ELECTROCHEM METHODS Fundamentals and Applications PANO DNS 37-054) LARRY R. FAULKNER| | I | | STUDENT SOLUTIONS MANUAL Cynthia G. Zoski ‘Geom: State Univer Johna Leddy Cnet of one To accompany ELECTROCHEMICAL METHODS Fundamentals and Applications Second Edition Allen J. Bard Larry R. Faulkner Department of Chemistry and Biochomsry nines of Teta ot Austin. Prepared By Drew Dunwoody Universi of fom John Wiley & Sons, Inc.PREFACE “The preparation of his Solutions Manual asa supplement to the 2001 edition of Electrochemical Mahods: Fundamentals and Applications, stored by Alen J. Bard and Lamy R. Fille, bas beena year-long underaking and adventure. We exend sincere thanks fo A. Bar, PH, He, DO. Wi, and P.Vanjsek for many elightening discussions a ths manual was being pepaed. We sre gateful for D.C. Dunwoody asistance with TEX. We lo extend thanks to Jennifer Yee and Linda Hey at Wily for faiitaing this project. ‘We welcome comments and queis on our approach othe problems. These may be adtresed to Cynthia G. Zosk(cheegepanther gue) and Jona Leddy Gleddy@bne woes iowa ed). ‘Addnal information and updates may also be found at wwwvley coniollegtbar Cia G, Zoe Jona Leddy “To xderboks or forester servo cll|-00-CALL-WILEY (25-545) Cop © 20 ha Wie 8 Sn, Algies aer netgear eter Sete Sea Sime ache pen secured eaten ea aoa naaat as maT san o47iaosz13 Pinan he Unt Seo Area ro9s76s4321 tea tly Vir pi ne —$ rr TPT TTTCONTENTS vevvvvvy verve vey ’ [VTRODUCTION AND OVERVIEW OF ELECTRODE PROCESSES 1 POTENTIALS AND THERMODYNAMICS OF CELLS 7 KINETICS OF ELECTRODE REACTIONS 15 MASS TRANSFER BY MIGRATION AND DIFFUSION 21 BASIC POTENTIAL STEP METHODS. 25, POTENTIAL SWEEP METHODS 47 POLAROGRAPHY AND PULSE VOLTAMMETRY $5 (CONTROLLED-CURRENT TECHNIQUES 61 METHODS INVOLVING FORCED CONVECTION: HYDRODYNAMIC METHODS 65 ‘TECHNIQUES BASED ON CONCEPTS OF IMPEDANCE 71 BULK ELECTROLYSIS METHODS. &% ELECTRODE REACTIONS WITH COUPLED HOMOGENEOUS CHEMICAL REACTIONS 95 ‘DOUBLE-LAYER STRUCTURE AND ADSORPTION 103 ELECTROACTIVE LAYERS AND MODIFIED ELECTRODES 111 ELECTROCHEMICAL INSTRUMENTATION 115 SCANNING PROBE TECHNIQUES. 121 SPECTROBLECTROCHEMISTRY AND OTHER COUPLED CHARACTERIZATION METHODS. 123 PHOTOELECTROCHEMISTRY AND ELECTROGENERATED CCHEMILUMINESCENCE. 131 [APPENDICES MATHEMATICAL METHODS 135 DIGITAL SIMULATIONS OF ELECTROCHEMICAL PROBLEMS 143,1 INTRODUCTION AND OVERVIEW OF ELECTRODE PROCESSES Problem 11 (a: In approaching this kindof problem, it is weil to list al the couples in Table CCl that are evan othe eytem, vis 0340 0159 0.00 oars Altematvely a graphical representation may prove usefUl, Here, the standard or formal potetals {oc each redox couple ae poted on potental ais, The species preset in solution re underlined. Noe the reduced half ofthe coupe is noted toward more negative potentials, The vera line ‘ndiates the approximate potential range where both halves of the redox couple can exist. For ‘lecvose ptentals postive of given ine, the oxidized half ofthe couple sable at the electrode ‘roe for electrode potetlsneative ofthe lin, the reduced form stable. Note a forn = I, ‘lectode potentials within II8 mV of E° require no less than 1% of ether the oxiized o reduced halves ofthe couple as given by log ff = —n (B ~ E°) /0.080. even you" oy Jeu ‘" oa Bangs. 14 09 oa E (vs. NHE) “Te composition of the system dictates hat the et ceo cue’) ote be mor postive thin Ebapjoy and more neque tan E8, yo OF Epp, ie, betwen about 0.34 V and 12 V ‘rs NH" Graphical thsi apprent ecnse thi i the voltage range over which the oxidied (Cat) and reduced species (tor H0) present nthe solution are mast adjacent onthe graph ‘This defines a one of ability set bythe oidized and reduced species. (Note at the cell wold ‘othe at equilibrium oxidized and reduced species of two or more couples wee preset such hat {hey wee on the our ide ofthe ines. Fr example, ifthe solution conned Cu and Or, ete ‘woud be a thernodymamie diving fre for hse apis to react spontaneously to fore water 3nd Cu.) Hee, the poeta isnt well dened ina themmodymame sese the eco snot ‘well poised, because no couple has both oxdaed and reduced forms present. Clelaton of(Chapter 1 INTRODUCTION AND OVERVIEW OF ELECTRODE PROCESSES ‘quiibrium potential by the Nest equation cannot be made. ‘Curent willow when he potential is moved negatively from the rest potential 0-340 V (or 0.3404 (012412) = 0.090 V ve. SCE) so that Cu" is reduce at the electrode surface fet. or +2emcu (Gest reduction, = 0.1 V vt. SCE) ‘A postive movement fom theres potenti fis causes significant current low when platinum and ‘water are onde. Praptt +2. (Gre oxidations, = L0 Vv, SCE) 2:0 = 0,448" +46 Actual, Pt would form a thin oxide film, then it would stabilize, and only the oxygen volition ‘easton would occur. The curent-poential curve would lok hike the following. 10) 0s K ° BHO 02 +441 +46 E,V va SCE | ‘Problem 13. The important reaction are Fet tenet E9207 Vv. NHE Sat +20 a Sa? E°=0.15 Vv. NHE (2) From (149) andn = 1, j= nFAmOCS = 580 pA (@. Because the concentration of stannic ion is half dat of feric jon but n= 2, and the mast transfer coefficients ofthe two ions are the sume, the limiting caret forthe reduction of Satis alo $80 iA. The balfave potential, E, fer the fre redocton is near B® = 0.77 V vs. NHE, ‘whereas that forthe reduction of sac on is near 0.15 Vvs. SCE. The ~ E curve eas follows | | | > 10 08 06 04 02 0p 02 04 20-0, at 4 24 oes EV vsNHE Problem L$. From equation (12.10), seat[t-9 (x34) © ‘Area sppears because Cy i expressed as capacitance per unit area The time constant is CA. Elm) ° (8) ° ‘This expression is rearranged wo fg = Sr a1 95% completeness. For the specified conditions, [RT To Pro [us [2-|20-[ 20 us 6 | 60 600, Problem.7_ (0, Fromequtins(149)and (14.17 forthe ining arent, = BARES = $4 = 107 ome = 1.67 = 0858 From gut (1419, Bia = BP — Hla Be = Bids Ve NEChapter 1 INTRODUCTION AND OVERVIEW OF ELECTRODE PROCESSES Chapter 4 ‘Problem 1.9 The relationships linking curet and concentration inthe seady-sate treatment of snes tansir ae uation (14.6) and (14.7. i= nFAmo[C3 - Cole =0)) 0 nF AmalCa(= = 0) ~ Ci ® Because C5 = 0, hefistof these is nFAmoCo(# = 0) o BecauteO dosnt existin the uk, exo carentcan ow. All curent gosto aide R. Problem Lt (String with expresion (14.16, ‘The limiting rate of oxidation is found when C( = 0) = 0, hence the limiting curent is Ex Eyat Bias] (ne sles foi 8 lows ig -nFAmACh © HE Eip) =o] 00 F(E~Ba)] == t- t= +e (8 (E-Fyp)) +e F (E- Bia)]) “The system i reversible, ence, pa poy BE yy Cole =0) ears Ent o Frome OL Cole = 0) = ee © ‘From equations (2) and (4), “ one 0 = Ste. o Sst (el) es poets Hin[a] o ® ‘Note tht this result isthe special case of (1.420) fri iszerand E = Er ia the Int tern in (8) o ‘The ~ B curve pote fom equation (8), resembles the folowing: iM foo ee2 POTENTIALS AND THERMO- DYNAMICS OF CELLS ‘Problem 2.1 According tothe comments n page 2 ofthe et he el potent a meas of {teeny sre ove cage ually Netween he wo cesvoer us, he cel peel fs positve. The sandr emf Bay = Foy ~ Fy secording to egation 2.141); der ‘andard condo, the emf yield the sandr fe entry at AG! = ~nF Et, szording 10 equaon (2128) If AG" <0, the reacn is spontnous (galvanic AG? > 0, the reaction ‘urbe dive by an exeral power source and te resco lec} (@)- Any reaction pai withthe form HalfRescions: 0+ $H0+ ne = R + gOH™ RY $0=0+¢H* +e as he net sum NetReactions: HyO.= H* + 0H" For example: al Reactions: 2140-4 2e we Hy #208" B= 0828 V vs. NHE Ht +20 B= 0.000 v8. NHE NetReacion HOw Ht +01 ca: Px Hala = 1) HOM = 1) NAOHCa = 1)/ Ha = 1)/Pt Right cestode at Ep, "0828 V v4, NHE Leftteewode a Ey, ~ 0.000 V ve. NEE ‘The right electrode is negative. The cell potential is 0.828 V. From equation (2.1.41), fay = Bue Bie ™-0828 Vso the cel mas be operated electroyealy nearing out the reaction. oo. Hal Reactions: NetReactins: — 2Ce* +Q+2H* = 2Cet* +10 cat: PLUCE(a = 1),02(0= 11 BQ‘Chaptor2 POTENTIALS AND THERMODYNAMICS OF CELLS Left eleorode at Ebr te "1.72 vs. NHE Right eleczode fs negative. The cell potentials 1.021 V. From equation (2.141), Bf, = ER {Edy = L021 Vso the cls clexolti othe reaction writen. Not hat Ce is meng he ‘Tol pent oxidants avilable i aqueous solutions. ‘Problem 22 Standard potentials must be converte to fee ences to calculate the comes stan- ‘Eee potendals Alternately, tabulated values ofthe fee enepes can be used to calculate the ‘Sandard potential for the net hael reaction, “The approach isto contr the half reaction of interest ito a fll reaction trough combination sith a appropriate bal reaction such asthe hydrogen rection half reaction, Hr tem Hay “The fe energy chang ste aol for heres fl ean which nam Ys #2 TES de sane pot, The fe energics sede to ave tis problem ae tabulated a> flows. Spies AG} keto) AG} dima) we ‘5436 3946 ara) “sos 609 13 50.00 2093 186 29 0.00 000 ( Thereaction (604) +H20 4p = COng +226 in added tote hydrogen reduction af reaction yield 4p) + #20) = CO + Ha) “The sandard fre energy change for this reaction is Recall te relationship between standard potential and free energy = Sf @ F o ‘Chaptor 2 Forn= 2, Edm, = —R34Hin = 0.04 V where Ef = Ef ion — Fe Bonico FRoyico = Bhs, ~ Eten = 0.00 -O1KV=-0.104V vs. NHE Problem 24 (2) Ag/ AgCI/K?,CI“(IM) /He:Ch Hg HgxClz +2e 2g + 2C1- o26sisv =e 2x (AgCl+e = Ag+CI-) ome Heth + 2g Fac = TET ‘AG <0; reactions spontaneous HgiCly +2Ag = 28g +2AgC1 (,Pe/Hy(1 atm) Nat, OH"(0.1 M)/Na*, OH (01 M)/O2 (0.2mm) PL B= 0401 + BIL og i = 0401 + 00148og 2 = 0450V = -0808-+ Mog prabyrp = ~08%8-+ 0.0296 og yp = -0.760V Em = By ~Bi= 1219 V (putes) _Aerativey, fr the ection a writen, Boag = 229 ~ RL og p= 1.29 ~ 001g yg = 1.219 ‘ote ie reaction the ae ha in) and tha he presse of he aos rata ‘Eval the sae, Th Brey mus be ena However he ange pl te estoy dost thi he poeta of te Kyopen ad oxygen elacuods to ore negative vals by $9. pet Snip Io pracal mn pl eth exelent or “vet widow" ages sotto Problem 2.6 The reaction of interes i POSO, ws PO? + SOP Pesos 2e—rossot _ass0sV ES em Pb) i2s1v) Bonet — “Seat 22, cat: Po/PR#*(a-= 1, NO3(a= 1) //Na*(a= 1), SOF” (a= 1)/ PHSO4! PS ‘The cell reaction i the solubility equiitium writen above. From equations 21.4) and (2.1.29), Eran = Even = Epsso,jps ~ Ebaeejey = ~0.3805 V ~ (0.251 