possible to determine the cr ochemticg! Ne O ay species in a mixture of sree atiog * whereas mostother analy nD) ang eeheye the total cerium concentration se Mean vantage of electrochemical mer Sing ey, mentation isrelatively newer ta ical instruments cost less a0 ths for atypical multipurpose £00, ang the range of $8000 to $10,999 imag troscopicinstrumentscost $5 99 8 A third feature of certain elegy 22 ment For example, ia os S mr or which may be an advantage oe neta they provide information abous aioe gt concentrations of chemical species. Gat thy ilogical studies, for example, act ia as calcium ani ium i snc Mo Thoughtful application of the various lytical methods described in Chapters 93 an understanding ofthe basic theory andiig aspects of the operation of electrochemical eet na chapter is devoted largely to these topic 22A ELECTROCHEMICAL CELLS A dcelectrochemical cell consists of two electrcalcae ductors called electrodes, each immersed ia a sunt electrolyte solution. For a current to deveopia aa itis necessary (1) that the electrodes be comseceder ternally with a metal conductor, (2) that the two dr trolyte solutions be in contact to permit moenestd ions from one to the other, and (3) that an dea transfer reaction can occur a each fhe mes trodes, Figure 22-La shows an example of oot electrochemical cell. It consists of 2 siver o od io oo "Some reference works on electrochemistry wi WY Nas AL Burdand|_R Falter, crocheted Meo (oe ‘Wiley, 20; 5 Bago and. Moet, een iztry 2nd ed, New York: Wile, 2005:D.. S74 wa ner aber, Elcocein fC) al 4. Korytaand4 Dvorak, Principles of Elro cy Wiley 193 Labor Te Ne ae PEEK WR He et clamical, and til useful, monoyep So ity is. Lingane, Blcroanabec! science, 1958.(oe = 0000 uk) Can +26 ‘ose » tag ~om0 nt ® Asin oo hand (8) A galvanic electrochemical cell at open cout; (9) a galvanic cell doing work; a) Faure 22-4 (ian electrolytic call oT Ponsa ney ‘cc adimmersed in a solution of silver nitrate and ® copper electrode ina solution of copper sulfate. The two solu tions se joined by a salt bridge, which consists of a tube filled with a solution that is saturated with potassium chloride or, sometimes, a different electrolyte. The two ends of the tube are fitted with porous plugs or disks that permit the movement of ions across them but pre- vent siphoning ofiquid from one electrolyte solution to the other. The purpose of the bridge is to isolate the contents of the two halves of the cell while maintaining electrical contact between them. Isolation is necessary to prevent direct reaction between silver ions and the copper electrode, The cells in Figure 22-1 contain two so-called liquid junctions, one being the interface be- tween the silver nitrate solution and the salt bridge; the second is at the other end ofthe salt bridge where the electrolyte solution of the bridge contacts the copper sulfate solution. As we show in Section 22B-2, a small junction potential at each of these interfaces may inlu- ‘ence significantly the accuracy of the analysis. 22A-1 Conduction in a Cell If we replace the high-impedance meter in Figure 22-1a with a low-resistance wire or load as shown in Fig- ure 22-1b, the circuit is completed, and charge flows. Charge conduction results from three distinct processes in various parts ofthe cell shown in Figure 22-1b: L In the silver and copper electrodes, as well a in the external conductor, electrons are the charge carri- cers, moving from the copper electrode through the external conductor to the silver electrode. 2 Within the solutions the flow of charge isthe result of migration of both cations and anions. Inthe half-ell ‘on the left, copper ions migrate away from the elec- trode into the solution, and sulfate and hydrogen sulfate ions move toward it; in the half-cell on the right, silver ions move toward the electrode and an- ions move away from it. Inside the salt bridge, charge is carried by migration of potassium ions to the right and chloride ions to the left. Thus, all of the ions in ‘the three solutions participate in the flow of charge. 3. A third process occurs at the two electrode surfaces. {At these interfaces, an oxidation or a reduction re- action couples the ionic conduction of the solution with the electron conduction of the electrode to provide a complete circuit for the flow of charge. Stmuiaon: aur more son eacemcboed “The two electrode processes reactions teste, Cale) Cu? 0g) 4 2 Ag*(aq) + ees, 2(3) & 224-2 Galvanle and Electrolytic cq, ‘The net cell reaction that occurs j Figure 22-1b is the sum ofthe two {bec hog, ‘shown as Equations 22-1 and 27-22 Ta Cale) + 2Ae Ou" + ayy The voltage of this cellis a measure ofthe this reaction to proceed toward equine 2? shown in Figure 22-1a, when the Ta concentrations (actually, activities) are cell voltage is 0.412 V, which shows that far from equilibrium. If we connect a reas load in the external circuit as shown is Foe ne measurable current inthe circuit result ada reaction occurs, AS the reaction proceds, tei, becomes smaller and smaller, andi ultimate rat (0.000 V when the system achieves equilibria. Cells, such as the one shown in Figure 21a1 22-1b, that produce electrical energy aecalledgaba cells. In contrast, electrolytic cells consume cen ‘energy. For example, the Cu-Ag cell can operteit electrolytic mode by connecting the negative erm ofa battery or de power supply to the copper dean and the positive terminal to the silver elerrade, 3 lustrated in Figure 22-1c. If the output ofthis 39 is adjusted to be somewhat greater than 0412 \ shown, thetwoelectrode reactionsare ene net cell reaction is 2Agls) + Cu —= Ag’ + Cb) A cell in which reversing the diretion ot 9 simply reverses the reactions at ther = and; Otto thera termed a chemically reversible cell 22A-3 Anodes and Cathodes 5 By definition, the cathode ofan ECHO od the electrode at which reduction =F" OF is the electrode where xian Ut definitions apply to both galvanic oS yy” and to electrolytic cells. For the Note that th ver haléeacton i ary and as tla.(cathode) Solid AgCl Figure 22-1b, the silver electrode is the cathode and the copper electrode isthe anode. On the other hand, inthe electrolytic cell of Figure 22-1c, the silver elec- ttode isthe anode and the copper electrode the cath- ‘ode because the half-cell reactions are reversed. 22h-4 Cells without Liquid Junctions ‘Asmentioned previously, the cell shown in Figure 22-1 tas two liquid junctions one between the silver nitrate ‘olution and one end ofthe salt bridge, the other be- {ween the copper sulfate solution and the salt bridge. Sometimes itis possible and advantageous to prepare ‘ls in which the electrodes share a common electro- pot ‘thus eliminate the effect of junction poten- tre an ramble of a cell ofthis type is shown in Fig- bani ite voltmeter were removed and replaced silver would inne behave ath cathode, Therese ABOU) + 6° = Ag*(ag) + C1(ag) saat ca "te, hydrogen is consumed at the plat- eons #26 i Teacton jg, ing cach term inthe gnu “8 Obtained by multiply. “im an aa AIO) + Had) mn rpyy 20) 20-4 01M HCI saturated with AgCl Silver eleewode 2A Electrochemical Cela 634 FIQURE 22-2 A galvanic call without a quid junction. ‘AgCI(s) = Ag'(oq) + CI(ag) Agen) + ARG) ‘The direct reaction between hydrogen and solid silver chloride is so slow that the same electrolyte can be used for both electrodes without significant loss of cell efficiency because of direct reaction between cell components. The cathode reaction in this cell is interesting be- cause itcan be considered the result ofa two-step pro- cess described by the equations ‘AgCi(s) = Agt + Cr” Ag’ +" = Ag(s) ‘The slightly soluble silver chloride dissolves inthe frst step to provide an essentially constant concentration of silver ions that are then reduced in the second step. The anodic reaction in this cell is also a two-step process that can be formulated as H,(g) = Hx(aq) H,(aq) —= 2H" + 2e7 Hydrogen gas is bubbled across the surface ofa pla ‘num electrode so that the concentration ofthe gas at the surface is constant at constant temperature and ‘constant partial pressure of hydrogen. Note that in this case the inert platinum electrode plays no direct rote in the reaction but serves only as a surface where elec- tron transfer can oocur. ‘The cell in Figure 22-2 is a galvanic cell with a po- tential of about 0.46 V. This cll a also chemically re- versible and can be operated as an electrolytic cell by applying an external potential of somewhat greater ~2 eee 632. Chapter 22 An Introduction to Electroanalytical Chemistry 20-300 A—- FRQURE 22-3 Electrical double layer formed. ‘at electrode surface as a reeuit of an applied potential. than 0.46 V. Note that you cannot tell whether a given electrode will be a cathode or an anode unless you know whether the cells galvanic under discharge ot electrolytic. 22A-5 Solution Structure: ‘The Electrical Double Layer It is important to Tealize that electrochemical mea- Surements are made on heterogeneous systems and that an electrode can donate or accept electrons only from a species that is present in a layer of solution that is immediately adjacent tothe electrode, Thus, asa re- sult of the chemical and physical changes that occur at the electrode-solution interface, this layer may have a Composition that differs significantly from that of the bulk of the solution. For example, let us consider the structure ofthe so- lution immediately adjacent to an electrode in an elec. trolyticcell when a positive voltage is first applied tothe clectrode (eg, the Ag electrode in Figure 22-1c). Im. ‘mediately after applying the voltage, there isa momen. ‘ary surge of current, which rapidly decays to zero if no Teactive species is present at the surface of the elec. trode. This currentis a charging current that creates an excess (or a deficiency) of negative charge atthe surface of the two electrodes. Because of ionic mobility, how. ver, the layers of solution immediately adjacent to the d flect is illustrated in Figure 22-3a, The surface of the (dato dn which he potential decreases linearly with distance from the electrode surface and (2) a diffuse layer (a; tod), within whic the decrease i approx. Bulk of solution Potential — mately exponential (See Figure 235) Tho ray of charged species and oriented 4, water molecules) a the electrodesolae called the electrical double layer, " 22A-6 Faradale and Nontaradalc Cur, ‘Two types of processes am Conduct cuenta wy electrode-solution interface, One type invoivesa tray transfer of electrons via an oxidation asia Home electrode and a reduction reaction atthe thet rp esses ofthis type are called faradaic procenes became they are governed by Faraday law, Which states tha the amount of chemical reaction that ocurat arabs trode is proportional to