Class The Lead-Acid Battery: Richard 8. Treptow its Voltage in Theory and in Practice Department of Chemisiry and Physics, Chicage Slate University, Chicago, Il 60628-1598 The lead-acid storage baeery is the most widely used rechargeable power source in the world today Iecerainly i well kknowa to anyone who owas and maintains aa automobile General chemistry textbooks typically discuss the battery but limic their coverage to a description of its components and the reactions occurring at its electeodes. In this azticle we expand that coverage by asking a very practical question: How does the voltage of the battery depead upon the state of ics charge or discharge? The guestion is addressed theoretically by use of the Nernst equation and practically by reference to acwel banery peeformance, As we uncover the details of this popular elactrschersieal device, we will improve cue under- standing of such fundamental concepts as standsed states, activity coefficients, and electrode overvoltage lead-Acid Battery Fundamentals The common 12-volt automobile battery consis of six individual cells connected ia series so that the toul voltage eneeared iscbrtimestharofeach call. Figue | iluraces asingle Cell ac wo stagesof is life cycle Is electrodes axe mera plates of lead constructed in the form of grids to maximize their surface area, The electrodes are immersed in an electrolyte of aqueous sulfuric acid, As shown on the cop of the figure, the call is Fully chazged and acting 2s a galvanic cell to supply clecrrical airtent to an external load. During this process the lead anode is oxidized co lead) sulface, an insoluble white solid, by she half vencrion Db(e) + HySOalag) > BRIO) + Zag) + 2 The anode has a negative change because it produces electrons. ‘The cathode consist of lead(IV) acide deposited on « kad plate. During dischazge the red-brown oxide is ecuced to Tead (IT) sulfate by the geaction PbO,{s) + 2H'{aq) + H,SOg(aq) + 26 PoSO, (9) + 2H,O(E) ‘The cathode bas a positive charge because elections are cone sumed there, The two helE-reactions can be combined to give the overall discharge reaction Pb(s) + PbO, (@) + 2H,80,(eq) > 2PBSO,(8) + HOLE) Sulfuric acid is consumed and water is produced in the reac- tion, Hence, both the concentration aad the density of the electelyte drop seadily during discharge. The stat of charge of a lead-acid bartery can be conveniendy detemined by measuring the specific geavity ofits elecrolyt= The cell is shown fully discharged an the bottom of Figute 1. ls wo eleewodes now have leet) sulfate deposited tom thele grids. Ie is acting ss an electrolytic cell while itis recharged by an external power source, With the electrical carent forced wo flow in the opposite dizection, the resctions described above are reversed and the acid) concentration steadify increases. Duving charging the former anode Functions, ts acathode, and vice versa, This change in coles oosurs with snyechargeable cll, Eleenchemicn| engineers sveid confusions 334 by tefecting to the electzades as negative or postive. These Gesignations do not change when the cell itches functions, Coll Voltage and the Nernst Equation Electrochemical theory can predict hove the woltage of lead-acid cell changes with the concentration ofits electrolyte, buc the process is noc simple. Ic is complicated by the fact that sulfuric acid is « nonideal salute. Ie is peesent in the cell achigh concentrations where its scxivty differs greatly from the ideal Behavior used to define its standard state, A further complication verules heeause water ia participant inthe cell reaction as well as the solvent for the acid, Mindful of these Feces, we will now calculate the cll voltage as a Function ofits acid concentration, Two theoretical models will be developed ‘which wear the mater of nonidealicy in different fashion Load (a) Gatvanie Cell oC =] poner Source (b) Eloaroyie Cet Figure 1. Two stagor of a laad-acid call [o} fully charged ond supplying curren! fa.an axternal lood and [bl fully discharged ond recniving curact froin an aotannal power sores Journal ofChemnicn| Education * Vol 79 No 3 March 2002 * JChemEd chem wise adApproximate Model The fest model is approximate in thac ic allows simpli fying assumptions, ‘The sulfuric acid in the clecwalpte is 35- sumed to be a strong monaprotic acid completely disteci- aved into H* and HO, ln the incexese of siznpliccy, che face thar HSO, is itself a weak acid is nor considered. "The ‘overall cell discharge reaction is thus written Phis)+ PoO,(6)+ 2H"aq) + BHSO, lag) + PESO, 6) 42H) to show each substance in the form which the model regards tw be its standard stare ‘The sandard free ansigy change fi the sescsion cam be caleuleted ia usual ishion Fora AG® = ZnAGPlproducts) — EmAGFleeactants) (1) where AG? is the suandard free-energy of