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Electrode Potentials
higher Fermi level into the metal with the lower Fermi level. This electron transfer results in a separation of charge and an electric potential difference across the phase boundary. The effect ofthe electric potential difference is to raise the energy of the conduction band of the second metal and to lower the energy of the conduction band of the first until the Fermi levels dre equal in energy; when the Fermi levels are equal, no further electron transfer takes place. In other words, the intrinsically lower energy of electrons in the conduction band of the second metal is exactly compensated by the electrical work required to move an electron from the frrst metal to the second against the electric potential difference. A very similar process occurs when a metal, say a piece of copper, is placed in a solution of copper sulfate. Some of the copper ions may deposit on the copper metal, accepting electrons from the metal conduction band and leaving the metal with a small positive charge and the solution with a small negative charge. With a more active metal, it may be the other way around: a few atoms leave the metal surface as ions, giving the metal a small negative charge and the solution a small positive charge. The direction of charge transfer depends on the metal, but in general charge separation occurs and an electric potential difference is developed between the metal and the solution. When two dissimilar electrolyte solutions are brought into contact, there will be a charge separation at the phase boundary owing to the different rates of diffusion of the ions. The resulting electric potential difference, called a liquid junction potentiol, is discussed in $3.4. In general, whenever two conducting phases are brought into contact, an interphase electric potential difference will develop. The exploitation of this phenomenon is one of the subjects of electrochemistry. Consider the electrochemical cell shown in Figure 1.2. A piece of zinc metal is immersed in a solution of ZnSOa and a piece of copper metal is immersed in a solution of CuSOa. The two solutions make contact with one another through a fritted glass disk (to prevent mixing), and the two pieces of metal are attached to a voltmeter through copper wires. The voltmeter tells us that a potential is developed, but what is its origin? There are altogether four sources of potential: (1) the copperzinc junction where the voltmeter lead is attached to the zinc electrode; (2) the zinc-solution interface; (3) the junction between the two solutions; and (4) the solution-copper interface. The measured voltage is the sum of all four interphase potentials. In the discussion which follows, we shall neglect potentials which arise from junctions between two dissimilar metals or two dissimilar solutions. This is not to say that such junctions introduce negligible potentials; however, our interest lies primarily in the metal-solution interface and solid or liquid junction potentials make more or less constant additive contributions to the measured potential of a cell. In
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was a physiologist at the University of Bologna. Luigi Galvani ( 1?3?-1798) Beginning about 1?80, Galvani became interested in "animal electricity" and conducted all kinds of experiments looking for electrical effects in living systems. Alessandro Giuseppe Antonio Anastasio Volta (17451827) was Professor of Physics at the University of Pavia. Volta had worked on problems in electrostatics, meteorology, and pneumatics before Galvani's discovery attracted his attention. IYilliam Nicholson (1?53-1815)started his career as an East India Company civil servant, was then a salesman for Wedgwood pottery in Holland, an aspiring novelist, a teacher of mathematics, a physics textbook writer and translator, a civil engineer, patent agent, and inventor of scientific apparatus. He founded the Journal of Natural Philosophy, Chernistry, and the Arls in 1797, which he published monthly until 1813. Sir Anthony Carlisle (1768-1840) was a socially prominent surgeon who dabbled in physics and chemistry on the side. Sir Humphry Davy (17?8-1829)was Professor of Chemistry at the Royal Institution. Dary was an empiricist who never accepted Dalton's atomic theory and spent most of his career looking for defects in Lavoisier's theories, but in the process he made some very important discoveries in chemistry. Michael Faraday (1791-1867) began his career as Davy's assistant at the Royal Institution, but he soon made an independent reputation for his important discoveries in organic chemistry, electricity and magnetism, and in electrochemistry. Although his electrochemical work was seemingly an extension of Davy's electrolysis experiments, in fact Faraday was asking much more fundamental questions. Faraday is responsible (with the classicist William Whewell) for many of the terms still used in electrochemistry, such as electrode, cathode, anode, electrolysis,anion, andcation. John F. Daniell (1790-1845)was Professor of Chemistry at King's College, London. Daniell was a prolific inventor of scientific apparatus but is best known for the electrochemical cell which bears his name.
by and that water was decomposed electrolysis. The Nicholson-Carlisle experiment, published in Nicholson's Journai only a few weeks after Volta's letter, causeda sensationin scientifrccircles throughout Europe. Volta's battery had provided for the first time an electric potential source capable of supplying significant current, and this technical advance, spurred by the discoveryof water electrolysis,led in the next decadeto the real beginnings of the study of electricity and magnetism, both by physicists and chemists. In the forefront among chemists was Sir Humphry Davy, who used the voltaic pile as a source of electricity to isolate metallic sodium and potassium in 1807, magnesium, calcium, strontium and barium in 1808, and lithium in 1818. Davy's assistant, Michael Faraday, went on in the next decadesto lay the foundations of the scienceof electrochemistrv.l
I The early history of electrochemistry is brilliantly expounded in Ostwald's 1896 book, now available in English translation (C1).
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Now let us see how electrical work is related to the experimentally measurable parameters which characterize an electrochemicalsystem. Consider an electrochemical cell (the thermodynamic systern) which has two terminals across which there is an electric potential difference, E.1 The two terminals are connectedbv wires.to an external load (the Q*
or
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surroundings), representedby a resistanceR. When a charge Q is moved through a potential difference .8, the work done on the surroundings is EQ. The charge passedin the circuit is the product of the number of charge carriers and the charge per charge carrier. If we assumethat the charge carriers are electrons,then Q = (number of electrons) x (charge/electron)= Ne
= Q = (number of moles electrons)x (charge/mole) np where F is the Faraday constant, the charge on one mole of electrons, 96,484.6 coulombs (C), and z is the number of moles of electrons transferred. Thus the work done by the system on the resistor (the resistor's energy is raised) is simply nFE. However, according to the sign conventionof eq (1.1),work done on the systemis positive so that the electrical work is negative if the system transfers energy to the sumoundings, (1.6) Substituting eq (1.6) into eq (1.5), we obtain the change in Gibbs free energ'yof the system,
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(r.7)
If E is measured in volts (V),,F in C mol-l, and z is the number of moles of electrons per mole of reaction (mol msl-l), then AG will have the units of joules per mole (J mol-l) since 1 J = 1 V-C. This quite remarkable result immediately demonstrates the utility of electrochemical measurements: We have a direct method for the determination of
I In Chapter 2, where we will be dealing with electric potential in a slightly different context, we will use the symbol O for potential. Here, we follow tradition and denote the potential difference produced by an electrochemical cell by the symbol E, which comes from the archaic term electromotiue force. The electromotive force or ernf is sJ.nonyrnouswith potential difference or voltage.
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Electrode Potentials According to convention,the free energy change for the cell reaction is negative if the reaction proceeds spontaneously to the right and, accordingto eq (1.7),the cell potential should then be positive,i.e.,the right-hand electrode (Hg) should be positive with respect to the left-hand electrode(Cd).
Figure 1.4 The Weston cell.
CdSOa solution HgSOa(s)
Let us see if this is consistent. If the Hg electrodeis positive, then conventional(positive) current should flow in the external circuit from + to - (from Hg to Cd) and electron (negative) current in the opposite direction. Thus electrons should enter the cell at the Hg electrode, converting Hg2SOato Hg and SOa2-[as in eq (1.9)],and leave the ceII at the Cd electrode,convertingCd to Cd2+ [as in eq (1.8)];this is indeed consistent with the overall cell reaction proceedingfrom left to right as in eq (1.10). The cell convention can be summarized as follows: For an electrochemicalcell as written, finding that the right-hand electrodeis positive, relative to the left-hand electrode,is equivalent to a negative AG for the correspondingcell reaction. Conventional positive current flows from right to left in the external circuit, from left to right in the cell. Negative electron current flows from left to right in the external circuit, from right to left in the cell. The left-hand (negative)electrodeis called tl:.e anode and the electrode process is an oxidation (removal of electrons);the right-hand (positive) electrodeis called the cathode and the electrodeprocessis a reduction (addition of electrons).1
I The identification of the cathode with the reduction process and the anode with the oxidation process is common to both galvanic and electrolysis cells and is a better
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the arguments of logarithms in expressionssuch as eq (1.12) are also unitless. In this chapter, we will usually assumeideal behavior and ignore activity coefficients. We will return to the problem of nonideality in $2.6. The Nernst Equation If we take eq (1,.11) be the overall reaction of an electrochemical to cell, then eqs(1.7)and (1.12)may be combined give to -nFE =AGo +.R?ln (oc)Y(oo)D (oe)"(as)P (1.16)
Ifwe introduce the standard potential, definedby Eo = -LGolnF E=Eo-,RTh(oc)T(ao)6 nfl (oe)"(os)P
(L.L7)
and rearrange eq (1.16) slightly, we have the equation first derived by Nernst in 1889: (1.18)
The Nernst equation relates the potential generated by an electrochemicalcell to the activities of the chemical speciesinvolved in the cell reaction and to the standard potential,E'. In using the Nernst equation or its predecessors, (1.7) and (1.17), eqs we must remember the significance of the parameter n. We usually use AG in units of energyper mole for a chemical equation as written. The parameter z refers to the number of moles of electrons transferred through the external circuit for the reaction as written, taking the stoichiometric coefficients as the number of moles of reactants and products. In order to determine n, the cell reaction must be broken down going on at the electrodes(the half-cell reactions) as into the processes was done in discussingthe Weston cell. If the Nernst equationis to be used for a cell operating at 25'C, it is sometimes convenient to insert the values of the temperature and the Faraday and gas constants and convert to common (base 10) logs. The Nernst equation then is
E = Eo- o.o;592 lc-qxqp)l los tL

(oe)"(oe)B
(1.1e)
Let us now apply the Nernst equation to the Weston cell. Identifying the appropriate speciesfor substitution into eq (1.18)we obtain (with n = 2 moles of electronsper mole of Cd)
'6 raldeq3 ul paroprsuocare aJuelsrp q1,nr 1ur1ua1od uorllrel srr4lJo spelap ar{J I Jo
'g'I orn8rg ur u/$oqs qcla>Is aql a{TI Surqlauos >IooI ?snruuaql p4ualod aq+Jo elgo.rdaq; T'sarrpunoq aseqd aql le sralaruerprBlnJaloru^\aJe ralo rorlloue oJ. anleA luelsuoJ auo ruo{ sa8ueqc pue uoqnlos e1d1or1aa1a aql Jo {Inq aql ur pue saporlrala aq? Jo aseqd rrllelatu aql UFIIIA 'IIac aq1 q8no.rql dFt e uo aas plno^\ uorlrole luelsuoJ sr lergualod aqJ, ,11ac uu Irlualod uolsod\ aql upFe raprsuoC Jo {ulql pue 'silac-JIBTI "ql aIqBIreâql IIB Jo uorlBurquo:) alqrssod d.rarreSursn polcnrlsuoc aq uc qclqa slloc aql IIE t{f1n 1eapol Suraeq uer1l rot{ler fgenpr,rrpur [ar-Jleq qcea raprsuoc uec aa, ,s1pse.rFurlepq? pue gr ecedspue oruq ur 8urles 1ea.r3 aq IIpr e.raq1 e 5uu(grsselc (U) puB 'uorlelosr ur pulsJapun ol a{rl plno^\ o^\ qcltl.6, ur uorlcor ele.redasE sallolur IIac-JIBq rlcea (I) aourssIIac-JIq lenpr^rpur go sarpado.rd aq1 Surssncsrp ur sa8eluelpe aJ eJoqJ .uorlceor suoJlcolaJo salourJo raqrunu aq1 .u aurruJe?ap Jo alotu .rad pe.r"ra;sueJl o? rapro ur suor?reer llac-Jler{aql ^\ou{ lsnru a^l paapul 'f1a1e.redas saporlrala 9al oql 1e aceld 3uqe1 suorlrear oq? Jo srurel uI IIaJ B Jo uorleradoaq1Jo {uTql o1 alqrssodsr 1r ,uoasdpeerp eABr{ sV a/$, slo?Iuatod naC-hoH
'otJnos .luorcgact prepuls e sB pasn dlaprrrruooq ser.{ IIor aqJ _1e11ua1od e.rnle.radruelIIBurs f1arrr1e1e.r seq pue olqrcnpo"rdae E dpseo sI ,5ogg '11ac uo1sa11 eqlJo prlualod orl;, .?uaÎos aqlJo uorle.rodeaa le A 08I0'I se qcns sa8ueqc 01 elr?rsuasur {1am1elar aq ol uaos sr 1er1ue1od aq1 'uzu,u.rp sluaJJnc llsrus fpo 3r 1nq ,dlqerca.rdde eJ uorlu.rluocuoesftn aFueqc ol pazrpuo aq ppor runfiupec or{l Jo q8noua ,11ac tuo.r; unaerp aq1 sr luaJJnc luarcrJlns JI 'luelsuoc sureruar (uoqnlos f,rnc.raru; rue8pnre aq? q run5upec Jo uoqerluacuoc aql lerIl poprrro.rd luelsuoc s1 dlrarpe pC oq? 'd11eurg '?uelsuor sureruar arnleradural aql JI luelsuor are sar?rlrloeuor -U7OS pue +zpC aql ?eql os .tOSpC ur palrnles sr uor?nlos aqJ 'sorlrlrlce lrrm aleq os pu slerraleru e.rnd e.re Tggz8g pue Eg
(02'r) tr
'z(.rlsruraqc lecrsdqd uollnlos o? Pu (^rB-I prlr.{J aql poraôrsrp or.{)scil.uBuz(poruraql suorlnqlrluoc ol 'ullrag pue ua8utlloC ?uplrodtul dueur apul lsuraN Jo sarlrsra^ruIf aq1 1e dllsturaq3 lears{q4 Jo rossaJord ro?Bl puB Srzdrel ;o flrs.rairrun aql 18 lulsrssB s,pl^\lso sB^1, (Tt6I-?ggT) lsureN roqllB^l uuBurreH
,tZ ofl (sH;)l?d$)(.-;F5t)urztr- = n scrtuuudporurorll 11oC lecrruoqcorpalg Z.IS
('osz8up;1P3rl
l2
Figure 1.5 Hypothetical electric potential profile in the Weston cell.
