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Mat.Res.vol.17no.1SoCarlosJan./Feb.2014EpubSep24,2013

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Asystematicstudyonelectrolyticproductionof
hydrogengasbyusinggraphiteaselectrode

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A.L.YuvarajID.SanthanarajII,*

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I DepartmentofMechanicalEngineering,VeltechhightechDR.RRandDR.

CtedbyScELO

SREngineeringcollege,Avadi,Chennai600062,ndia

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II

DepartmentofChemistry,VeltechhightechDR.RRandDR.SREngineering
college,Avadi,Chennai600062,ndia

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ABSTRACT

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Alkalinewaterelectrolysisisoneoftheeasiestmethodsforhydrogen
productionthathastheadvantageofsimplicity.Themajorchallengesin
thewaterelectrolysisarethereduceenergyconsumption,costandmaintenanceandtoincreasereliability,
durabilityandsafety.Inthisregard,theelectrolyticproductionofhydrogenissystematicallystudiedby
commerciallyavailablegraphiteelectrodeatroomtemperature.Theexperimentalresultsshowedtherateof
productionofhydrogengaswassignificantlyaffectedwhenthereactionparameterssuchaseffectofelectrolyte
concentration,temperature,appliedvoltageandreactiontimearevaried.Fromtheexperimentalresults,ithas
beenfoundthatgraphiteisagoodchoicefortheproductionofmaximumhydrogencomparedtovariousother
electrodes.
Keywords:electrochemistry,electrolyte,gasbubbles,hydrogen,renewableenergy,waterelectrolysis

1.Introduction
Hydrogenplaysanimportantroleasanenergycarrierforsustainabledevelopment18anditisalsoexpectedto
beusedassecondaryenergyinnearfeature.Hydrogencanalsobeusedasfuelforvehicleandrockets,as
chemical,forNiH2electriccell,fordirectcombustionforheat,andsoon.Besides,hydrogenisconsideredas
thelightestelementandanyleakageofhydrogengascanbedispersedquickly.Thus,hydrogenisbelievedas
safeasothercommonlyusedfuelsforfuture10.Presently,hydrogencanbeeconomicallyproducedfrom
hydrocarbonreforming,whichisneitherrenewablenorcleanfromthelifecyclepointofview911.Poweredby
solarenergy,hydrogencanbeproducedfromwaterviaphotocatalysis,thermochemicalcycles,andwater
electrolysis1013.Thesemethodsofferrenewableandcleanproductionofhydrogenfuelandtherefore,have
attractedincreasingresearchinterestsinrecentyears.Sofar,theefficiencyofphotocatalysisand
thermochemicalcyclesarestilltoolowtobeeconomicallycompetitive.Electrolyticproductionofhydrogenfrom
waterisgraduallygainingitsimportanceamongtheotherconventionalprocessesofhydrogenproductioninthe

contextofrenewableenergysourceutilizationandenvironmentallycleantechnology.Worldwideresearchis
beingcarriedouttomaketheprocessintocosteffective.
Anelectrolyzerisusuallysubjecttomassivecurrentvaluesinordertobreakthewatermoleculesintooxygen
andhydrogen.Inanyelectrolyticcell,electrodesarethemainphysicalpartofthesystem14.Outofthetwo
typesofelectrodes,activeelectrodesgetinvolvedintheredoxreactionbyaccumulatingorconsuming
materialsofelectrodes.
Steelandironarethemostcommonlyusedforelectrolysisofwater.Theseelectrodesareusedasanodeandit
issacrificedinelectrolysis,astheanoderusts(getoxidized)andthecathodederusts(getreduced).Many
workshavebeencarriedoutinstainlesssteel,brassandaluminumasanodes,duetothefamiliarcorrosion
resistantpropertiesofthesematerials.Unfortunately,stainlesssteelreleasestoxicmaterialswhenitdecays,
brassdepositscopperontothecathode(whichacceleratesrustingofsteel),andaluminumquicklydeteriorates.
Inthisconnection,thecarbonbasedelectrodessuchascarbonandgraphitearemuchmoreinteresteddueto
lowcost,goodelectricalandthermalconductivity,therelativelyinertpropertyinalkalinesolutioncomparedto
metalsandalsoforitsporousstructurewithhighpurity.Theporousstructurehelpsgraphitetoadsorbhydrogen
molecules15.However,thehydrogenproductionisnotsystematicallystudiedoverthegraphiteelectrodeto
improvehydrogenproductionbysimpleelectrolyticprocess.Inthepresentpaper,theeffectsofelectrolyte
concentration,temperature,appliedvoltageandreactiontimeontheamountofhydrogengasproducedand
consequentlyontheoverallelectrolysisefficiencyisexperimentallyinvestigated.

