WHATISpH

ANDHOWISITMEASURED?

ATechnicalHandbookforIndustry

CHAPTER1INTRODUCTION
WhyIspHMeasurementNecessary? 3
CHAPTER2WATERANDAQUEOUSSOLUTIONS
ThePropertiesofWater 4
IonProductConstantofWater 4
Molarity 5
CHAPTER 3 FUNDAMENTALS OF pH
DefinitionofpH 6
pHValuesandHydrogen/HydroxideConcentration 6
HowispHMeasured? 7
ActivityversusConcentration 7
TheNernstEquation 9
TheStandardHydrogenElectrode 9

CHAPTER4THEpHSENSOR
pHElectrodes 11
TheMeasuringElectrode 13
AsymmetryPotential 13
SodiumIonError 14
AcidError 15
Temperature Effects 15
TheReferenceElectrode 16
TheReferenceJunction 17
JunctionPotentials 17
GelfilledReferenceElectrode 18
Buffers 18
Calibration 18

CHAPTER 5 CARE OF pH ELECTRODES

Dehydration 22
FactorsDetrimentaltoElectrodeLife 22
Transportation 22
Storage 23

CHAPTER6COMMONAPPLICATIONS
CoolingTowerControl 24
FoodProcessing 24
CoalIndustry 24
PlatingWasteTreatment 25
UltrapureWater 25

BIBLIOGRAPHY27

GLOSSARY 28
Chapter 1 INTRODUCTION

Why Is pH Measurement Necessary?

AlmostallprocessescontainingwaterhaveaneedforpHmeasurement.MostlivingthingsdependonaproperpH
leveltosustainlife.AllhumanbeingsandanimalsrelyoninternalmechanismstomaintainthepHleveloftheir
blood.ThebloodflowingthroughourveinsmusthaveapHbetween7.35and7.45.Exceedingthisrangebyaslittle
asonetenthofapHunitcouldprovefatal.

Commoditiessuchaswheatandcorn,alongwithotherplantsandfoodproducts,willgrowbestifthesoiltheyare
plantedinismaintainedatanoptimalpH.Toattainhighcropyields,farmersmustconditiontheirfieldstothe
correctpHvalue.DifferentcropsneeddifferentpHlevels.Inthiscase,onesizedoesnotfitall.

Acidraincanbeverydetrimentaltocropyields.Rainwaterisnaturallyacidic(below7.0pH).Rainistypically
around5.6pHbut,insomeareas,itincreasestoharmfullevelsbetween4.0and5.0pHduetoatmospheric
pollutants.HeavilyindustrializedareasoftheUS,suchastheMidwest,havebeentargetedbyvarious
environmentalagenciestominimizethepollutantsthatcauseacidrain.Theburningoffossilfuelslikecoal,
releasesgasesintotheupperatmospherethat,whencombinedwithrainwater,changecompositionandcause
therainwatertobecomemoreacidic.

ProperpHcontrolkeepsmilkfromturningsour,makesstrawberryjellygel,andpreventsshampoofromstinging
youreyes.Inplatingplants,pHcontrolisusedtoensurethelusterofchromeonvariousproductsfromnutsand
boltstotoastersandautomobilebumpers.ThepHofwastewaterleavingmanufacturingplantsandwastewater
purificationplants,aswellaspotablewaterfrommunicipaldrinkingwaterplants,mustbewithinaspecificpH
"window"assetforthbylocal,stateorfederalregulatoryagencies.Thisvalueistypicallybetween5and9pH,but
canvaryfromareatoarea.