E=
Ecel = -Ecd2+/ed + EHezSO +lttg
(oca2.)
The Nernst equation for the Weston cell, eq (1.20),gives us the cell potential as a function of the standard potential and of the activities of all participants in the cell reaction. We would like to break eq (1.20) into two parts which represent the electrode-solution potential differences shown in Figure 1.5. It is customary in referring to these so-called half-cell potentials to speak ofthe potential ofthe solution relative to the electrode. This is equivalent to referring always to the electrode process as a reduction. When, in the actual cell reaction, the electrodeprocessis an oxidation, the contribution to the cell potential will then be the negative of the correspondingreduction potential. Thus in the case of the Weston cell, we can write for the cell potential (7.21) Breaking the standard cell potential into two componentsin the same way, the half-cell potentials definedby eq (1.21)can be written in the form of the Nernst equation such that substitution in eq (1.21)gives eq (1.20). Thus n6 RT rtcd2ycd = 6"9d2-tcd-"21r. h , @ c 4
Eug2soa/He= EoHsrson/H ,-#t"
1;#
Unfortunately, there is no way of measuring directly the potential difference between an electrodeand a solution, so that single electrode potentials cannot be uniquely defined.r However, since the quantity is not measurable we are free to assign an arbitrary standard potential to one half-cell which will then be used as a standard reference. In effect this establishes a potential zero against which all other half-cell potentials may be measured. By universal agreement arnong chemists, the hydrogen electrode was chosen as the standard reference half-cell for aqueous solution
I We will see in $2.5 that some properties (the electrode-solutioninterfacial tension and the electrode-solution capacitance) depend on the electrode-solution potential difference and so could provide an indirect means of establishing the potential zero.
snoanb'uou roJ srr+uarod aruaraJar urolqordaqr Jo uorssncsrp ,;;tj:tt": roJ Jo 'suorlelncler qrns Jo saldruBxa IBraAas qEnoJq? >Iro1r\IIr^\ a,& uor?cas srql uI '(9O) luBlsuoJ runrrqrlrnba aq1 a?InclBc Jo ,d?rauEluods Jo uorlrarrp -os1e aqt tclpard-'opy alndtuoc ol BlBp ler?ualod IIac prpuqs asn uec aru' '(/,I'I) ba dq uorpear IIac aql roJ a8ueqc d8.raue aa4 sqqrC prepue?s oql o? pa??Ior sr_IIOJB Jo Iequalod p-repuels oql aDurs .sIIaJ lBcrruaqcorlcala Jo roqrunu oFrBI B Jo sle4ualod aq1 lcrpa.rd uea aar ,(lfl{:f I{) sprlualod IIor-JIBr{ Jo suo4callor a^rsualxa orour ro ?.v aIqEJ Jo B?Bp aql qllla
sTyrrNsrod cuvorwrs .{o sfisn silros g.I
'7'V alqeJ xrpuaddv ur ualr,FsI ,(gIH) ueprof pue ,suos.re4 'pleg dq uorl_epdtuoc luacar aq? uro.r; ua>IB?,e1ep qcns Jo uoqralas 's1er1ua1od IIao-JIBTI salql olrsualxo dn 11rnq aABq sls(uaq? Jo
'apor?rala ue8o"rp,(qaqJ g.I a.rn8gg
,o
'o
ar{l Jo pqualod aqt snr{J 'A 000'0 go pqualod prpu'ls p".r:rrr$".l "q1 (8)zHe-aZ+(bB)+HZ uogcear IIac-JIeqaqJ -palqqnq sr se8 ueFolpdq qr-nl,!\raô ({cEIq umuqeld) runuqeld papplp dlaug ql1rr\paleor opor?ralaunurleld e jo slsrsuoc 'g'1 a.rnFrgur u^{orls ,epo.r1ca1e ueEorpfq eq;, ,.lfulsrtuaqcorlcala 8I
scrureulfporuroqJ IIaC lcruaqcorlcolf, Z.I$
uZl(l=D)+'6uZ'(I=e)+Hl(I =o'8)zHlld
apor?calauaSo;pfq aql Surureluoc sflac qcns dueru Jo slerluolod aql Sur.rnseeru '1ec-gpquZl+zuZaqlJo prlualod p.rupuelsaqi of pnba ir dg
14
Potentials, Free Energies, and. Equilibrium Constants
The half-cell reactions are combined to give the cell reaction -+ m.B+nC mA+nD
Eocell = EoNB-EoclD
Many half-cell reactions in aqueous solutions involve fl+, QH-, weak acids, or weak bases, so that the half-cell potential is a function of pH. while this dependenceis predictable using the Nernst equation, it isoften inconvenient to take explicit account ofpH effects and a variety of techniques have been developedto simplify qualitative applications of half-ceil potential data. An understanding of these methods is particulaily important in biochemical applications. Several graphical presentations ofhalf-cell potential data have been developedin attempts io make it easier to obtain qualitative predictions of spontaneity for redox reactions.
Building a hypothetical cell from two half-cells is straightforward on paper. (The construction of an actual working cell often can present insurmountable problems.) Consider two half-cells EoAIB A+ne- -+ B Eoc/n C+me- -r D
where we have multiplied the frrst equation by m, the secondbyn, subtracted. To see that the cell potential is just
and
(1.22)
we need a few lines of proof. when we add or subtract chemical equations, we similarly add or subtract changes in thermodynamic state functions such as U, H, S, or G. Thus in this case
AGocell- m LGoNs - n LG"g1p AGocell= m (-nFEoAlB) - n (-mFE"Cto) AGocell - -mnF(Eo 61s- Eocln) = -(mn)FEo cell where mn is the number of electrons transferred per mole of reaction as written. Why can we combine half-celt potentials directly without taking account of stoichiometric coefficienti, whereas AG's must be properly adjusted before combination? There is a significant difference between Ed and AG': G is an extensive property of the system so that when we change the number of moles we are discussing, we must adjust G;E,on is independent of the size of the olher hand, is an intensive variable-it the system-related to AG by the extensive quantity zF.
A IIZ0'0 =.a. Ll66'0= "g
'ap{uoJq reÎrs roJ oql luBlsuoc ?rnpord-dlrlrqnlos alndluoc (bB)_rg (s)8v (- _o+ (s)rg8v +
(s)FV e sFrlualod -a+(bB)+FV IIac-JIBr{ aql uo^rc u.I aldruBxg
'sluarualnseau Fllualod 11acpcnueqcorlcala ur sur8r"ro.naq1 arreq f.rlsruraqc uoqnlos snoenbe ur rolunooua oA\ s?uelsuoJ urnr.rqqrnba lerus d.ran .ro e3.re1d.re,r aq1 Jo lsoru ,paapul .BlBp IecrruaqJoJlcolo ruo{ dlsea d1a.tqe1a.r alnduroc o? aIqB aJo^\ 1r alt\ ?nq 'suor?BrluacuoJ luanlrlsuoc aql IIB Jo ?uauarnsEaru dq dlpe;p aurrrralap o? llnoglrp aq lqFrjrr 1r 'e3"re1sr )U.asnecag
z[-I]"[*ea.{l
ffi=4oI
x9'8=>l
JAI.CV- = )1uI .zI puB +6ad onrFo?-I qlyvl' +gadJouoqoear aq?roJ luelsuoc urnr.rqrpnbe ar{} alelnclec ol lerluo?od gac aq1 ruo.gpalndruoc a8ueqc dF.raua aaJJ PrBpuBls aql osn uJ a^\ snqJ 'suor}rpuoc lBcluraqt -or?ralauou Jopun uorlceal oql JoJ dldde plnoqs a8ueqa d8raua oa4 prepuals atus aq;, 'suorlrpuoc prupuels Jepun snoaueluods sr uor cu.ragdq uor oprporJo uorlptxo oq? snr{J r-Iolu f){ 8'9t- = oCV = "CY "E,ilZ--lFlogA 982'0 = +7a8,/+gad'og llatofl =
uI + +Uad <- -lZ, + +eo,tr.Z Z :puocasaql lcerlqns pue 6 fq uorlenba ?srg aql dldrlptu an ,uorlcear IIar IIeraAo aql ule?qo oJ -IZ <- -aZ+zI A g g g ' 0= - V z t o g
'(suoqnloso^{l aq? ale.redasol pasn o8pr.rq lIBs ol sraJarourl IBrqraA olqnop eql) (s)ldl(bB)+sad'(bB)+zodll (be;z1,1be;-1 g1s;16 IIac aq?roJ oCVpw ofl alndruo3 1.1 alduexg
LILL.g = +Zadl+tag.g +6ad <- _o+ +eod :e1epSuvrrolloJ aq?pug a^\ 't'V alqe,Lo1Suuragag slBqualodprepuB?sJo sasn auros g'I$
ga
t6
Electrode Potentials Subtraction ofthe first half-cell reaction from the second gives the AgBr solubility equilibrium AgBr(s) C A#(aq)+Br(aq) The standard potential of the hypothetical cell with this reaction is -0.7280 V Ecell = E"AgB"/Ag E AC*lAc,=
B+m e- -r C A + (n+m) e- -+ C E"Blc EoNc Converting to standard potentials, we have -(n+rn)FEo NC = -nFEoA.rB- mFEoglg or
Fo ^,^ -nEoNB + rnEoBrc
n+m "fttv-
LGo= -nFEo =70.24 kJ mol-l = K = 4.95 x 10-13 (tAg+aB'-
While potentials of half-cells are simply subtracted to compute the potential of a cell, there are seemingly similar calculations where this ipproach leads to the wrong answer. Considerthe half-cell processes EoNB A+ze- -+ B
Clearly the last reaction is the sum of the first two, but EoNC is not t'}ae It sum of Eo56 and.EogTg. must be true that + AGoA/c= AGoA,rB AGogTg
(1.23)
so that when half-cell potentials are combined to produce a new half-cell, the potentials are not idditive. The best advice for calculations involving half-cell potentials is: When in doubt, conuert to free energies before doing thi calculation. Since the desired result is often a free energy change or an equilibrium constant, this strategy usually involves no more computationsand is much less likely to lead to errors' Example 1.3 Compute the standard half-cell potential for the The and reduction of Fe3+to Fe(s) given Eopge+/ps2+ Eopsz+7ps' half-cell potentials from Table A.4 are Eo =0.771Y Fe3++e- + Fe2+ -+ Fe(s) E =4.44Y Fe2+ + 2 e-
'LTL4O Jo Iequalod prpue?saql ruo.r;lueraJ}rpdlluucgru8rs ,A ZgZ.0= oqJ ,"A sI TOICH I I I q eldnoc(II)a,{/(III)a,{ arll Jo prlualod 'g'V aIqBI ur ua,r-Fsr suo4nlos TOSZHIBruroJ ,ICH I IAtr pue I tr 'tOICH y I I I I roJ spgualod 1euuoJ aldwes a,u1e1uesa.rda.r.uorlenba Jo lsuJoN aql qlTrr{suorlBlnJleeur 'runrpaur aql o? aler.rdo.rdde spqualod 'pasn oq uoq? uer suor?E"rluoruor relory .?u?suo? IuroJ qlrirr "reqleFo? dl.reeu aJB s?uarculaoc.f,1vrrpeaq1 ,a1d1o.r1rala lJaur uB Jo uorleJ?uacuoc qEIq B dq dllsour paururra?ap sr q13ue.r1s cruol or{l araq^\ uor?nlos ur lq1 os -'uor?nlosorl?Jo (rl18uarls cuor) uorleJluacuoc e1d1o"r1ca1a puadep sluarclgaocdlrnrpe ,g.Z$uI aos IIr^\ aa sV 1elo?aql uo dp.rerur.rd
*"a4t .l ul *ad,L ii'za{l'tatroE = ,oE
sr lequalod [ac-JIBr{IBruroJatn pue oraz sr aprs pueq-tq8u aq1 uo rura?lsBI aq1 'pnbe are +zad pue +EaJJo suorla.r?uacuoc uaq/r snql aql [..e".{]___g
ffi
I *za'it/nar'g =g "t zu- .""a"1fr*.odn .iI
,ca.{t
*a'{lrtadofl= Q ;.Ui "t fusanr8 uorlenbe 'aldnoc (II)a.{/(III)a.{ aql raprsuoC .1 ?suraN aqJ slunba uorlenba lsuraN aq? Jo luarlonb uorlpr?uaJuot aql uoq^r IIar-JIBq aq? 3o pqualod aqt s9 paugaP sr 1er1ua1odIIat-JIeq leturoJ V 's|o4uapd Tnutot pailc -os q8no.rq1 sr s?uarJElaoc dlrrrrlcu 3o uralqo.rd oq? punor del1| aug 'pa.rrnbe.r
slolluarod louro& A 70.0-= (99.0 Ill'g)f = a,{i+eau,g
I L (aLl +7a ogT + +6alU+6adog; = a.{/+ga.{og. (s)ade -"g+*g"g :+gad Jo uo-r?cnparuo4oala-aarql aqt .ro3pqualod IIac-JIq aql uFlqo o? (gZ'I) ba Sursn paurquoe are slquolod 1ec-Jpq asor.{J
are s?uorcJlJaoc dlrnrlce lecprldtua ,suorlnlos paleJluacuor arour JoJ '(9'6 g) l(roar{l lnq 1a>1c49-adqaqSursn dlele.rncce dlqeuosea.r palnduroc aq ueJ s?uarcEgaordlt,rr?ce 'I I I0'0 lnoqe ueqt ssal suorlerluaauoc a1r(1o.rpa1a ro,{ 'suorlJaJJoc ?uarcllJartoflrn4ae ?noqlur a?erncre dlqeuosea.r uaql are sler?ua1od plepuels Sursn suor?Blncler pue lBapr paunsse aq ueo suoqnlos aln11p ,ira1 'suoqnlos 1eopr tr J I lcqaqlodr(r{ aq? are sarcads uor?nlos roJ qrrqa 'sale?s prepuels ol raJar sprlualod prepuels
LI
slErlue?od prEpuBlsJosasn etuos g.I$
18
Latimer Diagrams
suggesting that the activity coefficient ratio is about 0.22 in this medium. In i medium with coordinating anions, e.8'.,aqueous HCl, Fe(II), and Fe(III) form a variety of complexes. In order to compute the half-cell potential from the standard potential, we would have to know not only lhe activity coefficients but the formation constants of all the complexes present. The formal potential of the Fe(IIi)lFe(II) couplein 1 M HCl, -g'' = O.ZOO thus differs from the standard potential both becauseof activity V, coefficient effects and becauseof chloro complex formation. As long as the medium is constant, however, the relative importance of the various complexes is constant and the formal potential can be used as an empirical parameter to compute the overall Fe(II)Ee(III) concentration ratio.
