though the lefthand electrode, (Observations 1. Looking buck on this cell behavionr, one cam see 1 clectrode canbe ether anode or eathode as we wish iin an experiment 2. Ii imporait to notice tht the cells connected tothe voltmeters thal the Ke hand eletrde i linked to the positive pole snd the righthand eletrode to the negative pl; inthis ay, Eye >0 and he signs of Pand 9) are the same 3, Each electrode works as sngle-eleetode, not as mut-elecrode, and therefore the ‘0 individual polarisation curves cannot be summed. Example V3 Consider a Tedox chemical reaction that can be driven both in the forward and backward rection: R, +0, 20,+R; 4) Write the formula ofa galvanic cell which is completely charged (uppose that the inital reactant have the same concentration) 'b) Then write the formula for the cell in which the concentrations of the reactants become haf of the initial concentrations. ©) Finally, write the formula for the completely discharged cell and define it from the point of view ofthe fundamental types ofthe electrochemical cell. ‘Suppose thatthe equililrium constant is K >>I (ke, AG* << 0). Solution: for the forward direction Gane >0 (OF Ejomnt <0) i results that for the backward iretion AG savas > 8 (OF Enganaa <0). Suppose tat the equilibrium constant is K >> (ie, AG? <0). Theefe 2)" the galvanic ellis (PUR (eM) /70(em) PU) the electrode ection being Caw: O40 ER, (@)eatode: 0,428" Ry and the over ell reaction bein’ Ry #0, 8240,+R, » theeatis: 98 neste pie sumnccceebass te ()PU/R (0.5eM),0(0.5eM) 1/0 (0.5eM),R(0.5¢M)/PA(4) and it continues working 95a galvanic eel iff AG <0 ©) thecell is now an eletrolyser: connected with itslef Pt elstrode tothe minus pole of 1 povwer source and with its right Pt electrode to the plus pote othe povser source: ()PL/0 (eM) FR (eM) /PALs) the electrode reactions being (eatvode: 0,46" +R, (Hamode: Og 426° Ry and th overall reton being 0,48, 2248, +0 (end f Souter) Example v4 For the case conshdered in Example V.3 sketch the polarisation curves. Solution: tebe, Figure Example V4. (End of Solution, 'V.2 The Nernst law for an electrochemical ce ‘spose he eleccochemicl el: (0) PLO} Ry (70 /R(P% () 35 in the equim sine that when no ne curren lows eos the lectical tension (ifthe lechand PLis linked tothe minus pole and the ‘plus pole ofa voltmeter) is given by: S145) Oho W320) ren !8y ~ Eten. Oui where: %(OF) - Os i-0 wan) (Off 3 nhieo war) Ey =(@s-Osp)h-0=0 wary Een 01/8 E, ‘Taking into account each electode, cach electode reaction and each Nernst law one ean write: POR O42 SR, Earcyin, =F, + ETSI P/03/Rs 03-36": Eagon ty =BBy rn, +E WEE cone has for heen el the expression ofthe let tension Eyey*Brn0g Ra ~ Er 0y/Ry RT, 80; 3, n+ REIS (68 Sas Page eb ao) =F See pets) wie the standard cecal enon is given by FAP, wan 1 Eqy?0 wan) thats the lef-hand Pt acts as anode and the right-hand Pacts a cathode, therefore Ere04/8 “Fa and Brevog ny “EL (vas) and the polarization curves ofthe cell are those depicted in the figure shown in “Synthesis” ‘That means that at the left-hand electzode linked 10 the negative pole a netcxidation occurs very near fits equilibrium state Ryo O42 way, and atthe righthand electrode linked tothe postive polea net reduction occurs very ner tots equilibrium state 100 rere | 0) +23¢° Ry “Therefore the nt overall cell reaction is aR) +202 & 20,42) way 1 and 0; being reactans and O) and R being products ‘The Nema law forthe elestocherical cell must take into aecoun his occurrence of ‘the overall cell reaction and is formal writing must show this 2 Ege) vay Observations: 1. By multiplying the previous equation by —223F one gets the van't Hoff reaction isotherm nating sae onig2H%CEH] aT qe = 46" enTi@2H gam oan 2 1 Ejgy <0 the conection to the millivoltmete’s poles must be inerchanged {or galvanic cll. One can Know that a ell acs as a galvanic cll if non-zero current i observed msacured in the circuit when no power source is connected in the setup. Example VS, [Leas conser the electrochemical el (ta Za Cay Catt) in which (Z0?*]=0.2M and [Ce2*]=01M, each eeetruyte sl ‘equal wth 001 L One knows: E% s,,¢, 20337V and Eb.oe 24 8) Caleuate the reversible electrical tension ofthe cel 1). By adding in the right ale x of CuSO gy, the reversible electrical tension ofthe cell becomes E,, =1100V .Caleulate the amount of CuSO added. jon having the v 0768V at 25°C. 101Solution: 2) Obviously, Ey, ven by the equation + BT fa] Eq, = 6° EE cu] (ovhere E® = 28s, ~ES2ejp,} obtained hy making the difference between: Ege Eby sey PEINCU? sn ae ee ‘Therefore By 0839-076) LOT 2 1b) ARer adding CuSO) the NeW Es RT fn) a o02 2F "you" Ss 0.1x0.01 as oar 2 How Ely 11 itesults that —— = and that x = 0.065 g CuSOx) *-+0.1x001 (End of Solution) Example V.6. ‘Starting from the Nernst equation for a galvanic cell: RT, {Ou11Ra} Eg BPS n O ie FIR HO3) {in which, in addition, it i considered the assumption that the activity i» equal to the onceatration)thitk toa procedure of determining the unknown standard tension of the galvanic cell having at your hand millivelimeter and, of course, all the involved substances ‘Solution: (ne uses a usual potentiometric set-up (all the measurements are performed at er0-curent 1OVIRS) rere the rato (O20R a] rough hcl One eases Fy, a8 fintonof IOUT where te ato TE [0,1R3) (RIO) is atthe hand ofthe experimenter, Plting the couples of values (Ee, measured, In m2 iat acta | | | | | sed) one gets straight line having the ord ne intercept E* andthe shape - fom which ‘one can get z (numberof electrons exchanged between the two-reHox coupes), (End of Sotto) Example V.7 ‘Considering the redox chemi reaction: 2h) +210; 6210, +28 ‘As aredox titration reaction find the expression of Egai,we €=1) Solution: ‘The electrode reactions that can beaded in order to obiinthe redox chemical reaction are: Ot 2e° Ry 0; +2307 OR; the first being multiplied by ~2, and the second by +2, Obviously og a BT yg 2e Enawe? =D #88, +E 22 =D eB tsa and, ofcourse Rt 2b melt D 2 Bn, oD (6-1) 21850, and, epee: Enmwe Syn +E OF and, of course a 22E wwe ll 0318; c i ‘Summing the two equations, it results: (e422 .E well = fle = 2283 in, HE, HAE ‘Burt at the equivalence pont, there are the following two relations between the concenteations ‘ofthe reacting species: 22102]}=2[R\) 2,10,}=2,1R2) from which tres: 10) 1RaI RI" 6.1 these: {0,103} (RR 103eto this lst result, use in the last expression of Eva, we 1) one gets successively | ELECTROCHEMICAL CELLS WITH TWO ELECTRODES. (21 #23 )Eseywn(? =D= 7283, +28 Dyimy a UNDER POLARIZATION 8, +E Bay : VL Cells with two polarizable electrodes under electrical polarization poe a Let us supose the flowing elecwochemical et i 4 wer | ekewessaion o”m.xct | we QQ ry (8) 1 in which the two electrodic interfaces are polarizable, the electronic conducting phases being : rade ofthe same meta but of very diferent areas: A® >> A 1 "Taking into acount thle two elecrods are connected in series, the same caret tu of diferent sign passes through cach elec; cr absolute vale ithe same = Poveel =e] a) 4 i or eonsdeing the definition ofthe een density, one hs: fvee-A4= foveal ws | and hen: fhe Hwe Ave] 9, 108 10sA ola ™. E wer NEE we 4 wed Figure V.1.The polarization curve i vs. (which doesnot depend upon the electrode sea) andthe polarization curves I vs. E (which do depend upon the electrode area). The two Eye's are equal. Think of the Nerst lw! The same absolute value of the currents can be obtained by the action of different overvoliges acordingto the areas of the elestodes [toes] lwel fnwerl<|nwvel liwerl0 = anode electrode reaction 0426" Rat WE lnwer <0 > ssthodi electrode esction O+ze" > Rat WE* te scheme being the fllowing: Iso | wee ——+>— we The opposite case of P-<0 could be analysed in the same vay. Returning to the previous relation between the imposed cell polarization and the resulted overvollages, the ay in which the polarization is sated on each electrodes a Funetion of the ability of each electrode 10 become polarized. Ta kaw each overvolage 's Jmporant because we want to link the current density, (or the current, 1) tothe acting on ‘he eleciode reaction, not to the Pacing on the entre el ‘ftir ability is the same then: fre win ‘the polarization is shared equally between the bo electrodes (in act between