OtherpHapplicationsinclude:
Neutralizationofeffluentinsteel,pulpandpaper,chemical,andpharmaceuticalmanufacturing
Hexavalentchromiumdestruction
Cyanidedestruction
Reverseosmosis
Odorscrubbers
Pharmaceuticalmanufacturing
Chemicalandpetrochemicalmanufacturing
Coolingtowercontrol

WhetheradjustingthepHforaproperreactionormakingsurewastewaterisattheproperpHvaluebefore
sendingittothecommunitysewersystem,accuratepHmeasurementisrequired.Putsimply,pHisanintegralpart
ofoureverydaylife.
Chapter 2 WATER AND AQUEOUSSOLUTIONS

The Properties of Water

Wateristhemostcommonsubstanceknowntoman,andisthemostimportant.Invapor,liquidorsolidform,
watercoversmorethanseventypercentoftheEarthssurface,andisamajorcomponentoftheatmosphere.
Waterisalsoanessentialrequirementforallformsoflife.Mostlivingthingsarelargelymadeupofwater.Human
beings,forexample,consistofabouttwothirdswater.

Purewaterisaclear,colorless,andodorlessliquidmadeupofoneoxygenandtwohydrogenatoms.TheItalian
scientistStanislaoCannizzarrodefinedthechemicalformulaofthewatermolecule,H2O,in1860.Waterisavery
powerfulsubstancethatactsasamediumformanyreactions,whichiswhyitisoftenreferredtoasthe"universal
solvent."Althoughpurewaterisapoorconductorofelectricity,impuritiesthatoccurnaturallyinwatertransform
itintoarelativelygoodconductor.Waterhasunusuallyhighboiling(100C/212F)andfreezing(0C/32F)points.It
alsoshowsunusualvolumechangeswithtemperature.Aswatercools,itcontractstoamaximumdensityof1gram
percubiccentimeterat4C(39F).Furthercoolingactuallycausesittoexpand,especiallywhenitreachesthe
freezingpoint.Thefactthatwaterisdenserintheliquidformthanthesolidformexplainswhyanicecubefloatsin
abeverage,orwhyabodyofwaterfreezesfromthetopdown.Whilethedensitypropertyofwaterisoflittle
importancetothebeverageexample,ithasatremendousimpactonthesurvivalofaquaticlifeinhabitingabody
ofwater.

Ion Product Constant of Water

Water molecules are in continuous motion, even at lower temperatures. When two water molecules collide, a
hydrogenionistransferredfromonemoleculetotheother(Figure1).Thewatermoleculethatlosesthehydrogen
ion becomes a negatively charged hydroxide ion. The water molecule that gains the hydrogen ion becomes a
positivelychargedhydroniumion.Thisprocessiscommonlyreferredtoastheselfionizationofwater.

Theselfionizationofwaterdoesnotregularlyoccur.Thisreactioncanbewrittenasasimpledissociation
(Figure2).At25Cinpurewater,eachconcentrationofhydrogenionsandhydroxideionsisonly1x107M.It
isimportanttonotethatthenumberofhydrogenandhydroxideionsproducedfromthisreactionisequal.This
iswhypurewaterisoftendescribedasaneutralsolution.
Inallotheraqueoussolutions,therelativeconcentrationsofeachoftheseionsisunequal.Whenmoreofone
ionisaddedtothesolution,theconcentrationoftheotherdecreases.Thefollowingequationdescribesthis
relationship:

Theproductofthehydrogenandhydroxideionsisalwaysequalto1x1014(mol/L)2.Therefore,ifthe
concentrationofoneionincreasesbyafactorof10,thentheconcentrationoftheotherionmustdecreasebya
factorof10.Sincethisrelationshipisconstant,itisgiventhesymbolKW,whichiscalledtheionproduct
constantforwater.

Aqueoussolutionsthathaveahydrogenionconcentrationgreaterthanthehydroxideionconcentrationare
calledacidicsolutions.Whenthehydroxideionconcentrationisgreaterthanthehydrogenionconcentration,
thesolutioniscalledbasicoralkaline.

Molarity

Theterm"molarity"describestheconcentrationofasubstancewithinasolution.Bydefinition,aone"molar"
solutionofhydrogenioncontainsone"mole"ofhydrogenionperliterofsolution.Therefore,asolutionof10pH
has1x1010molesofhydrogenionsasshownbythefollowingequation:

Furthermore,asolutionof4pHhas1x104molesofhydrogenions,andsoon.Thisalsomeansthatoneliterof
apH10solutionwouldcontain1x1010gramsofhydrogenion,because1mole=1g/Lforhydrogen.