V) -omsevChapter? POTENTIALS AND THERMODYNAMICS OF CELLS. RES = 17.5 or Ky = 240x104 I Kip = MEEE = 17.5 00 Ky = 2.40 10° e Problem? The creations HalFReactons: —AgCl+ eCu) = Ag+ CI~ Fe sey) = Ft Net Reactions: AgCL+ Feb + (Cu! Because M isnot involved in the overall reaction, it canot affect the cell potential, which = fects AG? for this reacSon. One can consider the cell at open cielo term of the species st eultrium across vacous phase boundaries. mAg+ CI +R + (Cy) He = at © ® HAE = te ° WE ode = lg ae = ae © Ainge (2) 10) gives Bhan + BEET + ae © Subsiting Som (1) and (5) and recognizing tat HE + BS = o eves how + BMEL+ BEY = Dh + AG + By + SO © Expansion gives Hos + RP nlpys + 2668+ 2M! + OH — Bee Bae + RD nahn + SPO + Hae + ul + PInoy TROT 0 Chapter 2 Rearangemeat provides AE — Bt Ht = ou en Mle HE hoe WE WB tae ro oe ‘No ers describing energies in M appear, ths E des not depend on M. The term if appeared in equations (}) and 2) above, but they canceled ot. Disc ales of the interfacial potential Aiference, 6°* ~ 6, would aise for various species M, Bu the variations would be cxacly ‘ompensaied by variations ing ~ oF Problem 210 Consistent with he comments atthe sar of Problem 22, sound hemodynamic evelopment of standard potentials (E°) fr halfell rections must proceed though tee energy ‘calculations, not standard potentials (a) First, convert he two standard halfcell potentials into net reaction by combining the reac tins withthe Hy hall reaction Ht rend) Ths, Co 422 Cu osu =5 20H* + em Hite) O00) = oraiwcen “at 2B, AO} = nF Eg = -2F Ens wd Otter tect assy =a AH +6 = jHg) 40.00V) =F Sito “Wet i2, AG = nF EB = 1FEany ‘Tren, noe tat subacting the second reaction from the ist yields ult Hh ecusr ent ‘This has a standard he energy of, AG? = AG} AG =F (22g ~ Ea) o ‘This isa single electron transfer reaction, the emf fr this reaction is @Chapter2 POTENTIALS AND THERMODYNAMICS OF CELLS. Final the standard potential for the half rection ie found as Culte= cus “8 (Ht +6 $a) -o00v) =F Cutis Cus FH —O1EV = 8h, Pons hich is suis forthe standard potential ofthe halfeston, £9 = E93 + EP = -0.8 Generalized Form: The sbove processes can be generalized and smplifled because he reference Iatfreaction off is and =F canon ot Forth ion or beacon of he nar poets (G9 and Ef) of two half reactions to yield the sandard potential (EQ) of a third half reaction, aa nBen ° here the reactions have my, nz, and ny eeebons, respectively, Note that in ll the previous ‘roblems inthis Chaper, the special case applies where reactions are combined 'o yield net Sgt emh no epee, Ths 1 = = my, neon 9) ee 1 Bf = fe (@) This example is done using the generalized expression, equation (3). The haf reactions are combined by subancton of aa? ffom Ren. Not, hat the ealculatons yield half reaction (ie, ‘Bere te explicit eleewons i the al reaction) andthe generalized form i reuied Opedt fe 20 B= 1229 “GhOp+d saeco) B= -0.78 Shira where gw SRS AEE _ 441.2092 1.708 gop o z z Problem 212. The oa charge passed tough the cell const ofthe two component represnt- ing ionic (Gin) ad electronic (conduction. ton + o ‘The dim component is due ta faradie proces (Le, redution of silver) and canbe caluated as {allows for gay = nF % moles wher here = 1. L129- 1.009 TOTRT g/mol Gin = 1% 96685 Cmax worse ® Chapter 2 “The total charge pated is q= 024 x 6008 = 1200, Ths, gu = 1200-10783 = 12.670 ° and uw _ re “ge 0.106 ® ‘ves the faction of the uren passing through te cell due to electronic conduction, roblem214 (a). Type2, common anion. From equation (23.40), 0 From equation (2.3.14) and using Table 232, 80.11 +7634 = 12645, ® 40.82 4 7634 = 226.16 Aywct = ver #2er Ane. = weber ‘Substntion leads to Ej = 91.2 mV. The junction i dominated bythe very mobile +, whieh tends to place a positive net charg in the right han phase, (93. Fom ie Henden eution (2.339, = 462 The jut dominated CBR oR tat seat noe tre ne eft tad pe, The station pam wh tu OH oot asmnbl wi, hace slower bere ban n ‘Problem 2.16 By analogy to equation 2.420), the cll potenti in each cases Bm constant + tn (aner+tieoe) w where isthe interferant. The cell potenti i always the value expected for aves = 10-°M in {he absence of interference, For a 10% er, xt a yar 1109 = 0 10° “Ts A os st be} x 10-4 M The sts hat woud cause tiem ae BCaptor? POTENTIALS AND THERMODYNAMICS OF CELLS 3 KINETICS OF ELECTRODE REACTIONS Problem 3.1 (3) From equation 4.5), da = nF HCE Cf = 9.65 x 10-8 wA/om? o Problem 3.3 (2. All voltges are relative to NHE. alwl |e va po Las [ass [ose | 04 os oto foaser tare] OS * a “orf o20 oases] In fil (in A)Chapter3._ KINETICS OF ELECTRODE REACTIONS. Problem 35_ (a). Neglecting mass transfer effects, the tre current i given by equation (3.4.1) ‘The spproxiate caren is given by equation (34.12). Ths, the relative enor es rs — fe a o tore epi-ofl= ell ‘Retave Err for Linear n Chanctrsie TRV eM hra=T eae TIT 0 2» 50 “10 0 50 Problem 38 (0 Thera expression or theirs order rate recon is eat) SAO = —tymale) © For anni oncencation of no hiss oie by seprtin of variable as nh fam 7 x aaytaeo = nnaleag? = =n a Hkyt e nat) = mans ky] ° ‘At time t, sme fraction ofthe molecules dy decay. By averaging the times overall molecules and normalizing by nao, the average lifetime is determined. [ew Tae OD rom (1) and (3) above, = ~hynavexp|-kytldt o Chapter 3 [otraceolnnt ety cota © “This integrated by pats where Jud = ww — f udu, Let u = tand do = exp|—byt}dt, such that du = dnd v = == soph Panel (=e -pe 2) oO expikyif a 5 iy ~ fosters (Consider a zone of thickness d fom the electrode surfice in which al the molecules can be oxidized, Lethe elecvode area be A. Then, te numberof molecules that ean be oxidced at time Nol) is Nott) = AdCo(0,t) o ol0,t) she surface concenstin ofthe oxidized species a The decay rates Al — 69 (nots o sein aft order decay constant". (Consider the reaction rte per unit mea, (motes/(on?s)) (10) Colt) ay ‘Tht hy = A. From Past (tbe amogeneaas te = 7"; he eteropencous ate hy = dr So, the fvergeifeume of mies O before andere teogencos elecvon nse is = ati.‘Chapter’ KINETICS OF ELECTRODE REACTIONS (9. Fora lifetime oft ms, given d = 10A= Ln, ky = 10-T emv0-® 5 10°¢ cml. For eT ie ky = 100 eavs. Such tes ar readily sccesble in eleewochemical systems. For cyl ‘otammesc perturbations et macroscopic electodes and san rates of about 100 Vis, standard (Eo By heterogeneous electron tansfr ates > 0.1 xs are considered fast (revere) and fates < 10"? cml are considered very slow (areversbl). See Chapter 6, With microelectrodes, “Gandard bteopencous rates inthe ange of 100 ens have been measured. Note, however, tat Fis ® amplified by electode ovepotental through exp [~af (E ~ E°)], term which under ‘pial room temperate conditions exceeds 100 foe an overpoteatal of 230 mV and 16000 fo 300 nV. Thus fetes as shor a I sare possible, favored by high standard eterogeneous rates ad large overpotentals, ‘Problem 3.11 The tabulated data show hat Limiting cathodic eurentig = 965 Ais reached ‘ion = 300 and 1 = ~600 mV. Comparatively large overpotentals are required to enforce his ‘urrent, hence Tafl behavior shouldbe observed fbr cures less than ~ 10% ofthe imiting furtent.A Tafel plot ofthe datas shown below. {tog (in way oF /2ART. For T= 298K, 98, o ig = 9.5 A. From equation “The fire thee points provide a Tafel line wit Slope = ~6. this yields = OO, Extrapolation 7 = O gives log: oan, 95x10 WP = EAC ARE CY XL emt RT XT lor =98% 10% am/s (0) From equation (413), 8.1441 Jmol“2K-1 298 K Fes = 36485 Col OS 10-4 ~ 27 i From jt = 965 wA and equation (149), aoe 965 «10-4 A 0 FACE ~ BIBS Col TOI emt x LOKI wlan D10em/s Chapter 3 According to equation (1.428, the mas transfer resistance forthe oxidize form is « Problem 3.13 From equation (3.614), BEDE 66.140) 1 1 FoR ~ TIO XO where A ithe reorganization energy ofthe solvent and Fis 2« 7 10-! m, The reorganisation efi ceo igre inti = 0) at fom = A+ ion a From equation 36.108), 6.108) act = 2016 ev @ Probie 315_ Sarg wih eqn (624) fr D(a eatin 0.629 fr Dal, Sambinting i Wo( 8) Som eon 6654) and Wa 8) Eom spaon G29 ads Ste lmng ese NaCo(0.t) Done) = Heel exp [-(E — E ~ a)*/44T] a een ALE = Eeg,Co(0,t) = C5 and Ca(0,8) = Cs hat equations (1) and (2) ean be rewriten as Da(\E) = exp [-(B— BP + 4)?/404] @ Dol Ba) = Ae Sa exp [~(Bay ~ E° — 4)*/4AKT] 6)CChapter3._ KINETICS OF ELECTRODE REACTIONS. re 2 « Dal) = GA go [=a BP 8/7] 6 ‘Atte equim energy, the concentaton density functions Do(% Ezy) and Dy) a eal lg EN) NAO [ala B+ a) - ation (ar) © Solving for Ci one finds & (Bay— FON)? + (Bag — BY ~ 9) Sy a= Ea Bo 6 fi er in tt oO atte © [Note that equation (8) has the general form of equation (3.2.2), the Nemst equation. patsy 5 PPG However, uation (8) ie based on the disbuson of energy sates between the electrode and those ‘ofthe resctnls in solution, whereas the Nemst equation is based on thermodynamic equilibrium ‘between eleconctive specie insolation. Further, equation (8) desrbes the ene, and equation (@) describes the potent. Energy is convened to potential by dividing by ~rF. Equation (9) is ‘Served fom equation () by normalization by —nP- Is oed that k= R/Nq, consistent with ‘conversion from a per molecule a per male bai 2» 4 MASS TRANSFER BY MIGRATION AND DIFFUSION Problem 41. The only ionic specie in solution are Na* and OH, both presenta 010M. Using ‘equation (42.10), the wansfrence number for Na* is lsveslCwas Anes Tie Tovoe Bee + eon -ICoi Roa © Because [zee] = [zon [and Chas = Cons this expression reduces to eer so twee = Tee + loon ~ SOT 108 = 979 a where Xo has ben substinted fr A. From equation (2.3.6), ton- = 1~tyes = 080 © For 20 e passed exter, 20 « are injected atthe cathode and 20 ae withdraw athe anode. ‘Thus, 20 OH ate crested atthe eathde and 20 OH” are removed a the anode. These changes are shown inthe tlance sheet below aChapter 4 MASS TRANSFER BY MIGRATION AND DIFFUSION Cathode ‘Anode - I+ 2e4+—> 206+» 20,0 + 206 p10, +20 088 Loom» 100,+ 201404 20 anor} anor ane! _— | Migaicn 1604" pittwin sore sour nthe blk solution, charge is transporte only by migntin, a ction 080 being cared by OH Toving tothe anode and a faction 020 cared by Na* moving othe cathode, Thus, 16 OH” and eee at rough the blk and though difsion layers, x shown in he balance sheet. This