the curent,cled a fonda: current, ‘Under certain conditions a range of ota my be applied to cell that do not produce faadac pe cesses atone or both ofthe electrodes. Fart cesses may be prevented either because elects do ‘ot have sufficient energy to pass ove the poentilen ergy barrier at the electrode-solution interac (ter ‘modynamic reasons) or because the electron-raadet reaction is not fast enough on the time scale ofthe e- periment (kinetic reasons). Under these crcumsame, Conduction of continuous alternating curent can sil take place. With such currents, reversal ofthe cart Telationship occurs with each | hhalf-cycle as first megane and then positive ions are attracted alternately o be lectrode surface. Electrical energy from the eter Voltage source is consumed and converted to beat tstion associated withthe motion ens An Way to look at this consumption ol caceriaten the voltage changes, the ions inthe double ae Tearrange and adjust to the new potenti, eure ‘Arrangement requires energy. Thus, eachcapacitor, whose capaci- (enti) ting current in a cell is car- ann Pesci: Sap-4fora description of aciruit ssi fhe basic difference between a f,oiesond dic current, imagine an clec- piel mete entermal crcit tan electrode encom reaches the solution inter- enc of only two things. Itcan remain at etar rtace and increase the charge on the 200 vhich constitutes a nonfaradaic current. sear can leave the electrode surface and eripesis in the solution, thus Becoming a te andi curtet 'o:1lass Transfer in Cells ite Passage of Current . sane m eletrode can probe only a very thin layer ‘énitioa a the electrode surface (dp to d, in Fig- ‘eD), a faradaic current requires continuous ‘mer of reactive species from the bulk of the ‘hint the electrode surface. Three mechanisms ‘ig ahou this mass transfer: convection, migration, ‘afion. Convection results from mechanical mo- {Srfteston as a result of stiring or the flow of iit pas the surface of the electrode. Migra- rep Dement of ions through the solution shout by electrostatic attraction between the out the electrode of the opposite charge. Diffu- Pa Tea sesies caused by a concentration Seay, ‘is a detailed discussion of these mech- ‘Mass transfer in Section 22E-3. Raa tect Representation of Cells Roa aea phan notation to simply the de- 2 aad 9 or Cxample, the cells shown in Fig- we a, be described by | 19200) AgNOs(aq,- = 0.0200) Tamyii*(o.91 M), ia 7 ee : ‘C1"(0.01 M), AgC\(sa'd)lAg. Orinesne® Vertical line indicates a phase terface, where ‘potential develops. For 228 Potentials in Electroanalytical Cells 633 ‘example, the first vertical line in this schematic indi- cates there is a potential difference across the phase boundary between the zinc electrode and the zinc sul- fate solution. The double vertical line represents two phase boundaries, one at each end of the salt bridge. ‘There isa liquid-junction potential across each of these interfaces. Because the potential of a cell depends on the activities of the cell components, it is common practice to provide the activity or concentration of the cell constituents in parentheses. Tn the second cell, there are only two phase bound- aries because the electrolyte is common to both elec- trodes. A shorthand representation of this cel is PrlHi,(sat’d),HCI(0.01 M),Ag*(1.8 x 10% M)IAg, In this cell, the molecular hydrogen concentration is that ofa saturated solution; ifthe partial pressure of drogen isnot given, we assume that itis 1.00 atm. The in- dicated molar silver ion concentration was computed from the solubility product constant for silver chloride. 228 POTENTIALS IN ELECTROANALYTICAL CELLS In most electroanalytical methods, we measure either (1) the current in an electrochemical cell at a fixed po- tential or (2) the potential of a cell while the current is fixed at some constant level oris zero. In general, how- ever, in an electrochemical experiment we can control only the potential ofthe cell at a desired level and mea- sure the current that results, or vice versa. If we choose to control one variable, itis impossible to control the other independently. In this section we first consider the thermodynam- ies of electrochemical cells and the relationship be- tween the activities ofthe participants typical cell re- actions and the observed potential ofthe cell. We then. describe the source of the junction potentials that oc- ccur in most electrochemical cells. In Section 22C we ‘consider the potentials of individual electrodes making upeells. 228-1 The Thermodynamics of Cell Potentials ‘The potential of an electrochemical cell is directly re- lated to the activities of the reactants and products of the cell reaction and indirectly to their molar concen- trations. Although we often make the approximation that these activities are equal to molar concentrations,634. Chapter 22 An ltrodvtion to Electroanaltical Chetry always remember that this assumption may produce errorsin calculated potentials. We review the relation- ship between the activity of a chemical species and its concentration in Appendix 2. ‘Recall thatthe activity ax of he species Xis given by = yx1X] (22.3) In this equation, 1x is the activity coetficignt of solute XX, and the bracketed term isthe molar concentration of X. In some of the examples, however, for conven- ‘ence we will assume that the activity coefficient is ‘unity so that the molar concentration and the activity of a species are identical. How do the activites of reactants and products af- fect the potential of an electrochemical cell? We will ‘use as an example the cell illustrated in Figure 22-2for Which the spontaneous cell reaction is 2AgC\s) + Hy(g) —*2Ag(s) + 20° + 2H* ‘The thermodynamic equilibrium constant K for this reaction is given by (22-4 Pita (22-4) where a¥ are the activities of the various species indi- ‘ated by the subscripts and py, i the partial pressure of hydrogen in atmospheres. In Appendix 2? we show that the activity of a pure solid is unity when itis present in excess (thats, ayy = @qqq1 = 1.00). Therefore, Equation 22-4 simplifies to aoa, Pit It is convenient to define the activity quotient Q ‘such that K (225) (Px); ‘The subscript i indicates that the terms in the paren- theses are instantaneous activities and not equilibrium activities. The quantity Q, therefor, is not @ constant but changes continuously until equilibrium is reached; at that point, Q becomes equal to K, and the i sub scripts are deleted. The change in free energy AG for a cell reaction (thats, the maximum work obtainable at constant tem- perature and pressure) i given by Q (226) Seepage 967. 4G = Rring~ where R is the gas isthe temperature inten 816d aya Ry quotient OAK. The cei nian i free energy of the raya ye AG =~, where F is the faraday( ay electrons) and nis the i tony Pn sociated with the oxidation regu Cena! example, n = 2), Netion Prey ine Rr 2 = FT, Grieg? +e Pk ‘The last term in this equation isa called the standard potential forthe co et Er, 9, XL, Ela= Spink ey Substitution of Equation 2210 into Equtin 29 yields Fea = Boy ~ Sottclel Note that the standard potential is equ eal potential when the reactans and produc ee a et activity and pressure, Equation 22-11 is a form of the Nerst ei’ ‘named in honor of Walther Nemst (1864-19 ‘man physical chemist and winner of the 190 él Prize in Chemistry. This equation is wed in electroanalytical chemistry and forms the bs many applications. en — “pi iim guinea ‘testicle eo eb i Se the Nernt equation are aid w exh oe (aD Tr ahes bat 0s Sarr634. Chapter 22 An Introduction to Eleeroanalytical Chemistry always remember that this assumption may produce errors in calculated potentials. We review the relation ship between the activity of a chemical species and its concentration in Appendix 2. | Recall thatthe activity ax of the species X is given by ax = yx0X) (223) In this equation, 7x is the activity coefficient of solute X, and the bracketed term is the molar concentration of X. In some of the examples, however, for conven: ience we wil assume that the activity coefficient is unity so that the molar concentration and the activity of a species are identical. How do the activities of reactants and products af- fect the potential of an electrochemical cell? We will use as an example the cell illustrated in Figure 22-2 for which the spontaneous cell reaction is 2AgCl(s) + Hy(g)—2Ag(s) + 2c" + 2H" ‘The thermodynamic equilibrium constant K for this reaction is given by 2 gh eat, Bie "Wer" ag (22-4) Pa tract where a are the activities of the various species indi- cated by the subscripts and py, isthe partial pressure of hydrogen in atmospheres. In Appendix 23 we show that the activity of a pure solid is unity when itis present in excess (that is, dn, = Gqqq = 1.00). Therefore, Equation 22-4 simplifies to 5) It is convenient to define the activity quotient Q such that (a dort oo ah . a ‘The subscript i indicates that the terms in the paren- theses are instantancous activities and not equilibrium activities. The quantity Q, therefore, is not a constant but changes continuously until equilibrium is reached; at that point, Q becomes equal to K, and the i sub- scripts are deleted. The change in free energy AG for a cell reaction (thats, the maximum work obtainable at constant tem- erature and pressure) is given by >See page 967, AG = RTInQ ~ RTINK = RrQ K i Ry a me, , tatural, logarithm. This relationship mpeg M6 free energy fr the system depends on hes ne ' where Ris the gas constant (8316.1 moj-1 is the temperature in kelvins; In refers to, tem is from the equilibrium state a ingges 8%. quotient Q/K. The cell potential Ey ix rig’ 7 be ee energy of the reaction by the relation tt! te ee AG = ~nFE ag # Ca) on os example, n= 2). where Fis the faraday (96,485 coulomby 4 pee When Equations 22-6 and 28 are sity Py?