When we are interested in the redox chemistry of an element, a tabulation of half-cell potential data such as that given in Table A.4 can be difficult to assimilate at a glance. A lot of information is given and it is not organized to give a qualitative understanding of a redox system. Nitrogen, for example, exists in compoundshaving nitrogen oxidation states ranging from -3 (NH3) to +5 (NOS-)and all intermediate oxidation states are represented. One way of dealing with complex systems like this is to use a simplified diagram introduced by Latimer (H1) and usually referred to with his name. An example of a Latimer diaglam is shown in Figure 1.7 for the aqueous nitrogen system. In the Latimer diagram, any H+, OH-, or H2O required to balance the half-cell reaction is omitted for clarity. Thus, if we wish to use the half-cell potential for couple,for example,we must first balancethe equation the NO3-A,I2O4 .E' = 0.80V - ;NzOa + HzO + NOe-+ 2lFr+ "Figure 1.7 also includes a Latimer diagram for nitrogen speciesin basic aqueous solution. The Latimer diagram tells us that one-electron reduction of nitrate ion again producesNzOa, but the half-cell potentials differ by 1.66V. The reasonis clear when we write the half-cell reaction. The difference between the half-cell reactions is 2H2O -+ 2H++2OHthe Gibbs free energyof which is -2ft?ln Kw,160 kJ mol-1or 1.66eV. N O g - + H z O + " -- ; N z O a + 2 O H - . E o = - 0 . 8 6 V
Wendell M. Latimer (1893-1955)was a student of G. N. Lewis and later a Professor of Physical Chemistry at the University of California (Berketey). Latimer's contributions were primarily in applications of thermodynamics to chemistry.
sarcads aql araq$ uorlBruroJ Jo d5rauo aaJJJo pui{ B o? paFaûoc aq ut slqualod IIac-JIBr{uaq? (lurod ocuaraJor aql sB (}Ias?I ?uoluala oql) o?Bls 'lurod acuaraJar uounuoc ug.r?BplxooJaz asn a1!\ e ol aArlBIaJ saSuBr{c JI d8.raua oo.ryo? palJaluoc aJB slerlualod aq1 gr alqrssod sr uoilecgrldruis atuos 'sassaco.rd lerluanbas ur o^rlrppe dldrurs ?ou are ,uaas aleq all\ sB 'rlcF{rn sprluelod ur passa.rdxe. a.re det11 ,aceds lprus dlerrrlIar e olur uorleruroJur Jo pap lealE e ssa"rdruoc sruu.r8erp rarur?T aIIqA\
suro"tSotq aIDtS uoltDp?xo - &&taug aatg
A I0'0 = .4Z|"CY-= oE
r_Iourf00Lz-= oDV (00'8u+ 8'8)JU 808'U ft6'0,{Z - = oCV +
SI
uaq? IIac-JIEr.{ parrsapar{l roJ eEuuqcd8;aue oa.r;prepuels oq;

'Xd JA g0g'Z x Z,= oCV
"XdJg g0g'A=,CV zONH/-tONo -= gIZ oCV
-HOU +HZ e OTHZ + _zON +H e zoNtt + OzH + zONg e- _aZ+ +H g + _sON
:8uulro11og Jo ums aql sr uorlceor [Iac-JIu{i ar{l parrsapoql .00.7I = *Xd,g.g = o2.d,"ra1errr prcs snor?ruJo puB slue?suoJuorlezruorar{?pu 'A 76.0 ,uor1n1os prc ur uor?cnper aql roJ lequelod aq1 uaar8 uorlnlos crseq ur _uONot _eONJo uorlrnpar ar{?roJ pquelod IIaTJIqeq1 alnduroJ t.l alduuxg
eHN -
"lTllTlt-ll-t
r'0
tHuNe HOZi{N <- 6N e O?tt * ON e _6ON <- tOzN <- -eO'li p6'0 8u'0 r0'89t'0 9r'018.0 98.0-
'z(1.re1c roJ pallnuo uaaq a^Bq-suollreat llar-Jlq aq? aruelq o1 perrnbat rale^r ro suor aprxorpdq .ro ua8orp,(g 'suollnlos snoonbe crsq pu JrprJE ur saldnoc xopa,r u'aFol1ru snorrel aql roJ slerlualod IIar-Jlr{ aq1 Sur,r,roqs ure.rEelp raur?B.I 1,.1 a.rnElg
fn'I
It'I
r8'r-
LL\
69'T
00'r
tO'r
08'0
6T
sFrluo?od prBpuB?sJo sosn auros g.Id
20
ElectrodePotentials
of interest is formed from the element in its most stable form at 25oC and ftom electrons,H+ or OH- ions, water, or other solution species. Thus we could form HNO2 from NzG) by the following half-cell process: lru -r HNO2 + 3 H+ + 3 e2';2(g) + 2H2O The free energJ change for this process can be obtained from half-cell potential data such as those given in Figure 1.7. Since the reductions of HNOz to NO, NO to N2O, and NzO to Nz all involve one electron per nitrogen atom, the potentials can be added directly to obtain the (negative) overall free energy change for the three-electron reduction; changing the sign gives AGo for the oxidation: = = LGo F(1.77 1.59+ 1.00) 4.BB + F
AGo is usually expressedin kJ mol-l, but for the present purpose it is easier to think of LGolF, which is equivalent to putting AGo in units of (1 electron-volts eV = 96.485kJ mol-l). Similar calculations for the free energies of the other nitrogen oxidation states can be done using the data of Figure 1.7. These free energies are plotted us. nitrogen oxidation number in Figure 1.8. Free energy - oxidation state diagrams were introduced by Frost (1) and often are called Frost diagrams. These diagrams were populaized. in Great Britain by Ebsworth (2) and sometimesare referred to as Ebsworth diagrams.
Arthur Atwater Frost (1909-) was a professor of chemistry at Northwestern University. He is best known for his work in chemical kinetics and molecular quantum mechanics.
A free energ"y- oxidation state diagram contains all the information of a Latimer diagram but in a form which is more easily comprehensiblefor qualitative purposes. The slope of a line segment connectingany two points, LG"l\,n, is just the potential for the reduction half-cell connectingthe two species. Thus we can see qualitatively, for example, that Eo is positive for the reduction of NO3- to NHa+ in acid solution but is negativefor the reduction of NO3-to NH3 in basic solution. Speciescorrespondingto minima, .g., Nz(g), NHa+ (acid solution), NOz-, and NO3- (basic solution), are expectedto be thermodynamically stable since pathways (at least from nearby species)are energetically downhill to these points. Conversely, points that lie at maxima are expected to be unstable since disproportionation to higher and lower oxidation states will lower the free energy of the system. Thus, for example, the disproportionationof N2Oa to NO2- and NO3- is highly exoergicin basic solution. The point for N2O4 in acid solution is not a maximum, but doeslie above the line connectingHNOz and NO3-; thus disproportionationis spontaneous acid solution as well. in
se (dlrlBopruou SuqcalSau) pauuap sr ? olnlo: BJo d?I/\Ipe aqJ 'suorlBJluacuoc rBloru rraql ol lBnba dlolErurxordde uaâ ra8uol ou aJB sarJads asar{?Jo sarlr^r?rB aql l8rll azruFocar o? InJarBc aq 'IAI ?snru a^\ l_0I se paugop _Ho pue +H Jo sal4s prepup?s aql qtllv\ 'g'V oIqBJ ur uaar5 sr lsaralur pclFolorqgo suorlcar IIac-JIBr{aruos roJ slerlualod p.repuels FtruaqcorqJo uorlralloc V .)Iro ,og,oprygo aceli ur J ro ',9 ',CV Furlu.tr dq serlrluenb p.repuels Iecrruoqc Furpuodsa.uo,. aq? ruo$ paqsrn8urlsrp ,{11ensn ar sluslsuoc runuqrlnba pue 'sprlualod pJepue?s 'se8ueqc d8.raua oa.r; pJepuls lcnuaqaorg 'IN ''a'!'LHd sB -HO pue +HJo salels prepuls oql z,-0r= "[-HO] = o[+H] augapa.r dlpnsn slsruaqaorq pue 'sasod.rnd lucluaqcorq roJ Juarualuo-l sr satroqe asaq?Jo rar{?rau 'rala^\oq 'suorlnlos crseq dlSuorls Jo JrprJe d13uo,r1sur sJncro .(1e.re"r aJrI esnecag .suor _HO ro +H qll^t suopcea.i ,7I IIaJ-JIBq aq? acueleq ol asoor{J a^\ raqlaq^\ uo .Surpuadap 11d rc ,os;noc ,roJal stue.r8erp alets 0 Hd o? snql pue salels prupue?s I tr I ol Jo uorlprxo - d5.raue aa.r; ro sruer8erp raturlerl ur posn ro s{ooq d,rlsnuaq-. ur palelnqel slerluelod uorlcnpar pJepuls lensn aqJ .suorlelncleJ crureudporuraql ur pasn uolJo are lep 1er1ua1od IIac-JIeq puE d.rlsruraqcorq ur soIoJ luelrodrur deld suorlceal uorlrnpaJ-uorleprxo apls propuors locnuaqcorg aqJ
'suor?nlos (aurtpoqsBp) rrsqpup (aurtprlos)plc u! sa?els uorlprxo ua8o.rluaql roJ ruz.r8erp alls uor?prxo fE.raua aard g.I e.rn8ld
olBls uorlBprxo
zr0
z51
HN
I.
*9IHz
,6oN
-zon
toEN
"o"'
,,,.,,o........o...
ON
:xl
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HO6HN
ON
NH OZN
-e v<
-8oN
IZ
slB4ualodprpuBlsJo sasn auog g'1{
22
ai = CilCio
so that when C;o = 1 M, di = Ci. But when Cio = !Q-7M, o1 = tOI Ci. Consider the Nernst equation for the hydrogen electrode: E =Eo-ft=? lr, @:r,')2
F AH-
can With Hz(g)at unit activity,this expression be written E =8" *R! lnou.
11' ,tt'
T' Using the chemical standard state and -Eo= 0.00 V, we have g =R! ln [H*]
is expression state,the corresponding standard With the biochemical lr' 0.2tt) E = E'* R=? (ro?tnl)
For equal [H+], the two equations must give the same potential; subtracting one equation from the other thus gives
fr' or E' = -0.4L4Y at 25'C. Similarly, for a half-cell reaction A+mH++ne- -+ B E,=Eo _mA nI' ]llr_tO7
fi' =-&J ur ro?
.E' and Eo arerelated by
or, at25"C,
E' = Eo -0.474 rnln
Similar relations can be derived between AG' and AGo and between If and K (seeProblems). For an equilibrium reaction A+rn H+ + B we find that K=IO.7wK e.ZE) (1.26)
AG'= AGo+ mRT ln 107
or, at 25oC, LG'll<Jmol-l - AGo+ 40.0 m Conversion back and forth between chemical and biochemical standard states is straightforward as long as the reactions involve H+ or OH- in clearly definedroles and the necessarypK6 data are available.