ir clalalso be obtained via equason (43.3) by considering current flow at ether eecrode. ‘At the anode 20 OH are consumed, 16 of which ae supplied by migration. The remaining 4 Os hoe to the lect. No Na is consumed or generated, yt 4 Na” exit by migration. At ‘Busy sate they ust be replaced by ison to maintain a consantconcentatin itbuon PROUE'GS Slaose generics 20 OF and no Nat, while 16 OH leave and 4 Na* ave by ion ‘Tha, 4 OW" and 4 Na must difise outward per 20 at steady state. The ues fom (difsion complete the balance sheet. Problem 43 The thickness ofthe difsion Iyer canbe estimated from the root-mean-square fision length vena uation (643) B= Vm a3) “Ths, the minimum distance d between th working electrode srfice andthe el wall is d= S8 = SVD = Sy Tx om]ox 1s = 02 om 0 2 Chapter 4 ‘Problem 45 The geometry ofthe problem i as shown below. differential volume element Zz Sphere mney impish cones may hang alga ne ceding htc Howe ral pnt sts grenadine cmcersaton ee ae et dtsivenanspot cn oz only adil sce only along patie Comceiaton Petree, nn) ene * ti Grea pact i (nt) = -D9 Sols!) Jet) = Doe o Now cme he alune cles of ins dn . Shrae he um oftes of pene , No, nin ane Cement oe Sara ate tite ve emer of it i rg nary oe Ging ant in) Te nd uy tr oC ane te ‘eet ebay a Chen ran ama we Parsi ere : hugs me of mols oO win beeen No tx x dt x [Polnt) ~ (p+ dePlolr +dr8)] @ Jol + dt) = Johns) + ACE!) @ Bom tata {i= dntliors)—(orarrMBEDon} 5) ‘To obtain the change in concentration, Co(t), it is necessary to divide bythe volume oftheChapter 4 MASS TRANSFER BY MIGRATION AND DIFFUSION clement, whichis ra. aColr.t) {Eatery ema} e © ‘Tenet step requires that dCo(r) be converte othe rate of change BCo(r)/0t by rarang- ing this equation, and expanding the expressions in algebraically Sate [24 $] soisn a2 7] BD Because dr isinfnitesially smal the terms continng it within the parentheses are negligible. Thus, 206!) 26 fe ® Ssh fom el’ ft inn ges BColr.t) [PColr.t) |, 28Co(r,1) of 2Sebet 4 280et0 ay which i equation (44.18). Note that eater printings ofthe text had an error inthis equation, ‘which appears thee as equation (43.18) on page 132. Po 5 BASIC POTENTIAL STEP METHODS [Problem S.2- The equations fr planar and spherical diffusion are sini. «e ewes ® where} = 0 fra planar elecuode and} = 1 for aspherical electrode. The curents foreach are ‘hownin the prensheet. Note tht for A = 0.02 em?» 4 the radius ofthe spherical elecwode isrp=0.0d0em. EEBsoun-Be8s ‘The eleceoysis atthe spherical electrode exceeds that tthe planar electrode by 10% when a fewest _ Bath, , tpn ® a> aR Wi > > ia 2sChapter BASIC POTENTIAL STEP METHODS For this sytem, this comesponds to (ooo? ess ste o 1 “Thisis consistent with he values shown inthe spreadsheet fort = 0.5 8 Cote’ equation emuation (2.19) is Ao 2 “Things wih respect id he hr. at = BEALE © Fort = 10. and the valves listed shove, g(@) = 2.2 10°C. Faraday’ Law, Q/n = moles Secwolyzed,yekis 2.3 10-"" moles n 10a of {mM solution, tee are 10°® moles of mate- fia In 1 te fraction elecroyeed is 2:3 x 10-9 /10"or 0.0025% . Tus, under conditions for ‘onal votammetic measurements, the bulk concentration of the redox spcis isnt perusbed ‘Seni. Problem $4 The steady sate curtent at an UME is given by equation (5.3.11) ite 0 292x109 A THK SGABT C]mole 21.2 « 10°F onto x1 x 10-* mole 5.01 x10" om = 5.01 wom Problem $.6 The system i analogous that shown in equation (5.4.70). MXP? +20 = Mlb) + pT (Given the contiton outined afer equation (5 4.70), equation (5.4.80) appl 6480) [A plot of By vers InCyy vile slope of —pRT/ mE. The ikoept sequal to EY, ~ {Blake + ME in A. Linear cegression ofthe data yields EG, = ~0.0513In Cy ~ 0.566 with 10.9008, Thus “p= 2x 852! x -0.0518 = -B90 opis yy i Chapter 5 (@)- From equation (54.72), Ko = Cyu/CyeC' isthe formation constant forthe eation M2 4X" = MX, The sabiliy constant isthe Se as Ke. From equation (54.82), one ean salve fee Ko as follows: 2 pe, _ eM Ke = exp [~Fepl Bia ~ Eth) ~ pincy a ‘Because the diffsion coeficients ae equal forthe complex in and the metal atom, ma = mc, ‘An Exel spreadsheet can be setup a shown below . 2 ° 4 FIRTV") sas Eval) 081 En) oF (EacEiadRT Cx? In(Cx") pln(Gx") Ke 0488 41.1736, 010 230259 9.21036 7.corze121 cost 47.9606 050 -as0a1s 2.77259 7a17e3e121 “0566 5036248 100 00 744gcE421 ‘An average of he lst column lads to a stability constant of 7.6 x 10%, Akematvely, from equation 64.82), ar EE, me Zoincy + ine 492) er Hq~ Bip» ak. a plot of nF (EG ~ BR vrs Inj eds ape ofp and an tect fa Ks when ma =e, hincat een ofa gn lends tp = 2.998 = din Ke = 8098 (Gatte = Oot) ore = 158 10S T8 1 wht aes wi oe evi rol Problem 5.8 This problem develops the curent response fra sep at spherical electra to ‘an arbizary poeatial in a solution cotainng both the oxidized and reduced form ofthe couple ‘where the elton transfer kinetics are govered by ButlerVolmer kinetics. The generic form is developed inthe Laplace domain, and then limiting cases are considered and expresed inthe me domain. Limiting eases inelude transient and steady sate responses fr various elecvon transfer ‘as, O andor Rinitaly presen i solution, and planar and spherical electrodes. Hemisphercal ‘lectodes are inlded ifthe bemisphere protrudes fom an infinite insulating plane and the current Toe the spherical elecwodes is halved Fist, consider the solution othe general spherical problem without speciation ofthe surfice ‘boundary conditions. Ths problem is specif in equations (54.33) trough (5.436) andi gen eralized by Fiek’s second law in peril cordnaes(), the ntl condition (2), and the semi- aChapter BASIC POTENTIAL STEP METHODS indie oundary condition 6). o Cones ® ligctiti=o ® (Note that for s homogeneous system inially at equilibrium, lim C'r,t) and C(r,0) ae eu) snral cui atiaraiemenstyiangamacrnere poor Sgro and note lowing: . ® o © ‘Substitution into equation 1) yede the fllowing: 1dert) ~ ape + 160 re >L saeco nice) } 2 = DP vir) - Fe 2) ,eole a = 8) ® ‘Re> 1,6>> 1,and-y ~+ 1/6 Farber, athe system is everible, «>> 8, This redaces te above equation tothe folowing: rides” lea on “This invets with "6 (nt)? oye equation (30, roblem 12 The lysis olen arte ni te icon, 5), cnet of po omni cosh ores Te it spon pts heen FU ads it seta can roapleeemrt= m evai e! Hay (=e). Supepaton can end on dnl pnt dp rane bene) te cab pied ste spun ens ovr apesefOlot © eande Sm tn) (5 al sal ttn code scr pa a ong of ie Sova he fp Tt he es by onion te pt oe ped (Ce ether man ro ocr) the cd pr an be seid wits neg Be Sec cyte ofthe src corre nt fn pure ally, aoc ero slows the ptt eit fncton td (ob entre in «corn Fort 7, the probe i sei pl fic poeta ep toa : ‘ich elena vue Ase pblen vals hestan suc contcns rete) ‘Sipe buthO and Tis war ped prevy toe 510, xeon) (1 280.) _ p POL e0 2B 6 ACRE © 8Ch (a, t) PCL (2,1 Sh = De BED 2 Che. 5 o ® in Chit) = Ce © »(Chapter 5 BASIC POTENTIAL STEP METHODS ot] — nhs sf o = SiO) _ [aE = GOP oo [FF (e/-2°)] © 4 _ p echt ara” oo AOhss| o ‘As develope in problem 5.10 (equation (37), this ied the errent response forthe forward step (equation (5.7.13) where C3 =0. Hs) 2 FAvDe ~ Ji an Ox cairn ino. 4 [op-0ey aFAVDS ” Vai (=e) cy) ‘Aa, fom problem 510 egution (28) he concnbaton of Rath eco tice on he fer ep fon =f PAO = a 0% on inversion, cH0.9 = a ‘Atte electrode surface on the forward step, the concentrations of O and R (Co and Ci respec- tively) are pied, such hat (0.0) = eCh0. Co = OC aa ‘The srfce concentrations forthe reverse step ae ab pinned and ths rigorously specified. These ene ae independent of he cone sled on he oar pense he Sa CYl0,2)= Cf 0.0) = 05 = 6c as Chapter Fort > 1, define a pir of functions Fo(s;t) snd F(z) that characterize the perturbation in ‘oncenztion or concentration dierenial caused bythe reverse step. Fola,t) =S.(NCH lest) 09 Fale) = SDH t—7) a ik’ second law apis sch that aFole.!) _ p,Fole.t) ay oe Be 2Fale.t) _ py, Falet) SPA = aD 2 “Te intial concentrations ae both eet to 2x0 because there is no perturbation due tothe second sepattime = 0 Fo(z,0)=0 a) Falz,0)=0 ey ‘Aso the pretation on the reverse tp wil ot significantly affect the blk coneenratins Ia Reo =o ~ Ba Fates o ‘The surface boundary condition i defined by the change in concentration brought about by the revere sep, a5 well the temporal shift embeded in S(t). Fol0,t) = (0) [Co -Co] Co) u(t) = $0) [Ca ~ Cr] es) “The total lx of and Rat he elecwode must be conserved 28) ted = ie nM ot aChapter BASIC POTENTIAL STEP METHODS arate] oe L. aFote.] arate] Male : -o dine 4| . Given equation (7), @ “The rhersurfice boundary condition isthe nerstian condition, specified though equation (1). ‘By analogy tothe solution forthe generic semi-infinite case presented in Problem 5.10 subttion ‘Lequasens (20) trough (23) into equations (18) and (19) yes the folowing expressions = ‘coordinates Fe0 = Avse0[-/ 54] Falz,e) = Bls)exp - Va] es) oo “The Laplace transform of equations (24 and 25) and substitution of equations (28) and (29) yes A(s) and Bs). 7500.0) = ep(-o7) BE = a0) Fails) = 9-0] SRSA ~ woo Subeiion of utins (16 an 15) ye 1) =e A= Apliation of equation (27) generates the following = VoD eve] 22 = adipex or} BSA “This ie solved find Ci era TF a on oe oa 3) oy Chapter 5 ‘Note ha equations (13) and (14) yield the expression for Ci an thus on n= es C5 Co Se oo eee sine es - L] = a= SHH Substition into equations 28) and 29) generates 14 nen] ee Fe.0) = 00-54] en Finn eoo [fF] tee] oo ese Tole, s) = OF(e,s) + Folss) Talz,s) = Chlx,s) + Fatz,s) py ‘The total current on the reverse step is then define 35. 2) __p,&atas) __p Shea) _ p, oFates HG) = pale | - 0 ieal a From equations) nd (10), Bo. 1) _p, oF EA ~ nFAP® or | a _ WOSI G3 ), pew 1 = bse “ - le coympeelcel [1 -_t BF) ove" [ne ral oChapter BASIC POTENTIAL STEP METHODS eovroeelgtl ft. Siew ise Or upon inversion fort > 7, equation (5.7.14) is ound et) arate” eam ler) + Ba lecee] a 4 at NFAC3VDo ~~ Tatra * Fat a Problem 514 From ‘S14 From the dita inthe eatin of Figure $3. 