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Battery5WhatTakesPlaceDuringDischarge

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CHAPTER5
WHATTAKESPLACE
DURINGDISCHARGE
Consideredchemically,thedischargeofastoragebatteryconsistsofthe
changingofthespongyleadandleadperoxideintoleadsulphate,andthe
abstractionoftheacidfromtheelectrolyte.Consideredelectrically,the
changesaremorecomplex,andrequirefurtherinvestigation.Thevoltage,
internalresistance,rateofdischarge,capacity,andotherfeaturesmust
beconsidered,andtheeffectsofchangesinoneupontheothersmustbe
studied.Thisproceedingissimplifiedconsiderablyifweconsidereach
pointseparately.Theabstraction.oftheacidfromtheelectrolytegivesus
amethodofdeterminingtheconditionofchargeordischargeinthe
battery,andmustalsobestudied.

VoltageChangesDuringDischarge.Attheendofacharge,andbefore
openingthechargingcircuit,thevoltageofeachcellisabout2.5to2.7
volts.Assoonasthechargingcircuitisopened,thecellvoltagedrops
rapidlytoabout2.1volts,withinthreeorfourminutes.Thisisduetothe
formationofathinlayerofleadsulphateonthesurfaceofthenegative
plateandbetweentheleadperoxideandthemetalofthepositiveplate.
Fig.21showshowthevoltagechangesduringthelasteightminutesof
charge,andhowitdropsrapidlyassoonasthechargingcircuitisopened.
Thefinalvalueofthevoltageafterthechargingcircuitisopenedisabout
2.152.18volts.ThisismorefullyexplainedinChapter6.Ifacurrentis
drawnfromthebatteryattheinstantthechargeisstopped,thisdropis
morerapid.Atthebeginningofthedischargethevoltagehasalreadyhad
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arapiddropfromthefinalvoltageoncharge,duetotheformationof
sulphateasexplainedabove.Whenacurrentisbeingdrawnfromthe
battery,thesuddendropisduetotheinternalresistanceofthecell,the
formationofmoresulphate,andtheabstractingoftheacidfromthe
electrolytewhichfillstheporesoftheplate.Thedensityofthisacidishigh
justbeforethedischargeisbegun.Itisdilutedrapidlyatfirst,buta
balancedconditionisreachedbetweenthedensityoftheacidinthe
platesandinthemainbodyoftheelectrolyte,theacidsupplyintheplates
beingmaintainedatalowereddensitybyfreshacidflowingintothemfrom
themainbodyofelectrolyte.Aftertheinitialdrop,thevoltagedecreases
moreslowly,therateofdecreasedependingontheamountofcurrent
drawnfromthebattery.TheentireprocessisshowninFig.22.