Formation of exch species, Using data frem the liveatuse (2) as listed in Table we find that AG® = -371.1 kJ at 298.15 K. The standard ‘luge, or elecuomotve fore, ofthe cell can thea be obtained from the relationship AG? = -nFEy @ where » = 2 mol for this reaction and Faraday’s constant, F equals 96.485 Clmol. The eesulcis £y = 1.52 volts for this model The voltage at conditions other than the standard state can be determined fiom the Nemst equation: Eay=Bog~ (RTP) 10. @ svhere the reaction quotient Q contains the setivities of all species in the reaction. In general, the activity ofa species is adimensionless quanticy that adjusts for che fact thar che species may not be peesent in its standard state. The activity cam be regarded as the effective concentration of the species relative wo its standard-sace conceanation. To apply the Nernst equation we must express the activity ef exch species in the cell reaction, ‘The sandand state ofa liquid or solid is defined as che pare substance itself The Pb, PbO2, and PbSOg in our call rect this requirement, Hence, their acivities are constant and equal to 1. Thus fre~ #1m0,~ #1Rs04> HL ‘The HO in the cell is not pure, since it comtains dissolved sulfuric acid, Although water is not in its standard state, the appraximate model assumes its activity is unaffected by the soliate. Hence, we wire amon Finally, we must assign activities to the H' and HSOy ions in the reaction, The standard stave ofa soluce is by defincion an ideal solution whose concentration is 1 mole pet kilogram of solvent, In other words, it is the hypothetical condition the solute would reach if the activity it displays at infinite dilusen could be inatazed in preporticn to i concenmation until thar concentration eesches 1 molal. The approximate model sssumes the two ions behave ideslly. Hence, their activities are ™ so an fae and aso Table 1. Thermodynamic Proportios of Pure Substances ‘and Aqueous lons at 298.15 K [Substance AGEAma SA mot Pure Substances Pols) 00 248 POs “UT 686 PeSOytl 9200 1485 Hod “285.8 700 Aqueous lens lea 00 9.0 HS04 fo 8873 1318 S0,A%eq) 909.3 201 where mas and mysog ate the malalities of the ions, and is the standard concentration of | mola] All activities have now been asigned and Qcan be-written oe (4m) 4x0” "Those acdvities thar are fbvd at 1 need noc be included in the equation, Upon insertion of the activity expeesions we obtain Suibstiution of cis expression into the Nemst oquation enables us to celculate the voltage of a lead-acid cell having any acid concentration, For example, consider a cel whos: electrolyte is Oitmaa B.S, Since the model ae HS, tobe suong moneproticteid, we have mje= 0.1 molal and mizsog = rmolal, These values give Q= 1 - 10S, Finally, we obtain ka 1.80 voles by substiuucion inno the Nemsc equation.!The cal in this exemple understandably delivers less voltage chan che standard cell because its acid concentration is lower, Using the method ilusteated above, yy can be caleulved asa function of sulfuric acid concentration. Figure 2 displays the eesults of such calculations using cwo different styles of presentation, Graph 2a shows cell voleage versus log of the acid concentration. The relationship is linear, as should be expected fiom the form of the Neensc equation. In graph 26 the acid concentration is plotted linearly and descending from 6 molal, This inicial conceanacion is ypical of a freshly charged Iead-acid baseery. The graph shows che gradual decline of cell volage chrough the baresry lifetime Rigorous Model The second model is more rigorous in that it does not rely upon approximations, acknowledges thar sulfuric acid is diprotic and sble to dissociate fully into 2H and SOE ‘The overall cell reaction is written in the stple Phi) + PHO) + SE (aq) +2802 taq) > 2PHEOA) + HOE) to show etch substance in the form chat the model defines as js standaed stare, OF course, sulfuric acid achieves the full dissociation shown only at infinite dilution, Thus, the standard sue assigned to it by this model is puesly hypothedcal. In recognition of that fict we must not assume that the ions behave sdeally AChamaEd chem.wise.edu © Val 79.No. 3 March 2002 * Journal of Chemical Eduostion — 335Class Application of eq Land the appropriate thermorlynamic data from Table | gives AG® = -393.9 kJ for the reaction 4s weicten above. The standaed cell voltage can then be calculated from #q 2. ‘The result is Sy = 2.04 vols. These values reveal that the reaction is lightly mote favored in the formalism of che rigorous model. This should be expected since the fully dissociated acid of this model is immediately available to form PbSOg and HQ. “Activities must be assigned to all species ip this model -vithout approsimations, The Pb, PbO, and PIO, activites, can again be taken as I because these substances