-8 Jo uor?cEar or{? roJ luB?suoc unrJqrlrnbo puB a8uBr{t r(F.rauaao.r;prepu?s lecrruoqcolqaql ale1nrle3 A.1 aldruexg
uorlcear IIac-JIBq ur paalolur suoloedJo Jaqrunuoq? asneraq lnq ,Z Hd B uo ?B s?Insar snon8rquuun al uoql slerl.ualodp.repuels leJrruor{corq pasq suo4elnclec 'sa181s prepuBls rlrlurs uerr.rS sprcE{Ba1r\ a"re raqlo p_u sralsa eleqdsoq4 'I tr I,Jo uoqrluoruoc Ietol u q?I^{ _aig4g pue -rOdZHJo arnlxuu urnT.rqqrnba Hd or{t se aleqdsoqd erue8jourJo atels I prepuels eq1 Surdsrcads pagrlduns leq^\auos sr rualqo.rdeq; dq
o1,alqrssodur Jr ,rpclgrp ,. ,r.r$*#}|T"o},:fHn"*{lil':i ., rou
I I I I I I
'-7g4zH Jo raqrunu lJexo aq? snq;, Jo leql ol Fcrluapr lou lnq relrrurs I ,2.d e qtpl sarcads aar.F (pa$ua?sa)punoq ualJo sr ,uorlcear e o1 1r IIor-JIBq I ,l E ur paÎoûr sr aleqds-oqd uaq11 'Zg'0 = os 'IZ' 'elduruxaro.f l_vOazlHl/l_zloal{l sar?TleuorlcurlJ t 'l .reeus,o;ry.d \ Hd ?Bteql qlr L sl -?OdzHJo ,;1.daql I prcu {Bo/$ Sur.req sa1d1o.r1ce1ad1od lsaralur leJrruaqcorq sarcads I a.re go ,tueru leql sI uelqord aq;, 'uorlcear IIac-JIer{B ur pallolur are suor I -HO ro *ll dueur lateunpoJun I 'A Zgg'0- = or?''r-Iour 0'gg = Z.VI - Z'LZ+0.99 = ,CV pue ,'rl e OzH + HOOOOC8HC -aZ + +H Z+zOJ + HOOCeHC aABqa/I\'(ITD Surpe.rlqnspuB (II) pue (T)sbaSurppv ba I
*"1u*o"'f,x*f #:r*9"".,t,:iy:Ti'ff Hd uorlcunr ro i'#Itni:rJ;ffi |
I I
I I
I I
(I)
'flarrrpadsat 'i-1o* fq1'il pueZ'LZ=bxd ift'eOt'Z- = .C;di; ($I) <_ +H +-zOCOCeHC HOOCOCSHC (IT) all + -zg3sgC e- HOOCcHC a"ru sdalsuor?Bzruor aqI l_Ioru gg+= oCVr{?TA p'' f{ *OzH+ -zOCOC8HC -aZ + +HZ+ zOC+ -zOCtHC
ror p'Epu'ls p4.'eiod szar{? T;;::ffi
'r(lerlrlcedsar'6V'Zpue gL', aJEspnu crnrufd prre JqaJE go s,o;yd eq;, 'sp.rcelerlnau eq1 Eurrrloaur sseco.rdsno8oleue aql roJ pquelod prepuu?slerrruaqcaq1 elnduoc 'A 669'0- = ,g, Q)OhH+ (be)-zg36CtHC e -a 6 + (bB)+Hz + (8)zOC+ (be)-zg3eg3 'uor alenn.rr(do1se8 UOCpue uor e?slocB uorsroluoc Jo
alr{ a,rt'(gZ'I) ba Sursno?B+s pJupulslctruoq" aql ol Surlrerluoc i1-1our 6'7gI = ,gyu- =,CV sr uorlJeor f:I IIar-JIq aql roJ a8ueqc d8.rauaae.t; prepue?s lecrruaqcolq arlJ I I I I I I I I
_"1
24
Electrode Potentials phosphoglyceraldehyde with nicotinamide adenine dinucleotide (NAD+) and inorganic phosphate to give 1,8diphosphoglycerate. Estimate the chemical standard free energy change and equilibrium constant. The half-cell potentials from Table A.5 are RCO2PO32-2 H+ +2e' + RCHO + I{PO42- ,E'=-{.286V + NAD+ + H+ + 2 e- -+ NADH .E'= -{.320 V
and the standard cell potential at pH 7 is E = (-O.320)-(-{.286)= - 0.034 V AG'= +6560J mol-l (6.56kJ mol-l) .IC= exP(-AG'/RT)
t? -Anzr - aRcorPos2'o.H*0NADH @RCHO OHPO"2oNAD*
where R = CHOHCH2OPO32and all speciesare understoodto be pH 7 equilibrium mixtures. The cell reaction is RCHO + HPO42-+ NAD+ --r RCO2POg2- H+ + NADH +
The free energy change and equilibrium constant at pH Z are A,G'= -nFE'
so that
or
(ro?tHl)lrqenu] o- _ Inco2eog2J -@
The cell reaction involves four different sets of phosphate pKo's: If they are similar, the corrections will appioximately cancel;thus we use eqs (1.25) and (1.26) obtain estimates of K and AGo: K=7.l x10-e LG =46.6kJmol-1
This result shows one reason for the use of a special standard state for H+ and OH- in biochemistry. The reaction of NAD+ with 3-phosphoglyceraldehydeappears to be hopelessly endoergicunder chemical standard conditions. The values of AGo and K thus are misleading since at pH 7 the equilibrium constant is not so very small and significant amounts of
'Jo}^r Furcnpar go alqedec r(ueru a_reaJaql 'suaddeq 1r sy aldrcur.rd zgezll ur sr aldno_c e.rou; uefu1ssal drruaioa ?{rlo leql (ueql ea,rle8eu e {?!tr aldnoc due 'fl.repung .ra?B^tFurzrprxogo alqed-ecaldicur.rdur s-raldnoc OzWzO ar{? ?Bql ueql .ra1ea.r8 prlualod llacgpq e rifpr dldnoj Jo ,{uy 'uor1n1os snoanbe_uego dlqrqels crureur(poueaqlgo slirurl oql ougop asoql leql sr saldnoc zg76zg pue OzHlzO aql Jo ecuecgru8isaq;, 'saldnocz1gyoz;gpue OzHlzOaql q?I^r.req1aFo1 '6'1 a.rnFrg ur u^4,oqs osIB arB seldnoa (III-)N(O)N pue- (O)ly(IIt)X aqt Jo slerlualod IIac-JIer{aql Jo stold .6.1 e.rn8rg uI Hd jsn-pJlloyi sr pqualod IIar-JIBrl(III)N(NN aqJ .r_Hd Aru 69- = Hdp/A? tqt os t{O Z + -uON <- -a Z + OzH+ _tON OzH + _zON <_ -a Z + +H 6 + _sON
sr ssaco.rd aql 'uor1n1os crseqro l'rlnau uI .r-Hd nur 69- sr edols gd .sn A aqt ?Bq] os OzH+ zOmH <- -aZ+ +H g + _sON
B ^\oqs qrFU'\ suorlBrrBA11d - 1er1ue1od aaeq asBq {Ealll ro prce >IBa,$ e 8u_rnlonur sassaco.rd aporlcolg 'J"92 Ie lrun 11diad nur e lu) Z.69_ 3o adols e qlp\ Hd uI reaurl aq o1 pepadxa sr ler?ualod11ac1pqe snqJ
or (NN Jouorrcnpo.r ,aldru'xa aq1 rod ")1dj'J;Il:t::3t'f:i:ALT'$
Hdi}m808'z- oE=fl
tlU
aABqo^\'1enbaare sarlrlr?ceg pue V aql uaqr\\
;{,ttn)ve ,,, du _ ----ED = tt ZE, "fl fl g e -au++HIu+Y
pqualod q1r.u
go ferrr e sn salr8 uorlenbe ?suJoN ar{l ,sanle^ 11d .raq1o 1e swalids .rog 'srue.r8erp a?e?s uorleprxo d.8.reua aa.rgJo ,stue.l8erp .rburqul ,s1er1ue1od IIaa-JIBTIJo solqel dq_ pa,r.ras IIa^r are ; 11d .reau "ro 1e .{e1i o1 Fuqlr.u stsruaqcorq .ro 71 gd .ro g gd le suorlrar ur palsoJalur s?s(uaqC sutot?nrq gd - Iolluapd
eleqdsoqd 'sarcads Jar{?o aql qlur pe"reduroc q8rq sr uorlerluocuoc or{l JT d1.re1ncr1.red ,palcadxa are lcnpo.rd
-JIe-q raprsuoc 'sar;.raua ro ,rnrr,r"toJ'i,1:ir:Jil ea"; lerauo;eq1-ureFe
9Z
slEqualodprBpuBlsJosasn auros g.Ig
26
Elebtrode Potentials
specieswhich appear to be perfectly stable in aqueous solution which are part of couples with half-cell potentials greater than that of the OzlHzO couple or less than that of the HzO/Hz couple. This is a reflection, however, of the intrinsically slow OzlIIzO and HzOlHz reactions rather than a failure of thermodynamics. The reactions do not occur because there is a very large activation barrier, not becausethere is no overall driving force.
Pre dominanc e Area Diagrams
We see in Figure 1.9 that nitrous acid and the nitrite ion are in principle capable of oxidizing water and are thus thermodynamically unstable in aqueoussolution. Although this instability is not manifested because the reactionsare slow,it raises the related question: What is the thermodynamically most stable form of nitrogen at a given pH and electrode potential? Referring to the free energy - oxidation state diagram, Figure 1.8, we see that for both acidic and basic solutions the points for N(-I) and N(-II) lie abovethe line connectingN(0) and N(-III); these speciesthus are unstable with respect to disproportionation. Similarly, the points for N(I), N(II), N(III), and N(IV) alt lie above the are also unstable. The existenceof N(0) - N(V) line, so that these species any of these species in aqueous solution therefore reflects kinetic stability rather than thermodynamic stability. In fact, only NO3-, NH3, NH4*, and Nz are thermodynamically stable in aqueous solution. Furthermore, according to thermodynamics, NO3- is unstable in the presence of NHn+ or NH3. One way of expressing the conclusions regarding thermodynamic stability is by means of a predominance area diagram, developedby Pourbaix (3,H5) and thus commonly called a Pourbaix diagram.
Marcel Pourbaix (1904-) was a professor at the Free University of Brussels and Director of Centre Belge d'Etude de la Corrosion.
A Pourbaix diagram is a potential - pH plot, similar to that of Figure 1.9, in which regions of thermodynamic stability are identified. Lines separating regions represent the potential and pH at which two speciesare in equilibrium at unit activity. Pourbaix diagrams usually also include the region of water stability. The Pourbaix diagram for nitrogen is shown in Figure 1.10. We see that in most of the potential pH area of water stability the most stable form of nitrogen is Nz(g). At low potential and low pH, NHa+ i. most stable and at low potential and high pH NH3 is most stable. Nitrate ion is stable in a narrow highpotential region abovepH 2. Below pH 2, NO3- is in principle capableof oxidizing water, though the reaction is so slow that we normally do not worry about the decomposition nitric acid solutions. of
,eldruexa .rog .s8urpuno.r.rns oq? IucrruagJ alqrsraâl B Jo uorlJarlp aq? Jo suorlrpuoc aql ur e8ue-qc leurrselrugur ue fq uoqcaJrp ui pas.ra,ra.r eq UBDr{cql!\ auo sr ssaco.rd alqrsraâr B ,scrrueudporuraql uI .suor?rpuoc alqrsJa-Aar rapun paJnsBoru aq tsnru 1er1ue1od eq1 ,acuecgruFrs crrueu,{pour.ror1?aABq qcFlrr' sprlualod IIaJ ur?qo ol rapro uI
sTyrrNsrod TTsc do rNsrNsrlnsvsl [ 7.I
'4 raldeq3_ul puH slq?Jo aldurexa ue oas IIy$ a,!! lf.rlsruaqc snoanbe JoJ SarlTlrqrssodaq1 Su,rzrlensraur InJasn d.ran aq uec rue.r8erp xreqrnod e 'luecgru8rs arour sr dlrpqels crureudpouuaql oraq,/$.,pueq .req1o aql uo 'suralsds xopor aFqI oJoru Jod 'rue.r5erp oqluo .re-aooL lou op aroJarar{l pue alqelsun dgecrtueufporu.raql d.r1slureq-c -are qcr1^/r\ sarcads sa,r1o.,r.ur Furlse.ralur aql Jo lsotr{ 'InJasn dl"repcrped lou are uaFo"rliu Jo sa?B}s uor?Bprxo aql a{II stuelsds olq4s dlpcrleur4 .rogsrue.r8erp xreqrnod
'saldnoc ZHIOZH pue OZH1ZO aq1 Surarroqs saurt paqsEp aql uaa^{laq alqPls sr ra?d! 'sarcadspalcrpur aql roJ flrgqels crureudpouuaql Jo seare o1 puodsa.r.roc suorBar palaqBl aqJ 'uorlnlos snoanbe ur ue3o.r1ru .ro; luelSerp xrzqrnod) ruerSerp EarB aJueurrropard 91.1 e.rnigg gd
'saldnoc 21119711 pue OZHIZO aq? Jo stItuolod aq1 are (sourl paqsp) u.,{oqs osIV .(+tHN oyd aql) Jo 7Z'6 gd 1e aurl plql ar{t Jo pue (ZONH Jo oNd aql) 7I.t Hd^?B saull o^\t lsrlJ aq1go adols ur saxuEr.{r a1oI\I'saldnoc (III-)lv(0)N '(III)N/(A)N '(O)N/(III)N PUE aql roJ gd qll^\ slrluaqod IIac-JIeq ur uor?rrel aql Sur.roqs uer5elp Hd - Iurlua?od 6.1 arnilg gd
fl6r0r89V20
w6I0I89VZ0
(be)*?11tr1
(III-)NAO)N (III)N/(A)N (b)_8ON (O)N/(III
0'r L/g
c'T
LZ
slEEua?od prupuBlsJo sasn oluos g.Ig
28
i Ecell Ri.t* ftmeter and actually measure a voltage E = iRmel,r;r Combining these expressions, we get
p' - EcellRmeter " - Rrrr * R."t ,.