™ tlectrons) and is the numberof moles of sociated wih the oxidation reduction pace ea into 22-7 and the resulting equation is. pte) iar find that me io Ca Ryo RT, et Bea pind + pink re , ae nFek 5 “a ‘The last term in this equation is constant, whieh, called the standard potential for the cell i Te oe * - : 0, = RP, Ely = Tek (om oo Substitution of Equation 22-10 into Equation ng yields Passion 29 na pos iat ee, ahs Note that the standard potential is equal tothe cll icy Potential when the reactants and products are at wit tpg activity and pressure. a Equation 22-11 is a form of the Nemst equation’ _ named in honor of Walther Nernst (1864~1941), Ger me man physical chemist and winner ofthe 120 Nob Prize in Chemistry. This equation is used troughot electroanalytical chemistry and forms the bass fe O¥ many applications. ~ ut “Equations similar in form to Equation 2-11 are decibel w nomi relationships; electodes and sensors whowe behavior aa be desist) > th Ne eatin we i eh wean ei h (2.303 RT/nF when base IO logarithms are wsed) i onen cal ewe an factor. x itjunction Potentials ye solution of diferent compos- 90 ey with one another, there isa poe! ge incon oss the interface. This junction wi tn il js the boundary due to differences in Fs chee apis dire tsa guid jtion inthe system HO M)ICIO.01 ™M) nis and clrie ios fend to difse so poondary fom the more concentrated tothe 2 aye solution, ‘and the driving force for this 3 i oertioal othe concentration der te ein cates of varius ions under the inf a Tce vary consider (ha is, the mo- great. n this example, hydrogen ions cor ofS more mobile than chloride ons a aydogen ons tend to due faster than the 7 ions, and tis diference in diffusion rate pro- sees aero of charge (see Figure 22-4). The ise dite SCE (the right side in the figure) of the tively charged because hydro- rary becomes Posi ime more rapidly. The concentrated side, er, acquires a negative charge from the excess we ooig cri ios. The charge separation fe ars tends to counteract the differences in mo- Fiiesf the two fons, and as @ result, equilibrium is senadied, Te junction potential difference result- itm his charge separation may amount to 30 mV po ‘nasinle system such a5 the magpitude of the junction lued from the mobilities of However, itis seldom that @ cell tae has a sufficiently simple compositi ‘schacomputation.* Experiment shows that the magnitude of the june- {in petal can be greatly reduced by introduction (1 cncentrated electrolyte solution (a salt bridge) teen the to solutions. The effectiveness of @ salt tigre not oly ste concentration of the igresses but also as the difference between the ‘utilis ofthe positive and negative ions of the salt that shown in Figure 22-4, potential can be caleu- the two ions involved. of analytical impor- jon to permit rae 2er0, A saturated potassium chloride solu- Particularly effective from both standpoints. Its ee etn tt spprocinating junction potentials, yt Eeroche see AJ Bard and thos, nde, p. 69-72 New Yor! eros diaphragm aed wt foo tl Her FIGURE 22-4 Schematic representation ofa [rama reaeatc ove conesponds 1 eat mobil of he two fons, ‘ome concentrationis greater than 4M atroom temperature, and equally important, the mobilities of poset chloride ions differ by only 4%. When chloride ion in- terferes with a particular experiment, a concentrated solution of potassium nitrate can be substitute. With such bridges, the net junction potentialistypicallyafew nillivolts or less, whichis negligible in most analytical measurements. 22¢ ELECTRODE POTENTIALS It is useful to think of the cell reaction of an electro- chemical cell as being made up of two haif-ellrenc- tions, each of which has a characteristic electrode po- tential associated wit it, As wil be shown later, these tlectrode potentials measure the driving force for the fo balé-reacions when, by convention, they are both sven as reductions, Th, the two hall or elee- trode reactions for the cell LH, atm)|H1*(0.01 MCT (001 M).AgCiCsa'd)IAB shown in Figure 22-2 are Ags) + 26° —=2AKe) +20 2Ht +20 Hh) ‘To obtain te spontaneous cell act", the seoond hat reaction is subtracted from first to give ‘2AgC ils) + Ha 24800 * 2H" +2Ch and Eyrn, a8 potentials Exons slectrode a areactions, we may theD known for the 1¥O(636 Chapter 22. An Introduction to Elctrounalytial Chemisty the cell potential E, by subtracting the electrode po- ‘tential for the second reaction from the first. That is, Baa * Exc, Erm, A more general statement of the last relationship is Ean = Exgu ~ Ein 2) ‘where E,gu is the potential of the hal-cell written on the right in the diagram of the cell or in the shorthand representation, and Ee isthe electrode potential for the half-reaction written on the left. We discuss this convention further in Section 22C-5. 226-1 Nature of Electrode Potentials ‘The potential of an electrochemical cell is the differ- cence between the potential of one of the electrodes and the potential of the other, anditis therefore impor- tant to have a clear idea of what is meant by the poten- tial of an electrode. This potential is a measure of an electrode’ electron energy. For @ metallic conductor immersed in a solution of an electrolyte, all excess charge resides on its surface, and itis possible to adjust the charge density on this surface by adjusting the out- Put of an external power supply attached to the con- ductor, Asthis external source forces electrons onto the surface of an electrode, the electrons become more crowded, and their energy increases because of coulom- bic repulsion, The potential of the electrode thus be- comes more negative. If the external circuitry with- draws enough electrons from the electrode, the surface will have a positive charge, and the electrode becomes ‘more positive. tis also possible to vary the electron en- ergy, and thus the potential, of a metallic electrode by varying the composition of the solution that surrounds it. For example, there isa potential ata platinum elec- trode immersed in a solution containing hexacyano- ferrate(II) and hexacyanoferrate({I) as result of the equilibrium Fe(On)e + = Fe(CN) the concentration of Fe(CN)~is made much larger than that of Fe(CN),*", hexacyanoferrate(II) has a tendency to donate electrons to the metal, thus creat- ing a negative charge at the surface of the metal. Un- 4er this condition, the potential ofthe electrode is neg- ative. On the other hand, if Fe(CN)¢° is present in large excess, there is a tendency for electrons to be re- moved from the electrode, causing surface layerions to ‘Simulation: Learn more about electrochemical cell potentials. form in the solution and leaving a posi the surface of the electrode. The plana a then exhibits a positive potential, ‘We must emphasize that no method, the absolute value ofthe potential ofa sing Se because all voltage-measuring devices, ete differences in potential. One conductor uh vite sconnected tothe electrode understudy tp 2 sure a potential difference, however, the sen0 ductor must make contact withthe electrolyte, schon ie of the halel under sty This second sna evtaly create a solitslution inert ange acts a a second halfcll in which a chemin? rst also tke place if hag iso fow. ec associated with ths second reaction. Thus we uit measure the absolute value forthe desired hata tential. Instead, we can measure only the digs between the potent of interes andthe aes tet forthe contact between te Yolage means device and the solution. Ourinabiltytomeasure absolut potent forka. cel processesis nota serious problem betel hale potentials, measured versus common ret ence electrode, are just as useful, These Telative tials can be combined to give real cell potentials Ip addition, they canbe used to calculate equiumsee stants of oxidation-reduction processes, To develop a useful list of relative halter ee trode potentials, we must have a carefully defined rt erence electrode that is adopted bythe entire cheieal community. The standard hydrogen electrode, or he normal hydrogen electrode, is such a hale-cel, 22C-2 The Standard Hydrogen Electrode Hydrogen gas electrodes were widely used inearlyelee trochemical studies not only as reference electrodes but also as indicator electrodes for determining pHL ‘The composition of this type of electrode can be repre- sented as PLHy(patm)|H(oy- = x) ‘The terms in parentheses suggest thatthe potential a « the platinum surface depends on the hydrogen ion 8 tivity of the solution and on the partial pressure ofthe hydrogen used to saturate the solution. ‘The half-cell shown on the left in Figure 225 shows the components of a typical hydrogen electrode. The conductor is made of platinum foil that has beea pl ‘inized. Platinum electrodes are platinized by coating their surfaces with a finely divided layer of patioumY | lllrapid chemical of electrochemical reduction ‘of nd The finely divided platinum on the surface of the electrode does not reflect light as does polished platioum, so the electrode appears black. Because ofits , the deposited platinum is called platinum ek. Platinum black has a very large surface arca to casure that the reaction 2H + 2° HAs) js rapid at the electrode surface. As was pointed out ‘ater, the stream of hydrogen simply keeps the solu- tin adjacent to the electrode saturated with the gas. The hydrogen electrode may act as the positive or tte negative electrode, depending on the half-ell with which it is coupled with the salt bridge shown in Fig- we 25, When the cell is short circuited, hydrogen is sxidized to hydrogen ions when the electrode is an an- ode; the reverse reaction takes place when the elec~ ttodeis a cathode. Under proper conditions, then, the hydrogen electrode is electrochemically reversible. When the cell is connected as shown in Figure 22-5, theres essentially no current in the cell because of the ‘erhigh impedance of the meter. Under short circuit, themetris replaced with a wie or low-resistance load ‘shown in Figure 22-1b, and the reaction proceeds. Pad potential of a hydrogen electrode depends on temperature, the hydrogen ion activity in the solu- tion, and the pressure of the hydrogen at the surface of the cestode. Values for these experimental variables ‘must be defined carefully forthe half-cell to serve as a reference. Specifications for the standard hydrogen electrode (SHE) call for a hydrogen ion activity of unity and a partial pressure for hydrogen of exactly ‘one atmosphere. By convention, the potential of this electrode is assigned the value of exactly zero volt at all temperatures. 226-3 Practical Reference Electrodes Although the SHE has great fundamental importance, the difficulty in preparing the electrode surface and controlling the activities of.the reactants make it so” impractical that it is rarely used for routine measure- ments. Instead, reference electrodes simple to prepare, more rugged, and easier touse are nearly always substi tuted for the hydrogen gas electrode. One of the most common of these is the silver-silver chloride electrode. ‘This electrodecan be prepared by aplyingan oxidizing voltage to a silver wire immersed in a dite solution of hydrochloric acid. A thin coating of silver chloride forms that adheres tightly tothe wie, The wire S then immersedin a saturated olutionof potassiumechloride, ‘A salt bridge connects the potas chloride solution to the electrode system being studied. The potential of ~638 Chapter 22 An Introduction to Electroanalytical Chemistry thiselectrode is about +0.22 V with respect tothe SHE. ‘The electrode half-eaction is AgCl(s) +e" —=*Cl" + Ag(s) ‘A second widely used reference electrode is the saturated calomel electrode (SCE), ior ot of a ‘of mercury in contact with a solution is sor ih mercury(I) chloride (calomel) as well as potassium chloride. Platinum wire dipping in the mer- ‘ary provides electrical contact tothe other conductor, andasaltbridge to the second electrolytecompletes the ‘ircuit. The potential of this reference is about 0.24 V positive. The electrode reactions Hg,Chy(s) + 2e” 2201" + 2Hg(2) Section 23A gives more detailed descriptions of the silver-silver chloride and the calomel reference elec- ‘rode systems. Both reference electrodes can be pur- ‘chased from suppliers of electrochemical equipment. 