Aonemolarsolutionofsodiumhydroxide(NaOH),abase,isapproximately4%byweight,andhasapHvalueof
14.Aonemolarsolutionofhydrochloricacid(HCl),anacid,isapproximately3.7%byweight,andhasapHof0.
Bydilutingeitherofthesetwosolutions,themolaritywilldecreaseaswell.Forexample,diluting1mlofHCl
acidbyadding9mlofdistilledwaterresultsina0.1molarhydrochloricacidsolution,whichhasapHvalueof
1.0.DilutingsodiumhydroxideusingthesamevolumesyieldsasolutionwithapHvalueof13.Ifthisdilution
procedurewerecontinued,thepHofeachsolutionwouldapproachaneutralpHof7.

NOTE:Forevery10foldchangeinconcentration(example:0.1to1.0),thepHchangesbyoneunit.
Ifequalvolumesof4pH(0.0001MHCl)and10pH(0.0001NaOH)solutionsweremixedtogether,theresultant
solutionwouldhaveapHof7.

NOTE:HClandNaOHhaveopposing[H+]/[OH]concentrations.
Thesameresultwouldapplywhenmixingequalvolumesofa6pHacidandan8pHbase,a2pHacidanda12
pHbase,andsoon.

 6

Chapter 3 - FUNDAMENTALS OF pH

Definition of pH

Justasthekilometerisameasureofdistanceandthehourisameasureoftime,thepHunitmeasuresthedegree
ofacidityorbasicityofasolution.

Tobemoreexact,pHisthemeasurementofthehydrogenionconcentration,[H+].Everyaqueoussolutioncanbe
measuredtodetermineitspHvalue.Thisvaluerangesfrom0to14pH.Valuesbelow7pHexhibitacidic
properties.Valuesabove7pHexhibitbasic(alsoknownascausticoralkaline)properties.Since7pHisthecenter
ofthemeasurementscale,itisneitheracidicnorbasic,itiscalled"neutral."

pHisdefinedasthenegativelogarithmofthehydrogenionconcentration.ThisdefinitionofpHwasintroduced
in1909bytheDanishbiochemist,SorenPeterLauritzSorensen.Itisexpressedmathematicallyas:

where:[H+]ishydrogenionconcentrationinmol/L
ThepHvalueisanexpressionoftheratioof[H+]to[OH](hydroxideionconcentration).Hence,ifthe[H+]is
greaterthan[OH],thesolutionisacidic.Conversely,ifthe[OH]isgreaterthanthe[H+],thesolutionisbasic.At7
pH,theratioof[H+]to[OH]isequaland,therefore,thesolutionisneutral.Asshownintheequationbelow,pHis
alogarithmicfunction.AchangeofonepHunitrepresentsa10foldchangeinconcentrationofhydrogenion.
Inaneutralsolution,the[H+]=1x107mol/L.ThisrepresentsthepHof7.

Sincetheconcentrationofhydrogenionsandhydroxideionsisconstantinastablesolution,eitheronecanbe
quantifiedifthevalueoftheotherisknown.Therefore,whendeterminingthepHofasolution,(eventhoughthe
hydrogenionconcentrationisbeingmeasured),thehydroxideionconcentrationcanbecalculated:

pH Values and Hydrogen/Hydroxide Concentrations

InFigure3,thepHvaluecorrespondstothenumberofdecimalplacesunderthecolumnfor"hydrogenion
concentration."ThepHofthesolutionequalstheexponentialformofthe[H+],withtheminussignchangedtoa
plus.Itismucheasiertowriteorsay"10pH"thanitistocommunicate"ahydrogenionconcentrationof
0.0000000001mol/L."
 7

How Is pH Measured?
pHinanaqueoussolutioncanbemeasuredinavarietyofways.ThemostcommonwayusesapHsensitiveglass
electrode,areferenceelectrodeandapHmeter.AlternativemethodsfordeterminingthepHofasolutionare:
Indicators:Indicatorsarematerialsthatarespecificallydesignedtochangecolorwhenexposedtodifferent
pHvalues.ThecolorofawettedsamplepaperismatchedtoacoloronacolorcharttoinferapHvalue.pH
paperisavailablefornarrowpHranges(forexample,3.0to5.5pH,4.5to7.5pHand6.0to8.0pH),andfairly
widepHrangesof1.0to11.0pH.