reaction might be changed by an infinitesimal increase in the .o""""tt"tlori of a reactan"tor product. Similarly, an electrochemical r"tt it reversible if the direction of current flow in the external circuit ;;; b" reversed by an infinitesimal change in one of the contentrations. etie"""ti"uly, we can think in terms oi an-operati'on9l. definition of cell reversibility: An electrochemical cell is regarded.as "fl"1ro.tt"*itala small amount of current can be passed in either direction r""LrtiUf" if without appreciably affecting the measured potential The w:ords "small" and-"appteciable" are ambiguous; th9 meaning depends upon the context of the experiment. A cell which appears reiersible ih"r, *"u.ured with a device with a high input resistance measured iu"Jifr"t small current) may appear quite irreversible when io* inpui resiitance. There are a number of with i,; ; ;;tileier " behavior in electrochemical cells which are "i"."*-oiirreversible air."rr"a in more detail in Chapter 5. Irreversible behavior usually ,"rJtr from an electrode pro.uss-having slow reaction kinetics, in the ttunsfer processitself, in a coupled chemical reaction, in the "i""l.o1r ofreactanls to the electrode,or the removal ofProdgcts from the delivery etect.ode. For the purposes of discussion of cell p-otential howev"tl *" can think of an electrochemical cell as -"u.rt6*"nts, h";i;t un i.rt""nul resistance which limits the current which can be a"fl""?"a. Strictly speaking, in any reasonable model the resistance *oJa be nonohmi", i."., cuilent would not be linear in potential. We can, however,use a simple ohmic model to show one of the consequences of irreversibility. ConriJer ln electrochemicalcell with an internal resistance -Ritr1 connected to a voltage-measuring device having an input resistance n-.r", as sho*n in Figure 1.11. If we could draw zero current' the u"tott the cell te"rminals would be the true cell potential Esg11'In ";lff; practice, however,we draw a current
If the measured voltage is to be a good approximation to the cell Our perception of the potential. we must hive -R-et." tifti.,t. depends on the measuring instrument. reversibility of a cell thus
--,
'rE 'IIac u^tou{un aql- o? u^\orql uat{l sI rlJlrr\s oq; .paurruro?ap aq uec arr^.r.oprls aq? uo lurod .req1odue puu y uao^\?oq a8e11o.r, aq1 ,acuelsrsa.r ,pue ,sg o1 ur raurl sr a,rr taplls aql JI lenba uoq? sr de1 e.rrzrrapqsaq? pue y uaa^qaq do.rp p$ua1od eq; .t ralauouerrle8 aql uo Furp-eer luarrnc -otaz at:a?o1 pelsnipe sr lelsoarlr ar.{l pue IIar prepuels aqlJo lequalod aq? l ?as sr arr^\oprls aql .lrncrl' aql ol palcauuoJ (IIa, prpuels uo?so11\-B uauo) sg ac.rnos ppualod u^\ou{ B r{1l/v\ .,U. lelsoaqr B qll^r alqelsnfpe sr arrr'raprls aq1 q8no"rql luorrnr aq1 :g.t.re1feq e p?lcauuo, sr qclq^! ssorrB 'sllo^ ur palBrqrleJ &'arl!\apqs aJuelsrsor Jeaurl B saÎoûr '61'1 a.rn.8rg ur u^\oqs ,.relaruorlualod v .ra?oruorlualod Fuilcalap_Ilnu Jo asn sa{Bru ?uauraJnsBau 1er1ua1od poqlau Jo Icrsselc aq; sratauo!lualod
u\ou{unaqr;;:1;1T:'"i,Jfli{i::};:l"tl"iff ir""r*:,tr#ixt:i
'acuelsrse.r eFe>1ea1 aql pue aJuelsrsal ra?oru an.rl ar{l Jo uorleurquoc IaIIBTBd aq1 o1 pnba acuB?srsorralaur a^r?Ja.ga ur sllnsor (II.I e.rn8rg ur u.ly\or{s uB sB) rolaur .O aql ur e ,r{lt1r\1e11e.red ac_uelsrsarsIqJ O0I ,0I Jo eauelsrs-a.r Fura.eq qled.lua.rlnc e epr,r_o.rd uee Jo?Blnsur uB uo lrir.rdie8ug B uelo ro ,su1g dlo '1snq 'luepodun fllecqr:c satuoraq sluurruro? Jaloru aql uaa.&?aq luarrnJ 30 aEerleel 's1rnc.ilJ aDue?srsar q8rq d.ra,r u1 'ecuelsrsa.r lndui qFIq B q?F\4. aIqBIIBAe sr Ja?arullol B Jr uaAa asr.re feur uralqo.rd pcrlcerd raqloue ((J g0I<) arue+srsar leura?ur qFIq Fur.teq sllaa rog
T------t
ra?aru u.
JI"& --T-- -. --T--=-JIac
'sluauraJnsEarrr 1e11ua1od uo acuelsrsar a8eleal pue acuB?srsor aql [ar Jo s?coJJa iur^\oqs lrnrlC 11.1 orn81g
',{cerncce o? Ier?uassa sr slrluoc pue speal uBaIJ _ o? uor?ualle ql1,l\ enbruqcel leluarur.radxa InJareC .stualqord e8e>1ei1 qcns lsnt o1 auo-rd sr pue aculsrsor q8rq d.ra,r B seq sluaura.rnseau 11d .rogpasn ,{potuuoc oporlcala ssel8 aq1 iepcrryed uf .flqrqrsrolarl prB^/trol spuol snql puB acuBlsrsor IBuralul q8lq e sBr{ r{Jrq.r IIac due .rogparalunocua z(11e.raua8 ocuelirsar a8eliei jo rualqo.r,i bq.f, " sr 'ocue?srsar IBura?ur IIoc aq? qlll\ alqrBdtuoc uarr,apue aculsrsar Jalaru anrl ar{? uErI? ssal epnluFeru Jo srapJo IeJaAos aq .{etu qc5{ra ,t""lu ralaurur
6Z
slrluelod IIac Jo luourornseow ?'I$
30
(Es
Figure l.l2 A potentiometercircuit.
U,
Ex
LJ
Reversible cell potentials measured with a potentiometer are usually accurateto +0.1 mV and with care can be even better. The apparatus is ."iuii""fy inexpensive, but the method is slow, cumbersome, and ."qoir". rome tLchnicai skill. Furthermore, although in principle the plt=""ti"t ir read under zero current conditions, some current must be i"u*n in order to frnd the zero. The current is small, typically on_the orJ"t of 10-8A with a sensitive galvanometer, but may be large enough to cause serious errors for a cell with high internal resistance' Electrometers
with the developmentof vacuum tube circuitry in the 1930's, d.c. amplifiers with very high input impedances became available. such J""'i""r, called el'ectrorneters, are particularly well- suited to measurementof the potentials of cells with high internal resistance. A number of different designs have been used for electrometer circuits, but one which is partlicularly common in electrochemical instrumentation is the so-calLd uoltage follower shown in Figure 1.13. A voltage follower employs an operational ?mplifier,.indicated by the ^The output voltage of an operatignal amplifier is triangle"in the figure. propJrtional to t[e difference between the two input voltages with very 'nigt to g*" (> 104). In a voltage follower, the output is c-onnected the (inverting) input. Supposethat the output.voltage is slightly ""?"fi"" than that at trte positive input. The difference between the in-puts grJut"r if irifi U" amplified, driving the output voltage down. Conve-rsely, the stable, of course, iow, it will be drive! up. T_hegutput-is output voltage is when the ouiput and input are exactly equal. Since the input impedance
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32
lead wire
Eleetrode Potentials
lead wire
filling hole satd KCI solution 2Cl 2 emulsion
filling hole KCI solution
KCI(s)
ber junction
Ag wire coated with AgCl fiber junction
(b) (a) calomel electrode Figure 1.14 Reference electrodes. Saturated chloride electrode. Silver-silver
The half-cell reaction is
HgzClz(s) 2 e- -->2 Cl{aq) + 2He(I) +
E" = +O'2682Y
The standard potential, of course, refers to unit activity for all species, including chloride ion. In practice it is often convenient to use saturated KCI solution as the electrolybewith a few crystals of solid KCI present in the electrode to maintain saturation. In this way the chloride ion concentrationis held constant from day to day and it is not necessaryto prepare a solution of exactly known concentration. The potential of the saturated calomel electrode (abbreviated s.c.e.)equipped with a saturated KCI salt bridge is 0.244 V at 25oC. Because the solubility of KCI is temperature dependent, there is a signifrcant variation in potential with temperature, -0.67 mV K-1. When this is a problem, 0.1 M KCI can be used as the electrolyte; the potential and temperature coefficient then are 0.336V and -0.08 mV K-1,respectively. The silver-silver chloride electrodeis also shown in Figure 1.14. Its shorthand notation, Cl-(aq)lAgCl(s)lAs(s) leads to the half-cell reaction
AgCl(s) + e- -+ Ag(s) + Cl-(aq)
Eo = +0.2223Y
The AglAgCl electrode normally is used with 3.5 M KCI solution and has a formal half-cell potential of 0.205 V and a temperature coefficient of -0.73 mV K-1. The AgiAgCl electrode is operationally similar to the calomel electrode but is more rugged; AgCl adheres very well to metallic
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saportcalg JolDc?pul
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34
-#t"# E=Eo
or, at 25oC, EN =-0.440-0.0296pFe In other words, the iron wire electrodeacts in this case as an indicator of the Fe2+activity. Although it-is difficult to predict the rates of electrode processes without addlitional information, there are a few useful generalizations. First, electrode processeswhich involve gases are. usually very s_Iow unless a surface is present which catalyzes the reaction. Thus a surface consisting of finely divided platinum (platinum black) catalyzes the reduction"of H+ to-HZ, but ttiis processii slow on most other surfaces. transfers which do not involve second, as a general iule, simpte ele_ctron Fe3+ + e- -+ Fe2+, are usually fast chemicat boid breaking, e.g., compared with reactionJ which involve substantial reorganization of molecular structure, e.g.,the reduction of sulfate to sulfite. what then should we expect if the components of two reversible couples are present in the cell? Consider, for example, a solution Fe2+,I3-, and I-. Both half-cell reactions, containing p"-3+, E o= 0 . 7 7 t Y Fe3+ + e- -+ Fe2+
I3-+2e- -+ 3I-
E=Eop"r*1p,"*-fft"ffi
= .Uo 0.536V
are reversible at a Pt indicator electrode. Ifboth couplesare reversible, the electrodepotential must be given by both Nernst equations
E=E 6n-ffit"H
half-cell reaction thus proceedsto the right and the I3-/IThe Fe3+/Fe2+ half-cell reaction proceedsto the left until both half-cells have the same potential. In other words, there is a constraint on the activities of the four species
_Eoh,r. =ffi Eop"a*7p"2* tnffi#

2Fe3++3I- p
The argument of the logarithm is just expression for the homogeneous reaction
the equilibrium
constant
2Fe2++Ig-
and indeed in most cases, equilibration occurs via the homogeneous reaction. Frequently this means that one of the components of the mixture is consumed (reduced to a very low concentration). It is then most convenient to compute the potential of the indicator electrode from
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98
36
ElectrodePotentials
membrane permeable to only one species. A membrane with perfect selectivity is yet to be found, but there are quite a number of devices which come close.l There are several approachesto membrane design, and we will not discussthem all. The oldest2membrane electrodeis the glass electrode,which has been used to measure pH since 1919 (4) but properly understood only relatively recently. The electrode, shown in Figure 1.15, consists of a glass tube, the end of which is a glass membrane about 0.1 mm thick (and therefore very fragile!). Inside the tube is a Ag/AgCi electrode and 1 M HCI solution. The glass electrode is used by dipping it into a test solution and completing the electrochemical cell with a referenceelectrode. The glass used in the membrane is a mixture of sodium and calcium silicates-Na2SiO3 and CaSiO3-and silicon dioxide, SiO2. The silicon atoms tend to be four-coordinate, so that the glass is an extensively cross-linked polymer of SiO+ units with electrostatically bound Na+ and Ca2+ ions The glass is weakly conductive, with the charge carried primarily by the Na+ ions. (The Caz+ions are much less mobile than Na+ and contribute little to the conductance.) The glass is also quite hygroscopicand takes up a significant amount of water in a surface layer perhaps as much as 0.1 pm deep. In the hydrated layers (one on either side of the membrane) there is equilibrium between H+ and Na+ electrostatically bound to anionic sites in the glass and in solution. (7.27) H+(aq)+ Na+(gl) e H+(cl) + Na+(aq)
If the concentration of H+(aq) is low, this equilibrium shifts to the left; Na+ from the interior of the glass tends to migrate into the hydrated region to maintain electrical neutrality. Hydrogen ions on the other side ofthe glass penetrate a little deeper into the glass to replace the Na+ ions that have migrated. This combination of ion migrations gives sufficient electric current that the potential is measurable with a high-impedance voltmeter. Since the H+ ions are intrinsically smaller and faster moving than Na+, most of the current in the hydrated region is carried by H* and the glass electrode behaves as if it were permeable to H+ and thus acts as an indicator electrode sensitive to pH. In a solution with low [H+] and high [Na*], NaOH solutions for example, the Na+ concentration in the hydrated layer of the glass may be much greater than the H+ concentration, and Na+ ions then carry a
1 See books by Koryta (A11), Vesely, Weiss, and Stulik (D11), and by Koryta and Stulik (D14) for further details. 2 The first membrane potential was discovered by nature eons ago when animals first developednervous systems. A nerve cell wall can be activated to pass Na+ ions and so develop a membrane potential which triggers a response in an adjacent cell. Chemists were slower in appreciating the potential of such a device, but we are catching up fast.