0% 10° moliem®, A (10230 cm?" = 5.1 mean, for te rf a and, fora plot of Qt) vs. VE tei pce es a FQ). VE espe 35 1"* Ca te) = mPatycs [3M — oh ] 6810) exposed nem of equation (819 the intercept, although with larger ero, ee INPAlyC5/ UD Per eta ATR Note ial od om 174 ms", The slope of Q(t) vs. vi is pRB AAO Ce 0.174 meV V0 108 ms y= a FR BR UOD an? x (9AB5 CHmal)x Om IO malo = O0REM/s ien3) J Tis alu apes wel whe vat vp a a bu 0f 0116 00157 em Chris Lauer, and Osteryoung (JEAC 7, 60 (1964)). aoa ” Fratlem 816 fone Cade eh eto of Figur 583, fr the fred ep he dap i 980 x 10-4 $1 10-7 C. From equation (5.82) forthe forward hep the hae ‘2nFACR VDE a= es Oa + nl AE gs nF AT 42) From Figure $8.1, = 1, A O18 em nd C3 = 0.95 x 10-€ oem. The poteta) Chapter 5 stepped -260 mV past BY, so thatthe sep sto the mass transport limit. Ts, frm Q) vs. Vi, stoped (050 «10-4 o/s) vt > Do = | SFRcg) ~ [FTX (BEE C]mel) (OOTS ant) (095 IT malo = 252.10 an"/s o “ypc values of eifsion coeficiens in soluton are ofthe ode of 1° 010-8 i, with ‘Tae cocticit nos volte (ess com) organics fer than hee in water. The mot ‘SGmmon source oferorncaeuating iisioncoeicews suing nis of Mnnend of moom* forthe concerto ‘compari of equtions (582) and (5.86 dae athe hopes forthe ovat and reverse ‘pr stold be eq i he tye carter by simple mss resp limited oxidation and eRe ‘Th pe repre forthe nanon abot 39% lower an at orth rein, The inercep fre edvston and onidaon ae, especie, 7.9» 10°" Cand 6.6 x 107". ‘One posible cause of the diereces ales ad intrep ist te onde species DCB Stade where he eoced seis DCD? ela doesnt aor or adsorbs ls than DCB. 1 {fe noe exces for two fos ier, ten hs reece in te dierene inthe eres {ore frvard and revere Spe Ife adsorption associated with he forward tpi exensve Sought can cis th cancnaten prof suey hat he cosenexion prof of Rs ‘Supe tom hat expected fora simple mass anspor ited ection. ‘hn erative reason for he erence nthe slopes is hat DCB is bring consumed ough 2 ‘Mesa reason so ut is cononation ils an ta of DCB, ese, the orl potas Sheedy agate that race oxygen cul rac with DCB™ Problem 518. (0). uation (53.2) applies fore spherical electrode, bu for # hemisphere em- ‘ed ina seminiteinsting plane, hal he current is generated. The steady-state eurent i redo find the diffusion coefficient given aadius of 3.0 x 10+ em, concentration of 1.0 x 10° smoven?, and n= I 4 ap, ° 15x10 A SE ee FH KT BAS CTA (LOX 10 ley BOX TTT em) = 50% 10% om/s Do = (0) Anal. Chem, 642293 (1992), tables are provided for determining the standard hetero Sous rate costant and transfer coetiient fom AE), and AE q. For the values of AEs je = Bon and AE, = 315 mV, is found tha, = 0.38 and d= K/mo = 3.95, where so = Dojro = (3.0 10° gr [s) [5.0% 30-# cm = 0.01 cm/s. Thus, KP = 0.0885 ars 4s6 POTENTIAL SWEEP METHODS Problem 62. Equations (6.28) and (62.9) express the surface concentation of O and Rin terms ‘of convolution integrals ofthe cure. . 1 fa Colt) = C5 — arate | Toe @28) 1 Cn. = ee 629) “These canbe combined to yell equation (6.426. DY*Co(0,*) + Dyx?Cal0.1) o {cg -—b a [ tae] 4 PR = PO - eayRDe | i= 7""| * wPAVRDR, = Dice Problem 64 The expression forthe peak cuent in cyclic voltammetry under reversible condi tions i given by equation (52.18). cue MP ADYiCS a1 For chronoamperomety under mass wanspor limited conditions, the Come equation (equation Snipes toe AGE gay Experimental dst for cyclic voltammetry and chronoamperometry ona single sytem will yield ‘both (0) //S and (0). The ano of these two parameters yes an expression for determining sn vithout knowing A, Do, and C5 RE aye fen gl _ cuusay Frnt ADs?Cs ion ”(Chapter 6 POTENTIAL SWEEP METHODS. ‘The above ratio sequal 1 4.9950! ot 298K. ‘A similar procedure is not suitable for determining nfo iveversible reactions, bt does allow the ‘wunfer coefficient, a, to be detemined. Far an reversible system a 298 K, where the rte deter: mining step proceeds by single electron wanefer butte overall ress procedsby neers, ‘quaton (65.8) is appropriate. For comments on he incorporation of nin equation (63.8), se the text on page 236 just before the start of Secon 64 HD = (2.99 x 10°) ny@ADY"05, 63.8) ‘Combination withthe Cotell equation yields the following, which allows the detemination of for ireversble electon tanses independent of n, A, Do, and Cs, The nghtmos em applies 208K. (280 108) VaADY"CE _ (200 x10") VRE _ 1 ov AB ES, oF o Problem 66 Within the potential window of acetone, benzophenone (BP) can only ber ced and TPTA can only be oxidized. The standard potentials relative to SCE ean be fund ‘ec. (2) For potential scanned from 05 to 1.0 V,TPTA is oxidized as TPTA = TPTA* + eas forma potential of approximately 0.7 V vs. QRE. As the potential is seamed inthe reverse diction fiom 1.0 to 05 V the radical cation is reduced to TPTA. The peak heights, measired fom te ‘baseline forthe forward and reverse scans are the same, consistent with no honiogencous rea: ions ‘The peak spliting i about 100m, above the approximately 59/n mV expected for reversible ecton transfers (See the bottom of page 241 i he text) This peak epliting is consistent with ‘quasrevrible elecwon ranses fr scan ates normally accesible st macrosopic electrodes. For the potential scanned from -1.5 to -200 V, BP is reduced (BP + = BF) with formal _oiental of approximately “1.8 V vs QRE. As the potest] sean destion reversed the radial nin x oniized bac to BP. The measured peak eights ae the same, again consistent with no ‘homogeneous chemical reactions. The peak spliting i ~125 mV, consistent with quasiteverstle heterogeneous elecuontansfer at can rates normally accessible st macroscope dst, (©). The curentin his potential range i decaying because the cutet is st by the mass transport limite, linea ifsin of te reactant (TPTA) othe planar elecwode, Tht, the difson contol ofthe current for Crprg ~ Oath elecuode surface causes the crrent to decay a8 2 Under ‘mass tansprt limite, tnerdifsion, the fux of maser] wo the electrode deceates with time, 8 dos the cunt. The sume eet is observed in potential step experiments (Chapter 5). Inthe «yelievolsmmogra, his portion af the cure i alld the ifsional a nd asin potential step ‘experiments, te curentdesays a 27 “8 Chapter 6 (© Note that he current athe sar ofthe voltammogram i essentially 2e0, consistent with Hise ‘harping curent Thus, the cuenta observed at ~1.0V are consistent with difsionl tiling for the reduction of TPTA™ and forthe oxidaion of BE. The current at~10V is set by charging (rent sb well asthe residual iisonal ling forthe eduction of TPTA and forthe gxidation orn Problem 68 The cyclic volammagrm in Figue 6.10.3 is consistent withthe chemically r- ‘erable rection and oxidation of enypen. Te eakspliting of approximately 130 iV conse {Gntwith quateversble lctontantr lines on yc etme timescale for ane le too process The sampledcurent volamnmogram providesa linear plato Eversu log ig — 1/4 whe slope of 63 mV, consent with eter a everible ora highly aveversble elecuon tans- Ter in Sedton 722, foran inverse cleeton tansfr unde polarographic editions, equation G27 shows a pot of E vers log[(y~ 1) wil havea slope of 00542/a, For reversible elec- {fon tanaer kinetics one sampledcurentvollanmetic (le. polarographic) timescale, ua tion (1416) applies andthe expected slope is RET. As he response on eye volamrnetric timescale Se quacreverble, and he timescale for polarography is longer, he reversible nals SS opoprt for he polarographic at The ESR signa maeates tht he reduction product 2 radia ‘As small amounts of methanol are aed, the volummogrem shift toward postive potentials and ‘he forward peak increases in height wherea th reverse peak decreases, Thi behavior is consistent ‘witha chemeal reaction between the methanol and the redcton product. The limiting behavior Sh the poseace of methanol shows tat he reduction proceeds at-0.4 wots (far posive of at Found fr onygen sone) The polarographic creat is twice that found in the absence of methandl “The slope of the wave i 78 nV. These rev dicate that i the limi he reduction product is consumed by reaction with methnol A doubling ofthe limiting eurentis consistent with twice fsmany elton beng transfered in the presence of methanol, (@)- Orygen i paramagnetic spcis with Wo unpaired electrons. The redution of xygen with ‘one electon least the formation of superoxide (O;"), a species wth one unpaired electron that ISESR actne. The two eleczonredsetion of exygen leads to peroxide (OF), whichis not ESR “tive. Ths, the reaction being considered is 2 "e —= O;- (@). When methanol is reset the data are consistent witha doubling in the numberof electrons ‘Sensfewed. Consider equaton (72.1). Under the mass anspor limited conditions of limiting ‘Curent, the surface concentration is eo. The current is doubled compared to tat in the absence ‘of methanol, but the concentation znd otberexpermental conditions Fave remained te sare, so ‘nisdoubled. Te rection of; with MeOH wil shift the wave to posite potentials, The two ‘cevron rection of onygen lead othe formation of peroxide, as shown below. ”Cchapter6 POTENTIAL SWEEP METHODS Onten Or OF + McOH = HO; + MeO Ho, +e = HO3 HO; + MeOH = #03 + MeO intent with quasieversibe election (©. The eelic voltammogram shown in Figure 6.102 i consistent wih ibe (Rist knees The sampled cutee volsmmetc data ae consistent with an almost reversible ‘leon transfer as shown by the slope of 63 mV. The tinestle fr sampled current votanmetty ‘Sonera the timescale for eelie voltammetry, and the diffrence is sucien hat oxyBe fedoeton is quasteverbleon the shorter timescale tn unary oxygen lone undergoes oe elton eon sieoxie rail non. Ob o seestamamct ume, du aon guerre; na sampled caret vlan {2ipeitoeang) Snes, Sedation oor epee of etal, he 7 TeseeeeT to seon retin tf ee. The econ ofthe econ pot ih ‘Rofo sf he econ ole extone potentials The pelagic dan sug tha be etc forth proce res thn ees ‘he diferencia oxygen estonia he absence peace of rotons ihe in is Fraser oxen rere by to ofr lrtvors eer peroxide or wate. Super- ue ot gece. Problem 6.10 The polarographic data mggest that the electrolysis of is reversible forthe reduc fon Th eyelic voltammogram in Figue 610. indicates hat canbe oxidized at approximately (075 V and vedaed at spproximately-.5V. Both waves are consistent with no homogeneous re (a) Hea be oxidized to form I, grenradial cation as india by the ESR signal. Inte Exp ™ +08 V vs SCE “This canbe reduced back tI. From the eyti wollammogram, I can be reduced to forma agents chun