are in theie standard states. The activity assigned wo HO, on the other hand, must recognize that the water contains dissolved acid In general, « solute Lowers the sctivigy of its solvent. The extent of lowering can be determined from the decrease in the solvent vapor pressure. When water isthe solvenr we have gga tt® oe HO PSS ‘where Pye i the vapor pressure of water over the ceetion sod Pf,e ss the vapor presse of pure waren? Using this tnethod ty has been determined (2) over abroad range of t oncentrations fre Table 2). As shown in Figure 3 the activity ie ery nearly Lin dilute colutions, Buti drops sulfuric ack ‘when the concentration exzeeds L mola, The assignment of activites to Ht and SOG" muse acknowledge thac the behavior of these species is far from ideal, In general, deviations from ideality for « salute are accounted for by introducing am empirical correction Factor Yealled the activity ocefcient. The activites of the two ions eos #3 2 4 sce then written yar fy EE and aeoy 0 Eu! 8 16 1,80, Motaity Fy o 0 Eayl¥ HS, Malality Figure 2. lead-acid call vohoge verars acid concentration calla loted fromm the approximate mode where ¥. and v_are the setivicy coefficients For che eespective ions, m is the HSO, molality, and m® is the standard con- centration of 1 molal. I is not possible to measure the activity conficents of individual ions becuse fons ways existin pairs, 4 pair of tons can be measuted, Ibis defined as the geometsie mean of the individual activicy coefficients (9-5). This ve Seo Table 2. Activity of H.0 and Mean Activity Cosfticient of Se ee a 010 0.999560 0.5420 te 200 oases 1701s | Lees eelis omnshane uae nem sy et 336 Jounal ofChamical Education * Vol 79 No 3 March 2002 * JChamEd chem wise eduay 18 H,50, Morality 2 wo) 0 8 oe 4 ee H,80, Molalty Figure 4. Lead-acd call volage versus aeid cencentratian galex- lated from the rigorous model H,99 , Specite Grawty H,80, Molalty Figure 5. Voltage of an actual lead-acid cell during @ elechonge ‘and charge eyde of cencian current JChamaEd chem.wise.edu * Val 79 No.3 March 2002 * Journal of Chemical Education the ease ofa 2:1 electrolyte such as HySOy i is ve= ey "The mean activity corficient of H,$O.gin aqueous solution has been determined (2) over a range of concentrations from rmessurements of the electromotive force of galvanic cells chat employ the acid as theie elecxolyee (Gee Table 2). Figure 3 plots Ye versus HzO, molalicy, The coefficient equals 1 at infinite diluion because at thet concenuration the acid dis- sociates fly and its ions behave ideally. The value drops with concentration as nonideality ets in, Ie then inceeases ac high concentretion asthe salutien becomes deficient in water The reaction quotient forthe rigorous model is (s,)" (4a) (ae0a)* Q which upon substitusion of the expressions for the activities and the mesn activity coefficient becomes no)" =P Kh Insertion of this expression into the Nest equation allows calculation of che cell voltage at any acid concentration. For ample, in 0.1 molal H,SO, we have ay,9= 0.996437 and Ye = 0.2508. These values give Ruy = 1.79 volts. This result yes wll wih che volege We calulced eae foe de sae CSoceumtion ung the spprosimate model gure 4 shew Gal yltge versus ed sone acacding w theives model. The graphs are in the same style as those of Figure 2. "Fhe ewe sees yield seanp desl reuse scrpe ery low or high acid concentrations. At chese conditions che rigorous mdel shouldbe considered roe lid Tn the theoretical models the cell under consideration is in a state of thermodynamic equilibrium in char no current is lowing through it. The voltages we have calculated are open-cirewir voltages. In the next section we discuss a cell of Wifiseac ype leis «potcucal sll in the peoweo of betas hued ot dclieing slectelencegy ele notin race of equim 2g ‘Actual Battery Performance ‘The woltage a battery delivers when itis discharging or that it requires for charging is a matter of practical concern for electrochemical engineers (5-12). Figuee 5 shows the performance of rppical lead-acid call duving «cya in-which ics discharged and recharged at constant curt. Is voluge is plotted against the concentration and specific gravity ofthe clectrolyte As is typical of rechargeable batteries, the discharge voltage is consistendy lower than the chaeging valage. This behavior is atributable to several factors collectively now as cell polaricarion “Thuee wypes of polatzation occur in any elecrrochemical call hough which a current is Mowing. Actvacion polaricasion results from the chemical procasses occuring at the electrodes. "These include bond beraking and formation, selvaion changes, 337Class formation of new phases, und the transport of zeacting species through the electrode, Fach process bas an activation energy. that must be conscancly