the Iwo eeetode reactions) and the values ofthe overvllages are kaawn exactly their ability is different then the overvoltages can not be known without using an auillary cloacal setup to measure them, But ifthe WE* is ot polarizable (because either its sea is very large compared to ‘that of the WE othe electrode reaction occuring at its very fas wer 90 vi) and, therefore awe >? vias) the whole imposed polarization works as overvolage atthe wet the value and the sign of P and nye being the same. 07Inthe case described above, the WE* operates asa RE keeping « constant electrode potential hich i in fact the reversible electrode potential itself. Why? The current across the WE* is ‘sual in absolute value with that sross the WE. but the curent density cross the WE* is ‘much lower than that aeross the WE and, asa consequence, the overvolage on the WE* is also much lower than that on the WE .1F nyyge rt Fels Ewes > Eres We Example VL ‘Which ofthe following electrodes with the corresponding polarisation curves (see Figure {Example VI.) could be used as RE? Indicate the proper range of overvaltages in which ‘each of them could be use (taking into consideration the mature ofthe current that might be passed acras) 1 1 1 Figure Example Vi Solution Electrode E could be used only i across ita small anodic currents passed (this eurent needs a very small anodic » a a thermodynamic force) Blectode E could be used only if seross ita small exthodic eure is passed (his current needs avery small cathode 1 8 a thermodynamic force). Electrode E. isthe best, it might be used bath in anodic eurents and cathodic curens. In ‘ition its polarization curve is more vertical (has bigger slope) (End of Solution) YL2 Cells with one polarizable electrode and another non-polarizable electrode under an electrical polarization ‘As aresult ofthe previous discussion, the fllowing ells used in many experiments especially belonging to analytical electrochemistry: ———4 wig RE | ‘lectrolyte solution O/ RKC [ve e 108 in which the WE isan electrodic interface h isan ideal non-poarizable interface. The pol Figure V1.2: 1 a certain degree of polarization bt the RE iealion curves atthe electrodes are shown inthe Figure VL2, The polarization curves fora cell oftype WE~ RE. Considering again the usual formula fr eaeulatng the eletca tension ofa eel and i the RE is comected to the mins pole and the WE. is connected to the plus poe of the power souree, and ofthe millivolmeter too, one can wit = under azeo-curent: Ere. WE-RE * Ere. We ~ Bre wus, + under a non-zero current but not oo large: Ewe-ne= Ewe ~ Brea = Ere WE + WE ~ Er RE wht = Eve WE-RE* WE Making the diffrence of two electrical tension when a curent passes across the cell fand when no curren passes seross the cell one ha infact the polarization itself which auses the passage ofthe eurent across the cll: Pe Eye ne” Brey. WE-RE (wit) But the same diference is also fe overvoltage which causes the occurence ofthe electrse reaetion tothe WE 109‘we = Ewes ~ Ey WERE wus) ‘Obviously, the polaistion P and the overvoltage nye ate equals in value and have the same sign aw (v9) We can drivean electose reaction at the WE in a two-electrode arrangement, using suitable reference electrode, by imposing certain polarization which is entirely distributed lon the WE as a coresponding overvlage. Observation In this discussion one assumed that the ohmic drop is negligible because a large amount of an indiferent electrolyte i added. Inthe absence ofan indifferent elecrlyte one bas: Pane +R} «i209 Example VL2 For the fllowing cell (-)WE/O,R,KCI/RE(+) connected to # millvolimeter WE tothe minus pole and with the RE tothe plus pole 8) write the expression ofthe electrical tension under a zero-current; ') write the expression of the electrical tension under a positive polarization applied across the cell establishing the relation between P and Nye - the Solution 8) The electrical tension under a 2ro-curen is given by the following expression: Engine “Emuat “Ermine “Ement ~(Ebin +E 4 F 1b) The expression ofthe electrical tension under a postive polarization applied across the cell: Ewene =Enwene +P = Bag nt Eve +P Ete ~ Ewe vat ~(Erawe we) evs ~ Ene WE 1 results the searched relation P= mye and, therefore, «positive applied P gives vise 10 a negative my The WE plays the role of a cathode (Gnd of Solution) no V1.3 Cells with one polarizable electrode and another non-polarizable electrode under a “chemical polarization”. “Redox potentiometri titration” ‘This isthe ease of potentiometric titration, in which the oeeurrence of a suitable tivation chemical reaction taking place inthe bulk of the eledolyte solution, is followed insramentaly by means of the progress of at Teast one elena reaction which works at cqulcium (in zerorcurent potentiometric tiation) or near tne equilibrium (in non-zero current potetiometsic tration). ‘Suppose that the fllowing setup (consisting of a burete, 2 milivolimeter, 9 two cleetrde-cel i used 10 follow a redox potentiometc tieaion RE we Figure V1.3. The scheme for potentiometric titration. {or which one has the following conditions regarding te reversible electrode potentials ey < Ere 0) /Ry Een WEO3 /Rs «viz ‘The bulk redox chemical action ofiration i: Ry +0, 40,4 Re «v.aay hich must full the known conitins fr such tration reaction: 1 izevesbein the forward siren; + large erence between he two standard electrode potentials, , >> EB, + stlest one ofthe eos couple as to be elective. During the titan process the WE” follows the progres of the redox chemical teaetion occurring inthe bulk by means of a suitable eleevode reaction occurring tothe WE = before the equivelence point, the electrode reaction invelves the O} /Ry couple Ot 20" 2 Ry (via) = after the equivalence pain, the electrode reaction involses the O2 /Rz couple m03428" Ry via") ‘One can tink that these two eleeitode reactions accur successively and not simultaneously at the WE. There is @ reason for this behaviour. Let us consider, without demonsration, the following formula describing the mixed elecvode potential for a di-eleuode a6 a linear combination of the two individual reversible electrode potential: Enined* iE ms 04/8; + 82E:ev05 Re (viz) here @, and are the corresponding rection ransport numbers defined a follows: fil vis) |, and i being the corresponding curren densities fr Oy/Ry redox couple and for O3/Ra redox couple ‘When the redox chemical rection which occurs inthe bulk isin progress (<<, where is the degree of tiation) the activity of O3 (hich is the tating species) is practically zero (because of the complete reaction with Ry, which is the trated species) ‘Taking into account the Butler-Volmer equation and the formula giving the exchange current density wi26) win and, filly, @; = 0 and, of ‘results thatthe mixed electrode potential willbe even the reversible electrode for 0, /Ry electrode eaction it result that 1$=0 because a9, =0 and, therefore, ip Eon WE -RE(E) = Ee, W608) (0) (vig) ‘As consequence, the behaviour of the redox chemical reaction is followed by means ofthe elecirode reaction given by O}/R; couple to the WE. The electric tension measured between the WE and the RE is given by: Ee WERE) = Brey. W. 04/8) (09~ Ener. tg BT gt «vi29) ym ae om m2 toy Koowing tht during the tration the ratio 221° ipereases when F increases, it ag results thatthe reversible elotod> potetial Eyey.we.o,/Ry(F) increases (on the E-anis it shits positively -see the Figure VI}. Example VI ‘Consider the potentiometric ttracon of ©, (titrated species) by R, (titrating species) in ‘the condition: Eyayae < En, 0,/8;>Erent < Ere 8604) 18) Write the condition in order to have s titration redox reaetion b) Plot the ys. E curves for different titration degree f ©) Plot the Ey.,we-ae. YS f carve of potentiometric titration, f being the titration degree, | | | | Solution 8) To perform te indicated poteniometrc tiation it is necessary to have Ey. 0,°R; © Ee. WE O4/R5 ‘when the titration of; (irate species) with Ry (Grating species) is thermodynamically favourable, To have @ redox tiation reaction performed in a quantitative manner itis necessary, in adlton, to have evena strong condition: | Eye we,0,78, << Erey,we.0y/Ry | 0) Tae lain coves all mn) So ion we hth ne Fae Hern ri | we eis [ potent jump \re 1 | only Oy to, fan deereases 40, /ap decreases Enc deereases Eyaop in, deoreases Figure Example V3. us©) The tiation curve, qualitatively shown, is represented in Figure Example VL3. 