of radial anion I~, Ire Biya “146 Again, hss consistent with an ESR signal. The radical anion can be oxidized to regenerate The pei volummene wae at print +05 Vis coset with te etn ( (275 Recon tate oases Cltoonreteble poss an ested by apes iting rapt mi The sn ine of ogee exc The wave apr SET Sota ao chenaly eee The peak ping sppotnaey 190 mV fre ‘itclon eve whch sugges qustocrbleirereble mute ta reacton This partion SEIT prmctrvquton ©55),80m blog aproxiaty 01010 Chapter 6 (020 or Ais approximately 0.21904. The a0 ie, F, 1) i approximately 0.6, which sogget, fom results in Figure 6.42, that r= 0.3. As the Sfusioncoeiiet and concentration of remain the same, this is consistent with slower Kneis i the reduction of L (9. Forthe reduction, te cylc voltammogram has peak spliting consistent wit quasieversible (Gpprouching izeverible) nets, The slope of the wave ofthe polarographic experiment is 59 |BN, consistent with eter highly imeversible or reversible elecvon tansfr. For an ieversble process, equation (7.2.7) elds the slope of .0542/a. For 59m, this yes an a of 0.9. Such [renreme vale of he tanefer coedcient wou ead oa highly asymmetnevollammetnic wave ‘The wave shown in Figure 6.105 symmetric consistent with a tanafr coefficient near 0.5 or 03 as approximately calculated in part (0). The polarographic datas consistent with reversible clectron transfer The quaseverible behavior abrerved under eyelc volammee perturbation consistent with the mich faster timescale sociated witha measurement st $00 mV. The term reves charactenzes assem whee the ate of heterogeneous electon transfer is 5pid ‘compared othe rate of wotammetre pertrbation. Chemically reversible refers toa process where there ae no chemical reachons tht perth the concentration ofthe eletoactive species on the tessa ofthe measurement (@. The fusion curent constants deseribed by equation (7.1.11), arearangerent ofthe Lovie ation. aay Fora difusion coeicien of 2x 10" cm/s andm = 1, thi yields (Dax ents 317 (For the reduction, te pea spliting t $0 mii about 190 mV. From Table 652 this yields {oF spproximatly 04, For Do = Dm = 2% 10° om/s,eqeton (6.5) reduces to 1 = VeDoPO]RE =o BRID ov 298 K @ Here, K® = 0.005 ems. For different san rates, this canbe used to calculate and the find {By from Table 65.2. The peak curens are calculated using A'~ Yy/ to find K(A,a) from igre 6:42, which in tum yee the peak current rom equation (6.6) The peak cuents for the reerible oxidation are alulted using equation (62 19), the peak spliting is pinned at 59 mV. Allow a= 05: C5 = ImM; A= Lem?;n = I, Plots off and AE with v are shown below {for both the oxidation and reduction of I. The reversible oxdation process is marked as closed 11, Xis ‘consumed uch that, consistent wit equation (84.2), Se meayBi[% -cx000} O) Noe thts = £4. Fort > 7th ttl euret rat nth. ra += BFF = mB AV IDI[B ~ Coo, + maPAVEBR| [P-ee>] ‘att 11472, Col0s4) = Cx(0,) = Oand the shove reduces to BG a mpacoy/2 + mac © ea BF FACS Im, Di + nVBi] » Upon erin, nt BAD dBi env « But, 7 = Im. FAYDICG /BV¥. Ths, anak VDC; Beal fePiCe ay Ung Dj = naVDi, then ry 72 Problem 8.6 From eqution (8.71), the chage on Cin AF setby 10 V batery i found, 4 = Cry xV = 107 F x10 V = 10°C o 1 nF and Cy = 1 uF, the charge is conserved such that a= aij tau =10-§C @ ‘Also the voltage drop aro the two capacitors mt be equal. Tas, Sos = ey Ginj ~ Ga" OF sy Solution of two equations in two unknowns yields qu = 9.99% 10-* C and gay = 9.99% 10". ‘Thus, all ofthe charge i delivered from Cin 0 Ci ‘The total capacitance in the Figure 8.9.1 circuits found as follows, 4k eet ray tan ww awe o Cre r o “The time constant r = Ror = 100 0 x 10°? F = 10-7 s, From equation (1.2.6) the cuent for charging Cy ops io 3% of nil vale at ¢ = 3r and 1% of is inital vale at t= 5 ‘Thus, Cut 98% charged in~ 3 x 10" sor > 99% charged in ~ 5 x 10" ete ts Fmt S21 io =nPAbecs [ze +2] ous ‘Substtion into equation (8.74) yes the following By) = Be=0 +d [uderer a 6(Chapter8 CONTROLLED CURRENT TECHNIQUES = Bens AR fhe 5 = Bea ADE Le zy - Bie = 0) + ADOC | I +4] o Then, AB = 51) B= 0) = MEACEYPE fy, vETEH) © epetstn tooweormsnanncn roCa soa ince of nP ACV D5/VACe " ‘Problem 810 Barker studied the reactions of solvated eleetons in acid oltion. When no NO ‘was preset, ug traveled into solution without racing to produces species which could be elee- tulyzed at the eectrode surface andthe potential decayed monotonically a the epg dsipated the vicinity ofthe elecrode. When NaO is present in solution, the solvated electrons react 0 gen- cate OH". The radial is readily redoced atthe electrode asi difuses back wo the electrode ‘penerate an ational electron ranfer reaction and nua the poten 9 METHODS INVOLVING FORCED CONVECTION - HYDRODYNAMIC METHODS Problem 9.1 Information forthe Rotating Disc Eleevode (RDE): 0 on A x (0.20 em)? = 0.128 en? ents 0-2M = 10- molfom® Da = 51 {f= 100rpm = 100 reu/min x 1 min/OO 5 = 1.67 rev/s w= 2nf =n x 167 = 105 2* y= 001 eni/s Ateea (@)- From equation 839), “fee, ° reson ‘ty = 10° om andr = 0.2 gm, equations (1) and (2) lend, respectively, 0 vy = LTA x 10" cm/s and vy = 3.88 10-¥ cm/s 0) Atetectrode surice, where y = Ondr = 0,25 = vr =0. (6. The values Uo ie Sa he Levich constant are calelated a fellows. From equation (93.1), = ~o.s4sr (wn)? aay ns, tent = 0129 en/s “Chapter 8 HYDRODYNAMIC METHODS. From equation (93.22), fe = O6mPADYM VCH 032 (0.62 10.126? (Beat) 5 (1054-1) pa Oorentjay 154 pA From equation (9.3.23), mam aatieg ® sstxiorta - RRS CY rmal) (0.126 em) TOE mak omy = 127 x 10™* em/s Fromenutin 9328, a= 2 © = FESHES - sor ten From ae 38, Lech Contant = i 6 134 10-F 4 A755 G05)" 0 motfonsy S78 AP oni /met ‘Problem 93. Ths problem is based on the data in Figure (9.38), From the Figure legend, f= 2500 rpm = 2500 rev/min 1 min/B0 ¢ = 41.67 rev/s We tefaPe x Aor em 282/s w= 62 ‘Auelectrode, A = 0.196 on? C5, = 1.00 mM (saturated) = 1.0%10-* mol/em? (024 Hs0 + 2e == HOS + 08 na? (0) The Doin 01 M NAH i fd om ie i — Fea in Fgwe (3.80, whee a 6.5 x 10~* A. From equation (9.3.22), “COS be 8 TaRAN TCG, © aa (65 x 10-44) (0.016m%/5)" TaD WEABC] mat (CAseamt) (16-26-77) O-Fmal ® (@), The Koutecly-Levch sution (93.39) shows that a graph of 1/i,e versus w/ends to an Intercept of /ix. rom Figue 9.38, the intercept at 0.78 V se 4! = «i? m2 mA, This yields = 83% 10" A. From equation @3.38), W) = ER, ° 83x104A TREC al 0 De) TF) 22x10" em/sat075V ‘Problem 9. This problem is based on Figure 9.102, which features RRDE voltammograms for the reduction. Fe(CNE + Fe(CN)S ‘The data provided areas fellows. 48.6 reu/s DnfaIn(986e)= 905! WNT C= 80 mM = 5 «10°F molfent 0.188 cm = inner rai 5 = 0325 om = outer radius #31} = (032K) ~(01860m)? = 2.77 «10°F ont (=r)? = 0287 on? pe O01emt/e HE = 215 em jor (0 From Figure 9.102, oChapter 8 HYDRODYNAMIC METHODS ae Ego se From equation (94.19), y= -(5%) oa) = (Bias From equaon (945), py = fate dink (4) ® 062 x DBRT 5 O87 om? x IT = arr tot ent Do = (421% 10- omt9)028)7 = 5.8 10°F ents » (From equation (93.22), 4a = 2c 2 = companys o 0 pA y preva = 73a? (©. Values for ince td ine $000 rm ae found ough the ropa (9.3.22) between « and w/?, ‘Sus fom Fe 102 aed , an {= 8000 reu/min = 5000 reu/min 1 min /60 = 83.3 rev/s J = 2x x (68: rev/s) = 52256 1 GMP mga? 229 99 fg 6 tose 90QUA 5 4A ® chapter 8 trio n= eh x (BEM) masta © 20) inalio=ozs) nd (BA) =a5t ma © ‘Problem 97. Atw = 0, the Cotell equation (5211) holds, und for > 0, he Levich equation (053.22) olds. The ratio leads to Wa aPADMAC ga w? aOR | _nPADG' CER? gowitp5¥* ® Ua DeanFADE PCS Experimentally one must surat the Cte measurement is made unde te limiting current tonditns and inte seer ofcomrectve eects, “Terao snes mas tespot ied leroyisand te sme date aye phenoment 9- ‘Mbit bob measurements ere ane herpes or homogeneous kn effects. Sinee ae capa menses an tober» test esucen, thi cnnot bee cae Se hed ers foes whee re sen cis and he OOOO Uy Ess chen fort > Rs Ci ott Gvbl lye elects dono nerf roblem9.9 From the discussion in ection (9.3.6), the lower rotation Kimi is > 100/rf © were ris the adi of the disk. Forv = 0.01 em2/s and ry = 0.1 emyoo > 10.6%, The upper Timi for is goveed by the onset of tublnt fw such th cB 1 vfef 2108 6? ® In practice, howeves, the upper imi requnty at 10,000 rpm or = 1000 4°. Therefore, he ‘ge oft in RDEW 10s" < w < 10005" coresponding wo ties of | ms 45° asus decreases A plo of cot # = 1/tang vernus is shown, Note that £ = Eyyp = E° when Do = Dri then, # isthe operative heterogencous ate. For these conditions, equation (10.525) applies, and itsimplies as shown for D = Do = Da where 8 tn, = 0325) 1.30 2 120 3 8 410 1.00 0 50 100 150, 200 250 300 (7) Regression yields cot @ = 1.08 x 10-94% + 1.0000, The slope = y/D72/X°; for the values here, /D/B/l = 1.08 «10° #72, Consider Figure 10.3.3, which shows th el nd imaginary vectors ht define the response for f quasieversibleelecton tanefer The el vestor, measured slong the same vector 25 Ee for 1 phase angle of is Ry + 7/u%/2, The vector 90° out of phate defines the maginary Term, (2/8, The rai ofthese two terms defines cot. From equation (103.9), Ratofo'l® © cory wRc, = RatcieeChapter 10 TECHNIQUES BASED ON CONCEPTS OF IMPEDANCE ‘Thus the rato ofa current measurement onthe real axis made at O* displacement with respect to Bac anda second current measrement 90° out of phase (guiratre cue) wil yield coc [Nol tht this assumes effects from uncompensated solution resistance and double layer charging sre negligible ‘Te make a good measurement of &, the frequen must be high enough tit he measured value ‘of @ must be less han 45". AS above, this condition ie favored by higher Requency (ster re, ‘surement). Here, fequences greater han 10 Kl are needed to rece @ bya least one degree, (Commercial nstumetation is avaiable at generates feguenccsof20 Mile Problem 10.10 Consider the cic in Figure 10918. The data are tobe plotted, as shown in Figure 109.3, 8 The objective i to id te impedance fr his cit and to consider oly the rea pat ofthe impedance, a icone vith dat i the fon ofZ(o). Te needed impedance cession we 25 flows, Fer pall component the reich tal inpedanc bet y sm of oe ‘expos impedances. Fors parle sir (Ri) nd coacior (Ce impedance expend 1a 27 Rt o For components in series, the