226-4 Definition of Electrode Potential ‘An electrode potential is defined as the potential of a ‘ell in which the electrode under investigation is the right-hand electrode and the SHEs the left-hand elec- trode We must emphasize that, in spite ofits name, an electrode potential is in fact the potential of an elec- ‘rochemical cell that contains a carefully defined refer- ence electrode on the left. Electrode potentials could ‘more properly be called relative electrode potentials, but they seldom are. Note that this cell potential may be positive or negative depending on the electron en- ergy of the electrode under study. Thus, when this en- ergy is greater than that ofthe SHE, the electrode po- tential is negative; when the electron energy of the electrode in question isles than that of the SHE, the electrode potential is postive. ‘The cell in Figure 22-5 illustrates the definition of the electrode potential for the half-reaction M+ 20° ==M(s) Inthis figure, the half-cellon the right consists of a trip ‘of the metal M in contact with a solution of M2*, The half-cell on the leftis a SHE. By definition, the poten- tial £ observed on the voltmeter isthe electrode po- ‘ential for the M?*/M couple. In ths general example, ‘we assume that the junction potentials across the salt ‘A.D. McNaught and A. Wilkinson, Compendium of Chemical Termin. 247 (The Gold Book), 2nd ed p61, Maden, MA: Backwel 197, bridge are zero we further, M* inthe olutionis exactly 9) hte the standard electrode potential tog Feat siven the symbol £°. Thats, the gy tential for a half-reaction is the jer tlctgy@ ent acan td protic ge gl IEMin the figures copper, and itty tivity in the solution is 1.00, the 2M rights posve andthe obsered pg as shown inthe figure. The dental soa hich Would oeurifthe volinetr en ty by wire, is Telaceg CaP + HG) =80u6) 4 a Because the hydrogen electrode ison sured potential is, by deft, ge thea, tial for the Cu-Cu haltcell Nor Py, Pa thatthe electrode is positive with respect to per trode; ths, we wt erie CH +2 ACH) Be so39y 1 | | / | ' ' EM in Figure 25 is cadmium instead of the solution has a cadmium ion acity of ee tentials oberied tobe C403 V Int on sium eletrodeis negate, nde epee sez sig. The spontaneous cel eat wea Cals) + 2H = 64 + Hg and we may write Ca + 20° = C4(s) E's -04ny A zine electrode in a solution of inion a unity act. ity exhibits a potential of -0.763 V when coupled wih ‘he SHE. The zine electrode isthe negative skate in the galvanic cel, and its electrode potential sea negative, ‘The standard electrode ‘Potentials for the four balf- cells just described can be arranged in the order. Cu + 26° —=* Cus) 2H +2 HYG) Ca? +20" = Ca(6) BP Zn™* +2e° =*Zn(3) EY = -0768V ‘The magnitudes of these standard electrode potsr tials show the relative strengths ofthe four iui ge ies as electron acceptors (oxidizing agents). In okt words, we may arrange the ions inode of ir de creasing strengths as oxiding agents "> H' Cd?* > Zn**, or alternatively, the elements in order allsongs 15 ring agent Ou < f oa Beco onmal chemical reaction, ve one ing from reactants on the ne Oe prs on the right side. By $i & ae on of Pure and Applied Chem ce paveation, when we consider an cee its resulting potential, we con- etna 1.0000" Be Aen for els calle the PG se ies that we always measure the cel 6s pectin the pose lead ofthe vol a ag electrode in the schematic or Ft example, the Ag electrode in the ex- gavage common, oF ground lead ofthe pn) trad cle (the Cx electrode sg. MAR" (0.020 NAB this convention, the value of Ean is eS endey of HE cell reaction to occur soos inthe direction writen from left to ott te recon of the overall proces bas oe Treg edo Cx inthe ethan come Seed ing reduced to Ag metal in the ern compartment. n other words, the reaction 1 pes onrurtng i the cells considered to be Cus) + 2Ag* —= Cu + 2485) ‘of the IUPAC Convention eect implications of the sign convention may not ‘cov Fit, ifthe measured value of E.. is post inthe ight hand electrode is positive with respect to telf-hand electrode, and the free energy change for ‘ereaton as written is negative according to AG = -af.q (Equation 22-8). Hence, the reaction in the dion being considered will occur spontaneously if ‘walls short-circuited or connected to some device ‘opaonm work (e.g. light a lamp, power a radio, start ‘at).On the other hand, if E,.y is negative, the right- ‘endelectrode is negative with respect to the left-hand ‘stad, the free energy change is positive, and the no in the direction considered (oxidation on the ‘eduction on the right) is not the spontaneous cell ve waa, Previous copper-silver cell, Fua = and the oxidation of Cu and reduction of 22€ Elerrode Poentisls 639 ‘Ag* occur spontaneously when the cells connected £0 a device and allowed to do so. ‘The TUPAC convention is consistent with the signs thatthe electrodes actually exhibit in a galvanic cell ‘That is in the Cu-Ag cell, the Cu electrode is electron rich (negative) because of the tendency of Cu to be oxidized to Cu**, and the Ag electrode is electron de- ficient (positive) because ofthe tendency for Ag® tobe reduced to Ag. As the galvanic cell discharges spon- taneously, the silver electrode is the cathode, and the copper electrode isthe anode, Note that forthe same cell written jn the opposite direction ‘AglAg* (0.0200 M) |Cu?*(0.0200 M)|Cu the measured cell potential would be Ema = ~0412 Vs and the reaction considered is ‘2Ag(s) + Cu2* = 2Ag* + Cu(s) ‘This reaction is not the spontaneous cell reaction be- cause Ey is negative and AG is thus positive. It does ‘not matter to the cell which electrode is written inthe ‘schematic on the right and which is ‘written on the left. ‘The spontaneous ell reaction is always Cu(s) + 2Ag = Cu?* + 2AR(8) By convention, we just measure the cell in a standard manner and consider the cell reaction in a standard di- rection. Finally, we must emphasize that no matter how wwe write the cellschematicor arrange the cell in the lab- ‘oratory if we connect a wire or a low-resistance circuit tothe cell,the spontaneous cell reaction will occur. The only way toachieve the reverse reaction is toconnect an ‘external voltage source and force the electrolytic reac- tion 2Ag(s) + Cu?*—*2Ag" + Cu(s) to occur. Half-Cell Potentials ‘The potential of a cell such as that shown in Fig- ure 22-5 is the difference between two half-cell or single-electrode potentials, one associated with the half-eaction at the right-hand electrode (Ey), the other associated with the half-eaction atthe left-hand electrode (Eys). According to the IUPAC sign con- vention, as long as the liquid-junction potential is negligible or there is no liquid junction, we may write the cell potential Ezy a8 Eau = Eng ~ En a8 given by Equation 22-12 Although we cannot determine absolute potentials of electrodes such as these, we can easily determine relative electrode potentials as dis- cussed in Section 22C-4.640 Chapter 22 An Introduction to Eletroanalytical Chemistry ign convention mustbe based on hate pro- cama ina single way —that is, entirely as oxi- dations or as reductions. According to the IUPAC con- ‘ention, the term electrode potential (ormore exactly, relative electrode potential) i reserved exclusively for half-eactions writen as reductions. There is no objec- tion to using the term oxidation potential to indicate an electrode process written in the opposite sense, but an oxidation potential should never be called an electrode potential. 226-6 Effect of Activity on Electrode Potential Let us consider the half-reaction PP + qQ4-- + ne" = R48 ‘where the capital letters represent formulas of reacting species (whether charged or uncharged), e” represents the electron, and the lowercase italiclettes indicate the ‘number of moles of each species (including electrons) Participating inthe half-cell reaction. By invoking the same arguments that we used inthe case ofthe silver silver chloride-SHE cell in Section 228-1, we obtain At room temperature (298 Ki), the collection of con- Stants in front of the logarithm has units of joules per coulomb or volt. Therefore, RE _ 83163molK™ x 298K nF 1x 96487 Cmol! = 2568 x 10"IC _ 2568 x 107 Ls a ‘When we convert from natural (In) to base ten loga- rithms (log) by multiplying by 2303, the previous ‘equation can be written as E = 50-2059, Galas)» mG) Og) For convenience, we have also deleted the i subscripts, Which were inserted earlier as a reminder that the bracketed terms represented nonequilibrium concen. Mation, Hereafter, the subscrips will not be used; you Should, however, eep in mind thatthe quotients that appear in this type of equation are not equilibrium Constants, despite ther similarity in appearance, Equation 22-13 isa general statement ofthe Nemst equation, which can be applied to both halt-cellreag- tions and cell reactions, (2213) ry the half-cell potential when te ay zero. This condition occur, ene ie tue tient is equal to unity, such as, for ttt ti fallen and rod eM the standard potentialis often, etna Ta Potent ofa hale reaction (yn tng Unit act eg The standard electrode pote, tant physical constant that gi ia a jteer tion ofthe relative diving fore fora aay it Keep in mind the following fou ‘ate Gonstant. (1) The electrode poten deendeatiitistohave gitcane at which it is determined must be standard electrode potentialisa rela sense thatitisreally the potential orang cell in which the lft electrode reference electrode — the SHE. signed value of zero. (3) The signof ay tals idenicl with hat ofthe conduaergg | hand electrode ina galvanic cel, withthe kt eae, being he SHE, 4) The stendard potential of the driving force for abalteacon. Asch ie | dependent of the notation uted texas, thetaeg | Drocess Thus although the pote rhege | AB HE ARG) B= sormpy depends on the concentration of ser ions, itis he same regardless of whether we write the half eatin as the preceding or as 100 Ag* + 1006-100 Ag(s) Wi Es s0npy ‘The Nernst equation mus be consistent vith heh Teaction as it is written, For the reaction ‘written for one mole of silver, the Nernst equation is E = on - Og | ays ‘and for 100 moles of silver, osm, 1 E= 0799 - oe 0.0592 1 = 0.799 - =" 190 log —| 0.799 “Feo [5 1 = 0799 ~ 0052p, Le 1 Bae Standard electrode potentials have been tubule for many