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38
Other Solid. Membrane Electrod.es Liquid. Membrane Electrodes
Because of the importance of the hydration of the glass surface, glass electrodesmust be conditioned before use by soaking in water or an aqueoosbuffer solution. The glass surface is dehydrated on prololged e*posure to nonaqueous solvents or to aqueous solutions of very high ionic strength. Nonetheless,glass electrodescan be used (e.g', to follow acid-base titrations) in alcohols or polar aprotic solvents such as acetonitrile or dimethyl sulfoxide provided that the exposure is of relatively short duration. Glasses containing about 20Vo Al2Og are significantly more sensitive to alkali metal ions and can be used to produce electrodes which are somewhat selective to specific ions. Thus a NazO - AlzOs SiO2 glass can be fabricated which is selective for sodium ions (e.9., ftN^.K = 0.001). Although these electrodes retain their sensitivity to =-100), they are useful in neutral or alkaline hydiogen ion (&1g6.11 solutionsover the pNa range 0-6.
Rapid progresshas been made in recent years in the design of ionselective electrodes which employ an insoluble inorganic salt as a membrane. For example, a lanthanum fluoride crystal, doped with a little EuF2 to provide vacancies at anionic sites, behaves like a membrane permeable to F- ions. The only significant interference is from OH- ion. F- and OH- are almost exactly the same size, but other anions are too large to fit into the F- sites in the crystal. The LaF3 crystal, together with a solution of KF and KCI and a Ag/AgCl electrode, gives a fluoride ion-selective electrodeusablein the pF range 0-6. Other solid membrane electrodes make use of pressed pellets of insoluble salts such as Ag2S. In this case, Ag+ ions are somewhat mobile in the solid, so that a Ag2S membrane can be used in a Ag+selectiveelectrode. Other metals which form insoluble sulfides could in principle replace a Ag* ion at the surface of the membrane, but in practice only Hg2+ is a serious interference. Since Ag+ can move in either direction through the membrane, either away from a source of Ag+ or toward a sink-a source of S2--the Ag2S membrane electrode can be used either for measurement of pAg or pS in the range 0 to 7. Other solid membrane electrodesare commerciallyavailable for Cl-, Br-, I-, CN-, SCN-,NH4+,Cu2+,Cd2+, and Pb2+.
By replacing the glass or inorganic crystal with a thin layer of a water-immiscible liquid ion exchanger,another type of ion-selective electrodemay be constructed. For example,by using the calcium salt of an organophosphoric acid in an organic solvent as the liquid ion exchanger and contacting the ion-exchangesolution with the aqueous
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'-7,f9 pue '-7913 '-8ON'-IC '+\l'+7r-3 roJ elqelreê dllen.raruruoc oJ sapoJpala sr (u![+zC]/no[+6e31;ul ot aue.rqruaurpFbIT'pedolarep luuor?rodo-rd 'a1f 1o.r1ca1a snoanbe zICeC qllaa' 1er1ua1od auerqruaru e snrIJ 'poure?qo aporloala pFV/8V B sT auerqruau aql Jo aprs rauur aql uO sr (suor luap^rp Joqlo ol aa.rFep aluos ol pu) suor +6eJ o1 alqeau.red uralsds oueJqruaru e 'eue.rqruaru sno.rod ulq? q8norql uoqnlos lsol
saportcTlg rorDclpul aaltcapslo sadfra n41O
'roleFrlsarrur polsaJa?ut uB lte^t i{clqt\ ,t5o1otqpue 'd.rlsnuaqcolq 'd.rlsnuaqc uI suorleclldde 1er1ua1od 3o spuesnoql d11e.ra1r1a-re 'dlluecgru8rs a.rour 'pue 'a3.re1sr saporlcala araqJ t'd1prde.r Furatot5 sr 'uor?nlos ur sPrce ou$ue-T o1 spuodsar alqcalas-uol Jo pIaS aq1 'd1.rea13 qJIq^\ paurBlqo sr aporlcala ue 'aseprxo prcB ourruB-T pazrlrqouur 'dl.reprurs 'eorn qlrm epo.rleala sse13e Surleoc fq Jo srsdlo.rpdq pasdplec -asearn oql dq pecnpord '*?HN o1 spuodsar oporlcala er{;, 'apor]cala sse13 Sursuas-uoqec uo aptruelt(.tcud1od 3o ;ede1 uFIl B ur asearn etudzua eq1 Surzrlqoruurr dq palcntlsuoc aq uc aporlcela o^rlrsuos -Barn e 'aldruexe .rog 'sarceds .raq1odueru Jo uo4calap aq? ol popualxo aq uec qceordde slql 'aueJquaur B ur arudzua ue Surle.rod.rocurdg 'zOC roJ sB Ilaia se '2911 pue 8951 pollossrp 'suorlectldde roJ oIqBIre^ dllerctaunuoc ore saporlcalg 3o l(leue,r ap! \ ol alqepualxo sr 'suorlcar lcruaqc d.reurpto Surnlo,rur rualsds uor??Bar e go uorlrsodralur fq sarceds Jar{lo oruos o1 puodse.r ol papaluoc sr apor?cala 'paurclqo sr zg3 paÎosstP a^r+calos-uor uB araq^\ 'enbruqcal srq;, o1 amsuodsal opo4cala ue 'Zg3 ol olqearlrJad auerqtuatu e fq uoqnlos 1sa1 aql ruo{ palutedes sr qcrq^\ SocHeN Jo uorlnlos snoanbe alnlTp -e qllna aporlcala sse13 freurpro uB Jo auerqruau sse13 aq1 Sulpunouns dg
68
saporlcalgo^.rttolas-uol9'I $
40 Direct Method.s
The measurement of pH using a glass electrodeis by far the most common of all electroanalytical techniques (9,D7,D10) and is also characteristic of direct determinations using cell potentials. A typical electrodearrangement for pH measurementsis as follows: Ae(s)lAgCl(s)lKCl( M)llH+(aq)lglass 1 lHCl(1 M)lAgCl(s)lAe(s)
AgCl(s)+ e- -+ Ag(s)+ Cl-(1M) H+(aq) -+ H+(aq,1M) The free energy changefor this plocessis
i.e., a solution in which a AglAgCl reference electrode and a glass electrodeare immersed. The half-cell reactions, Ag(s)+ Cl-(1M) --+ AgCl(s)+ e-
lead to no net change so that the overall cell reaction is the nominal transfer of H+ from the test solution to the 1 M solution inside the glass membrane
L G= R T , " #
sothat the cell potentialis

or, at25oC,
E =Y ln os'
,tt'
EN =4'9592o71
Thus the cell potentiai is directly proportional to the pH of the test solution. In practice, this may not be exactly true becauseof a liquid junction potential at the salt bridge linking the reference electrode to the test solution and a small potential intrinsic to the glass electrode. Thus buffers of known pH are used to calibrate the pH meter so that the pH is determined relative to a standard rather than absolutelv. Most of the commercialion-selectiveelectrodescan be used directly just as the glass electrodeis used to measure to determine pX = -log o11, pH. Two general proceduresare used commonly. (1) Calibration curve. The potential of a given cell can be measured with standard solutions and a potential us. concentration curve constructed. The concentrationof an unknown may then be read from the calibration curve given the potential of the unknown. When this method is used, it is important that the unknown solution have the same ionic strength as that of the standards so that the activity
'Ztt *
Z*t
= "zs
se ale8edo.rdsrorra aql 'tC x = z 'uo11ce.r1qns uolllppe uI I ro 4
'pappB _dJo '0[-,{]'ecue.raglp salourJo raqrunu aql o? spuodsarroc oqJ [-g] = 80'0 + 98'Z = (997'0)3oII1uB o[_d]/I[_d] a^Bq o/$'suorlerluocuoc reloru dq sar1r,u1Jaql acelda.r uuc a^\ leql SuTrunssv (op[D)8ol= Igd - Ogd
= = il0.0+ 997.0 2690.0/(t000.00tA0.0) Igd-Ogd + eal'3u11ce;1qng 11a3 p,g- Igd 2690'0 -.9 = 9000'0 00t0'0+ = 9000'0 0260'0Jarg- ogd a690'0 + "g t?q? os ,"-g--T tIIJE- oE= fl prlualod iloc aql selr8 uorlenbe lsu.rep eq;
fAr'8o --- 't
'srorro cgetualsds lno loual o1pele8qse,rurd1n;e.recuaaq eêq plnoqs poqlau aql 'osec ror{lra uI 'ralseJ flensn sr poqlou uorlrppe u^rou{ aq1 'patu.rog.rad o1 e.rusasdleue rrralB fluo JI 'ouop eq 01 are sesl(pue eq dueru Jr alqeJaJa.rd poqlaru alrnc uollerqrlec aq1 ,e1n.re sy sr 'rorra alqulooJrocuneErel e acnpoJlur ppo/'a poqlour uoqrppe u^rou{ eq1 '.reaur1?ou se/rr alJnc uorlerqrlec aq1gr 'pueq Joqlo oql uO .srorro cqerualsz{setuos Surprorru dlqrssod 'suo4rpuoc lualuornsOlu aruEs aql rapun uo4nlos erus eql uo paurelqo sr uo4eJqrlc ,luelrodurr aroru pue 'a^Jnc uorleJqrlBc E runrpal oql lnoq?I/lr pourruJalep sr uorlerluaruoe Jo aql leql oJp arnpaco.rdsrql go sa8eluelpe aqJ .alees oql salrqrlt ?taJJaur ralaru?Ioa aql Jo asuodsa.rIeluoruanur eq1 ,papa?op arulsqns or{l Jo lunoruu unaou{ e Surppe uaql pue uoqnlos u.&rou{un uB Jo pquelod aql Sur.rnseau lsr1l dg 'poqlau uol11pp prupuulg (6) 'Fcquapr aq osp plnoqs 'slue5e Surxalduoc se qcns 'sarcadsrorllo Jo suor?BJluaruoc aqJ 'luelsuoa urerual sluorcglaot
euo4eurruJa?op oq? uI r(lurelracun aq1 sr leqn 'nru g'0+ ol elerncce arB slepualod aql JI aoprrongJo uoqe4uacuoc puuo aql su/$ 'Aur 'uor1n1os prepusls -,iI IAI's_0I l"rli!\ 01,-sEA\pqualod aq1 x 00'u Jo -1ut0I Jo uoqrpperotJv 'coga 1BAru 1,6-serr\pquelod 'eporpala acuaraJarICEV/8V B pue aporlcala alrlcalos Ilac oqJ -uor oprJong e 3u1sn pazfpue selrr aprJong uorleJluocuoc Jo ulrrou{un ue Suppluoe uoqnlos e Jo Tru 00I 1,.1 aldruuxg f.qaruorluelo4 dq srsdpuv lecnuoqC l'I$
42
Electrode Potentials mL/110mL) mol L-1X10 tF-h - [F-]o= (2.00x 10-3 - tF-lo= 0.181x 10-3 mol L-l tF-h Substituting [F-]r = (2.86t 0.08)[Flo, we obtain t tFlo (2.86 0'08- 1) = 0.181x 104.
orl
M lFJo = (9.?i 0.4)x 10-5
Titration Methods Ag+(aq)+ RSH(aq) -+ H+(aq)+ AgSR(s)
1 In multiplication * (sn y)2.' I
Notice that in the exampleabove,the fluoride ion concentrationwas determined to approximately 4Voexpectedaccuracy. Such accuracy is characteristic of direct methods. For concentrationsof chemical species above 10-4M, there are usually methods (such as the titration methods discussed below) which are capable of considerably greater accuracy' But for very low concentrations,a direct electrochemicalmeasurement may well be the most accurate method and frequently is the only method available.
Potentiometric methods can be adapted to the detection of the endpoint of a titration. If either the titrant or the substancetitrated is detected at an indicator electrode, a plot of the cell potential us. the in volume of titrant shows a sharp increase or decrease potential at the endpoint. pH titration curves of acids and bases are familiar examples of this method. Other ion-selective electrodes can be used to determine titration curves. For example,organic thiols may be determined by titration with silver nitrate standard solution where the silver ion concentration is electrode. The titration reaction is monitored with a Ag+-selective Typical solubility-productconstantsofsilver thiolates are less than 10-16; th,us the silver ion concentration prior to the endpoint is very low and rises rapidly when the endpoint is passed, so that a sharp break in potential is obtained. In many cases, nonselective indicator electrodes can be used to monitor a titration and to detect the endpoint. Example 1.8 Compute the titration curve for the titration of 25 using a mL of 0.01 M FeSO+in 1 M HzSOawith 0.01 M Ce(SOa)z
or division, z = x! ot z = x I y , errors propag ate as (sz I z)2 = (sr l d2
l*acl n -'saci'iqr.gg "*z-;*i "t ;; dq ue.lr8 sr prluelod 'pappe Sutaq sT +rac ssatxa puB uorl3ar uollJlrl IIaa aq; aql dq pacnpo.rduaaq seq +8ac Jo lolu r-0I x 9'7 lpazrprxo uaaq sBq +6ad at{f IIe f1pn1.urr 'lurodpua aq1 puofeg 'A Z8:0= f, sr lQualod1aa aql, 'hl e-9I aI{?pu f-0I x 8'8 sI ollBr uol?BrluacuoJ +gad//+Zad x 6'I = t*7a31 = [+gag1se,rr8uorssetdxaluelsuoc runuqrllnba '1urod = aql ecualerrmbe lV aql puu IAi900'0 = [+ga31 [+gag1 'A 9t'0 = 8. sr [Br]uo1od oql puB 9'IlI lec = [+geg171*aad] uot{l or}BJuorlBJluocuocaI{J/ 'urBuror lsnur sI x 9'I puB +gad loru f-0I x I eq ?snuruoq? oraql +60S '+}oJ loru i-0I 3o lour 7-0I = (r-'I Iotu I0'0xT I0'0) papp aABqa1!\aturs 'popp uaaq sq luBr?r? 0I uaq^\ uorlen?rsaql raprsuoc Jo J* l*e'{l _ 3oI vw.o_!::___r zogo.0 gg.0= E - L.r":l
l*4.{l
oq? dq peururra?ap sr 11oc aql Jo pquelod aq;, 'aldnor +6e.{/+ga,![ aq 11[,ra apo4rala ld orll Jo p4ualod aq1 'lurodpua aq1 o1 d61 'q8noue lsJ sI aler uorlteor a{f,, '610I x 0'l = (JA/"CV arll Jr uorlaldtuoa o1 oE 1plra' -)dxa = spuodsa.r.roc qcrq^l x ?uBlsuoc runr.rqrFnba uB o1 'A = oCV oABr{ollr snqJ 9l'0 = 89'0 - ?7'I r-Iou f{ 8L = og,4sr prlualod IIac FrrrroJ aq1 ieldnoc +gaJ/ape3 aql pu eldnoc +za.iu+sa.{ oql arB slloc-JlBq ol!\l aql qclq^\ ur (luoulrodxa eq1 ui pa.rnseau Sureq auo aq? lou) fiat lecrlaqloddq aq1 raprsuoC 'uorlcear aqt roJ luelsuoc runFqrpnba aq1 elnduroJ lsrg ad\ +gal + +ga$ <-- +poJ + 16eg +gal <- -o + +tao sr uo4cBal uorleJlrl otIJ
+6ad {- -a + aga$ A 89'0 = ,.9 :spqualod FruroJ qll { oporlcala urnu11e1d aq? lB saldnoe alqrsralar ru.ro; aldures aql pue luerlr? oql qlog 'apor?JoIa aJueJaJar leruolEc pelBrnlBs B pu epor?colo rolBcrpur ld
g "-g- i";;i ut1ft'- aalt*sar.g= L*z"ul
iI
I\?l'l
= ,ofl
8'
dq l(.r1aruoqua1o4 srsdpuv 1ecruraqC l'I$
44
r.25 ElV 1.00
'Electrode
Potentials
0.?5
0.50
Figure 1.16 Titration curve for titration of 0.01 M FeSOa in with 0.01 M Ce(SOa)2 1M H2SOa.