60, bo, t cn, =0eR; t ae lecrode_ 01-427 69 Ry \ 2 so cheat tion _-eoaton of tiation Oy 4287 oR 0, 800, 908 ny hen, *0 f v Figure Example V3. (End of Solon) Example Via ont titration R, +0; —+0, +Ry the expression of Ejyove-nr for f0172 Inthe case of the redox chemical reaction Solution For 172 the titration redox reaction is half completed and the WE takes reversible electrode potential Eyqye(F=I/2) and the measured reversible tension of the cell is Eyeawe-ne(F=1/2). Therefore, the reversible electrode potential can be expressed with respect to ©, /R,redon couple only. (Obviously, one may WH the Egy ye(F = 1/2) with respect to O, /R. redox couple too, but because the 0; concetration tends in fact vo zero it is somehow fietitous to consider i), Therefore, one gets RT, 2o(f 1/2) rvweae tl =1/2)= Biya, ES aaa) Emme se 2 (BT ytalt Frawell 212) 288 SE era) “Eb Because a f=1/2 setts equity (0,}=[F)] (End of Soluion) na When the redox chemical reaction is accomplished, the equivalence point is reached but the activity of Ry is now practically zero as well asthe activity of the added Op. The equivalence point is reached but itis not seen a it happens in volume titration because there iso indicator added tothe solution. ‘The addition of O» fom the burete continues even afer the equivalence point is reached. Now, there is no redox chemical reaction in the bulk of the electrolyte solution, but the chemical composition of the solution is changed by the adliion of Oy. The electrical tension measured between the WE. andthe RE. is given by: Ere WERE) = Er WE,03 183 (F~ Ere ne er 130) 21a OE MD Example VS Obtain the expression of F.,qp-ne for ration Ry +0; +0, +R, in the ease of the redox chemical reaction For fl the tration redox reaction is completed and the WE takes reversible electrde Potential Ey, ye(f=1) and the measured reversible tension ofthe eal Eye we-ne(t = 1) The reversible electrode potential of the WE at FI may be writen both with respect 10 (0, /R redox couple and with respect to 0 /Ry redox couple. Therefore RT, Sat f= Y= B89 +E nee”, Fmt =D=BBn, en RT, aop(f=0 Epuatans(T=1)=E3, nj +E nae rte re ear a ean ‘Adin the two expressions and dividing he sum by 180, one has: rene tbartthns p Epeneane (Fee Bag revere (=D) 7 RT, 8o)(F =o, (f=) Besa hm ead ‘he equlitrium ofthe redox chemical esction** * 2 10,]= 23182) ailR, Pr gRy +240, «2 220) +21R is strictly zero due tothe equatons® describing 102) (End of Solaion) Now, ag, =0 and therefore ff =O and jy =0. The @) = 0 and the 2; ‘mixed electrode potential will be the reversible electrode potential for O2/Ry electrode reaction tse and therefore the user WE-RE(EY = Ep WE,03/R3(P) Ae) 80, (f) ing that testo 222° inreases especially due tothe son of Op, it results at Knowing teat the a specially the reversible electrode potential Ex weog ng (0) creases too (onthe E-axls shits ively se the Figure VI. ree Gone, the penal jump can be caleulted from the reverse elecwode potentials afer eguvslenc (et befor f.001) and before equivalence lt befor f0.99) AB ap = Eps WE 09/8 (P= 1.001) ~ Ese 9,047 (F=0.999) eh 13) + Bin yesatrorm — * ag Bn ~ 0.348% AE® — 038 ovis) It results that the potential jump atthe equvelence depends upon the diference ofthe two standard electzode potentials (as main dependence) and the initial activities ofthe iated species Ry and the iatng species O> Let us follow all this electrode diseusion of a potentiometie tration in the Figure 'VI.S, whichis the tation curve itself a5 its recorded or dawn ftom experimental dat, only Ry only Ry so, 7a inereases Ee, 03/ Rg iMeTeases Figure VI4. The evolution ofthe polarization curves at the WE during tiation process. 116 Bren WERE stecwode |, ze" eo Ry react Oy42 Ry er, Seo, t — jeg tex chemical €o, =Oeg; t : reaction of titration rs f Ne v Figure VL. The cassical poentiometrie redox titration curve [From Figure VIS, as well as from the Figure VI, it ean be seen that the greatest change ofthe working electrode reversible electrode potential is produced near the equivalence point. The explanation is thatthe response of the WE jumps from the last polarization curve ‘of the ©}/Ry couple direetly on the first polarization curve ofthe Oy/R> couple (these two curves have the same f: f =I, for which the redox chemical reaction is accomplished, but they are separate at least by the difference between the standard electrode potential) ‘There are to almost horizontal portions of the titration curve. In these portions there is only a slow increase of the electrical tension of the cell (in fact of the reversible electrode potential) in accordance with the Nerast law. ‘As one already knows, the reversible electrode potential isa function of the ratio of activities of © and R . For equal activities of © and R, E=E° and it is apparently that in fact £° is somewhere in the middle ofthe E vs.ag /ay. curve and the slope of the line i slow for ao and ap which do not differ very much, The slope varies much fr from the E® value, tthe beginning and at the end of curve Example VIG Considering the well-known potentiometric redox titration of Fe? with Ce", in acidic solution, plot the Eyey,ye(f) ¥5. f potentiometric redox titration curve. Note that EeacggeTEESOTIV, OED EZ ALOV, wef =102M Fe pe etree re 8 =e} = 107M am - te TE WOFM amd Va ne = Vy OAL Solution: Before the equivalence point the concentration of the speciss involved in the equilibrium uw$V -et¥ a) ae epaca]= S10 View eee eee vavath) Ahercfre the reversible cecttoe potent is given by ATMS Dp, RT yg efVat0)__ Fpl EG ‘te he eile in econo ft specs inv nie eis re") Ejgwe(O =e} BT lM ee ‘Varying. Va(f) in the range 0 Mi eq) Aj (ea) (vs) Hyp OA (00) 4G, = 40° + RTIn MEAL wns) right-side half-celt: Mijj+ Ait > Miifea) + Aj(ea) (vi19) a4 p68) Gy =AG* + RTI AE way and therefore the van't Hoff isotherm ofthe overall cell reaction isthe algebreie sum AGy ~ 86, = RTIn—MEAL viz) Suita Dividing this equation by -2F =-F, beeause 4G, and AGy (and, of course, AG too) refer tothe passage of one mote of elecrons across the cel, one has the electrical tension ofthe celett BT, MAG >o cms) hich i obviously psiive (remember thatthe cll works spontaneous!) Considering the usual formula for calculating the em (em = eletramotve force) of @ salvanic ell which i postive emf = £3 = i cv and since the emy ofthe cationic cell without transference is postive i results that the extreme left electrode works indeed as anode and the extreme right electrode works indeed as cathode. ‘The expression of ES could be written as follows: Htgtuae Wy wns et Rintowa «m6 where the aaa ithe mean avy ofthe este MA” Examples Hg,K/KCKa')/AgCl,Ag, AgCl/KCI(al")/K, He PAH /HCI(a")/ AgCl, Ag AgCI/HCi(a")/Hig,PL Vina Annee Forte flowing sin cl witout nnstoenc AIM*A™(al)/MIM*A“(a! A «vay with al < al", the em/is given by the relations written below: ant RE MAA 9 cvs) m2 (oss «vilis) ons) ‘Ag, AgCl/KCIa!)/K, Hg, /KCKa!)/ MgCl Ag AB ABCV HCKGa!)/Hp,PUH, /HCK(a")/ AgcL Ag VIL Comparison 1. Considering the simple ell M/M*A™(a)/A. writen as fellows Reversible Reversible cectode with Mraciay | electrode with respect M* respect io A” eae a head sail where the Feflchand electrode interface is denoted as Acad! and the righthand elecirodic Interface as vil, we can notice thatthe discussed cationic nd anione cells can be written in shor as follows eatibti-head tuilehead-headtail 2. Forthe same a! and a" activities in both cells one has: ea eR hh leds n arene er cial eg tape 3. The electrode potentials: = atone cell - ion cell anode x V, cathode ~y V, anf = (x= 3) V>0; anode y V ,athode x V emf =(x-y) V>0. bsMIM? A3(a!)/A/MEA3(Q")(M with a! M, therefore it sa cationi cell. There is an intemal clectode (bi-polar elecrode) acting as a physical barier against the mass tansport therefore without transference, without guid junetion, thou guid junetion potential Due tothe given intial condition, the coll go towards the equilibrium state by increasing a and decreasing a” in order to balance/equate them finally. Therefore from le to ight MIM anode: MP 426" OM AIA” cathode: Ate oa AIA” anode Ae en ‘M/M* cathode M* 4207 9M. ©) Lefhandhacell Mg #2Ayy > MPP$2475 Right-hand half-cell Mbt +243" + Man + 2A can Ma #24 > Mig #24 cel Mit 4245 MJ" 42a7 1. Obviously, the vant HofTisthern of reaction is (er algebra caeulations) = erin sat ui tai and dividing by ~2P=QF (to ve one mole of Mor M?