supplied if the cell is requited co produce a current. Concentration polericasion results from concentration gradients that develop in the electrolyte where it contacts the electrodes, These gradients cause the concentrations of reacting species atthe electtdes to differ from those of che bull elecaotyte. These firs ovo types of polarization cause a drop in the cell Jecuomotive Force attbutable wo aspecific elexrode The drop is known as the electrode overvaltages . Obmic golarication, on the other hand, sccurs in the bull of the tlecoolyee Ie results from the resistance the electolyt= fers to the movement of ions through it, In kesping with Ole’ law, the voluge los is IR, the produce of current times eesistance Each type of polarization ctuses a deop in the veltage delivered by a discharging cell. Thus Fitscacge = Feat — Meatuede ~ Manode IR where Zua is the openccitenit voltage and the terms sobweacted from it ze the electrode overvoltages and ohmic less."The vlt- age required to charge a eel, om the other hand, can be calcu lated by adding che three polarization terms. Blecceode over- voltage and obmic lass account forthe face that the charging. and discharging curves of Figure 5 differ from one another and from the open-cizcuit curve of Figure 4b, The advanced lisersrure can be conzuleed For further devas (12) Figuee 6 isa cutaway view of an semua) lead-acid barry “The components shown are the pesiive and negavive plates, a layer of lead(TV) onide, and a porous separator. Separators ae thin sheets placed becween the plates of a baxtery. They tre permeable to the electeolyte but they prevent the plates from making direct contact and short-citeniting the cell, Conclusions ‘The cell voltage calculated by the approximate model agrees well with that of the rigorous model when the acid concentration isin the 0.1 oo I molal range. Appsrendy che sssumptions of the model are acceptable in this eenceneraticn range. In more dilute solutions the model loses accuracy because the deprotonation of HSQ, is not considered? At conesatmations greater than moll its assurmpricas of ieality begin wo falter, In spe of these limitations, the approximate model can ceeve as 4 Jswaing experience for geneeal chemistry smudents, It serves well ro illustrate a practical application of the Neast equation. Scudents can be challenged vo create 2 plot of cel voltage versus extent of discharge. The rigorous model yields accurate open-cecait volages at all concentrations For physical chemistry students ic provides experience in dealing with solvent and solute sonideality. Heweves, i is also limiced in thacic gives only the voltage ofa cell chrough hich no curreatis flowing. A complete understanding of the practical lead-acid cell equizes knavrledge of such Faczors as électode overvoltage and ohmic loss Notes 1, When performing calculations with the Nernst ajustion icichelpfial to note that AY = 0.025693 volte at 298.15 K 2. This equation is modified for highly accurete work to tae lee asnount the wanideslity of mater vapor 938 Figure & Cutaway view of on indusriollaad-acid battery: Photo ‘couresy of Independant Bathory bhonFachinors Association, [IA 3. The approsimats model cam be innpraved at lew consen- teasions by hing ino aosoune ther sn dike solutions «.substansial Geetion of the HSO,; present iedeprotonated. The H! and HSO omoentrations used to evaluare Q can be comcted for chat fact However thecontection makes the model considerably move mache tmtically comple, and it hac only a very small effat on the cal culated vale of Ban Literature Cited 1, CRE Fandbook of Chemitiry and Physic, Sst ed.s Lide, D R., Bd. CRC Preis: Baca Raton, FL, 2000 pp 5-45-88. 2. Staples, B.R.j. Phyo Chem Ref. Dave 1981, 10, 779-797, 3. Rock, FA. Chenscal Thermodynentcs, University Science Books: Mill Valle, CA, 1983: pp 362-367, 4 Rel, ©. E, Chenoa! Thermodjnantion MeGean-HUk New York, 1990; pp 203-234. 5, Slots, Ms Rosenberg, RM, Cheninal Therm dynamics Base Theory and Meds, 6th od; Wiley: Nowe York, 2000; pp 426 464, 8. Bode, H. ead-eid Barovien Wiley: New York, 197: pp 40- 157 7. Comprise Tavis of Beemochentar Ve 8: Blcrshemsial Biegy Comvrion and Sorege, Books, ).O°M,, Ei Plenum: New York, 1981; pp 371-384 8, Gromptan, T. R. Zavery Refirence Books Butterworths: Lon- don, 1990; pp 1/10-1/45. 9. Crom, D. R Principle and Applicasions of Rlcrochenisiry, th dp Blarkle: London, 1994 pp 143-148, 241-044, 10, Handbook of Rawerie, 2nd ods Linden, D1, Bas MeGrave Hill New York, 1995: pp 2.1-2.19, 4.1-25.39. LL Vinwent, As Seroset, B. Afodere Burris uerasctore 4 Blectrockemiedl Power Sours, Indl; Arnold: London, 1997: pp 39-55, 142-161, 12, Atkins, 2 A. Pipi! Cheiory, 6th ed Freemans New Yoo, 1998; pp 877-892 Journal ofChemnicn| Education * Vol 79 No 3 March 2002 * JChemEd chem wise acls