0.25
51015n% Vol. Cea+/ml
30
ln.&*l los E = L.44- 0.0592 " L::-+ - 0.t44
Lc"*1
When 30 mL of titrant has been added,there will be 0.5 x 10-a concentration mol of Ce4+present in excess. The Ce3+/Ce4+ V. and ratio is 2.510.5 the cell potential is E = 1".15 Carrying out several such calculations,we can sketch the titration curve shown in Figure 1.16.
1.8 BATTERIES AND FU"EL CNT,T,S
Throughout most of the nineteenth century, electrochemical cells provided the only practical sourceof electrical power a-1da great deal of Lffort was devotedlo the developmentof inexpensive,efficient power cells electrical generatorscame and storagebatteries.l When steam-powered into use ln the 1880'sand electrical power began to be widely distributed, electrochernicalpower cells started into a long decline. In the recent past, galvanic cells have been used mostly as small portable power
1 A battery is a collection of two or more cells connectedin series so that the battery potential is the sum of the individual cell potentials.
+fiI)uz e OaH+(s)zoutr{ (bB)-HOZ+8ozutr{ Z+G)uZ

uoqcar IIac at{J 'A g'I-8'I o} sasearcop prlualod aq? pBoI rapun ?nq 'A gg'I lnoqe go pquelod ?rncrrc uado ue seq IIat 11oc pa.reda.rd dlaaau y 'raulBluot IIoo aql sruroJ qclqd\ apou JuIz aq? puB (,,r"p,, sI IIar oq? ?Br{? os .re5e ro qcrels qlraa pa11a8sr qru{ia) ary(1o.rpa1a '1,t1r,u1cnpuoc snoanbe aql urorJ 6OuIN aq1 saleredos Jorrrq ;eded y eq1 a,ro.rdurr o1 elrqderF al?lq e qll^{ poxru) zoulN 3o .rede1 >1ctq1 'tr1'1 a.rnFrg ur u^roqs sr e dq papunoJrns sr apoqlet por uoqrec atlJ ( s) C |( s)I O zury' 1sI zg ui,11 )I CtHN' (be) + zuZlG)uZ ;(be '1ac eq;, '11at ,{q fgecrleruaqcs paluasa.rda.r aq uec qcrql{ ?qcuelcaT E pal1et saurloluos sr pue 8g8I uI gtlcuelearl sa8loap ,(q paluarrur IIac B ol uroq papuocsop sI slq8qqseg .ratu,od pasn ,,14c frp,, pallec-os or{J,
dl.jueJ aaeq qJ.rttA\ slec f.rerur-rd uotutuoc oa.rrll raprsuoJ lsJS ad\ 'u5rsap ur sacuorosrp ol speai uor?crmJ ur acuoraJtrp oqJ 'a1cttc leuoge.redo eq1 yo slred luupodrur dgenba ere Sur8reqcer 'pueq roq?o aqt pue SurS.reqcsrg 'r(8.reuoIBcIrl?aIa orols o? Papua?ur sr uo 'fee11eq e8e.rols y 'sase8 zO pu 611 ale.raueEar ol spra\>Irq unr oq dleur.rou lou ppo/tr IIac IanJ aql pue 1ac lqFqqseg e aF.reqaar o1 ldruage 'flpplcala se fS.raua aq1 Furpe.rlxo 'JalB^{ o1 ueffxo lou op dlensn a16 'papretsrp uaql sT pue pue ua8o.rpfq slrarruoc lJe.rcaceds ur IIo) IanJ v flrcr-rpa1a o? papaauoc uaoq seq f,5.raua lecrruoqt aql l1e I4Irn pasn sr flac 'puetuap uo dlpgpela dlddnsa.r uaql PUB d.8.reua leJrruaqc tqFrlqseg v se d.8.reuaIJIrpaIa orols o? papualul are qcrqâ's77ac ttopuolas pve 'd.8;eua FcIJ?caIa o1u1 dS.raua 1ecluraqc 1"raluoc ol papua?ur are r{Jrq.4d. 's77ac i(r.nutrd :sasselc o1r+o?ur papl^Tp aq uee sllot lecrruaqto4calg '(6C) '(7C) dpaselelua^ ro '(gC) raqclald '(9C) uPun{S pue d>1z1o8eg ?sIrFuV '(ZC) aas 'uorleurroJur roqpnJ Jod '.{8.raua 1ecrr?cala [alue141 fq s>1ooq aruos o1u1 f5.reua IBcrruaqc lJaluoc qcrq&\ sIIac Iecltuoqcorlcola 'aur8ua go uorlerado aq1 fgaFrq ^4.arlal llrta arrl 'uorlcas slql uI leaq E r{}I,$ aIqFSod st ueql dcuangga .ra1ea.r8qcnur qll^{ poôrgte eq aldrcur.rd ur plnoc IIoc lecTtuaqcorlcale uB era d8.reua letrJlcala o1u1 dS.raue pocnpoJ IanJ lrssoJ Jo uorsJoluoc 1taJrp pue uoqnllod pluaruuorraua 'aÎsuedxa go adoq aql ra.Uo sopqoluolne patamod-cr.r?calg flerluelsqns a.Ioru pu JecJucs auocaq o^q slenJ lrssoJ sB puB luotuuoJrûa l(11uece.r arll JoJ pauracuoc aroru aurocaq seq dlarcos s (II'0I) palraal ser{ socrnos roaod s silot lecTruoqcoJ?cala ur ?soJalul '(sarJalteq olrqouo?nu ''E'a) suralsfs a5e.rols dS.raua ''E'a) sac.rnos alqepod se ro ('44 'sdo1 s,uarppuc 's?q8rltlseg ur pasn sIIoJ
frtq,, aqtr ,,77a3 '(uI) opouJurze Fuvr.eq 'acuelqruese.r 11e
sIIaCland prre sol.ra]lg 8'IS
9p
46
contact caP insulation air space carbon rod cathode manganese dioxide paper spacer
zinc anode Figure 1.17 Construction of the ZnlMnOz dry cell.
gelled electrolYte
insulating disk
The cell leads to an increase in pH which is buffered by the- NHaCI' reversible, so_that diy cells are not readily ,.L".ilo" is only pu.ti"tt'V ThL i"acl nature of Zn(iI) depends on the pH and NHaCI or "".f,"rg"a. corcerrT".tiotr. It may be precipitated as i hydroxide or oxychloride as an ammrne complex. on diffusion into the MnOz remain in solution There is some pfrur", however, precipit-ation as ZnO'MnzOs- -occ-urs: this phaseis responsiblefor-theirreversibility !"ia"""" that formation of Z,nlMnOz iiy cells have a relatively short shelf life becauseof tfr" ""U. "i whiih amount to an internal short circuit. Because diffusion processes the cells aie inexpensive,however,they have been widely used' Because of the Jut!. markei foi tnis kind of cell, a considerable effort has been expendel on improvements of the Leclanch6cell. When by KOH is the electrolyte, the cell reaction is îfi;Cl-ir-r"ptu.ia transformed to + Zn(s)+ 2 MnOz(s)+ H2O -+ Mn2O3(s) Zn(O}l)z Becausethe electrolyte is not gelled and is more colTosivethan NHacl, the lit-"'* .r" ro."" pu.klging prob"lems,the solutions to which increase tn" cell. Howei"rlti" shelf iife of an alkaline cell is much longer .o.t Lf out ihan that of the Leclanch6 cell, and the alkaline ZrlMnOz cell turns applicationswhere a steadylow-levei drain of power i" U" *"ff adaptedto is ,eqoir"a, a situatiori *h"tu polarization of the traditional dry cell would lead to degradationof performance' The MercurY Cell one of the few commercially important cells which does not have nineteenth century *igi"r i. the alkaline zinclmercury cell, developed for the U. S. Armyduring World War II' The cell,
,zJ c4eqrpBpuu 'zJ ls'uorsuedxa IeruJoq?os\ ol uorssoJdruoc crlqBrpE 'TJ le uorssa.rdruoc leruraqlosr) alcde loureC B q?Ir!\Fullerado aur8ue uB rod 'palgu11s1 ssaao.rd Jo ,(cuarcg;alerr?aJoar{} oql unurxeru oqJ b1m= f,iuaroglg :1b-) uorpear Icuuaqc aqt uI polloâ leaq aq? ol (m-) s8urptmo.r.rns aq1 uo auop >Iroa\ar{?Jo orleJ or1l sB paurJapaq uuc aur5ua aql Jo dcuercg;a aqJ '{roa o? polroluoc d1pr1;ed sr uor?rearuor?snquocotll Jo leaq aql 'our5uo e leaq B ur porrrnq sI IanJ uoqreco.rpdq ro uaSorpdquoq.&1 sIIaC pn{
3o sualsds acueprns aq? uT pu saqclrd.pu' spre Fur.reaq ,;;;H;:i ", .ro; 'pa.nnba.r sr IIaJ alqurlar dnFn ,IIBurs d.rarre araq^4.suor?nlrs ur f1e3.re1 uaaq alr{ suoqecrlddy 'sa.rnle"radurol raâol dlluecgru8rs .raq8rq 1e l(lpgssercns saleredo osle 11 'or1e"rlqErern-o1-fF.reua e d.rnc.ra* eq? ueql a3e11on 1Br.{./t\ouos sBq snql pu 'A g'I lnoqE ,11ec .reqFr-q seq 11ar e rallrs aqJ 'eF.reqasrp Suunp luelsuoc ssal sr lequelod aqt q5noqlle IIaJ f.rnc"reuror{l Jo sa8elueape arll Jo .fueru seq IIoJ srrlJ (s)FV(s)zOuFVl(bB)-zt(HO)uZ.(be)HOXI(s)z(HO)u ZIG)vZ zgz7yluz aq} q 11ac :11ac d.rnc.raur aqlJo a^qglar asoleV
IIaC raal?s aqJ 'suralqo"rd leluoruuoJraua sluase.rd lesodsrp leq? pue Co0I lnoqe ^toIeq sa.rnle.radrual 1e, flsnolrdrce.rd sdo.rp 1nd1no .r.aurrod ?eql ore sa8eluelpesrp 'or?Br .rofeu eq;, aurnlo,r-o1-d3.raua qFFI e pu oJII gleqs Fuol '1er1ua1od o^Br{slac d.rnc.reur oq? luelsuoc d1a,rqe1e.r o?uo4rppe u1 .do1 aql olur passa.rdsr apous tue8pue curz ar{?pue lBrraleru ?uaqrospe 11ac go redel B ur pauruluor sr a1d1or1ca1a ourF{IB aqJ 'd.rnc.raru pInbTI fla8rel saruoJaq.rafe1 srql 'a.8.reqasrp uodn .osec Iaols pe1e1d1ar1cru E Jo ruo??oqoql olw passa.rdldlrrrrlcnpuoc arr.ordtur a1rqde.r8e111r1 o1 B q?!rr\paxFu) apoqlEc aprxo crrnJJoruB rl?r1{r papnrlsuor sr IIac ar.{J 'uorleluaunJlsur Jruorlcala ur aJuaJaJar a5ellorr e apuo.rd ol pasn uooq ua?Joa^BrI slloc d.rncreur,dl8urp.roccy .e8.reqcirp Suprnp lulsuoc arour qanru sr lequalod IIaJ aql i11nsa.rE se pue 4(11O)vZ 311 <- O6H + gE11+ug + uolpar 1g1ac gfigrytg oW r(q peumsuoc1ou sr a$1o.rpa1a eq1 ,1ac .sorper d"rp zgu141,nrz e{qun 'J?a 'sprc Sur.reaq,saqeleao, oq? Jo?srsurl .rau,od pasn dlaprm r[.re,r pue A gg.I Jo pqualod lmc.rrc-uado seq ol sr ue (D8H (s)o8H1(be g gluz.(bB)Hox l(s)z(Ho)uz l(Elfi)uz ;_.r1 L}
sllac Iond prrB salral?Bg g'I$
48
Eldctrode Potentials
Ifl''lt"*.' ;t;;i';.1
efficiency is expansion back to ?1), it can be shgyq that the maximum the engine limits between which th;'il*p"r"t"re ilffi.;1;;;-6 operates: (1.29) Efficiency=(Tz-TilTz because of In practice, efficiencies are considerably less than theoretical friclion and heat loss. from an In contrast to a heat engine, the work obtained for the cell reaction' Using the cell i.*"q"ui to-j6C "f".t"o"fr"*icai the efficiencYis definition above, (1.30) ?AS Efficiency = AG = 1AII ^H "efficiency" -of a-n When AfI and AS are of opposite si.gn' . the criterion, is elgaler than 1' wld ["r"d i,n t1..e electrochemical power situation), the ""ri, when AIr and As arl r"lr, ""g"ti"" (the more common is usually much efficiency decreaseswith increasing temperature but is !r-a1dlv3 ngw idea' ostwald irtit ;d; that of il;;; "'ii"ti ""si""in"maximum efficiencies in 1894 (13) and i;ffi;ffi'ffi"itff"rence i"Lr cells should be developed to replace t1'.1;1".h;;h;;..r il;;;;J heat engines. the Example 1.9 Compute the maxjmum effrciency and *tt". one mole of HzG) reacts with O2@) !9 *o.t *""1*"* HzoG) (aii"L-Cutttot engine-oferating between 600 K ;;;il.; electroclemical cell operating under 11]-jf;a'6ti;-"" ;;;s6b conditions at 298 K' standard kJ mol-l' The standard enthalpy of formation of HzO(g) is .-242 is 50Vo'so that the maximum efficiency According to "q-ii.i6i the maxiinum useful work, assuming that A'FI is temperature is independent, 121kJ mol-l. ------rt of formation of HzoG) is -229 kJ e stairaura-rr"" ""ergy ette"fr is theoreticallv cglygrtible to .rf init *ol-i;;;J = x work. The efficierriy then is (2291242) 700vo 94.6Vo. "tu.t.i."t
was Professorof Physical Friederich Wilhelm Ostwald (1853-1932) ^Ci"-i.lty-"t Together with Arrhenius and the UniveiJity tiLlip'ic' 3"" ofthe fou"d?f oltly.:l::l van't Hoff, ostwald it";AJ"d--"'. phvsical
lot tre maintaineJ an active.scien-tific career on ;;;i;;;t"", grtranic cells and as a founder of The ro.r,i, *oir.-* i;".';;;;il.;a Chemical SocietY of London'
or generation il1".'i;#;;.;?; i;'p& qoqryl'A-u barriqter s-ri w'ifii"i" R: e;;;3 iieri-reso) was a the side' bv He
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- H O Ze - e 6 + O z H + ( 4 z o g -aZ+ O6HZe -HOZ+ @)zH