* insted itis necessary to have the passage oF moles of € arss the cell) ne gets: rae Spas egy 2. Obviously, EE" may be expressed as: ES = Evenest “Ereasin + Enc ms Se rerecaate ate eee ere Solo saponin May tet Bina) : Sia ena yg) tee ple yam and after some algebraic calculations one gets the final EG oblaned above (nd of Solution) Example VIL2 ‘Transform the expression: From thermosynamies, one knows tat For the first requirement one ses the and, of course, one gets For the second requirement, fo this particular type of eectralyeone can write and replacing in the given relation of ES! one gets: egy -28E 220. (End of Slaton) 1s‘VIL2 Concentration cells with transference (with liqui junction) VI12.1 Cationic ee ‘Let us consider the following cationic cel MIM"AT(a!):MtAT(alhM «vias alcall «wna, ‘1s formed by contesting two half-els with identical elects immersed in electrolyte solutions containing the same eletroative cation belonging to the same electrolyte, but of ferent activities the electroces are reversible with respect tothe cation M', but the wo electrode reactions occur in opposite directions; 4+ theto hae, fact their electrolyte solutions, are meeting at a junction wich allows the mass transfer across it, but exterally they are connected by means ofa suitable electrical circuit corresponding to 1 galvanic cell; ‘+ ue to the connection made by a Tigud junction which permits the mass transfer, the ‘concentration cells with transference, ‘+ due 10 the activities inequality the cell isnot at equilibrium and it can supply electrical cenecgy; during its discharge, the two activites move in opposite directions: the lower will increase and the higher wil decrease, so thet they become equal at equilibrium: in his tate the ‘ell can ot offer electra! energy any longer (the discussion was already made); ‘one could say thatthe supplied clecrcal energy is lower in this case in comparison with ‘the eatone cell without ransference because the transference liself needs energy to ovcur Reversible | Reversible elearode with | yr analy meaceally | tesrode with respect to M* respect to M* Detling more the cationic cll with transference: anede(] marca!) M*A~Gal") [eathodet] Mt se ; + theaions A” cay LLFC, ie, t_ miles of A cary the current crs the left-side hal-el from the right othe left (€)s “Therefore, in the lelside lfc here is ain of M* (1-1,) molesof M! = +4 moles of M* sain of AX +1 moles of A ‘or evena gain of +1. moles of MYA +n the rights ide helFcell the passage of IFC of postive electricity i assured by the migration of M* in the eletri field direction (which is characterised by a transport number 1) and by the migration of A~ in the opposite direction of the electric field ‘owhieh is characterised by 8 transport number + of tre + the cations M* camry FC, ie, 1 moles of M* cary the ‘current across the right-side halcll fom the left the right (9); + the anions A” cary LFC, ie, meles of A~ carry the current ‘across the right-side hall from the right tthe left («-); ‘Therefore inthe right-side hal-cell here is Tossof Mt =(I=t,) moles of M* = ~t_ moles of M* lossof A” t_ moles of AT: for even ass of ~t_ moles of MA nt‘+ _Attherightsde electrode, as forthe activity alto decrease a eathoic electrode reation hast occur Mite om wus) the pasage of 1F C consumes I mole of M" inthe right-side hal-cell (because I mole of M deposits and passes through the electrodi interface from the lt othe righ). ‘Therefore, across the liquid junction t, moles of MY and \_ moles of A~ wil pas from the rightside half-cell to the left-side hal-cll, in accordance with the following overall cell LMP +CAT CLM + LAi, (vn.20) LMTAT © Mpa, (v.20) (MA) © LMAy, (vi20") For this oveal cell reaction, the Gibbs energy change i given by: «nan From which one can obtain, by dividing by ~2F =—F (because + IFC of positive clecricty passes across the cell), the expression of the emf, Es aii cvn2) ‘hich is obviously positive (the cell working spontancousy). From the defi and from the sgn of EG one can deduce the role ofeach electrode ion of the emf ns ‘The previous expression of Ei could also be writen follows peat et BEin ‘a en wns) eit nse (vii where he sayy the can ati ofthe eleaolyte M.A Examples: H,K/KeMa!Y:KCKA" YK, He Put HICK a!):4CIK6" 113, PL 1VM.22 Anion ce Fer the following anionic cl with ransteence AIMTA MMT ANG! FA. (v.25) with a! M, therefore itis a cationic cel, Between the two electrolyte solutions aliquid junction is formed and the ‘mass transpor islet accur unimpeded. Therefore: with ansfeence, with liquid junction, ‘wth ligui junetion potenti, 1) Dee to the given inital condition, the cell go towards the equilibrium state by increasing 4! and decreasing 2" in order to balance/equte them finally. Therefore from left 1 ight MIM?" anode: MP 420" M, MIM?® catods M2426" 9M 6) 2PC of positive elecicity pass from the left to the right installing an eletrie field orientated from left right, From lef to ight M/M" electrode: 1 mole of M generates 1 mole of Min the left compartment as & consequence of the passage of 2FCof postive eleetcity in the forward direction; therefore gain of #1 mole of M2"; Lefthand halell: 1, moles of M!" migrate in the forward direction transporting 1,2PC of positive electricity in the forward direction; therfore & moles of M2*; 421. moles of A~ migrate inthe backward direction transporting {2FC of positive eeetricty in the forward direction; therefore a xin of 421_ moles of A~s Surveying inthe lefthand compartment one has again of +(1—1,)=4t_ moles of M in lfthand compartment; again of +21. moles of A” in lef-hand compartment, loss of = Right-hand alfcel t, moles of M1 migrate in the forward direction transporting 1,2FC of postive electricity inthe forward direction; therefore 3 ‘in of +4, moles of M2"; 130 =21_ moles of A~ migrate in the backward direction transporting {2FC of postive eleewicity in the forwatd direction; therefore a loss of -21 moles of A“; MIM electrode: 1 mole of M?* from the right compartment generates 1 mole of M 58 consequence ofthe passage of 2FCof postive electricity in the Forward direction; therefore a loss of =I mole of M2 Surveying, inthe right-hand comparment one has loss of ~1=t,) = =t_ moles of M2" in igh-hand compartment; ‘oss of -2¢_ moles of A in right-hand compartment Therefore one has the cel overall reaction CMI +2045 MP 62 Ap 8) Obviously the van'tHofT isotherm of reaction i (afer algebric calculations: 46 =1.RTIn METS and dividing by -2F = -2F (wo have one mole of M or M* involved it is necessary to have the passage of 2 moles of e” across the cell) one gets Rr, aa (Bre of Solution) Example VILS ‘Transform the expression: egy Riya aap ay (from Example VIL3) in order to appear ally, and ols, and aly, amd aly,» respectively ‘Solution: 2}, ad ofcourse, oe gets From thermodynamics, cme Rows that ay, 9, For the first Fequirement one uses the relation ys, RT oF RT egy = Stn = For the second requirement, otis particular ype of electrolyte om can writ aug, “sa, and replacing inthe given relation of ES one es(End of Solution) ‘VIL3 Concentration cells with eli ted liquid junction potentials VII3.1 Cationic eet Lets consider the following cation eel: ‘ MIMta-taMa-(a!y7M, evn) al cal vay in which the to halFcels are joined by a salt bridge (denoted by 1) containing stone. clecroyte na saturated elecrayte solution, whose ions have almost identical eletrochemia] robles. As aresul, te to gud junetion potentials formed atthe two contacts between the exremites of he bridge and the electrolyte solutions ae very small The current i ried ‘through the beige by eaton migration and by anion migration. ‘One supposes hat the obmie drop could be neglected because the two electrolyte solution have large conductivities (in each eleewolyte soluion a there is large amount of indiferen electrolyte, KCL). ‘The emf (ented as Eh of this cationic cll is given by B= 03-05 0} 04+ 04-04 +0 -0,+0,-0; cna Ee ~Egu+Eqi- where sb stands for salt bridge and Ij for liquid junction. Because ug, = Uc, one as Ey rEg 40 viz») and, of couse, it results thatthe ES% is given by Bid = Bf -E (vn30) ‘Considering the Nernst expression forthe electrode potentials a 5 wnsn 12 «vn32) nai mss) owns and asuming that: cvs) one result that ot36) ‘The Debye-Huckel theory, in its fist approximation, assumes that ons having charges equal in absolute vale, also have the same activity coefficients. But even out ofthe frame ofthe fits approximation, for I -valent elecuoyte this assumption could be considerate Valid Finally the em ofthe cationic cell with eliminated junction potential is Samay (anda? ch = AT. Rtg fae (ua) (vm37) ee en oe IMA” (al )UMTAT (aA (V1i.38)with a! at |0}> Jan) .», negative then the galvanic cll wil dissipate pan of the heat ofthe x, (verll cell reaction equal to 2FT(2E),.,, as heat given up othe suroundings; a Pn, 8 heat given upto re * under thermal insulation condition, when no exchange of heat between the cell nd surroundings posible, the temperatu of the system incoaaey c 4 <0 ar" FE > a FE <-AH {ac} any 3 ¢ By, amo tenth vei cl eter sn el om he soins or cissipates eat into surroundings the temperature ofthe system remains unchanged. 