tal impedance is set by the sum ofthe impedances. For a esistor (Ry) and capaci (C) series, 1 BD, ® ane ° ‘According to Figure 10.2 and the discussion on page 412, the values of R, and Cy ae found fom the high fequency data. It wil simplify the analysis if hese cucu elements sr cllesed with he wal impedance Fis, consider he circuit shown in Figure 109.19 ae series circuit where Re iin series with an impedance Zp et by the tre parallel components, Cu; 2 in series with Cand Ry i veree with the parallel components, Cand Ry, Then, 2a Ret Ly o Zope Z—Re o * Chapter 10 Second its ow posible to consider jus the thee parle components. Decompos this circuit ino oo parle ingens, oe ty Cy a Be bye remain two nce, Seced fs Zap As Ce ad Ep ein all, 2a ond ro ew of repo inpelanes & © Fy HOt Ze ‘Then upon substi of equation 8), o ® From the discussion athe botom of page 411 tough page 412, the resistor R, has only a real ‘component, bit he the component re complex (Acpndent on ju) and hus fave rea and rag- ‘nary parts. For the eal part, dependent ono, te eqution (23) becomes Z 8 Palo) = oe o "The data plone in Figue 10.9.3 ae of this form. Ieremains to reduce the circuit characterized by Zip 1 series RC cicut. Consider te branch composed ofa parallel component of Cy and Rey in series with My. Fis, reduce the parallel ‘components of Fm and Cm tan impedance Zy 3 aod papricn 9) Hs ‘Or upon taking the reciprocal and using the complex conga to segregate the ral and imaginary pans, ——— ay = — fa _, _ j_ Onn ay T+ CuK)? °1+ (Cm Fe)Chapter 10 TECHNIQUES BASED ON CONCEPTS OF IMPEDANCE a “Te circuit snow ofthe form shown below. ‘The impedance Za is composed ofthe two components Zand Zi, such at 1 +E a6 > e ae Re i 7 . 14 (Caf)? WAVER THC * Roa hfs wai] Oa, = Lect? +All aha) C0 ca Beg + Bip [1+ (Cp Fieg)") + WACLR CF + ju [OL (Rim + By [1+ (Cen) |) ~ Om) R » nnaepebgqecm racine ome eon sm stem | aT aca ORR ec mo Te impedance Zinn with sch nt sip. X = 14 (Ca 2 = Zn le ro) : - a X + uCLCu RB, + j0Cy [Roa + RX + RX] Rat Belt Cat ~ Cat Zag 7 BaF TGR FHCRC IE 4 6(CLR, Fin FRX) =e]? 1+ (©OnRa) (0, with pplication ofthe complex conjugate to break Zap into the eal and imaginary pans, consider the banchcompord of R, an Cin series, The impedance ofthis branch, 2, ng = Bact Bp +°CLRCal + [CR (Re ReX)~ Cn) G9) to = XT PCC, + FOC [m+ REX + RX] X22OCal— uC + TX +X] “ "XH HCG Rey = oC Pn + OXF REX] = nt ByX + WPCRCnRE] [X +u?CSCml “The circuit now in the flowing form: [+ ACEC PAI HRC? Man + RX + RX]? 4 PCLICLR, Ren + RoX) ~ GaP] (n+ RoX + REX] Ce DXF ACEC + OPCS [lg + BX + HX m jul at aX) ~ Ca] [X +02. 1 ix FuPCLOnRE) SWACG [Rm + RX + RX} R ju CilBen+ BX + RX [Pet BgX AC REC] i + POC aR! + FOZ [Rig + Rp X + RAP (Use of Maple doesnt simplify this expression to any more tractable expression) EA [Now Zsthe impedance which an be viewed asa resistor and capacitor in series, as exemplified by equation 3), where 1 Pip = Ron oy, a9 5 a(Chapter 10 TECHNIQUES BASED ON CONCEPTS OF IMPEDANCE ap = Hin tHe HPC Ga [N+ PC.CaIE| CSIC + aX) ~ Cah a he X 6X) ES ACLC mE BCE + FER? @) [enti t +WACS Rn eX ¢RLAT a ‘ei J ‘he dcuion ov pag 412 fer a ses estan capacitor shows tht he el prt of ‘impedance is expressed by equation (10.9.8), as modified for this circuit. = Bera From enon), 1 1 Fe PH) = Ra ae @ Tha pl sown in Fg 1093 ya peo C5 dn necp ff, whe 1 Ry asin capecitve td restive elem tt chases he ae hee Satcncwr chan oa ae Fm te the ih ey eps hats Rn C.F ow equ ‘sponses, equations (20) and (21), where as w + Oand X ~+ 1, yield a Ral y= Rat Re es Clg a5 Tali equi, Zo) it by te esi congo i te ch eed by Za, Ths promi cae tw Rese, ep che tnd eet lowe gece pus mca ey conic poate eg vers en Anette uc, cope abo Cs BC fa dependent gee as fy ind Maps he snapon wap accu eee Feat conpenate hye cane tcl wi dames Spee oy By = Pn BX 5G 11 BULK ELECTROLYSIS METHODS Problem 11.1 In this problem, So is tinted with I using oneelecrodeamperomety. AL the following fractions, the species in solution are as follows: J Speciesin Solon athe Start of he Tirtion Conditions 0 nly Sat os sat, Sa 10 sir" cay Sots te ‘The ~ E curve below is shown a diferent actions fof So? tated, ‘A platinum electode held athe potentials ised wil espnd tothe corresponding half-reations: Breetrode Voge (V) Halt Reaction @ +02 pt 20-21" and Su? = Sut + 20 ® oT yt 2e 2 © 04 Sot +2022 Snl and It 26 = 21 ‘These potenti ae indicted on thet ~ F curve with doted lines. The tration curves ae shown below oy(Chapter 11. BULK ELECTROLYSIS METHODS Problem 11.3 In this problem the use of oe-lecwode potentiometry involves the measurement ofthe potential ofan indicator elceoe with respect to aTeleence electrode with sal cathodic ‘umen pplied othe indicator eleeuode In two-eleewode potentiometry, «small const cent ‘pplied between to polarzableelesrodes shuld be the same a the anode and the athe In problem 1.1, Soi tiated with. Shown Below isthe ¢~ curve at various factions wit the Impressed anodic and catadic curents shown. In order to draw de tiraion curve one nests only to look st where i and ig intersect the i ~ E eurve and extrapolate down to (for ne electrode amperomety) and A (fr two-electrode smperomety) onthe comesponding feurves, | 1 | swtezise boon f g é “The tivation curves for Sn tivated wit I ate shown below, Fr the oneeecre tration, E fran impressed ic was wed. Chapter 11 ‘The shapes ofthese two tration curves, forthe case where one ofthe redox coupes is not re- _veribl, fer fom those shown in Figure 11.53 (Editon 2) and Figure 10.54 (tion 1). Problem 11.5 (9). Atthe Ag elec, Agel salt] ypt0 100% Ag Ag te > 100% 1°) = 10% 10-? mmol mmol T= = 1.0% 10"? mmol. x $0 = 0.080 mmol rom equation (113.11) Q = nFN, aay 1% 96485C/mal x 5.0% 10-Fmet Thus, for t=1006 i=482mA 2002 t= 2I mA ee According to typical applied curent ranges and tration times cited on page 433, app = 4B A ‘over 100 # woul be sable. ‘hei — B curves at outing Pelecwode would look as follows: Os 85Chapter 11 BULK ELECTROLYSIS METHODS cvescey ‘Problem 11.7. The assay os wanium sample can be abbreviated as follows: Uren 28 uogt #20 wre 2, yt © (2, Ader texans), where 0 2 Ue ohiion contains [0] iM. The folowing 86 species ar alo added [Fe] aM [Ce] =50mM [1,805 =1M ‘The gol isto sketch thes = B curve ata Ptroatng disk electrode from -12 Vt #17 V vs NHE. ‘The following halfseactions are considered. Note that for rescon (8), the potential is eaeulated as oulned in problem 2.10 Vor +e = vop Bf =008V os NHE % Vos sat se = UM 20 BY =062V os NHE ° vob saree = ute fe TPL cosmvenns veto a worse gre aS ae 2Fet + UH +210 = Ie +UOH aH? EE, =0495V sNHE Celt rence ee AAV oe NHE © BUY s2ee HEY 035008 NEE ° ‘Note that the eduction potential for hydrogen is taken from the potenti shown in Figure 11.10. Based on equation (7) nd equation (2.129), APE 2% 96485 x 0405 V Ta Kee . 1 HO" S314 aby ¥ 20815 K g) Kan = 51x10" ‘which demonsoates thatthe equlibium of reaction (3 is strongly favored fom left right. Thus for every mol of U*!, 2 mol of Fe are used up, 2 mol of Fe" re produced, and | mol af UO3* ‘is produced. Afler mixing the key solution component are [ret] = 4ma—2mM = 2mat [re] = ama [we] = 0 [o#| = 1mm [ee] = somaChapter4. BULK ELECTROLYSIS METHODS. “The iB curve would look as shown below. Noe that the knees for UOPT/U ar slow and the reduction wave occurs outside the potential window Zea a 08 EWvveNneD ++ Uo,iU* is somennat reversible and oscurs at mare (+) E (), The chemistry i otined in pat (2). The coulometic ration wil ivolve the oidation of Coie Cet ata Pt lectodefllowed bythe eacton Ce!* + Feb — Co*-+ Fe, (Forte follwing stages in he tration, the concentrations are Percent Titated ron Species Cerium Species ° Upet]= (rer) amt [ce] = 50mm 0 (re) = 3M [Fe] = 1mM [Cet#] = mM [Ce 100 mM [Cet] = omM: [Co 150 mM [Cet] =ImMt, [Ce] = 49M iso ~02 evened (@, Amperometie titaton curves (Chapter 14 ‘+0av Tosy 2atectoder com . 7 +13 y cae (Ws NHE) +09 +07 u 10 7 Problem 119) Three potentials were chosen: (0.0 V, which sin he vicinity ofthe Fe* +e —oFe* reduction (09, whichis inthe vicinity ofthe Fe** ~sFe}* +e oxidation and the Cet* +e C* exidation 1.7, which is inthe viii ofthe Cet> — Cet + oxidation »Chapter 11 BULK ELECTROLYSIS METHODS “The solid ine denoted corresponds to the situation where the mass transfer coefficient forall species are equal whereas the dashed line shown as (b) coresponds to the situation where the ass ‘tansfer coefficients for ron ions are 25% ager than thos for the cerium species. The increase in ‘he tigation curve is greater after f = 1.0, comesponding tothe fist appearance of the Ce +e Ce reduetion wave. The nation curves mst wef in a praca ation ae those at 0.9 V ‘because the endpoin at f= 1 is clearly at zero. Note ta the solid ines coresponding o equal ‘mass transfer coefficient have ivarant slope, Thus they ce not useful in finding the equivalence poi. Problem 11.11. The constants given inthe problem include: V=100 on? = 01 (ae) = 0010 ar A= 10 ont, rotating disk electrode 195 mA constant = 80 mA x 10° mol/an? (o.ati=80mA, Cums = BOA 5 0010 M mat x10? o one can use equation (11.3.1) and solve for C(t) calelate i) soma Ol = Eas ~ TE x oo OE whee the value for mg wa calculate in problem 1110 agx1oM —@) 90 Cchapr 14 ©. anoles ectrlyeed = (0010 M ~41 x10" M) x04 L “mat 0) sn = SN HAC, rm (0. = 5851 10-4 ma 6485 C/mal = 564.6 (@Fromeqaion(136, BB =e i-n o G0) = From problem 11.1 p 3, At this pont, (5(0) = 41 « 10-9 MM because this is the concentration afer 706. The ine required to go fom thie concentration t0 0.1% of the original bulk concentation or C5(¢) = 10-* x 0.01 M= 10-* MF. This, fom equation (3), 10"? 