Leadsulphateisbeingformedonthesurfaces,andinthebodyofthe
plates.Thissulphatehasahigherresistancethantheleadorlead
peroxide,andtheinternalresistanceofthecellrises,andcontributesto
thedropinvoltage.Asthissulphateformsinthebodyoftheplates,the
acidisusedup.Atfirstthisacidiseasilyreplacedfromthemainbodyof
theelectrolytebydiffusion.Theacidinthemainbodyoftheelectrolyteis
atfirstcomparativelystrong,orconcentrated,causingafreshsupplyof
acidtoflowintotheplatesasfastasitisusedupintheplates.This
resultsintheacidintheelectrolytegrowingweaker,andthis,inturn,
leadstoaconstantdecreaseintherateatwhichthefreshacidflows,or
diffusesintotheplates.Furthermore,thesulphate,whichismorebulky
thantheleadorleadperoxidefillstheporesintheplate,makingitmore
andmoredifficultforacidtoreachtheinterioroftheplate.Thisincreases
therateatwhichthevoltagedrops.
Thesulphatehasanothereffect.Itformsacoveroverthe
activematerialwhichhasnotbeenactedupon,andmakes
itpracticallyuseless,sincetheacidisalmostunableto
penetratethecoatingofsulphate.Wethushavequantities
ofactivematerialwhichareentirelyenclosedinsulphate,
therebycuttingdowntheamountofenergywhichcanbe
takenfromthebattery.Thustheformationofsulphate
throughouteachplateandtheabstractionofacidfromthe
electrolytecausethevoltagetodropataconstantly
increasingrate.
Theoretically,thedischargemaybecontinueduntilthe
voltagedropstozero,butpractically,thedischargeshould
bestoppedwhenthevoltageofeachcellhasdroppedto
1.7(onlowdischargerates).Ifthedischargeiscarriedon
beyondthispointmuchofthespongyleadandlead
peroxidehaveeitherbeenchangedintoleadsulphate,or
havebeencoveredupbythesulphatesoeffectivelythat
theyarealmostuseless.Platesinthisconditionrequirea
verylongchargeinordertoremoveallthesulphate.
Thelimitingvalueof1.7voltspercellappliestoa
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continuousdischargeatamoderaterate.Ataveryhigh
currentflowingforonlyaveryshorttime,itisnotonly'safe,
butadvisabletoallowabatterytodischargetoalower
voltage,theincreaseddropbeingduetotherapiddilution
oftheacidintheplates.
Thecellvoltagewillrisesomewhateverytimethe
dischargeisstopped.Thisisduetothediffusionoftheacid
fromthemainbodyofelectrolyteintotheplates,resulting
inanincreasedconcentrationintheplates.Ifthedischarge
hasbeencontinuous,especiallyifatahighrate,thisrisein
voltagewillbringthecelluptoitsnormalvoltagevery
quicklyonaccountofthemorerapiddiffusionofacidwhich
willthentakeplace.
Thevoltagedoesnotdependupontheareaoftheplate
surfacebutuponthenatureoftheactivematerialsandthe
electrolyte.Hence,althoughtheplatesofacellare
graduallybeingcoveredwithsulphate,thevoltage,
measuredwhennocurrentisflowing,willfallslowlyandnot
inproportiontotheamountofenergytakenoutofthecell.
Itisnotuntiltheplatesareprettythoroughlycoveredwith
sulphate,thusmakingitdifficultfortheacidtoreachthe
activematerial,thatthevoltagebeginstodroprapidly.This
isshownclearlyinFig.22,whichshowsthatthecell
voltagehasdroppedonlyaverysmallamountwhenthe
cellis50%discharged.Withcurrentflowingthroughthe
cell,however,theincreasedinternalresistancecausesa
markeddropinthevoltage.Opencircuitvoltageisnot
useful,thereforetodeterminehowmuchenergyhasbeen
takenfromthebattery.

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AcidDensity.Theelectrolyteofaleadstoragebatteryisa
mixtureofchemicallypuresulphuricacid,andchemically
purewater,theacidformingabout30percentofthe
volumeofelectrolytewhenthebatteryisfullycharged.The
pureacidhasa"specificgravity"of1.835,thatis,itis1.835
timesasheavyasanequalvolumeofwater.Themixture
ofacidandwaterhasaspecificgravityofabout1.300.As
thecelldischarges,acidisabstractedfromtheelectrolyte,
andtheweightofthelattermustthereforegrowless,since
therewillbelessacidinit.Thechangeintheweight,or
specificgravityoftheelectrolyteisthebestmeansof
determiningthestateofdischargeofacell,providedthat
thecellhasbeenusedproperly.Inorderthatthevalueof
thespecificgravitymaybeusedasanindicationofthe
amountofenergyinabattery,thehistoryofthebattery
mustbeknown.Suppose,forinstance,thatinrefillingthe
batterytoreplacethewaterlostbythenaturalevaporation
whichoccursintheuseofabattery,acid,oramixtureof
acidandwaterhas'beenused.Thiswillresultinthe
specificgravitybeingtoohigh,andtheamountofenergyin
thebatterywillbelessthanthatindicatedbythespecific
gravity.Again,ifpurewaterisusedtoreplaceelectrolyte
whichhasbeenspilled,thespecificgravitywillbelower
thanitshouldbe.Inabatterywhichhasbeendischarged
tosuchanextentthatmuchoftheactivematerialhasbeen
coveredbyalayeroftoughsulphate,orifaconsiderable
amountofsulphateandactivematerialhasbeenloosened
fromtheplatesandhasdroppedtothebottomofthecells,
itwillbeimpossibletobringthespecificgravityofthe
electrolyteupto1.300,eventhoughalongchargeisgiven.
There.must,therefore,beareasonabledegreeof
certaintythatabatteryhasbeenproperlyhandledifthe
specificgravityreadingsaretobetakenasatrueindication
oftheconditionofabattery.Whereabatterydoesnotgive
satisfactoryserviceeventhoughthespecificgravity
readingsaresatisfactory,thelatterarenotreliableas

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indicatingtheamountofchargeinthebattery.