2, Pom 0-H Example VIILI For the galvanic ce (HG. H$0 4/2080 yg Z0,H-) ‘he temperature dependence ofthe reversible electric tension is given in the table below: BW) [aaa naa Tass nag ee Pe we) fe 3 0 15 0 3s 8) Wit the eesrode reactions: ) Name the kind of exch eleetrod. ©) Calculate AG,4H and as at 22°C. Solution; 8)0) Ha. Hg,S04, 80% isan electrode of second kind Hg,S0, +2e" <2 2He +s0? He} +e" eo 2h Hg,Zn/Zn* isan electode of amalgam. 2m" +26" (Hig) <> Zattg) 9) is necessary topltE vs. and then wo obtain the slope of the graph et the indicated {emperature as well as the electrode ptenil athe indicated temperature, ‘The graphs. Hg} +S0F <2 He,80, 18 _nonetgg EV) 0.00121 | | has 120 . ma is "eases TH.) Figure Example VIL} ‘The slope is -0.00121 and the electrode potential at 22°C is 1.417 V. Therefor: AG = ~2FE = 745625. mol"!, AG =—2FE = aE 2745623 - mot, as = 2 2E ar AG + TAS = 205670.5) mor! (End of Solution) VHL2 Determination of standard electrode potentials and mean ion activity coefficients NIL2.1 Determination of standard electrode potentials by redox potentiometric titration In the case of redox potentiometric titration R40) > oer; te etn caren te Fie VI ss, forehead point hell enson meas betwen he WE (hs pol) cote se RE in ps dete y SEED i TSC <) Enweatll ) one has the ondiate intercept whichis B® = E° Keowing E° = E° for each Bes Ereangciragcr* KMOwiMe BET paciiagcr 44 sed, one caleulaes the Fe icyey By wing the following equation: evlo)+ 2 ney vs Vian «vin.23) VIIL3 Determination of chemical constants VIIL3.1 Determination ofthe constant of the solubility product ‘Let us consider the following cel COM MapAacy A? (ey) REC) cv for which the reversible eletial tension has the expression: Ere) * Eres atga fnttante ~ Env ° ant «vas, +e ~ Ena gag Eon Mg AstmMants “oF Mata ~ Ere RE the electrode reaction occuring othe eathode being Mai +26" 9 mM 64a? cv26) and considering thet yg, =I and ayy =1 Considering the above electrode reaction asthe sum of MEM aye" Agur ‘Ag/Ag* isan electrode of fist kind; cathode); Ag te Ag ») _Thereversible electric tension ofthe cell i, successively: resus thatthe standard electric tension of the cll ue from which one Bes the K aga K yagi (End of Solution) VINL3.2 Determination ofthe constant of sta Let ws suppose the following cel: ()M/C,IML} Ke, ),L* (6,)/ REC) «vts) for which the reversible electrical tension i given by: Beer Eun nats “Eck ar “yer cums) ony oO age In which was used the condition 2y =1. The eorrespending electrode reaction was considered to be that which involves the complex ion itself DLT 420” co M4? (vss) Considering the above electrode reaction as a sum of MO + aye” <9 (vin36) MES IL co IMME (m6) ‘he last one being controlled by the constant of tabiiy Kg = cvs, fe electrical tension ofthe cll in the following form: Bren roma ~ Ere, (vit) : Ey eM se es ne oF Ne 9(vs) inwhich vas made again the simplification yg By comparing the wo expressions ofthe reversible eleical tension, in fact of the reversible electrode potential, one has: Rr, : AE yg el Ke (vunao) Toate nase Een ae a from whieh one can cate the constant of stability Fe se eate? Kany THOM Sa HAO «van By using the cond way of expressing the reversible elestcal tension ofthe cell and knowing the standard electrode potential of the M™M /M redox couple one can express the ‘constant of stability patie rust Stent Ey tar Ta er mine «via Kau Gn) where: paginas “fe cms am orf mas’) f, being obtained fro: the fone strength ofthe electrolyte soluton. VIIL3.3 Determination ofthe constant of acidity Let us conside-the following cel (JPL F(a) /HA CG, NBA (€2).NaCIles)/ ABC, Ag(+) (VIILEA) ‘having the following expression forthe reversible electrical teson: Ere Sevsenttgcr En ° ° Rr, cE — inte Eye ys A Ebaye ‘ARCUAger Conon ea) ° : ® "AgCH!Ag.cl” em sare. where =e ‘nec ager ~ Eoin, For the weak acid HA dissociation one hs: HASH +a jetta at | and it results tha: Sache fia. oh Replacing this product into the reversible electrical tension ofthe cell one has RY, SHAG, RT, fay Diner ta fae RT gg, BT falar eee (vias) cvm.as) (var) «vas cvs) (vias) wis) cvm.so) cvmso,«vise coms) RT, 91 fting En = B° + Ey 18 By ting Eg, B+ in 1 onic strength tending to zero, 10, when each ion activity coefficient tends to unity ql, fg PT and f,. >, @ steaght line from which, by extrapolating, results the 1, forclferent values of ef cp and c5 one obtains for ernest ~ Ein ton wh res K, Example VIILS Calculate the redox eq rium constant ofthe following redox chemical reaction: 2Cu" @ Cu + Cu ITV and Ef, D34V . Which of the two cations of the one Fey aes" conyers mer sie nqpne aac satin: “The redox chemical reaction: rev @ Cv +C0 isthe algebraic sum ofthe following clecode reaction: cu +e" 2 Cu" Cu® +26" 29 Ce ite multiply the frst one by -2 and the second by =. Atequilbeium E 02100 “Enea ice RT ieee nay ice ‘The cation Cu**is more stable than Cu due 10 the fact that Kya 21. The Aisproportionaion reaction occurs spontaneously (End of Solan) 182 VIIL3.4 Determination ofthe redox constant Standard electrode potas! may be used to calculate the redox equilibrium constant ‘of redox chemical reaction wit) the purpose to know whether that reaction proceeds or not ‘quntttively and whether it maybe usefully employed analytically. ‘Le us consider the following redox chemical rection 228420) & 720, +2 cv.) ‘hich canbe the sum ofthe following electrode reactions: O42 © Ry cvi.s3) 03 #236" 6 Ry vss) ‘When the redox chemical reaction atin the equilibrium stat: Ener tecn = Er ach evans) RT RI 20; 9 RL n= B94 Lig 222) vis tpg an = Boe (vines) the inital reversible electrode poentalsincreasing/decreasing nd decreasnglncreasing in order to become finaly equal desending on thet inital relation: Eye smalle/greater than Ea From the above equation one has 153cvm.s6) cvmsn) Example VIIL6 For the galvanic cel: Pt, H, (laim) / CH COOM(0.5)/ HCOOH(0.5M)/ H, (atm), PL the reversible electrical tension i 0.0295 V. a) Indicate the azode and the cathode. b) Knowing that K,.cy,ou = 18-10", determine the acidity constant of HCOOH . ©) Then write the expression of the standard electrical tension of the cell and calenlate it. Solution; COD sg Be CHCOD, fe "ne cmpnne br a ster apes of scr ur ph coop egal a /H a 126 «ty wt ema BEat y= AEinks snd ep dese ws ease 226 i ey BE Ba at =e Wess fra we ‘and obviously 138 but ere 6) ep, therefore: Ent "Eke Ie resuts that gy Kot 1B xe OB 176,104 (End of Soluion) VIL. In idual overvoltages measurements ‘When a non-zero current lows across ar working lectode, its electrode potential fers trom the reversible electrode potential by overvoliage To measure the overvoltage under which the electode reaction works, its necessary to create an awuiliary circuit formed between this working electate and relerence electrode Whose elecirode potential takes the reversible value ‘Two measurements ar needed * one when no current pases through the working cel i 0 re { i the electric tension between either WE, or WE and RE is givenhy the expression 1520 twe, =O Peo, of course, 9 mh of course, Eres WERE ™ Eres We ~ Bre RE vin.) + another