half-eactions, Many have been eee ; directly from voltage measurements of cellpete ort een lta sre set" however, to calculate E° valeg we Hi et of oxidation-eduction im permet dt ligt ch 9 100 the values found in the iterature jt odin tis WAY.” Gose purposes, afew standard electrode sr enn Table 2; mor comprehen in Appendix 3. The species in the Jeo od pat of he equation ia Table 24 fey eden, asinccated by the age pos as ly are therefore the most effective ox Ge age proceeding down the left-hand side of eis serting eis sales eats er than the one above it, as indicated “ 7 ly negative standard potential, The ys i eats the bottom ofthe abe ave little eee See and, they do tend to proceed in the eotte The rips te 8 nS ¢ most effective reducing genase ist appear elowe sight- ya ofthe equationsin the table. pains of standard potentials provide infor sain opring the extent and direction of electron- ger eats between the tabulated species. sgt for exarple that inc is more ea pond than cadmium, and we conclude that when aie of ine immersed in a solution of cadmium 1 liccadmium will deposit onthe surface othe fac nicl dissolve and produce inc ionsaslongas seen appreciable concentration of cadmium fons ies. On the other hand cadmium has No ten- tonto reduce zinc ions, so piece of caémium i> veredina solution ofzincions wil remain unaflected. ‘Hao shows that iron(II) isa better oxidizing sgattan todd fon, Therefore, ina solution OP thin an equilibrium mixture of iron(Il), iodide, i} and triode ions, we predict that iron(H}) and ‘tnd will predominate— 120.8 Measuring Electrode Potentials Atop ine SHE is the universal reference standard, ‘must emphasize once again that the electrode, as Aeaxibed is almost never used in the laboratory; tS ‘hp esr sand te roi earache ‘etek Date, 16 Mice “Cao and VK. Ts of Sndard Ezcrode Potentials New York: Wily 0" UBM Auten and. ‘Harris, Chemical Electrode Pon a: Phun Pe 182 Same compaion Aas! rycen ned cornea +30 O40) +46 m9 NER 2 ee Es a FRG) + 2eseraeg a iy) + H NOD Cmte, ee oan ra : Bi se egy eR os meas ee co Fae mt) dee aor Za $e a)? i ean see Arend ora nee Aypouhetical electrode to which ex ‘mined potentials can oeraened ea etl putation. The reason that the electrode, 2s defined ‘cannot be prepared is that we are unable to prepare a solution witha hydrogen ion activity of exactly unity. Neither the Debye-Hiickel theory (see Appendix 2) ‘nor any other theory of electrolyte solutions permits the determination ofthe att coeticien of hyror gen ions in solutions with ionic strength approaching nity, as required by the definition ofthe SHE. Thus, the concentration of HCl or another acid required 10 give a hydrogen fon activity of unity cannot be calcu [ated accurately. In spite of this limitation, data for more dilute solutions of ai, for which att coef tents can be determined, canbe wed to compute hy potheial potential at ni activity. The ‘example that Flows ilustrates how staacaFé potential can be OP ‘tained in this way. EXAMPLE 22-1 D,A-Maclnnes* found that @ tion similar to tat shown in gt tial of 052053 V. Te cells call without Liquid june- 22-2 has a poten described by sx 10°? MY ACIS IABmy Chapte 22 Aa neon ecroaalyicl Chemiry Calculate the standard electrode potential forthe hall reaction ‘AgCi(s) +e” = Agte) + : ‘The electrode potential forthe right-hand electrode is Eg * Exga ~ 059210840, = Ehga ~ 00592108 %0-CH where yc isthe activity coefficient of CI". The left half-cell reaction is r Htte = SH) and ‘The measured potential is the difference between these halfcell potentials (Equation 22-12) Eau = (Enya ~ 0592108 ¥¢- Cyc) Pi - (2 000 — 00592108 ) YurSua. Combining the two logarithmic terms gives Yor Gh Eas = Ege ~ 0.0592 og 7S mE a ‘The activity coefficients for H* and CI” can be caleu- lated from Equation 22-3 (Appendix 2) taking 3215 X 10"? for the ionic strength y; these values are 0.945 and 0.939, respectively. If we substitute these activity Coefficients and the experimental data into the previ- ous equation and rearrange, we find Elgg = 05263 + 00s = 0223 ~022V (3215 x 1079 (0.945)(0.939) oer (The mean for this and similar measurements at other concentrations of HCI was 0.222 V.) 7 220-0 Calculating Halt-cey) Potentials from E” Values ‘We illustrate typical applications of the y, tion to calculate hal-el potential Nery, examples. th the ta EXAMPLE 22-2 ‘What i the electrode potential fora ingofacadmium electrode immerse jaa is 0.0150 M int Cd?*? ‘oon Solution From Table 21, we find CHF RCH) Be yyy (Ca) and write Pon z ‘rica concentration into tig ‘We will assume that agg = [ Eca= Eby Substituting the Ca?* The sign for the potentialealcuatedia indicates the direction of the re cellis coupled with the SHE. Th shows thatthe reaction ‘din Example action when ths hae fact that itis negate Cas) + 2H? = Hy) + ca" ocurs spontaneously, Not that the cleus poe tial isa larger negative number than the standard ele trode potential itself. This follows from mas-law cn siderations because the half-reaction, a6 writen, bs less tendency to occur with the lower cadmium ise concentration, cf EXAMPLE 22-3 Calelate the potential fora platinum etn ‘mersed in a solution prepared by saturating 20.0 solution of KBr with Br, Solution The half-reaction is in Vv Br(Q)+2e" 2B B= 5lowing Br, indicates that the apatne H aque- at saturated with liquid Bry. Thus, wt the sum of the two equilibria “ el) — Brel sat’d a9) pr(sat’dag) + 26° —2Br" [Br] = one, the Nernst equation for cat tg ress oe 6s — 00582 jpg BE ge 2° 100 of Br; in the pure liquid is constant and nest yy definition. Thus, gant p= 1065 — Jog(0.0150)" =1173V cups 22-4 the potential for a platinum electrode ‘leah in a solution that is 0.0150 M in KBr and go x10° Min Br. souton pisermple the hareaction used inthe preced igexample does not apply because the solution is no donger saturated in Bry. Table 22-1, however, contains ‘ie llfeacton Bri(ag) + 2e° == 2B ‘heap implies that all of the Br; present is in solu- tion and that 1.087 V is the electrode potential for the halfxeaction when the Br- and Br,(aq) activities are ‘00 mol/L. It turns out, however, that the solubility of | | Brin water at 25°C is only about 0.18 mol/L. There- fore the recorded potential of 1,087 V is based on a hy- pobetal system that cannot be achieved experimen tly, Nevertheless, this potential is useful because it odes the means by which potentials for undersatu- ted gstems can be calculated. Thus, if we assume ttt activities of solutes are equal to their molar con- ‘atrations, we obtain E°=1.087V -p = 1997 — 2952 jog BEI 2 Bal 22 Bap - 2522 (50% 1077 7 8 {9 x107 = 1106V 20 Blecrade Potentials 648 88 was the situation situation when the soluti _ ral jon was sat ‘and excess Br,(!) was present. tats ss E te te tty .00% 30 ran 220-10 Electrode Potentials in the Prosence of Precipitation and. ‘Complex-Forming Reagents Th 7 flowing example shows that reagents hat react vith the participants of an electrode process have & Significant effect on the potential forthe process. — EXAMPLE 22. Calculate the potential ofasiverelectrodein asotution thatis. ‘saturated with silver iodide and has an iodide ion activity of exactly 1,00 (Ky for Agi = 83 x 107"). E°= +079V Agh +e" = Ag) E = +099 = .0§9210g 7 Solution ‘We may calculate ayy from the solubility-product con- stant. Thus, gives 1 Ky This equation may be rewritten as E = +0199 + 0.0592l0gK,, ~ 0.0592loga,- (22-14) i we substitute 1.00 for a,- and use 83 X 10°" for Key the solubility product for AgLat 25.0°C, we obtain E = +0.799 + 0.0592 log 8.3 x 10°” 0.0592 log 1.00 = -0.151V ‘This example shows thatthe half-cell potential for the reduction of silver ion becomes smaller in the presence fiodide ions. Qualitatvely, this isthe expected effect pecause decreases in the concentration of ser ions diminish the tendency for their reduction. ‘Equation 2-14 relates the potential ofa silver elec- trode tothe iodide on activity of solution that is alsoil je can be siver nie, th ofthe iver on ati (wth ‘potential forthe simple set f-reactic f the iodide ion activit arenes Psccote potential forthe silver (tote half-reaction). The siver-sver iodide f-reaction is usually more convenient. . ae pote ofasilver electrode ina solution cOn- taining an ion that forms a soluble: complex with ‘silver oncon be handledin a way analogousto the treatment vive, For example, in a solution containing thiosul fate and silver ions, complex formation Occurs Ag’ #250" = Ad(S.03)2" A448,033" ae sor ‘where K; is the formation constant for the complex. ‘The half-reaction for a silver electrode in ‘such a solu- tion can be written as ‘Ag(S,0,))" +” = Agls) + 2,0" ‘The standard electrode potential for this half-reaction is the electrode potential when both the complex and the complexing anion are at unit activity. Using the same approach as in the previous example, we find that Ke Eo= 0.799 + 0se2log (22-15) 1 Data for the potential of the silver electrode in the presence of selected ions are given in the tables of standard electrode potentials in Appendix 3 and in Table 22-1. Similar information is also provided for other electrode systems. These data often simplify the calculation of half-cell potentials. 