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Aslongasadischargecurrentisflowingfromthebattery,
theacidwithintheplatesisusedupandbecomesvery
muchdiluted.Diffusionbetweenthesurroundingelectrolyte
andtheacidintheplateskeepsupthesupplyneededin
theplatesinorderto,carryonthechemicalchanges.
Whenthedischargeisfirstbegun,thediffusionofacidinto
theplatestakesplacerapidlybecausethereislittle
sulphatecloggingtheporesintheactivematerial,and
becausethereisagreaterdifferencebetweenthe
concentrationofacidintheelectrolyteandintheplates
thanwillexistasthedischargeprogresses.Asthesulphate
beginstoformandfilluptheporesoftheplates,andas
moreandmoreacidisabstractedfromtheelectrolyte,
diffusiontakesplacemoreslowly.
Ifabatteryisallowedtostandidleforashorttimeaftera
partialdischarge,thespecificgravityoftheelectrolytewill
decreasebecausesome,oftheacidintheelectrolytewill
graduallyflowintotheporesoftheplatestoreplacethe
acidusedupwhilethebatterywasdischarging.
Theoreticallythedischargecanbecontinueduntilallthe
acidhasbeenusedup,andtheelectrolyteiscomposedof
purewater.Experiencehasshown,however,thatthe
dischargeofthebatteryshouldnotbecontinuedafterthe
specificgravityoftheelectrolytehasfallento1.150.Asfar
astheelectrolyteisconcerned,thedischargemaybe
carriedfartherwith'safety.Theplatesdeterminethepoint
atwhichthedischargeshouldbestopped.Whenthe
specificgravityhasdroppedfrom1.300to1.150,somuch
sulphatehasbeenformedthatitfillstheporesintheactive
materialontheplates.Fig.23showsthechangeinthe
densityoftheacidduringdischarge.

ChangesattheNegativePlate.Chemically,theactionatthenegative
plateconsistsonlyoftheformationofleadsulphatefromthespongylead.
Theleadsulphateisonlyslightlysolubleintheelectrolyteandis
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precipitatedassoonasitisformed,leavinghydrogenions,whichthengo
totheleadperoxideplatetoformwaterwithoxygenionsreleasedatthe
peroxideplate.Thesulphateformsmorequicklyonthesurfaceofthe
platethanintheinnerportionsbecausethereisaconstantsupplyofacid
availableatthesurface,whereastheformationofsulphateintheinterior
oftheplaterequiresthataciddiffuseintotheporesoftheactivematerials
toreplacethatalreadyusedupintheformationofsulphate.Inthe
negativeplate,however,thesulphatetendstoformmoreuniformly
throughoutthemassofthelead,becausethespongyleadismoreporous
thantheleadperoxide,andbecausetheacidisnotdilutedbythe
formationofwaterasinthepositiveplate.
Changesatthe,PositivePlate.Inafullychargedpositive
platewehaveleadperoxideastheactivematerial.Thisis
composedofleadandoxygen.Fromthisfactitisplainly
evidentthatduringdischargethereisagreaterchemical
activityatthisplatethanatthenegativeplate,sincewe
mustfindsomethingtocombinewiththeoxygeninorder
thattheleadmayform.leadsulphatewiththeacid.Inan
idealcell,therefore,thematerialwhichundergoesthe
greaterchangeshouldbemoreporousthanthematerial
whichdoesnotinvolveasgreatachemicalreaction.In
reality,however,theperoxideisnotasporousasthe
spongylead,anddoesnotholdtogetheraswell.
Thefinalproductsofthedischargeofapositiveplateare
leadsulphateandwater.Theleadperoxidemustfirstbe
reducedtolead,whichthencombineswiththesulphate
fromtheacidtoformleadsulphate,whiletheoxygenfrom
theperoxidecombineswiththehydrogenoftheacidto
formwater.Thereis,therefore,agreateractivityatthis
platethanattheleadplate,andtheformationofthewater
dilutestheacidinandaroundtheplatesothatthe
tendencyisforthechemicalactionstoberetarded.
Thesulphatewhichformsondischargecausestheactive
materialtobulgeoutbecauseitoccupiesmorespacethan
theperoxide.Thiscausestheleadperoxideatthesurface
tobeginfalling,tothebottomofthejarinfinedustlike
particles,sincetheperoxidehereholdstogethervery
poorly.

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