when a non ~ zero eurent passes though the working sll ws, 20 * [wes #0 five, >00r<0 P20, [#0 mean (were <0) anf, Ie, 0 the cecrc tension between ether WE) or WE and RE is givenby the expression: assEwe-ne = Ewe, ~ Eve = Breve, we ~Ereere css) rev. WERE +N 1 rs : ‘ ~» OQ o>! ov tA . WE, WE; =~ ‘Lugdin capillary Figure VII. Experimental setup allowing the measurements of indivial “Therefore from two readings one has the overvolage: wes > en ERE cotso) The Luggin capillary, brought as close as possible to the WE surface, largely removes the ohmic drop contribution to te measured electrical tension, Each electrode in turn is combined withthe RE, and the to electrical tensions are ‘measured for each current imposed across the cel 136 1X, ELECTRODE KINETICS 1X.1 Introduction 1X.1.1 Electron distribution in metal and in the electrolyte sok Let us consider the following electrode: PL/O/R,KCI ‘inthe metal, the valence electrons are delocalized forming in a first approximation, the 0- called electronic gas" which i fee to move inside the metalic network 1© the electrons eceupy energetic eves from the lowest one tothe highest one ‘he higher ocaupied energetic level fora metal is characterised by the Ferm energy, Ef this level isthe HOMO (highest cccupied molecular orbital) for metal; 10 for anodic overvoltages (1)>0) the HOMO has a corresponding. Fermi ‘energy which smaller than the Fer energy for a zero-overvoltage n> Epo EF this relationship means that there are energetic levels which become occupied hen a negative (eathodic) overvoltage ats in he electrode rection; In this ease, te electrons are injected into the metal through the extemal = in the elecalyiesnlaon the electrons belong to the ionic and molecular species Which are presented het: 10 inthe O species ther is a fist lowest unoccupied molecular orbit, ese LUMO, availible for aeceping the electron; (© in the R species there is a last highest occupied molecular orbital, called HOMO, abe to donating the electron ‘Between these two orbitals, LUMO belonging 10 © and HOMO belonging to R and the corresponding levels belonging to the metal, the lst occupied level at Ferm ‘energy and the fist uncecuped level a Fenn energy, occurs the electrode reaction Ouumo +h © Rriono 137in oxidation the electron leaves the HOMO belonging tothe R speciesand aves to an unoccupied lve belonging to tne metal bu placed below the HOMO of Rs + imredueton, he eeciron comes from an ungecupied level belonging to the metal but placed above te LUMO of © to the LUMO belonging othe © species, Considering ony the thermodynamic reason (and not the kinetic te8s0n), the relative position of the HOMO of R, LUMO of © and Ep of meta decide the electon transfer Sirestion SB emoeo anode cathode oxidation reduction Ore eR Ore oR Figure 1.1, Spontaneous ease of electron transfer E, LA Enomoe —* nso Euumoso Ef a cathode oxidaton a Ore eR ee Figure 1X2. Non-spostaneous case of electron wansfr. The intervention of overveltage = the electrons belmg also to the K* species and othe CI” species Kr wastaptastagt cr sastaptaetap® 138 bot in which there is a very large energy gap between the HOMO and LUMO ; these two levels are also very far from the Fermi level ofthe usual inert metal sed 38, WE. oF ce: (© it is very difficult to reduce the poussium cation K* which is @ week ‘oxidant; but iis more diffieult to oxidise i (© is very difficult to oxidise the chloride anion, CI”, which is @ week reductat; bu itis more dificult reduce i, “The very large energy gap makes these two ions behave as indiferensuppoting ions Example IX.1 ‘Sketch the energetic diagram regarding the position ofthe Fermi level and HOMO and LUMO levels in the case ofthe following galvanic cell: PL/R, 1/0, /Pt. Solution Both electrode reactions occur spontaneously when the electric circuit i opened (that means ‘that the electric current can flow across the cel. Therefore (at anode and ¢ is cathode in 8 galvanic cell ease) Enomo., 4 ER, ERe Fuoco, Figure Example X.1 ‘because both siectrode reactions take place spontaneously atthe electrodes (E3, < Eyam) and EF, > Euunoo; » (End of Solution) 1X.1.2 Electrochemical energetic barrier. Eyring model. “To the electodic interface there isan eletrochemieal energetic barter which can be regarded asthe superposition ofa chemical energetic barrier and an electrical energetic bare. ‘One can assume that the electrochemical fee enthalpy change, AG. conto the letrochemical barrier, iis chemical component AG contos the chemical barrier and its electrical component 2FE controls the electcal taser a= 4G Fe, ax 159chemical Potent cnerastic energy barier ee ° leerocherical snerastio erie 60 Go Gp =Sq Reaction coordinate parE lecricl nergtic bier Figure IX. The superposition ofthe chemical and electrical bariers inorder to obtain the electrochemical bari 403 =O" Gy 162 =G"-Go (1x2) 8G = Gy ~Go = AGE -act For the forward direction, to reat the reactant (() needs the forward activation energy. Only the panicles having this supplementary energy may reset to give the product (R). This 160 activation nergy is AGZ . On therisng port ofthe curve the system wses the BGE amount to limb up. After passing the peak onthe descending part ofthe curve, the system returns the 4G? ~AG = AGE amount, Here AG being negative, the energy retuned is greater than that, sed, Considering the Eyring theory, the forward chemical rte constants given by: a) absent the chemical barter cae) For the backwaré divecton, 10 react, the produ. needs the backward activation energy. Only the particles having te supplementary energy may feact to give the reactant O This activation energy is AGE. On the rising part of the curve, the system uses the ‘3GZ amount to climb up. Afler passing the peak, on the descending part of the eurve, the system returns the AGS + AG = 6G amount. Here AG being negative, the enery retumed is smaller han that used Considering again the Fyring theory, the backward chemical rate constant is even by’ 0x3) (the electrode potential is tken zero forthe chemical baer eae) ‘Electrical barr: For positive elecwode potemial the eleccal energy for thse 2e™ is given by the product FE (x4) ‘hose linear shape is presente inthe figure above sothial tan yang the to revs tes ne obs the resuking baie which onl the ead ection ropes, Teeny ofthe macs (0+ 2s lowered fm Gg 4 = Gate eee of he pod Kreis hese al he eerie ae refered taaiet RD 11‘The energy of the activated complex (4) is lowered from G* wo G* = G"-(1-By2FE where B is called symmetry factor of the electrochemical barrier. It shows that enly 2 fiction of the applied electrode potential and, of course, of the applied lecricaleneray, i used to lower the energy ofthe activated complex, Therefor, has values *anging fam 2r0 to wit ‘Obviously, now the Gibbs energies ofetvation ae: ax) = AGE ~~ PFE B62 GG G* ~(1~ BFE ~(Go ~ 2FE) (xs) = AGE + fare andthe potentisl-deperdent constant are (x6) 0x6) tal ge He ‘The significance of the chemical rate constants, Kk and Kf), could be now better understood - the eondiion of having a zero value far the electrode potential is necessary to 162 ‘As concer te eathodic electrode reaction, onthe contrary one as Et sé = kl = By, = kao $ tot (One can also notice that during the cathodic electrade reaction when the electrode potential is shifted negatively, the cathodic activation energy becomes larger and larger. and, therefore, the anodic rate consant becomes smaller and smile, the ealhodie current density becomes more and more cathode: Ey sgh > kb oy stuf ahha wed ‘As concer the cathodic electrode reaction, onthe contrary one as EL @0d¢h = kt > yrkaot Fe, = tka T The overall current density i given bythe sum of the two partial eurent densities: Tei +i =-2Ftkyap — keto) pe «x9 =-aFijare Example IX.2 Looking ‘at the i-E equation of the polarization curve in steady-state pprosimationicondition fora slow (irreversible) electrode reaction: ae Pa ark it results that, at least theoretically, a continuously increasiag of the electrode potentiat ‘ther inthe positive (anodic) direeton or in the negative (anodic) direction gives rise to ‘either a very, very large anodic current density or to» very. very large cathodic current ‘density. Theoretically the current seems to be infinitely large when the electrode