2.Experimental
TheexperimentiscarriedoutasinthesetupshowninFigure1.Itconsistsoftwocompartments(IDandheight
ofeachcompartmentwere6cmand20cm,respectively)intheelectrolyzeroftotalcapacityof1.5liter.They
areconnectedbyanarrowrectangularconduitofsize(15cm4.5cm4cm).Cylindricalrodsnamely316L
stainlesssteel,EN8,Carbonandgraphiteelectrodesareusedwithuniformdimensions(diameter=20mm&
length=80mm)andalkalineKOHwasusedasstandardelectrolytes.Thedistancebetweenthetwoelectrodes
iskeptconstantatavalueof2cm.ACpowersupplyisconnectedtoabridgerectifierthroughastepdown
transformer(500VA,Input:0220/230VAC,Output:024VAC).Theelectrodesarethenconnectedwith
bridgerectifier(ACtoDCconverter).TherangeofDCoutputisvariedfrom0to12V.Avariacisusedtovary
theappliedvoltage.Ammeter(020ADC)andvoltmeter(050VDC)areconnectedrespectivelyinseries
andparalleltotheelectrolyzertomeasurecurrentandvoltageappliedtothesystem.Thegasesobtainedfrom
theanodeandthecathodelimbsarecollectedseparately.Thevolumeofhydrogenproducedistwicetheamount
ofoxygenproducedanditcanbemeasuredbydowndisplacementmethod.

3.ResultsandDiscussions
3.1.Effectofelectrolyteconcentration
Basesandacidsareknowntochangethenonconductivenatureofpurewater.Thesecompoundshaveagreat
reducingeffectontheovervoltagevalueofanelectrolyzer 16.Theyimprovetheionicconductivityaqueous
electrolytecompounds.However,theconcentrationlevelofacidicandalkalisolutionsarelimitedinpracticedue
tothehighlycorrosivebehaviorofelectrodes.Inthisregard,theconcentrationofelectrolytewassystematically

variedfrom0.05to0.4MconcentrationasshowninFigure2.Thestudyrevealedthatthehydrogenproduction
graduallyincreaseswithincreaseinelectrolyticconcentration.Thismaybeduetotheamountofcurrentthat
passesdependsontheconductanceoftheelectrodesandelectrolyteconcentration.Inanotherperspective,the
increaseinhydrogenevolutioninincreasedelectrolyticconcentrationisduetoagreaternumberofeffective
ioniccollisionsperunittime.

3.2.Effectofdecompositionofgraphiteelectrodes(Anodicreaction)
TheeffectofvariouselectrolyticconcentrationsongraphiteelectrodesisstudiedandrepresentedinFigure3.
Theresultsareshownthatwhenthereisanincreaseinelectrolyticconcentrationfrom0.025to0.5M,the
gradualdecompositionofanodicgraphiterodisobserved.Thedecompositionbehaviorofgraphiterodis
calculatedbyweightlossaftertheelectrolyticprocess.Theweightlossmaybeduetohighelectrolytic
concentrationinthepresenceofappliedvoltage.TheKOHactsuptothesurfacecarbonofgraphitematerialand
itleadstotheelectrolyticsolutionturningintoblackslurry.Fromtheresults,weconcludedthatthehigh
electrolyticconcentration(above0.025M)isnotbeneficialforlongtimehydrogenproductionwithout
destructionofgraphiteelectrode.


3.3.Effectoftemperature
Temperatureisknowntobeoneofthemosteffectivevariablesontheelectricpowerdemandofanelectrolytic
cell.Electrolysisprocessismuchmoreefficientatincreasedtemperatures17.Inthispartoftheexperiment,the
electrolytetemperaturehasgraduallyincreasedfrom270to353K(Figure4).Thestudyclearlyrevealsthat
whenthereisanincreaseintemperaturethehydrogenproductionincreaseslinearly.Thereasonsforthis
behaviorcanbedrawnfromthethermodynamiccharacteristicsofawatermoleculesinceitssplittingreaction
potentialisknowntoreduceasthetemperatureincreases.Moreover,ionicconductivityandsurfacereactionof
anelectrolyterisedirectlywithtemperature18.Hightemperaturewaterelectrolysisrequireslessenergyto
reachanygivencurrentdensityinanalogywithalowtemperatureprocess18,19.Themainoutcomeofthestudy
isthatasubstantialpartoftheenergyneededfortheelectrolysisprocessisaddedasheat,whichismuch
cheaperthanelectricenergy.Inaddition,thehightemperatureacceleratesthereactionkinetics,reducingthe
energylossduetoelectrodepolarization,thusincreasingtheoverallsystemefficiency.


3.4Ohmiclosses
Theohmiclossesareduetotheresistanceoftheimperfectelectrodesandthenatureelectrolytes.The
resistivityofthegivenelectrolyticsolutioncanbecalculatedbyvaryingthecurrentdensitywithrespectto
appliedvoltageasshowninFigure5.Itisclearlyshowsthat,theohmiclossofthealkalineKOHisperfectly
linear 20.Inmostcases,theohmiclossisconsideredtohavetherelationshipofI(Current)andR,whereRis
constant.So,theequationisrelatedtotheohmiclossisV=IR.Fromthelineargraph,theresistivityof
aqueousKOHiscalculatedas19.5ohms.