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ohmic heating of the electrofte solution, most successfulfuel cells use a thin film of solution or in some cases a thin film of an ion exchanger betweenthe porous anodeand cathode. Cells Using Other Fuels While the greatest development efforts thus far have been on the H202 fuel cell, Iarge-scaletechnologicalapplications of fuel cells depends on the use of other, rnore readily available fuels, such as carbon (coal), hydrocarbons (petroleum or natural gas), or carbohydrates (plant material). Researchdirected to the developmentof such fuel cells began in Germany during World War II and has continued, mostly in Europe, since then. While there has been signifrcant progress and pilot-plantscale fuel cells have been built, the processesare not yet competitive with traditional steam-poweredturbines. For more details on fuel cells, see Bockris and Srinivasan (G1), Pletcher (G6), or reviews by Eisenberg (15) or Cairns (16). Storage Bq.tteries
Energy storage cells (secondary cells) have somewhat different requirements than.primary energy conversion cells. A storage cell must be capable of many charge/discharge cycles with high energy efficiency; thus there must be no irreversible side reactions or processes which convert components into unusable forms. Because storage cells are mostly used in situations requiring a portable power source, the energy available per unit weight should be as large as possible. A common figure of merit applied to storage cells is the energy density, expressible in units of J g-1 or kWh kg-l (r kWh = 3600 kJ). By far the largest use of storage cells at present is in automobile batteries. Here the major requirement is that the battery be capable of delivering high power for a relatively short time (to start the engine). A Storage cells are also used to power many small appliances. potentially important application of storage cells is in powering electric Electrically powered vehicles were popular in the cars and trucks. period around World War I but did not successfully meet the competition of the internal combustion engine. With society's recently acquired awareness of the environmental damage of automobiles, there has been a revival of interest in electric cars and in efficient light-weight batteries to run them. Another potentially important application of storage cells is as load-leveling devices at power generating stations.
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52
ElectrodePotentials
devote a large fraction of their load-carrying capacity to batteries, a restriction which has severelylimited devblopment. Example 1.10 Compute the theoretical maximum energy density for a lead-acid cell, taking into account the weight of reactants in the cell reaction and neglecting the cell housing and electrolyte solution.
The Ed.ison CelI The alkaline iron-nickel cell can be representedas The half-cell reactions + 3 NiOz(s)+ 2}{2O + 4 e- --+NigOa(s) 4 OH-(aq) + 3 Fe(s)+ 8 OH{aq) -+ FesOa(s) 4 H2O + 8 ecombineto give the overall cell reaction 6 NiOz(s)+ FesOa(s)-+ 3 Fe(s)+ 2 NisOa(s)
The electrical energy deliveredat 2 V is t|elec= nFE = 386 kJ mol-l
The weight of one mole of the reactants(Pb, PbOz,and 2 HzSOa) ls 642.5g, so that gmol-1)= 601J g-1 Energy density= (386kJ mol-1)/(642.5 the cell is usually not more t}aan30Vo or 0.17 kWh kg-t. Because discharged and the neglected weight is substantial, the practical energ"y density is in the range 80-200J g-r.
Gaston Plantd (1834-1889)was Professor of Physics in Paris; he is best known for his work on storage batteries. Thomas Alva Edison (18471931) was a prolific inventor whose persistence made up for his lack of formal scientific training. Although Edison acknowledged a debt to Michael Faraday for his electrical and electrochemicalinventions, his approach was less one of pure reason than an exhaustive trial of every possible solution to the problem at hand.
Fe(s)lNiOz(s),NisOa(s)IKOH(aq)lFesOa(s)lFe(s)
This cell was perfectedby Edison in 1910 as a power source for electric vehicles. The nominal cell potential is about 1.37 V but varies considerablywith the state of charge of the cell. Since the electrolyte is not consumedin the cell reaction, a relatively small volume is required and the cell can be more compactand lighter in weight than a lead-acid
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ElectrodePotentials
The cell voltage is about 2 V, dependingon the state of.charge,and tlre theoretical ma=ximumenergy density is about 5000 J g-1 (1.4 kWh t<g-r). The major problem with the cell is the membrane. Na atom diffusion into grain boundaries in the B-alumina membrane causes short circuits and itructural failure. The sodium-sulfur cell is probably not practical for electric vehicles (heating the cell to 300"C before operation is one problem),but as a power plant load-levelingdeviceit has somepromise'
REFERENCES 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 72. 13. 14. 15. 16. 17. 18.
(Reference numbers preceded a letter, e.g. (A1), refer to a book listed in by the Bibliography.) Soc.1951,73,2680. A. A. Frost, J. Arn. Ch.em. Educ. Chem.1964,1,I23. E. A. V. Ebsworth, J. P. Delahay, M. Pourbaix, and P. van Rysselberghe, Chem. Educ. 19ffi,27,683. Z. L919,67,385. F. Haber andZ. Klemenciewicz, phys. Ch.em. Chemistry1984,13, 191. R. W. Murray, Electroanalytical J. Janata,AnaI. Chem.1992,64,796R. N. H. FurmaninTreatise on Analytical Chemistry,I. M. Kolthoff and P. J. Elving, eds,New York: Wiley, 1963. Part I, Vol. 4, p 2269. S. Wawzonek in Physical Methods of Chemisfry, Part IIA (Techniques of Chemisfry, Vol. I), A. Weissberger and B. W. Rossiter,eds,New York: Wiley, 1971,p 1. R. P. Buck in Physical Methods of Chemistry, Part IIA (Techniques of Chemistry, Yol. I), A. Welssbergerand B. W. I Rossiter,eds,New York: Wiley, 1971,p 61. 1975,10,239. of Electrochnmistry D. P. Gregory,Mod,ernAspects 1975, 10' 339. Modern Aspectsof Electrochemistry K. V. Dordesch, J. McBreen and E. J. Cairns, Adu. Electrochem. Electrochem. 11,273. Engin.1978, 1894,1,129. Z. W. Ostwald, Elektrochem. Mag.1839,14,127. W. R. Grove,Phil. Engin. 1962,2, 235. Electrochem. Adu. Electrochern. M. Eisenberg, Engin. 197L,8,337. Electrochem. E. J. Cairns,Adu. Electrochem. J. Burbank, A. C. Simon, and E. Willihnganz, Adu. Electrochem. Engin.1970,8,757, Ekctrochem. P. C. Milner and U. B. Thomas,Adu. Electrochem.Electrochem. Engin.1967,5,I.
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1.6 Devisegeneralderivationsof eqs(1.24),(L.25),and (1.26) 1.7 A silver electrode is immersed in 100 mL of 0.1 M KCl, and the solution titrated with 0.2 M AgNO3 solution. The potential is determined us. a standard AglAgCl electrode (with 3.5 M KCI electrolyte). Calculate the cell potential when 1, 10, 30, 45,50,55, and 70 mL of the silver solution has been added. The solubility product constant of AgCl is 2.3 x 10-10.Neglect activity coefficients. Plot the calculated potential us. volume of titrant.
1.9 The celi l1I
1.8 Overman (Anal. Chern.1971,43,616) found that an iodide-selective electrode can be used in the determination of Hg2+ by titration with a standard NaI solution. When he titrated 50 mL of unknown Hg2+ solution rvith 0.0100 M NaI, he obtained the titration curve shown in Figure 1.L8. What was the concentrationof mercuric ions in the original solution assuming that the titration reaction produced insoluble HgI2? This titration procedure worked for Hg2 + concentrations down to about 5 x 1"0-6M, but at lower to concentrations,endpoints were found which corresponded ratios of iodide to mercury of more than 2:1. Why?
M)llcd2*(0.0092 M),cN(O.094M)lcd cdlcd2+(O.00972 z has a potential of -0.4127 Y at 25"C. If the only significant reaction between Cd2+ and CN- is the formation of Cd(CN)a2-, what is the equilibrium constant for the formation of the complex ion?
1.10 The quinhydrone electrode is sometimes used to measure pH. Quinhydrone is an easily prepared, slightly soluble, equimolar mixture of benzoquinoneand hydroquinone. The reduction of the quinone is reversible on platinum: CoIIaOz 2}l+ + 2 e- I CoHa(OH)z ,Eo= +0.700V + In practice, an unknown solution is saturated in quinhydrone and the potential measured with respect to a saturated calomel electrode. (a) Show that the potential of the quinhydrone electrodegives the pH directly. (b) Suppose that a cell potential of +0.160V is measuredus. s.c.e. What is the pH of the solution? (c) The quinhydrone electrodeis not usable abovepH 9. Why? The adult human brain operatesat a power of about 25 W. Most of the power is used to operate "sodium pumps" in the nerve cell membranes,which maintain the internal ionic concentrationat
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Electrode Potentials From data given in Table A.4, compute the standard free energy of disproportionation for the following reactions: 2 Cu+ _+ Cu2++ Cu B Fe2+ _+ 2 Fe3++ Fe 5 MnO42-+ 8H+ -+ 4 MnOa- + Mn2+ + 4H2O Can you generalize from these results to obtain a criterion for the stability of a speciestoward disproportionation based on half-cell potentials?
l.l7 L18 The silver-zinc cell,
1.15 The potential of a glass electrodewas 0.0595V us. s.c.e.when the electrodes were immersedin a pH 7.00 buffer solution and 0.2598V when immersed in a solution of unknown pH. (a) Calculate the pH of the unknown solution. (b) If a possible junction potential introduces an uncertainty of 10.0005V in comparing the potentials of the known and unknown solutions, what is the uncertainty in the pH of the unknown?
f.ie a sodium ion-selectiveelectrodedevelopeda potential of 0.2631 V us. s.c.e.when immersed in 25.00 mL of an unknown solution. After addition of 5.00 mL of a 0.0100M Na+ standard solution, the potential decreased 0.1921V. to (a) Calculate the sodium ion concentration in the unknown solution. (b) If the uncertainty in the potential measurementswas +0.0005 V, what was the uncertainty in the sodium concentration of the unknown? The potential of a glass electrodein contact with a solution with and -0.690 [Na*] = 0.10M is -0.450V at pH 8.00,-0.568V at pH 10.00, V at pH 13.00. (a) Compute the potentiometricselectivity coefficient,ftH.Nu. (b) At what solution pH would the apparent pH (computed assuming pH linear in potential without correction)be too low by 0.05pH unit?
Zn(s)lZnO(s)IKOH(aq, 40Vo),K2ZnOz(aq)lAgzO(s)lAg(s) tras had limited application in storage batteries. (a) Write the half-cell reactions and the overall cell reaction. (b) If the cell potential is 1.70 V, what is the maximum possible energy density?

PRGR Elctrchmstry 01 ElectrodePotentials

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PRGR Elctrchmstry 01 ElectrodePotentials

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