potential {is infinitely large to (either anodic or cathodic) sit possible? Solution [No. The eurent increases anodically or cathodically being, infact, under a mixed contro: on ‘one hand itis important the electrode potential value, on the her hand tis important the concentration values ofthe R species inthe anodic range and © species in the eathodie range. ‘The reacting particles ae the real subject ofthe eletrode reacion and, finally, their amo 1/2 the activated complex (ransiton state) resembles more the final state, namely R ‘Several pictures, presented in Figure IX.4 re interesting: ' 1 1 eee : Figure 1X4. The allure ofthe elecrochemical burier according to the value of the symmetry factor and the influence oft on the shape ofthe polarization curve (The arow shows hove ‘much the energy of the transition sae is lowered in each case, and, ofcourse, how much the modi ativation energy itself is lowered). Example 1X4 cone ose Examining the igure IX4 and using Equation j=-2F(KZaye 7 —Kiage *” ) show from a mathematical point of view the vertical correspondence between the allure ofthe slectruchemical barrier and th allure of the polarization curve, Solution Consider B=1-B=1/2. At increasing anodic electrode potential the frst exponential imcreases as fas a the second exponential at decreasing cathodic electrode potenti. On the ‘other hand, the second exponewtal at increasing anodic electrode potential and the first ‘exponential at decreasing cathode electrode potential behave in the same way. Consider P<1-D (ie, B<1/2). At increasing, anodke electrode potential the first ‘exponential increases faster than does the second exponential at decreasing cathodic electrode potential. On the other hand, the second exponential at Ineresing anode electrode potent decreases faster than the first exponential at decreasing eathoic electrode potential, Consider B>I-B (ie, B>I/2). AL increasing anodic eleewode potential the first exponential increases lower than does the second exponential at decreasing cathodic electrode 16spotential. On the other fand, the second exponent at increasing anodic electrode potential ‘ecreases slower than theirs exponential at decreasing cathodic electrode potential (End of Sotaion) IX.14 Electrode reaction sit complex assemble of charge transfer step, mass transport by n step and chemical reaction sep ‘The electrode reaction is usually more complex than ether the charge transfer reaction (which is compulsory) cr the mass anspor by difusion (whichis also compulsory). The electrode reaction could also contain assorted homogenous chemical reactions. Such a chemical reaction could be chemical bond frmation or chemical bond breaking. Therefore, ‘most ofthe clecrode reactions occurring in electrolyte solutions appear asthe combination of thee base phemmens: charge (electron transfer between the metallic surface and the electro active species Jn OHP (for usbsorbed species) o and IP (Tor adsorbed species): + transport of species by difusion orfand migration arand convection fom and to the ‘metal surface to and from the bulk ofthe eletrolyte solution; ssociated preceding or/and following homogeneous chemical reactions. “The Kneis ofthe veal electrode reaction is refed by the eetionship between the current orcutent density flowing through the working electrode snd the elestrode potential or ‘overvoltage ofthe working elecuode. This relationship depends upon the exact manner in hich they are couple, ‘The reaction tht occurs atthe electrode surfce is named electrochemical (denoted as EE) and the reaction that occurs inthe electrolyte solution is named chemical (denoted as C) “The former isan heterogeneous reaction, the late isan homogeneous reaction ‘The mechanism of such an electrode reaction could be very complex and the mechanistic study of it isthe main gol of eleerode kinetics. Several electrochemical techniques, intensively used by non-electrochemists too, are ‘very rich in information. Among them: = eyelievoltammery (CV); ree current polrography (DCP ), rotating die eledrode (RDE ). In addition, many other lechniques, belonging to physical chemistry arsenal, are intensively used by elearockemists wo, Among them: ~ UV visible spetroseonys AR speetoscops, + _Electon spin resmance (ESR ) spectroscopy. (fen these two different groups are coupled giving the spectroclectrochemical techniques and anew field well-known a spectroclectrochemir. “The simplest eletrode reaction studied by the electrochemical techniques isthe ane — electon sie (He single electron transfer), with no coupled chemical reaction, denoted. Even tis simplest elecrade reaction isa two - step combination: the electron transfer step and ‘the mass anspor by dffision step “There are two exzeme eases ofthis mechanism: + themechanism E, called also clectrochemially reversible, Nemstian or simply fast; 16 (© when the charge transfer step procceds at the thermodynamic electrode potemial or in it immediate vieiniy; another name is electrode reaction with pure diffusion overvolage; + the mechanism E; called also elecochemicalyireversible cr simply slow; ‘© when the charge transfer step proceeds at an electrode potential which is meh larger than the thermodynamic eletrode potential: another name i= electrode reaction with pure charge transfer overvoage; Between these two extreme cases there is an intermediole mechanism Ey called ‘quasireversible. In the following, only the simple E electrode reactions involving only the charge (lecton) transfer between the metallic surface and tbe O and R species in HP will be ‘considered. No significant structural change will be considered (hrovgh many E. clectrade reactions may involve significant structural changes so that C chemical reactions need to be included, Example 1X5 Examine the polarization curve in the Figure, obtnined under stationary condition, Answer the questions: Does it represent an anodic ora cathodic electrode reaction? How many difusion plateaus appear on it? Explain why finally the current increase indefinitely? ‘Supposing that in the studied aqueous electrolyte solution initially: ‘there are two different reacting species X and Y with X more reactive (X and Y in ‘the same concentration) ‘there is only one reacting species Z ‘and that in both eases the same total reaction for each wave. (Use the rea unt of electricity is passed, write the electrode m between the limiting difusion current and the concentration of the electroactive species stale, esr Fs te aay a eee ip esrer thickness and, isthe eletroactive specs concentration, minus sign holds for R species and plus sign for © species) One assumes that & is given and known and Dx, and Dy are equal clectrode reactions. ‘Thee are twe anodic difusion plateau ‘The final continuously increasing anodic wave appears due to an anodie electrode reaction Involving the water molecules (hich are in avery, very large copeenraion compared tothe elecrontive species) ‘The height of each diffusion plateau scems to be the same, In adltion Dy =Dy and Dyes =D; I rests that in each electrode reaction is involved the same number of electrons, usally 2= 1. The two proposed mechanism ae: 1 XOX ae YoY ae a, BOT ane 242% oe (Er of Station 1X2 E, mechani 1x21 Theory 4m the E, mechanism, the electrode reaction is very fast or reversible because the charge (electron) transfer step is in equilibrium in the timescale ofthe experiment while the fusion is notin equilibrium being a rate determining sep (rs). Therefore, in the E, ‘mechanism, the charge anser step occurs much asier by comparison with the mass transport by difasion step though, being coupled in series, the rate ofthe overall electrode reaction ia the sme ime, te rate ofeach ofthe two steps [Because the miss iransprt by dffsion is ard this E, mechanism occurs with pure gitsion verge (he ate of he overlelectode rection ing governed bythe ae of iffision) ‘When po current pases through the electrode (I= 0, '=0) the electrode potential E {takes the particular value ofthe reversible electrode potential Ejy (E=Eyy =) ‘The reversible electrode potential Eg, has 8 Nemstian behaviour with respect tothe bulk activities 9 and ag which are, infact, the OHP activities Sq and iy Fo =A ay =ap xs) the reversible electrode potential being the thermodynamic