22¢-11 Some Limitations to of standard Electrode Potentag ‘standard dlectode Potentials ae of tance in understanding electroanajyao, Mati should emphasize certain inherent gale ee of these data, however tag te ‘substitution of Concentrations for, ‘ ‘as a matter of convenience, mola; rather than activities ~of reactive potting sein making caletations with heen ty Unfortunately, these two quantities re in dilute solutions. With increasing elecuaeSloy trations, potentials calculated wing ge ™ eg tions are in general quite different from, tho et by experiment. To illustrate, the standard elect, ‘the half-reaction SSA SAY, ~~) S SAR SH ode pot ak ata Fe +e" 2 ptt is +0771 V. Neglecting activities, we preg SS Se oye latinum electrode immersed in a solution eet? of Pine mol/Leath of Fe and Fane fat Soot perchloric acid would have a potenta] tite | yo equal to this value relative to the SHE. ie poe ver, we measure a potential of +0732 V viens, | perchloric acid concentration is1M. Wecaneg, 1 #8 reason for the discrepancy if we write the Nernst, elo tion in the form ™ apt B= £9 o0ss2iog FE] - = E? = 0.05920g7 1 ‘Yee [Fe*] fal Pot where yeas and ype are the respective activity ow Hae! cients. The activity coefficients of the two species ae) sing less than one in this system because of the high iowc te previc strength resulting from the perchloric acid andthe 4 qaiye salts. What is more important, however, isthat tear] md tivity coefficient ofthe iron(II) ion ssmaller tants slat of the iron( I) ion, As a result, therato ofthe acti tt; coefficients as they appear in the Nernst equa # pail, larger than one, and the potential of the talee's ace smaller than the standard potential. Mica Activity coefficient data for ions in solutes ote tina types commonly used in oxidation reduction itn Nap and electrochemical work are somewhat iit = Yaty result, we must use molar concentrations #99 Ri; activities in many calculations. Using DO ig Mia tions may cause appreciable errors. Such bey Ge] Tworiat Learn more about standard co = potentials Ss* however, because relative changes i KAN eb ti soe the dito \ eo are suficiently accurate for 4 ee ws 9 ef tandard electrode potentials fur- eetiaed by station, disocaton, associa foes formation reactions involving the 528 gees. example of his problem isthe (eet ge potential of the iron(IM1)‘ron(tt) an equimolar mixture of tons it ic acid has an electrode fete FV, ubsiuting hydrochloric ai (e806 eonceatratin for perchloric acid alters the ee tential to +0.700 V, and we observe a va +0600 V in 1 M phosphoric acid. These ‘ aie of * potential oocur because iron(II) forms Fomplexes with chloride and phosphate ft does iron(I}). As a result, the actual concen- of iron(II) in such solutions is is tat of uncomplexed iron(U), and the net ef- waitin the observed potential. ‘penta can be corrected for this effect ony ifthe ais invoted are known and equilibrium con ‘ete processes are available. Often, however, fion is unavailable, and we are forced to oo information 4 tgetuceffects and hope that serious rors do not seri the calculated results. sais ‘imal Potentials: Theampenste partially for activity effects and errors ‘ruling from side reactions, ‘such as those described in te previous section, Swift proposed substituting a (auity called the formal potential E°' in place of the tunid electrode potential in oxidation-reduction ‘ahitions? The formal potential, sometimes re- faedtoasthe conditional potential, of a system is the Meal ofthe half-cell wittrrespect to the SHE when Seretations of reactants and products are 1M theconcentrations of any other constituents of the ‘hin are carefully specified. Thus, for example, the potential forthe reduction ofiron( Ill) is +0.732 ted Fete acid and +0.700 V in 1 M hy- sagan’. Using these values in place of the stan e potential in the Nernst equation will agreement between calculated and experi- Yay Fi Risa Neainh Stem of Chemical Analysis, p. 50, San France: 22D Cal Cal Pati rom EecoodePtetale 645 formal potenti in subsequent ials as well as standard potentials, and Pr chapters, we will use whichever is more 4 Reaction Rates ae appearance of half-seactin ina tble prlangaye ae atl a necessarily imply that to the half-reaction, Many fhe date neh abe were calculated from. y of data in such tables ‘equilibrium or thermal data, and thus, no actual potential measurements on the elec- trode system of interest were ever made. For some half-reactions, no suitable electrode is known. For ex- ample, the standard electrode potential for the process 2CO, + 2H* + 2e° —H,C,0, was determined indirectly. The electrode reaction is ‘Not reversible, and the rate at which carbon dioxide combines to give oxalic acid is negligibly slow. There is no known electrode system with a potential that varies in the expected way with the ratio of the activities of, the reactants and products of this reaction. In spite of the absence of direct measurements, the tabulated po- tential is useful for computational purposes. 22D CALCULATION OF CELL POTENTIALS FROM ELECTRODE POTENTIALS ‘An important use of standard electrode potentials js the calculation of the potential of a galvanic cell or the potential required to operate an electrolytic cel ‘These calculated potentials (sometimes called thermo- dynamic potentials) are theoretical inthe sense that they refer to cells in which there sno current Addi- ‘be taken into account when there is tional factors must th a current in the cel Furthermore, these potentials do vst take into account junction potentials within th tall Normally junction potentials can be made small enough to be negleted without serious eror {op to 108 0) voimeters, ce der esenialy2ro-curteat contin, $9 ‘nfs fact, with modern sal and procial cell potentials becomes tials can be measured ron ane seitgeal Chemistry (646 Chapter 22 An Introduction to Eloctroanalyticl I from the differ- We calculate the voltage of a ce ‘ence between two half-cell potentials as shown in Equation 22-12. Euan = Eng ~ Eun where Eqgy and Eyq are the electrode potentials forthe two half-eactions constituting the cell. Consider the hypothetical cell ZalZaSO(ang+ = 1.00)||CuSOg(acy+ = 1.00)|Cu both .00, the ‘Because the activities ofthe two ions are | standard potentials are also the electrode potentials. ‘Thus, using £° data from Table 22-1, Fea = Exgu ~ Ex = Eda ~ Ein +0337 ~ (0.763) = +1.100V ‘The positive sign for the cell potential indicates that the reaction Za(s) + Cu®* +Zn2* + Cu(s) occur spontaneously under standard conditions, and ‘elemental zinc is oxidized to zinc(II) and copper(II) is reduced to metalic copper. If the preceding cell is written in the reverse sense, thatis, as CulCu** (ag = 1.00) || Zn?*(az,s = 1.00)|Zn ‘We write the cell potential as Eras = Eggs ~ Ere, = Ey — Edy = 0.763 — (+0337) = -1.100V ‘The negative sign indicates that the following reaction is not spontaneous under standard conditions. Culs) + Zn?* secu + Zn(s) Thus, we must apply an external voltage greater than 1.100 V to cause this reaction to occur, EXAMPLE 22-6 Calculate potentials for th (@) concentrations and (b) activi ies: Zal Z$O4(c2.s0,),PbSO,(sat'd)| IPb where Czaso, = 5.00 X 104, 2.00 x 10°, 1.00 x 1072, 2.00 X 10%, and 5.00 x 107% Solution () Ina neutral solution, little HSO," will be formed; thus, we may assume that [802°] = cxaso, = 5.00 x 10 ‘The hatf-reactions and standarg Potent, PESOAs) + 26° = POG) + 503- Bs. Zn? +2220 BOL 1268 The pte ea cde he, ‘The zinc ion concentrations als 509 10", ‘ang 0.0592 Ezy = ~0.763 - 921, ™ * 500 Io = -0.860 V Because the Pb electrode is specified ay te hand electrode, Seti Fea = ~0252V ~ (0.860 V) = 069 y Cell potentials at the other co calculated in the same way, in column (a) of Table 22-2, ©) To calculate activity coefficients for SO¥*, we must first find the ionic Equation 223 (Appendix 2). We assume that concentrations of Pb?*, Hi, and OH” ae sible compared to the conce CEDtrations can be ir values ae given Za ang strength us trations of Za ang SO. Thus, the ionic: strength is 1 1H = 3{5:00 x 10 x (2)? + 5.00 x 10-4 x ey) = 2.00 x 103 In Table a2-1, we find for $0", ay = 04, and for Zn", aq = 06. Substituting these values into Equation 22-3 gives for sulfate ion = 00509 x 2 x V2.0 x17 714328 x 04 x V2I0 x17 = 0859 x 107 0.820 0.820 x 5.00 x 10"¢ = 4.10 x 10 Repeating the calculations using a Zn** yields ~ log ys0, so Aso. =06 fo Yau = 0825 aq = 4.13 X10 corres eeetic ti a ~ spe Nest equation forthe Pb electrode now - 0.0592 7 2 -03590-—3* log4.10 x 10 In 7 Fug -0250- tore value calculated vsing concentrations jisabout 1% different from this value. Values listed in column (b) of to compare the calculated cell po- ‘town in the columas labeled (a) and (b) in “2. withthe experimental results shown in the roma Clearly, the use of activities provides @sig- tian improvement at higher ionic strengths. 2% CURRENTS IN ELECTROCHEMICAL CELLS Faye, ett te of electroanalytical method is measurements made in the absence of appre . ges pomsionetris methods, which are dis- Chapter 23, The remaining electroanalytical din Chapters 24 and 25, all involve Pa et ‘measurements. Thus, wa, tus the behavior of cells with significant schwsite and VK. LaMer,J. Amer 1 A Cowpe of me. Chan Sou, 08,300 rope dramatically when there is current inthe al, 222E Correntsin Electrochemical Cala 647 As noted earlier, electricity is carried within a cell by the movement offs. With sal creo ‘Ohms law (See Section 2A-1) is usually obeyed and we may ‘write E = JR, where E is the potential difference in volts responsible formovement ofthe ions, isthe cu- rent in amperes, and Ris the resistance in ohms of the electrolyte to the current. The resistance depends on the nature and concentrations of ions in the solution. ‘When theres a direct current in an electrochemical cell, the measured cell potential is usually different from the thermodynamic potential calculated as dem onstrated in Section 2B. This difference can be at- tributed to a number of phenomena, including ohmic resistance and several polarization effects, such a6 charge-transfer overvolage, reaction overvoltage, diffu- sion overvoltage, and crystallization overvoltage. Gen cally, these phenomena reduce the voltage of a gal ‘anic cell or increase the voltage required to produce current in an electrolytic cell. 226-1 Ohmic Potential: IR Drop ‘To develop a current in either a galvanic or an clec- trolytic cell, driving force in’ the form of avoltageis re- quired to overcome the resistance of the ions to move- Rent toward the anode and the cathode. Tust as metalic conduction thisfrce flows Ohms ands equal tothe prduet ofthe current in amperes and the resistance of the cel in ohms. This voltage is generally retpred to asthe fic penal or the IR PoP ‘The net fect of IR drop isto increase the potential ‘operate an electrolytic eel and to deen nic cell. Therefore, 4 potential of a galva avr subtracted from the theoretical required to the measure the IR drop is always su cel potential. That is!" Eas = Big ~ Fu sv ase tha the juin ptt -1R (216) ‘roti and subsequent disaston is gigi compared 08 potentials648 Chapter 22 An Introdetion to Elctroanelytical Chemistry eC EXAMPLE 22-7 ‘The following cell has a resistance of 4.00 2. hee its potential when it is producing a current of 0.100 A. ‘Ca|Cd?* (0.0100 M)||Cu?* (0.0100 M)|Cu > Solution By substituting the standard potentials and concentra- tions into the Nernst equation, we find that the elec- trode potential for the Cu electrode is 0.278 V, and for the Cd electrode it is -0.462 V. Thus, the thermody- namic cell potential is, E= Eoy~ Eca = 0.218 ~ (0462) = 0.740.V and the notential to yield the desired current is, Ex = 0.140 V ~ IR L 740 V — (0.100 A x 4.00 9) = 0.340 V EXAMPLE 22-8 Calculate the potential required to generate a current (0f 0.100 A in the reverse direction in the cell shown in Example 22-7, Current Electrode potential In this example, an external po,.... 