NOTE: pH paper is typically used for preliminary and small volume measuring. It cannot be used for
continuous monitoring of a process. Though pH paper is fairly inexpensive, it can be attacked by process
solutions,whichmayinterferewiththecolorchange.
Colorimeter:Thisdeviceusesavialfilledwithanappropriatevolumeofsampletowhichareagentisadded.
Asthereagentisadded,acolorchangetakesplace.Thecolorofthissolutionisthencomparedtoacolor
wheelorspectralstandardtointerpolatethepHvalue.

Thecolorimetercanbeusedforgrabsamplemeasuring,butnotforcontinuousonlinemeasuring.Typicallyused
todeterminethepHvalueofwaterinswimmingpools,spas,coolingtowers,andboilers,aswellaslakeandriver
waters.

ApHmeterisalwaysrecommendedforpreciseandcontinuousmeasuring.MostlaboratoriesuseapHmeter
connectedtoastripchartrecorderorsomeotherdataacquisitiondevicesothatthereadingcanberecordedor
storedelectronicallyoverauserdefinedtimerange.

Activity versus Concentration

Glasselectrodesaresensitivetothehydrogenionactivityinasolution.Consequently,theconcentrationof
hydrogenionisnottheonlyfactorinfluencingthepHofasolution.Theconcentrationofotherchemicalsinthe
solution,ortheionicstrengthofthesolution,isalsoamajorinfluenceinthemeasurementofpH.

Theterm"ionicstrength"describestheamountofionicspeciesinasolution,aswellasthemagnitudeofcharge
onthosespecies.Examplesofionspeciescompoundsaresodium(Na+)sulfate(SO42),calcium(Ca2+)chloride(Cl
),andpotassium(K+)nitrate(NO3).Presenceoftheseionsinsolutiontendstolimitthemobilityofthehydrogen
ion,therebydecreasingtheactivityofH+.

Theconceptoflimitedmobilityofthehydrogenionisanalogoustoapersonenteringashoppingmall.Ifthe
shoppingcrowdisverysmall,thepersonisfreetomoveaboutthemallinanydirection.However,ifthemallis
verycrowded,theshopperhasadifficulttimemovingfromstoretostore,whichseverelylimitstheiractivity.Itis
thissameprincipleofa"crowdedenvironment"thatlimitstheactivityofthehydrogenion.
ThefollowingequationmathematicallydescribesthiseffectontheactivityofH+:

where:f is the activity coefficient

Insolutionswheretheionicstrengthisverylow,theactivitycoefficientis1.00,makingtheactivityofhydrogen
ionequaltoitsconcentration.Astheionicstrengthofasolutionincreases,theactivitycoefficientdecreases.
Thishastheeffectofloweringtheactivityofhydrogenion,whichisseenasanincreaseinpH.Thefollowing
exampleillustratesthispoint:

Example:ThepHofa0.00002Msolutionofnitricacidcanbecalculatedusingthisequation:

Thevalueof[ f ]canbederivedfromvariousequations,orfoundinpublishedtables:

CRCHandbookofChemistryandPhysicsbyRobertC.West,Ph.D.,Ed.,CRCPress,Inc.,BocaRaton,FL

LangesHandbookofChemistrybyJohnA.Dean,Ph.D.,Ed.,McGrawHillBookCompany,NY,NY

Theproductoftheactivitycoefficientandhydrogenionconcentrationisequalto0.00002.Thismeansthatthe
ionicstrengthofthesolutionhasnoeffectonthepHcalculation.