electrode potenti itself 2+ RE, ae oF ap stat E(i=0=E%+ ay (xs) When across the elecrode @ non-zero curent pases (1# 0, 10) the electrode potential E, (Ev Eyey. 0), has a value which is different from the thermodynamic electrode potentiat but is piven by the Nerst law with respect to the OHP activites Se) and 4p. ese are now different fom these in the balk Bora Ip vay (10) RY RT a ; ir Oye By SE nO ype, BE jg 80 x) Bae oy= Bry SE x c Making the difference between the E and Ey, one bas the pure diffsion overvolage: x12) The curent density, trough the eletrodic interface, is given by Fick's fist law viten as folio ‘forthe reduced species R wich experiences an oxidation (anodic) electrode charge transfer 0+ CR 0x13) ay S| oxy i=2Fly (the anodic eutentis taken as negative ina deiven cell); ‘+ lar the oxidised species © which experiences a reduction (cathodic) electode charge swansfer ove on on) inate ro a 8) (teeta cre in iv Sect pce soy xis 169‘where Dy isthe diffusion coeticient, Further diseuson abou the sign inthis two equation is required: ‘+ for an anodic net current density (taken as negative) the R species are oxidised (ie, ‘consumed athe elec interface, in OHP )and the R species must difuse tothe electodic inerfce; his sont possible when the vale SA. spose (his i slope in ay va x Plot; a the sume time the O species are formed a the electrodic interface (in OP ) and the (© species must diffuse away from theeletrdic interface; this spy possible when the valve dag & is negative (this isals0. slope in ag v5. x plot), + similarly, fora cathode net current density (taken as positive) the O species are reduced (Gc, consumed at the sletrodic interface, in OP ) and the © species must diffuse to the sleodi intra; his ely posite when the valve Sis postive hiss slop in 440 ¥5.% plot) a the same time, the R_ species are formed atthe electrodic interface (in ‘OUP )and the R. species mus difuse avay from the electro interface this i only possible hen the valve SSR isnegatve (hiss loa slope in ay vax po) our our Figure IX.5. The concentration profiles in the case ofthe equilibrium (right) and fr anodic non-equilibrium ease le), According to the Nemst diffision-convetion layer approximation when the clectrolye solutions sted or the electrode is rotated, a practically stationary liquid layer having a thickness 6 is Formed at the metal srface. Within this saionary layer ofthe 70 thickness 6, the mass transport by diffusion ofthe electroactve species O and R could be ted by replacing the general concentration (activity tL By wyer rated by replacing the general concentration activi) patient SP (2) bye near Hh 4-8 concentration (activity) gradient "1 (°"*) esabtisted through the entire diffusion ayer According to this approximation, the eurent density can be expressed by the following two equations x9) 1270 (9-%) was) For an anodic curent density, 1<0, one has By 0. one has dy > ag and Hp ag: For a cathodic current Bp 0 and Wig a ign =~2F PB ay (x7) 3 ‘hich explains the constancy of the anode eurent density ‘When the electrode potential is shied negatively, at a cenain value, a limiting cathodic current density is reached, the father decrease of the electrode potential does not change the current density value. In this case the species are reduced as fst a they arrive in (OHP by difasion, their activity being zero and a maximum possible diffusion gradient brings the © species from the bulk to the surface. Therefore: 4-90 tnd Wigan ret? ag oir The needed ratios of the activities in the ffsion overvolsge expression, can be easily derived $ x18) 50 xis) m“sutetitting them inthe diffusion overvolage expression, one obtains the ration beeen the electrochemical quantities (19) jon from which one can deduce the expression ofthe curent density as a funtion ofthe dfTsion overvolage: (x20) ia Tae faa tae in which the kinetic parameters the symmetry factor and the exchange curent density 7°. donot ppear but the fio parameters ste mass anspot by fio coccens 8 svt 20 sein slo et iy ia Testy sain ee ever) ve ee rat ih tions cleciochemical techniques it isnot posible to obtain the kinetic parameters of the foo fast {reversible} charge transfer rection because this step occurs at equilibrium. fave potential Equation of the polarization curve by using the half-wave ‘When the curent density through the WE the pantiular value: 4 wan the electrode potential E ofthe WE takes the paricular value EF) whee: EM =), iguiae 0x22) Considering the definition ofthe overvliage as = E~Eyey the expression conneting the fvervoliage with the logarithmic term of current densities canbe writen in the for: EBay + BE ita =D x2» FP igele-)) m which ean be rearranged as follows Ee Egy +E tn ale + En eae 0x24, so + Tn Bato» BT gat 2 Doan Filan “here the meaning ofthe limiting diffusion current densities was use Seung now the reversible electrode potenll by means of the Nernst law one buns: 1 ATygt0.e gay MgDic RE iol eer aot Dg af nl wet Bg De. «RE ig dae! 2'Do* oF inten x29) Imposing tothe erent dehy the condition of being the semsum of the wo ining {fasion curent densities, 1 this ast equation one has RTD, py <6? SPB 1X26) popes Erne 0x.26) because: 4 0x27) 2 fin addition, the to difsion coeticiets are equal, Do = Dy, the halvave potential becomes equi! to the standard electrode potenti EM x28) “which shows that the half-vave potential is a thermodynamic parameter and not » kinetic jarameir (he Ef?’ snot a umeion ofthe Kinetic parameters, the exchange current dens 'P, and the symmetry factor, 9). Remember that the standard electrode potential 1s # namadynamie electrode potential for fast electrode reactions. aa oe the equation of E and using te fst meaning ofthe ha-wave penal, ‘one has the searched equator: vssy RT jg inet Bees (x29) Gon By plotting be electrode potential E agains fone obtains a straight line BE. hoe slopes BE and whose ordinate inereep is Eff The slope sa revrsiiyeriteron or test for an elerosereaction: i the slope is BE te eects actions eversible(t itis sexsary ohn th runer of econ ined) E 7 E ! " END > Epa j o aT | : ata + date ‘ig + Bt i n+ ie co ls ae. eo BE 2 tia 59 | Figure 1X7. The position ofthe hal. wave elecode pote ix comparison withthe reversible eee potent : iniae=i ER imidta | Example IX.6 ie a) Find the 1~i expression for the following fast (reversible) electrode reaction O42 2K. , fae ») Obtain tue = expression fr the assumption fgg ig Figure IX.6.The representation E against In-8&—" giving a straight line tate = Nae a ta a Naa * = oO ‘Obtain the expression of the half-wave electrode povential. sctng 2 et othe reversiity ofthe clesrode ration. Discussion: (see Figure 1.7) = eT, - at Eas r a | Ouof the equitibrium one writes the Nernst equation with respect othe activities in OHP + iri= ttle cotten Ef5 > Egy (n> 0)and i<0 at Eff: ‘hich are efferent fom those in the blk + Sauce ovat + itt !aeti 50 hen EF R, +R. Give the expression of its standard electrode potential Solution Obviously, the iE equation is i=—2F(RSae™P™™ —heq.a9,e°%), At equilibrium (i= 0,6 Ey) one has kgaze"P2 = K2nq, a €%8% from which, by solving with 179RT, ke Fespect 10 Egy, One Bet Egg = EE jn spect es al : kr, pation, Egy =£° + EE hy ae (tnd of Staion) 1%.3.2.2 Very small overvoltages, The low-overvoltage approximation For very ow overvoltge the following condition has tobe fufied| # (1-8) =n 51, foranodie overvoltages O-HEns, tage # B22 n 1, for cathodic overvolages pans, ag Let this overvltage be taken tobe: i 40 it results E5420 and Ry 0 the electrode reaction being fst (reversible; onthe contrary a for #0 itresuts “240 and Rey > the eletrade rection being sow (inreversble). cy = for very slow (irreveribe) electrode reactions when #® tends to very small values (Gends to zero, mathematically speaking) the slope ofthe » versus | curve tends to infinity an the charge transfer resistance isl tends to infinity Poo, Bow, Rare despite the passage cf a very small curren density i across the interface, the fvervoltage 7 tends to be infinity, andthe electrode interface departs easily from is reversible electrode potential (this is precisely the behaviour ofan ideally poarizable ‘leotrode) the electode potential can be varied at will by an external power source ‘sthout passing significant current densities: 18h