0.010. aix 1 cote 24 BB- exp [-10%4] © Solving for time ead tot = 6016 « (9. The toa charge passed is called as fllows. = 80x 10-4 A x total me = 60% 10"9 Ax (60164+ 7062) = 5980) ‘From problem 11.10, the total charge pased for /2* reduction was found to be 193 C. From equation (11.2.8) the over curenteiiency is . at 1958 x 00% = BEE x 100% (Overal current efieiency ® ‘Problem 11.13 Consider soliton continng two reducible substances, and Oat concen- trations Cb, and Ci, repecively, where the reversible reduction + me m Ry oscure fist, and then, at mote negative potentials (e.g. 500 mv separation), the reversible reduction Oa + 86 = RR, The soltionisandwiebed na thin layer cell of hicknes [where hee sre wo working ele<- trode, such at described in Secon 11.72. The ine ofthe experiment is much lnge han /D, 1(Chapter 11 BULK ELECTROLYSIS METHODS so that mass transfer canbe ignored an only electrolysis is important. From Faraday’s Law, he moles of 0; electoly2ed are roles of Oy electroyzed = 0 0 atthe O; concentration a time f ean be exresed a5 Couto o ‘where V, the volume, is the product of the elecwode area andthe cell thickness. The coneen- ‘eation ofthe reduced species Ry isthen given as Cn) = ® ‘Substintion ito the Nemst equation leads a 0 itm ee my FV ® “The transition time occurs when the numerator equals zero, hus, causing E + oo-The transition time, 7, forthe fst pecs, ©}, is then = Res ° Jn temerity =i nn tnt ‘he sum of the tanstion times forthe fst and second reactions. That 7 71 + 72, Whee Ty ‘omespond othe transition time fr Oy ands tothe transition time for O since the tansiton forO,, Thus, by analog to Secon 85 fora two-component seminftesystem, the ttl applied vaya NM EME ° en svt aie Fl) ® ‘Equation (7) demonstrates how the tanston times depend onthe geometry ofthe thin layer cell, andthe components ofthe cll solton. This equation isto be compared to equation (8.56) fr the semi:nfinte cae of» two-omponentmixtire, Similar othe eminfite case, as long ashe 2 Chapter 11 4 = E waves ae wel-scparted, the total crrent is simply the sum of the individual currents, The ‘ifrences arise the boundary, where the thn layer cll has «boundary set bythe Hichness ‘whereas in the semi-infinite case, one ofthe boundaries is essentially a co. Ths inthe sem ‘nf ease, mass transfer oosurs by ifson and thee isa D*/® dependency. In the thin Iyer ‘eel considered hee, under conditions of til elecbolysis, there sno mass wansfer and thus there ‘sno difision coe cient dependency. Problem 11.15 As deposition ime inereses, the siping wave becomes more and mare s5ym- ‘metic with rounded humpe developing inthe i ~ E curves. Based onthe etic by Laitinen 10d Watkins (Anal. Chem. 47 (1975)1352) these humps appear to be de othe reduction of rational ‘monolayers of AgBr dell atached tothe Ag surfie. These monolayers would become thicker ‘a depontion ime inereaes, thus leading to the seipping waves observed in Figure 11-102 ‘The main problem present in a vollammec sipping analysis, sch asthe one presented in this problem, tat its assumed that heres are! proportionality between the spping peak cent nd the amount of AgBr leczodeposied. This is generally an svalid assumption beeause the peak shape is ahighly vaable especial formal deposited quantes. One can overcome this probe by measuring the chroncoslometri charge rather thn the pek caret. In eronocoulomeny, i 's possible wo unvael diffusion fom adsorption processes using the procedure in section 5.8, Problem 11.17 Atan HMDE equation (118.1 canbe used io calculate Cy, whee itis assumed that the deposition potential i such haf = ip Additionally «typical HMDE radius of 0.1 em i assured. Thus ite AXS min aFU/Syred ~ Ta deass Z x (4) xr x nis Sg 871 x10" majom? For Cy and iy = 1 pA atv = 50 mV/s, spreaishet can be constructed to evalute equation (11.83) forthe dition cocicient Dy. A vale of Diy = 1.60% 10-® or? i found. Equation (11.83) can then be used to cael the peak current sweep rates of 25 and 100 mV/s. Values (ofp = 0.708 A (o= 25 mV/o)and 142 uA (v = 100 mV) are found, ‘To calealate at an MFE, one can refer to equation (1.8.5) FAC BPPPAAC, a ass) nd note the lines dependence of i on seep rate and Cy. Ths, calculate j at sweep rates of 25 and 100 mV/s one can we the ro ® ®_ se Chapter 11 BULK ELECTROLYSIS METHODS 2025 uk =50.0 6A o be rotation rate of the elecwode i doubled from 2000 rpm to 400 rpm, an inereasein the peak creat would be expected trough the Cy, varable in equation (1118.5) during the deposition period Le. when the rotation rates doubled an ierease in the amount of Pb deposited into the MFE canbe expecied. From equation (2.3.2), this increas wil be approximately 2 times that 812000 pn 0 that a pak current of approximately fOr 0 Im 5 28 2 25 WA x 1AM = 95.4 HA © ‘As fm thickness increases, thin ayer behavior i los, being replaced by semi-infinite inca i= sion behavior soc that y cc w/. According to Figure 11.84 (2), asthe film hicknes inreass, the peak eurent decrease in magnitude fra given sweep rate. Moveove, ifsion depletion sets ino that theferpping peaks ae broader an lee sharp thn nthe ue MEE counterparts 12 ELECTRODE REACTIONS WITH COUPLED HOMOGENEOUS CHEMICAL REACTIONS Problem 12.1 This problem looks t how te eelic voltammogram foran E,CE, reaction changes a the time scale of the experiment is varied through the sweep rate. ‘There wil be two sets of ‘oxidation seduction waves" the fst coresponding fo the reduction A + ¢ ~ B, andthe second (hich occurs afer the homogeneous reaction BC) comesponding tothe redicion C+ € Fst ofall refering to Figure 6.21, approximately 200 mV is needed ta waver a linear sweep wave. Thus, ata sweep rte of SO mV/s, the time required wo eaverse the fist pak s about 4 § 40 halves, so at allo B is converted to C trough the homogeneous reaction leaving none ‘be oxidized onthe reverse Sean, Because all of B+ C, the rection of C+ ¢ =D resulls 8 ‘reversible cycie vollammogrim. Ata sweep ate of | Vis, the Fst peaks wavered in approx mately 200 ms, coresponding to two bles of B, Ths, not lof Bi lor to the fllowng homogeneous rection and slight peak caret is chserved on the eur sweep. The second wave isi everible, but he peak height ae smaller than at SO mVis. At emeep rate of 20 V/a, the time to raverse 02 Vis 10 ms, which s ten imes less han the halite of B. Ths, only a sal ‘mount of Bis lost othe following reaction. Ths, the first wave appears almort reversible, and the second waves reverse but with peak cues ess than those een at | Vi ‘The following voltammograms were generated using DigSim 3.0 (Bioanalytical Systems) by M, [Rudolph and SW, Feldberg. The mechanism was specified a et cee ‘Te np parameters consistent withthe above mechanism are abused as fllows, The homoge- neous ate constant fy = 6.58 5-1 found in problem 122. Esur (v0 Eowitch (Vp -12 Bend ():0 (vi: 00 Aerpereare (K):2982 Ru (Ohms: 0 ca:0 cles: leewode geomety: planar area (ond: 1 9(Chapter 12 ELECTRODE REACTIONS WITH HOMOGENEOUS REACTIONS. icon: semi-infinite pre-equlibrium: enabled foal reactions species parameters Canal{A] 4 0.001 Canal(B) 41: 0 Canal{C} 41): 0 Cana] O47: 0 Problem 123 From the discusion in Section 123.3 (a) and Figure 123.10, one conludes that the mechanism is EC, Atgec BSc From Chapter 6,a reversible yi voltammogram without homogeneous kinetics is charsterzed ty AE, = 50/n mV at 25°C and p/p = 1. From the table accompanying te problem, Gs ‘ebavioe is en ateweep rates of 100 Vie and 200 Vis. At sweep rates less than 100 Vis one esta the Epa vale shifts ina positive direton fom the reverb value at 100 and 200 Vs, ‘gui becomes ineeasngly les than unity, andthe rato ge/v!? changes only slightly between 96 we, Chapter 12, (0.1 mVie and 20 Vi. Tis bevior i indeative of an B,C, mechanism, Problem 12.5 In yeic olummety, fom Figure 65.2, and for reduction that i reversible, Ejjz is located approximately halfway betwen the cathodic peak potetal Eye and the anodic ‘peak potential Eye iespecve of sweep rate. The halfwave potential is defined as (ootnote b ‘oder Table 62.1) ar, (Da) Bnw et + a (B) o Usually Do and Dp are assumed to be equal so that EY = Ey, thus allowing the standard (cra) peta ts doin Howes, Do snd Dy eke ecm Sm and SS (ten 628 for) reper, edt deine By cae ay teen tw vars toyeld 2° Othe usunpns nde n= 12 parle te scing postal ra kaa put td bene ofhonogmce sn bog ie tbe electrode proces is BC, then from Figure 12.3.10, ne ses transition fom acyl wolam- smogram wih oaly cathodic peak (for afedston tox reversible cyclic volammogam wit both fn mosic and cathodic peak atthe rweep rate isstedily inereased. Moreover, one observes a ‘hiftin the peak potetal, whichis generally positive ofthe reverible Evalue because ofthe fol- lowing reaction, in «negative detion (toward the reverible eure) with increasing sweep rate ‘Therefore, inthe preseace of an EC mechanism, the standard potential measured fom acyclic ‘voltammogram would be more postive than the tue standard potent {there isa slow electron transfer toa chemically stable product, then both the cathodic and anodic peak potential are shied outwith espect io the reversible cyl vliummogram such that the Desk spliting A increases. This is llusated in curves 3 and 4 of Figure 65.3. It as been ‘emonstraed [Pl end Leddy, Ana. Chem. 67 (1995) 1661-1668] at By ieaproximately {Qo within | mV) midway beween the cathodic peak potential Eye and the anodic peak potential pe for K~0.002 emi and A y=145 mV at 100 Vs. Outside of his range, the approximation es not ald Problem 12.7 (The mechanism fran EC; reaction follows: tions (123.34 and (123.39, respectively. Let = (ht), A = (fr), and Ag [At the taniton me rz, Co(0,*) = 0, allows the following expression o be writen for the ‘encenzation of species O and ‘ Co Sapir ltr = eran mt)? © Col0.8) = eaprmrTlet(h) ~ et] ® ”(Chapter 12 ELECTRODE REACTIONS WITH HOMOGENEOUS REACTIONS Cni0.9 % ~Col0.!) = aa) ® ‘Substnuing equations (2) and (3) ito the Nera equation east the following expression forthe B-~ tourve for czonopotetiometry with following catalytic reaction. o (). Ask — 0, ~ 0, and 7s ~ 0, so at fom equation (A.2.), the enor function can be Simplified wo o a pops Bea | © ich ot il othe ~ exec ora sin evo ton a en ‘equation (8.3.1), aay (04 As — otis hat kos that ef) +1 and) — and ba hace pon ee at E's ont (2) Eye oes when t = 1/4. Ts, Om /2, ad (i)! (2 a Schaal couon ads” VU aM HME = (8/2 = Nf Bynes o A plotof Bh (Byj« — E) vlog. is shown below 98 Chapter 12 oo EER 10 20 30 gL __.