3.5Effectofappliedvoltage
Theinfluenceofanappliedvoltageonthehydrogenevolutionreaction(HER)canbestudiedovercylindrical
graphiteelectrodeatthetemperatureof593Kwitha0.025MconcentrationofKOH.Theappliedvoltageis
variedfrom4.5to12VandtheresultantgraphasshowninFigure6.Itshowsthat,therateofproductionof
hydrogengasgraduallyincreaseswithincreaseinappliedvoltage.Theplausiblereasonistheuniformcharge
densityincreasesonthesurfaceofcylindricalelectrode.


3.6.Effectoftimeonstream
Inordertostudythesustainabilityandstabilityofthecylindricalgraphiteelectrode,theeffectoftimeonthe
hydrogenevolutionreactionisstudiedundertheoptimizedreactionconditions.Theobtainedresultswere
illustratedinFigure7.Fromthefigure,itwasobservedthatinitiallythehydrogenproductionwasreachedto
maximumof800cc/minandtherebydecreasedtoattainthestablestate.Theunchangedprofileofhydrogen
productionfortheperiodof90minutesdemonstratesthatthegraphiteelectroderemainsstablestatewithout
anydestructiononthesurfaceoftheelectrodethroughoutthetestingtime.Afterthereactiontimeof90
minutes,thegraphiteelectrodeisregeneratedbydryinginflowofairat50Cforfivehoursandthe
experimentisconductedundersimilarreactionconditions.Therateofproductionofhydrogenismuchmore
similartothatofinitialrun.Thismeansthegraphiteelectroderegainitsoriginalactivityofitsregeneration.
Theoverallperformanceofthegraphiteelectrodehasshownanacceptablelevelofstabilityunderthepresent
experimentalconditions.


3.7Effectofelectrodesonthehydrogenevolutionreaction
Theefficiencyofgraphiteelectrodeiscomparedwithcommerciallyavailablevariouselectrodeslike316L
stainlesssteel,EN8andcarbonrodsandtheresultsareshowninFigure8.Theactivityofvariouselectrodes
followsthetrendGraphite>EN8>SS316L>Carbon.Fromtheexperimentalresults,itwasobservedthat
eventhough,thecarbonandgraphiteelectrodesareallotropyofcarbonmaterials,theefficiencyofhydrogen
productionismuchhigherongraphiteelectrode.Theplausiblereasonsitmaybeduetotheeitherlayerof
structuregraphiteelectrodeortheporousnatureofmaterialwhichsignificantlyenhancesthediffusionofwater
moleculewithoutanyblockage.Ontheotherhand,thecontacttimeofwatermoleculeperunittimeismuch
higherongraphiteelectrodethanthecarbonelectrode.Therefore,fromtheaboveresultsitmightbeconcluded
thathydrogenevolutionreactionispreferentiallytakingplaceintheinternalporousstructure.Further,the
significantcorrosionbehaviorcanbeseenonbothstainlesssteelandEN8electrodesbyusingalkalineKOHas
theelectrolyteanditleadstodecreaseintherateofhydrogenproduction.Theobservedtrendismore
pronouncedonEN8electrodecomparedtothestainlesssteelelectrode.Amongallthecylindricalelectrodes,
graphiteisfoundtobethebestchoiceforhydrogenevolutionreactionunderthepresentexperimental
conditions.

3.8.Kineticstudiesonelectrolysisofwater
Theratedataforthealkalinewaterelectrolysisisstudiedoncylindricalgraphiteelectrodeanditcouldbefitted
welltofirstorderratelaw.Thefollowingrelationshipderivedbetweenrelativeconversion'X'andcontacttime
hasbeenusedforevaluatingtherateparameters.

Where,'X'isthefractionalconversionofhydrogengas,'k'istheapparentfirstorderrateconstant.Fromthe
slopeoflinearplot,thefirstorderrateconstantvalue'k'canbecalculatedbyusingequation1,whichisusedto
determinetheactivityofelectrodesthroughtheevaluationofactivationenergy.Theapparentactivationenergy
iscalculatedas7.5cal/mol.

4.Conclusions
TheElectrolyticproductionofhydrogenissystematicallystudiedbyusingcommerciallyavailablegraphite
electrodeatroomtemperature.Onincreasingtheelectrolyticconcentrationthehydrogenproductionisgreatly
increases.However,thegradualdecompositionofanodicgraphiterodsisobserved.Fromthestudywe
concludedthatthehighelectrolyticconcentration(above0.025M)isnotbeneficialforlongtimehydrogen

production.Theefficiencyofgraphiteelectrodeiscomparedwithcommerciallyavailablevariouselectrodeslike
316Lstainlesssteel,EN8andcarbonrods.Amongallthecylindricalelectrodes,graphiteisfoundtobethebest
choiceforhydrogenevolutionreactionunderthepresentexperimentalconditions.Furtherresearchisnecessary
todevelopthislaboratoryscalestudyintoapracticalreality.

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Received:December4,2012
Revised:August26,2013

*email:santhanaraj08@gmail.com

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