4 1.140 V is needed to cause car eat Pee | dissolve at a rate required fora cera Cig A. 226-2 Polarization In several important : measure the current in a cell as a fun. 1, tiods function of yt and construct current versus Voltage carves et data, Equation 2-16 predicts linge?" tween the cell voltage and the cures he. trode potentials. In fac, carers ees frequently nonlinear at the e Sunder ght 8 cumstances, the cell is polarized, Polaratan cur at one or both electrodes. To begin our discussion, itis wet y current-voltage curves for an ideal polo et idea! nonpolaried electrode. Plait 8 electrode can be studied by couping it with ee ode hati not aly pole. Such cee large surface areas and hae half cel recon rapid and reversible. Design details of M slectrodes are described in subsequent hapten ‘deal Polarized and Nonpolarized | Electrodes and Cells ‘The ideal polarized electrode Temains constant and independent of potential ont Wide range. Figure 22-6a sa current-voltage cue bg an electrode that is ide ally polarized in the region be- tween A and B. Figure 22-66: shows the current- telationship for a nonpolarized electrode that behaves ‘ideally in the region between A and B. Fortis eee trode, the potential is independent ofthe cument. is one in which coret tL. . 5 | cde pea L_, o ‘for an ideal (a) polarized and (b) nonpolarzedyotage cue per curent yeon A and B (ue fine) and Soo (oay rel qisacurrentvolag 96 exhibit nonpO ns A and B. Because of e curve for a cell hav- arized behavior be- the internal resist- the ‘current-voltage ‘curve has a finite aie (Gquation 22-16 ther than the inf- br othe onpolarizedelectrode shownin 2a hr ea Fe ration oc One ‘orboth electrodes, = thesia So Theup- ite gecrve gies the CTEM ON relation- is ing as anclectrolytic cel: the galvanic cell. vet eypolritiono {uisloverthanexpected. saucesot Polarization in Electrolytic Cells Fee: 28 shows three regions of a hal-cell in a” ttnlyic cell where polarization can occur. These woe dete itself, a surface film of So- Mnimaaely adjacéiT to the electrode, and the Sserton Fortis half-cell, the overall elee- eatin is a Ox + ne" = Red jx i‘ ' a ecmelireeaie steps shown in the = however, limit the rate of this overall reac~ ek we tw ine coenon dat ede cents 4 Sees aie. Ths price afore erg ‘are ‘most often studied. Some electro- anode cent as postive. When ookog en aera ew comet # 228 Caren in leche Cals 649 tion, which thus limits the magnitude ofthe current: One ofthese step in the rection, called mass ran involves movement of Ox fromthe bulk ofthe solution to the surface film. When this step (or the reverse mass transferofRedto the bulk imitsthe ratte ove reaction (and thus the current), we have conc ‘polarization. Some half-ell reactions byanin- termediate chemical reaction in which species Sub x’ or Red’ form; this intermediate is then the actual participant inthe electron transfer process. I the of formation or decomposition ofthe intermedia im- its the current, reaction polarization ir stances, the rate of a physical process tion desorption, or erystalization limits the éurrent In these cases, adsorption, desorption; OF i polarization occurs. Finally, when the currentis by slow rate of electron transfer from the electrode to ae exiged species the surface film or from the °° duced species to the electrode, We have charge-transfer polarization. It is not unusual to find several types of polarization occuring simultaneous!- the difference between the actual jeetrode potential E and the thermodynamic equi librium, potential Ey, Thats, n= E- Eq (2247) ‘onal potential beyond the thermo- the reaction to occur at where Exg Here, nis the additi ramic value needed to cause ‘cable rate. For cathodic reactions an appre is negative, E must be more negative than Foy and nis reqatve. For anodic reactions where Faqs tive, E reaeipe more positive than Ey and 7 Pos! Concentration Polarization Concentration polarization occurs when The rate of transport of reactive species to the electrode surface is ver pffcient to maintain the current required by equation 22-16. When concentration polarization be- sins a diffusion overvltage SPP=A™ pofanidealnon- polarized anode anda recteode immersed in a solution of a small cadmium ¢ ‘cadmium ions. ‘The reduction: ‘of cadmium ions isarapid reversible process s0 that When 8 potential is ap- urface layer of the solution plied to this electrode, the pomes to equilibrium with the clectrode essentially{650 Chapter 22 An Introduction to Electroanalytica Chemistry Blecrode Sortie layer Pry — o>) Coenen by change Tacton = FIQURE 22-8 Stops inthe reaction Ox + ne ton ne” == Red at an electrode. Note that wransfer the surface layers ony few molactles thick (Adapted from A.J Bard and LR Physica chemi Fauloer, Eocrochomical Methods, 2nd ee) =) SY) Mass ed, p. 23, New York: Wily, 2001 change reaction =o) Reprinted by pernision of John Way & ‘Sons, nc) instantaneously. That is, a brief current is generated that reduces the surface concentration of cadmium ions to the equilibrium concentration, c, given by 0.0592 1 2 Be Ea = Edy (22-18) If there were no mechanism to transport cadmium ions from the bulk of the solution to the surface film, the current would rapidly decrease to zero as the concen- tration of the film approached co. As we shall see, how- ever, several mechanisms bring cadmium ions from the bulk of the solution into the surface layer at a constant rate. Therefore, the large initial current decreases rap- idly to a constant level determined by the rate of ion transport. It is important to appreciate that for a rapid and reversible electrode reaction, the concentration of the surface layer may always be considered to be the equi- librium concentration, which is determined by the instantaneous electrode potential (Equation 22-18). Its also important to realize that the surface concen- tration cy is often far different from the concentration in the bulk of the solution. This is true because, even though surface equilibrium is achieved essentially in- stantaneously, equilibrium between the electrode and the bulk of the solution is established quite slowly and may require minutes or even hours. For a current of the magnitude required by Equa- tion 22-16 to be maintained, reactant must be brought from the bulk of the solution to the surface layer at a rate dn, Ide that is given by 1 = dQidt = nF dn,ldt where dQ/dtis the rate of flow of electrons in the elec- trode (or the current 1), n is the number of electrons appearing in the half-reaction, nq is the number of moles of analyte brought to the surface, faraday. The rte of reaction (molel) car be cL TAL where A isthe surface area ofthe ¢ Jisthe flux (mol s“! em"), The two be combined to give Pinte writen ectrode (cm? ng equations can thea nEAI (ay When the mass-transport process cannot mee the de- ‘mand for reactant, the IR drop in Equation 216. comes smaller than the theoretical value, anda diy sion overvoltage appears that just offsets the decree in IR, Here, we consider an electrolytic cello whch wwe apply a negative voltage to produce a reduction at the cathode. We assume that the anode is nonpolar. ized. Thus, with the appearance of concentration po larization, Equation 22-16 becomes Feet = Eextote ~ Exsote ~ IR + Neto Where Taos Fepresents the overpotential associaed with the cathode. A more general equation for acelin which both electrodes are polarized is East = (Eeatnase ~ Ensoe) + (hates ~ Taos) ah WheTe Mhaod is the anodic overvoltage. Note that tb overvoltage associated with the cathode is negaive and the overvoltage at the anode is postive. Toe oe voltages at each electrode have the ete of reducing the overall potential ofthe cell. Anslogé can be written for a cell in which the reaction wet study is an oxidation at the anode Tutorial: Learn more about cells under 908 standard conditions. ~, ~ RS ¥ ~. ~ yoy Ve SEVEN SIE TE EOE EEE LFof Mass ‘Transport yan smvestgne the mechanisms BY so ip ar aBsPOn from the bulk ° ayer (or the reverse) be~ ie insights into how con- oa roe prevented or induced aes ted in Section 2A-7, there transport: (1) diffusion, section. ign 00a concentration difference be- wes Wer ution, 8 Happens When face (or oxidized at ions or molecules vegoncentrated region 10 the rgitsion des given BY igure deldt = Ke ~ a) (22-21) concentration in the bulk of the gett? oi equim ‘concentration atthe cle is wrtionality constant. AS vot 2 propo a by the potential of an ee jcanbeclcuated fore ad ipo value of os fred the Nemstequa- post) whe? potentials are applied t0 we bere ‘aller and smaller, and the serer and grater. Ultimately, w ae ‘ meee wit Fespect 10 and nn Tecomes constant: That iy when ¢->0, deldt = Ke (22-22) concentration polarization is iets condition, wr he electrode operates as a elplie elect0de- vga sth process by which ions move under je field It is often the pri- the bulk of the solution jul The electrostatic attraction (or repulsion) be tena partalar ionic species and the electrode be- ‘messmaleras the total electrolyte concentration of ‘iewltion becomes greater. It may approach zero tte active species is only a small fraction, $4¥ _ total eoncentration of ions with a given cmc also be transferred mechanically t0 enc Thus, forced convection, such 9s hin Na tends to decrease concentration an. Natural convection resulting from tem- 3 nay eae aoe toma- rt & nig ea moe about mas tamer L 228 Gurren in lerecherica Cols 65% arization is ob- ‘convection are froman elec retical cur To summarize, concentration pol served when diffusion, migration, and intcetep trmmport ho reaant surface at a rate demanded by the theo rent, Because of concentration polarization, ee smustbe applied an electrolytic — the thermodynamic potential ‘Concentration polarization is important in several electroanalyticl methods. In some applications St¢P* are taken to eliminate it;in others, however, it is essen- tial to the method, and every efforts made to promote it. The degree of concentration polarization is influ- enced experimentally by (1) the re - tion, with polarization becoming low concentrations; (2) the total clectrolyte concentra tion, with polarization becoming more at high concentrations; (3) mechanical agitation with “zation decreasing in well-stirred solutions; and {4) electrode size, with polarization effects decreasing as the electrode surface area increases. 225-4 Charge-Transfer Polarization Charge-transfer polarization occurs when the rate of the oxidation or reduction reaction at one OF both Sletrodes isnot sufciently rapid to yield curren's of the size suggested by theory. Overvoltage ov charge-transfer polarization has the following char acteristics: 1. Overvoltages increase with current density is defined as the current Per [A/em’] of electrode surface). 2, Overvoltages usually decreas temperature. 44 Overvoltages vary with the chemical composition ofthe electrode, often being most pronounced with Sater metas such as tn, lead, zine and particularly mercury. 