______*# _, [Problem 129 The solution to this problem follows ftom the discussion in Section 12.7.1. The reaction follows exalytic £,C, mechanism in which Met renee MP M+ dtp ‘The pre-elecuoysiscurent (0) is caleulated as follows: 40) = nFAmocs, o c 210-2 5 yg-2 15 96485 S x 50em? x 10°22 5 1 0l 8 904 x10"? A= 4824mA “Te residual cents given a 000 mA otha the comete re-let cient is (0) arr = (4824 ~ 05) mA = 481.9 mA = 682:mA o “The eadysate cen ig = 248 5 mA ota the oected erent is tana = iA ° (2), Te peat et drat const fo thisrection i cleulted ing equation (127.11), oChapter 12 ELECTRODE REACTIONS WITH HOMOGENEOUS REACTIONS © mo 10725 xS0em? 6g = GA 4 Ee 5x0 © 0.08% = 26x 10 + o (@), Under steady site conditions, time t ~ co. Ths, equation (12.79) can be writen 8 a —_ Clos) = Choo) = 2] ® snd equation (127.8) 8 Gis) = Ginn) =C- Goi afi- 2] =oit-0m1 05 Cins(00) = 0.95 « 0.014 = o.008594 Problem 1241 Figure 123.2 sows css vlammograns forthe CE, mechani where Orenc ‘The relevant constants for this problem ae as fllows: C7, Do = De = 10-¥ emis, K 10-5, hy = 10-85 by (@). The approximate concentration for species O atthe start ofthe eele volammetrc scan is found from equation (12.34). cx Cols.0) = Fay o B10"? Mx 10-3 "7 mal PRI oct tot (©), Assuming thatthe preceding reaction does not affect the shape ofthe eyelie voltammogram, ‘he peak cient i calculated from equation (62.19). oo" 0 gated tents ot 2)" 4 2 fo¥]arercieta 09 Chapter 12, ‘Tis peak curent i Figure 1232 fore —_ god agreement withthe peak caret of (2.7 ~ 29) x 10 A observed in Vi13 DOUBLE LAYER STRUCTURE AND ADSORPTION Problem 13:2 Consier equation (133.10 (@) 2258 [= (8) -] sai pee tye en (2) = 2B (ree) - BF) (4 = AE fea (38) =] 28 0 (2) wert apie eon hag. Take te gare roto wh ide | 2 a2 a | [om (22) -] ® | ba tea fm ie Weigh = coh — o | ‘a, ee ete tego 13310 fond [EB an (38) samy Problem 134 Consider equation (13327). Mx erent anh [5 os -=2) (332 103ae i ee (Chapter 13. DOUBLE LAYER STRUCTURE AND ADSORPTION ‘Expand by noting that sinh u = 0.5 [e* ~ e*] se [BRT econ?) ze = tel (ag = [pkrcan? (co iE: me Dice wire dy 2 earat x a {aft Gleiof Sel SESS he} Rearmed {sp (oleh eo sh = [-ah] eo [ance } (IPRS) ° Note that cosh u = 0.5[e* +e). o [seg] ca itr (60 ~ 1+ (RPggone | Be cont [ae (40 — )] 104 Chapter 13 From quton (13225 and (13326), o © Tren, t-te Ses ° Baton (6 rts to egiaton 133.28) where doM ty = Cy " ane alee 7 Bo [EAE cosh ia] “The ei equation (13329) 32) ith soln. a Figure 139.1 hg lectoespilary carve is shown for Nagy, The potaial of ‘The excess charge on the met, 0, i found fom the derivative of the plot of y versus —E according to equation (12.2), 03.22) ‘The diferent capacitance, Cy, is found om the derivative ofthe plot of versus B, according toequaton (132.3). eM a= 0323)(Chapter 13 DOUBLE LAYER STRUCTURE AND ADSORPTION ‘Ts, the differential capacitance is found from the second derivative ofthe elecocpily curve with respect ia potential. In Figure 13.92, the diferentl capacitance curves are shown. The curve for NagSO4 is roughly 2 gel paola similar to those observed for other elecolycs snd modeled by Govy-Chapenan ‘Theory Figure 13.3.5). For thew heptane, the capacitance is oughly invariant between 04 and “14 V. This is consistent with he adsorbed n-heptano forming a expactve layer atthe terface between the solution andthe electrode. Denote this capacitance as Ci. In Grahame’ review, he specifies the equivalent excl forthe whepanol and NspSOq aye asthe resistance of the dsobed layer in paalel wit its capacitance whereas the solution existe and double yer ca ctnce ae in seis. Che si sees with he double layer capacitance, Cay, which incest fapacitance of the Helmhol layer and the difue layer. Fr capacitor in series, the total capaci tance, Chl Sty the reciprocal sums 8 Cty = Cg! + Ch. Tas, the sale capacitance dominates the capacitance of the intefuce. Between -04 and -1 7, thie the eapacitance ofthe adsorbed hepiancl In the presence of n-heptane, the potential exceeds the range 0.4 to AV, the electrode is suiinty polarized that its charge ie compensnted by the Son in solton rather than he pol slohol molecules andthe heptanal is dsplaced fom the electrode surfice bythe ons. Outside the range -0.4 1.4 V, the differential capaiane forthe NezSO, and the NozSOq with heptane ‘superimpose. The sharp diferental capacitance waves are associated with the sudden change in ‘the charge inthe interfacial epion. Problem 13.8 Fora Langmerin isotherm where @ = F/T, equation (138.7) appli. where isthe satrtion coverage of 8x 10" mol/em? and sume the ati is weaken a the concentration. I o o For, = 5x 10? em/mol, this yields the fellowing Langmerian sorption isthe. 106 Chapter 13, 107 os os 04 02 00 2 2 s 3 loga “The linearized isotherm applies when, rom equation (2), 8 ~ Aa. For histo be comet within 1% fit voomaet o © For, = 6x10" om? /mol, he inerized version aplics for a < 0.01/9, = 210-8 mel/em® [Not that tis coresponds ote approximate limit for early linearity inthe isotherm above ‘Problem 13:10 First consider the adsorption kinetic for single species, whee the change in 4 te coverage is et by teat of adsorption minus teat of desorption. The rt of adsorption is et by the rte constant, ky, the solutonconcentaton, C, and the faction of empy surface "The at of desorption is set by the rate constant, ks, andthe coverage. Then, Bem beac) Ras o RG Aika BG At ease, dt = 0. Tus, = = bys. Be thas+ BesGl] ® shag Bet ~ T+ alba 2 Ms 107(Chapter 13 DOUBLE LAYER STRUCTURE AND ADSORPTION For il ae 9, = ks, hisreduces to equation (13.5.8 fora single species. TBC. Nartea (338) ‘Now, by analogy consider the competitive adsorption of two specie, and j. The occupied surface faction is 1~ 8,0, The sesdy sate ae capes or oft andj Eston y pressions fr he coverage of andj are #, a ° 4 Bm Bs For 8, = kek and = Bh the above yield 6) ~hasBs 0 o o o B,G0-%-4)-6 = 0 im ~8B,C)~ 8) (840,41) +050, = 0 © ‘This yields two equations intwo unknowns. Equation (6) reaanged othe followin: tye P Ea BE +1) ra o Substitution ino equation (8 yes an exeesion in “08,05 ~(8,05+1) (AS-gueen) +86 = 0 0) Os +1) (BC+ tfc BE RE89) © seyegoes 0, [AEBG+ BO + G+) _ Bet 2, a = of BG+aGri Chapter 13 (Or equation (1359) found =r 13.59) BG+BGFI ae Substinsio of nto equation (6 yields equton (135.10). g = SG=MBE+) an i eis 8C:+1) BG i ~ GTR = IGG+ BC+ 1 (B41) SRG TG AG. HGeAGri Bs =a @c+n) (0, equation (135.10) is found P48, T= 5G sea sl) Problem 13.12. Consider equation (137.4), Ectew(-sfésen|-of (E-2”-)] a7 (Note that 9 = B ~ B®, Bauaton (13.74) i rearrange tothe following: ini = ta [araitel] - 276-01 (n-#) ° = tn [araatct] + f¢o(@-2)-af0 “ae plots re pts of ns ver 9. The slope is set by Bai/On, whee ia fston of 9 Ths, Sint = aps sa 2282 Tt = of +H(0- 9) ® (, Rearanging equation (13.74) yields exp 2/6) = WFARICS exp [af (9 ~ 62) o 109(Chapter 13 DOUBLE LAYER STRUCTURE AND ADSORPTION ‘Taking the log ofboth sides yes the equation forthe “corrected” Tafel slope, tn ftexplsfe tn [arAnged] - af (9 - ¢) o ‘Aplotoin exp ff] versasn-¢, wl yield sap of of nd aninteregtafin [nF ARBCE) Problem 13.46 The Frumkin isotherm accounts for interactions between the adsorbate, either tractive (¢/ > 0) or repulsive (<0) Equation (13514) desrbes the Frumkin isthe ) a ‘The dimensionless term. deserbes the concen eft, The mot ret way cle te therm sto cledte fC, forarange of, The uotarm na plot of wena Cee sopended mreadiet show the reqpses fr gf of, snd 2 Far = Oye ot is {ngmerian and ne plot ronal date. When’ 2 he ateactone wesc andthe ads ayer sored at oer xC, Corey, fr =e maton ae ‘pulse and phe C iregued i dre nonlye formation e Deve ogee ict no 7 t 14 ELECTROACTIVE LAYERS AND MODIFIED ELECTRODES Paar eee a eae eae eee Jn Figure 14.3.4, consistent with only adsorbed O elecvoacive. The relationship between peak ‘tent, fy and surface coverape Ms given by equation (143.2) oF ATS = SATS ane 14322) ‘To account for n ibe than I, the equation is modified as follows, consistent withthe usual cluster ofnP/RT- anF2 Aut t= ear a 017 om? andv = 0.1 V/s, From Figure 143.4b ip = 2.2 10-* A jp = ERR @ ‘TTB rp = SenBer © nant axans SS KIT DOE ie BATT OT PLOT Var 10-" molefont 9.5110" ole/on x 64910 male/male = 5842109 nten/on? ‘This comesponds to 1.77 x 10-¥ cm? = 177 A? per molecule, wel below a compact monolayer Problem 144 The equations for the cronocoulometic response to forward and reverse poten- tial step are given by equations (143.23) and (163.36) Ont ry = MEADE" nears +e 04339) InFAC Do} (, , ainFATo Gilt > 7) = BEA PON (14 AAT) oranFAro+ Oe (14336 ao @ m(Chapter 44 ELECTROACTIVE LAYERS AND MODIFIED ELECTRODES wher ithe ime forthe forward sep and eo BEN a Qc canbe enfuted from he slope ofthe data Qy vera #7 scoring to ution (143.3), were 5) = 2nF ACS (Do/n)! Ike given tat = YF + VF=7~ VE. A plotofQ, versus Yd ate, whee 5, = MEMGDOIN(, © a ean ATo = 5,(1+95gate) Ths, S_, . ana 31 Ge O any, Ste for ey approximated 0.97, i oud ron Egi6 8 ® ‘Note that his method woids evaluation of Qu and, as tees on slopes as opposed to interop, ‘trelis on statistially more advantageous dat, [Problem 146- (a. The moles of Hin the cel ae determined from the concentration and cell volume moles of HQ. = 01x10" matesfon? x1.20n? 40x10") = 48x10" mates ‘The cell olume is 48 x 10°? em, Iti given tat afer filing the el the fist time, electrolysis ofthe sltion solubilized species yields 32 uC, Faraday’s lw allows the ealeulton ofthe moles ‘of material HQ in coition, Under the experimental conditions, oly the solution species can be eecwolyzed. = 2 motes ® 2x 106C Ty B6485 Cjmale a 1 710" motes m2 Chapter 14 “Thus, fom the initial numberof moles nthe cll (4.8 10") and the moles remaining in solution her adsorpon (1.7 10"), the moles of adsorbed HQ are found: 48% 10-10— 1.7 10-18 3 1000, The call is emptied and supplied witha ifesh aliquot of hydroquinone solution. ‘Tae clecrolysis ofthe ston species reques 96 which rm Faraday law coresponds to Sx 10. moles o esentaly all of he hydroguinane provided by the fes aliquot. Tus, all {he 0 adsorbed fom the fist aligut, andthe adsorbed material forms a dense packed monolayee. ‘Tis assumes that the hydroquinone adsorbs ely on the platinum. The area per molecule is then calculated as follows ro = SEL mM 60 10 moleten/mole ° = 198 «108 molecules fom? “The cross sectional area per molecule, i found fom the reiprocal o = GAAY/motecules (0). The two probable eretatons for adsorbed hydroquinone ae flat and edge on. The sea of G2 xlyrmotecules crudely coresponds toa eque area 8 A on ase. The adsorption of by ‘roquinon parallel othe surface ofthe elesuade such that HQ lies a on the surface is most ely. 3