4, Overvoltages are especially processes that yield gaseous {drogen or oxygen, but they are saben a metal is being deposited oF Jndergoing a change of oxidation state. Situation 5, The magnitude: ted because it is deter- density (current unit area ve with increases in ignificant for electrode ‘products such as BY frequently negligible when an ion is a sent aps yn eet SO Re cree at 1 bak A Dette B.A” {aces are in Analytica! fae New Yor: McGrew 155652. Chaper 22 An Invoduction to Elonroenlytial Chonstry titrations (ol) Potentiometric FIGURE 22-9 Summary of common electroznalytcal methods, Quant Parentheses. (Ior i= current, E = potential, R = (of charge, = time, vol = volume of a standard species.) ‘The overvoltage for the evolution of hydrogen and ‘oxygen is especially significant. The difference between the overvoltage of these gases on smooth and on pla- tinized platinum surfacesis striking. For example, fora smooth Pt electrode immersed in 1 M H,SO, at a cur- Tent density of 1.0 A fom’, the evervoltage i 0.68 V; for 4 platinized Pt electrode under the'same conditions, the overvoltage is only 0.048 V. This difference is pri- marily due to the much larger surface area associated with platinized electrodes, which produces a real cur- rent density significantly smaller than is apparent from the overall dimensions ofthe electrode. Platinized sur- faces are always used in constructing hydrogen refer- ence electrodes to lower the current density to a point where the overvoltage is negligible, The high overvoltage associated with the formation ‘of hydrogen permits the electrolytic deposition of sev- resistance, G = conductance, solution, m = mass of an tity measured given in a | eral metals that require potentials at which yoga ‘Would otherwise be expected to interfere. Forex, the standard potentials of hydrogen and zn get that rapid evolution of hydrogen should oor below the potential required forthe depatin d Zinc from a neutral solution, Nevértheles, ac a ‘be deposited quantitatively using a mercury oF op Per electrode, Because of the high overoig hydrogen on these metals (L07 V and 1 spectively, under the conditions cited inthe ee Paragraph), litle or no gas is evolved dus electrodeposition. ‘The magnitude stone crudely approximated from emi avaiable inthe iteatre. Cleat t= in which overvoltage plays a partcaaou very accurate,+968 OF ELECTROANALYTICAL Teno letroanalytical methods hay amc int ; sero erenaleas ve ean erfacal methods, in which current in nO any of the methods that ae geaealy ‘ypen nr amicsl cells playa vital part, are of several (oe dscsed in tht book, are shown in gelato the method shown onthe tin Fg St ae methods are divided into prs cd into inte Potential ofthe cll is contoled wile Fee" Pgs and bulk methods, Interfacial methods,” these mangas °F Ober variable are made. Generally, on widely sed than bulk meth methods are sre Ore 1ethods, are 4s ‘Sensitive-and have relatively wide goo Nena that occur at the intrfac be, ‘YOM Tange (ypc, 10” 1 10°" M). Farher- ote, many of these procedures can be carried out ‘it microliter or een naoliter volume of tmp these methods may achieve detection limits in the pisomole range. eee In constant-current dynamic methods, the current pad 0 Pe surfaces and the thin layer of solution, eae tess srs, alk methods, incon je red on phenomena that oor in the balk een every effort is made to avoid interfacial foal methods can be divided into two major es state methods and dynamic methods, de- foam meter there i current in the ees ‘ell. The static methods, which require po- onmoetic measurements, are extremely important inthe cell is held constant while data ae collected. Dynamicmethods ofboth kinds are discusted in Chap- ters24.and25, Mostf the electtoanalyial techniques shown in Figure 22-9 have been used as detectors in various chromatographic procedures (see Cha ters25,27, and 28), peu QUESTIONS AND PROBLEMS sve are provided at the end of the book for problems marked with an asterisk. [Xf Podlems with this icon are best solved using spreadsheets. ‘*01 Calculate the electrode potentials of the following half-els (@) Ag’(0.0261 M)IAg (b) Fe2*(6.72 x 10-¢M),Fe?*(0.100 M)|Pt (©) AgBr(sat’d),Br”(0.050 M)|Ag ‘02 Calculate the electrode potentials of the following half-cells. (a) HO(1.76 M)|H,(0.987 atm),Pt (0) 10, (0.194 M),1,(2.00 x 10™* M),H°(3.50 x 107? M)|Pt (0) AgsCrO,(sat’d),CrO,?"(0.0520 MIA "23 Foreach of the following half-cells, compare ele ‘rom (1) concentration and (2) activity data. (2) HCI(0.0200 M1),NaC(0.0300 M)|H(1.00 atm),Pt (0) Fe(ClO,),(0.0111 M),Fe(CIO,);(0.0111 M)IPt ™ Fret of the following hal-cells, compare electrode potentials $ (1 2) data. (1) concentration and (2) activity io x 107 MOF (@) s(C10,),(3.00 x 10° M),Sn(C10,). ie M)IPt 1) sno ean 12M Sa{I0, (0 x 107 MONECIOACED 4 .ctrode potentials calculated calculated : is following: "5 Cakcuae the potential of a ver electrode in ome wa the (2) ascution that is 0.0150 M inf amdsaturney cn (t) asolution that is 0.0040 M in CN” andElectret! Cheiry 654, Chae 2 Anno (ete soi that ests fom 2500 of 0050048 Wit ng of 100M AS" ie of 0100M KBE ie ‘caleulte the electrode pot Sa (@) C0} (400 x 10") M0) {&) U0#"(0.200M9,U*" (0. tials forthe following systems: ‘Cr?"(2.00 X 107? M).H"(0.100 MP (0 M),H°(0.500 MIP th theoretical potent ofeach ofthe following cls the m7 ‘nano written or spontaneous in the opposite direction? Song xy). x 107 UPLOAD I (0 Malgg (20 «10 MIPHC00% 17 .V""00 1095 200 x 107 MIP -saokse* 7 ore ca00 B10"? M) Fe?" (3.00 x 10" M)lISn*(5.50 x 10°, at*(350 x 10°*M)]Pt «228 Calelate the theoretical potential each of the following el. thet ca spontaneous as written or spontaneous in the opposite direction? {4 BABI (2.0400 M), #10200 MIT (0100 Ag st dg 8 zalzn"(130 x 10" M)Fe(CN) "(450 x 10™ MD.Fe(CN)." (20 10°? M)IPt (€) PuH(0200 aim |HCU7.50 x 10-4M), ABCISAEDIAR +229 Compute E* for the process Ni(CN)2° + 2e° ==Ni() + ACN call rgg. given that the formation constant forthe complex is 0 x 10% 22:10 The solubility product constant for Pb, is 7.1 X 10-? at 25°C Calulate£°for the process PbL(s) + 26° —=*Pb(s) +21; 2241 Calculate the standard potential forthe hal-raction BiOC(s) + 2H* + 3e° —*Bils) + Cl + H,0 given that Ky for BIOCI has value of 81 x 10" 22-12 Calculate the standard potential for the half-eaction ANC,0,)5 + 3e7 Alls) + 26,02" it tne formation constant forthe complexis 13x10", ~ +2213 From the standard potentials TI +e ATMs) EP = -0336V TICs) +e" Tis) + Cr EP = 05579 calculate the solubility product constant for TICl #2214 From the standard potentials ‘Ag,SeO,(s) + 2” == 2Ag(s) + SEO” Ag +e" Ag(s) £°= 0.799 F*=0355V calculate the solubility product constant for Ag,SeOx- — SSRN, NS ~ S SS BRR FREER EE eSE SSS £4 € FFEFs qgoee tbat We wish to produce a currey ivr? * 10° M),V2*(4.48 x ra 910.750 A in the mss eign the el hes a i MIB O08 2) 7 “ga potential ofthe cel. ternal resi 0,Agps cal Te * gO One BST X 10° M,V0" 049 x 1: grat X 10° MIC .50 x ane 4 interna resistance of 381.0. What wi a is drawn from this cell? t willbe thei intial potenti lif current bn of the galvanic cell yi (482 x 10M) FE(CN) 899 x 10-9 A yom lFaCN) ee Fs-caclate the initial potential when 0.0442 a £8.95 17 ag pdowing data are similar to those piven 4s drawn from ths Te svenin Example tt oo goss 052053, gos (0B ORDR os 05609 09259 0.49257 : am gor! 09173 0.47948 ozms paneer teense toa | 0135 0.9031 0.45861, 022058 . i tyr = 08S ITA otto 0.8843 0.43783 022047 056s 0.8660 041824 © 022260 5391 0.8293 0.38222 022056 es 7871 034199 022044 a) Create a spreadsheet t0 calculate the standard electr ® ‘Ag-AgCl electrode using the method described in’ Senet | ‘elamns forthe activity coefficients and the standard potential. Calculate qialues for H’ and Clr for each ‘molality. Then find 7. at each molality. Use the measured values of E to find E° at each ‘molality. (6) Compare your values for the activity coefficients and standard potential with thor of Maclnnes, and if there are any diflerencet between your values and those in the table above, suggest possible ‘reasons for the discrepancies. (9 Use the Descriptive Statistics function ‘of Data Analysis Toolpak toad — the mean, standard deviation, 95% confidence interval, and other useful sta- tists for the standard potential of the ‘Ag-AgCl electrode. ; (@ Comment on the results of your analysis and, in cular, the quality of Maclanes' results. tiknge Pr Panty 1D Asapartofa study to measure the dissociation constant of aetic aid Hat tad Ehlers needed to measure E” for the following cell: — ; 9. Pati Te rape of Eesrochenisry Tab 130.8 Sa cas me Holler, Applications ‘of Microsoft® Exc ‘54 (4), 1380-57.PLH,(1 atm)|HCI(m),AgCi(sat’d) Ag, (a) Write an expression for the potential of the cel. (b) Show that the expression can be arranged to give RT Eo B= Fla typ te Morma where myo: and mc are the molal (mole solute per kilogran centrations. a solvent con, (©) Under what circumstances is this expression valid? (@) Show that the expression in (b) may be written E + 2klogm = E° — 2klogy, where k = In10RTIF. (e) A considerably simplified version ofthe Debye-Hickel expres ‘ald for very dilute solutions is og y = -0.5'Vm + imaneernete Show thatthe expression for the cell potential in (2) may be writen set E + 2klogm — kVm = E°~ 2kem (0) The previous expression is a “limiting law” that becomes linear asthe aan the electrolyte approaches ero. The equation assumes the form” y= ax +b, where y = E + 2logm ~ km; x = m, the slope;a = ~2ke, and the y-intercept b = E*. Harned and Ehlers very accurately measured | th potential ofthe cll without liquid junction presented at the beginning re problem as function of concentration of HCl (mola) and temperature and a ained the data inthe following table. For example, they measured the coe heel at 25 wih an Cl concentration of O01 mand obit value of 0.46419 volts. Potential Measurements of Cell PtH,(t atm)|HClim) AgCi\sat)|Ag without Liquid Junction as a Function of Concentration (molly) and Temperature (C) moll Ey Es Ew Es Ew Bs Ey by 0.005 0.48916 0.49138 0. 49338 0.49521 0.44690 0.49844 0.49983 0.50108 0.006 0.48089 0.48295 0.48480 0.48647 0.48800 0.48940 0.49065 04916 0,007 04739 0.47584 0.47756 0.47910 0.48050 0. 48178 0.48289 0.48389 0.008 0.46785 0.46968 0.47128 047270 0.47399 047518 047617 0471 0.009 0.46254 0.46426 0.46576 0.46708 0.46828 0.46237 mms 04 0.01 04578 0.45943 0.46084 0.46207 0.46519 04619 046159 asses oon 042669 042776 042802 0.42825 0.42978 0.43022 cgoK9 8 rns 04108 os 040859 040931 040993 0.41021 O1041 a4t056 004 039577 039624 039668 039673 0.39673 039666 039638 a 0.05 0.38586 0.38616 0.38641 0.38631 0.38614 0.39589 03850 been 106 037777 037793 037802 037180 0379 037% O51 gs 007 037093 0.37098 0.37092 0.37061 0.37017 0365 0368" Og tos 036197 036195 036179 03608 036382 03600 we ss 0.09 035976 035963 0.35937 0.35848 0.35823 agsrst 03568 oy aso 03510 Oo m, od 035507 0.35487 033451 0.35394 0.35321 a8 (0.23627 0.23386 0.23126 0.22847 ozasso 0779 021 —— X i.