Iftheionicstrengthwere0.1,thenewpHcanbecalculatedusingthisequation:

Iftheionicstrengthofthesolutionwere0.1,theactivitycoefficient,[f],wouldthenbe0.75.Theproductofthe
activitycoefficientandhydrogenionconcentrationisnowlessthan0.00002.ThiscausesthepHcalculationof
thenitricacidsolutiontoincreaseby0.12pHunit.Inthiscase,theionicstrengthhasamajorinfluenceonthe
pHofthesolution.
 9

The Nernst Equation

Thegeneralmathematicaldescriptionofelectrodebehaviorwasdescribedbythe19thcenturyGermanchemist,
HermannWaltherNernst(18641941).HeintroducedtheNernstequationin1889,expressedas:

where:

E = totalpotential(inmillivolts)betweentwoelectrodes

E0 = standardpotentialoftheion
R = universalgasconstant(inJoules/molKelvin)
T = absolutetemperature(inKelvin)
n = chargeoftheion

F = Faradayconstant(inCoulombs/mol)

ai = activityoftheion

Theentireterm"2.3RT/nF"iscalledtheNernstfactor,orslopefactor.Thistermprovidestheamountofchange
intotalpotentialforeverytenfoldchangeinionconcentration.Forhydrogenionactivity,wheren=1,the
Nernstfactoris59.16mVforeverytenfoldchangeinactivityat25C.ThismeansthatforeverypHunitchange,
thetotalpotentialwillchange59.16mV.

Thefollowinggeneralequationmaybestatedforanytemperature(sincepHisdefinedasthenegativelogarithm
ofthehydrogenionactivity):

However,theNernstfactorwillchangewhentemperaturechanges;Tisnotconstant.At25Ctheslopeofthe
pHelectrodeis59.16mV/pHunit.At0Ctheslopevalueisapproximately54mV/pH,andat100Ctheslope
valueisapproximately74mV/pH.ThemillivoltoutputoftheglasspHelectrodewillchangewithtemperaturein
accordancewiththeNernstequation.Asthetemperatureincreases,sodoesthemillivoltoutput.Specifically,the
slopeoftheelectrodeiswhatchanges.
Thechangeinelectrodeoutputversustemperatureislinear,whichcanbecompensatedinthepHmeter.The
linearfunctionfortemperaturevs.pHchangecanbeexpressedas:

IfanuncompensatedpHsystemwerestandardizedinpH7bufferat25C,andthenasampleat23C
measured4.00pH,theerrorwouldbe0.018pHunit(.003x2Cx3units).Forameasurementof4.00pHat75
C(probablyclosetoatypicalworstcase),anuncompensatedpHsystemwouldread4.45pH.

The Standard Hydrogen Electrode

Theglassmeasuringelectrodehasitselectrochemicalrootsplantedintheearlieruseofthestandardhydrogen
electrode(SHE).TheSHEistheuniversalreferenceforreportingrelativehalfcellpotentials.Atypeofgas
electrode,itwaswidelyusedinearlystudiesasareferenceelectrodeandasanindicatorelectrodeforthe
 10

determinationofpHvalues.TheSHEcouldbeusedaseitherananodeorcathodedependinguponthenatureof
thehalfcellitisusedwith.

TheSHEconsistsofaplatinumelectrodeimmersedinasolutionwithahydrogenionconcentrationof1.00M.
Theplatinumelectrodeismadeofasmallsquareofplatinumfoil,whichisplatinizedwithafinelydividedlayer
ofplatinum(knownasplatinumblack).Hydrogengas,atapressureof1atmosphere,isbubbledaroundthe
platinumelectrode.Theplatinumblackservesasalargesurfaceareaforthereactiontotakeplace,andthe
streamofhydrogenkeepsthesolutionsaturatedattheelectrodesitewithrespecttothegas.

It is interesting to note that even though the SHE is the universal reference standard, it exists only as a
theoretical electrode that scientists use as the definition of an arbitrary reference electrode with a halfcell
potentialof0.00volts.Becausehalfcellpotentialscannotbemeasured,thisistheperfectelectrodetoallow
scientists to perform theoretical research calculations. The reason this electrode cannot be manufactured
becausenosolutioncanbepreparedthatyieldsahydrogenionactivityof1.00M.
 11

Chapter 4 THE pH SENSOR

pH Electrodes

ApHelectrodeassembly,orsensor,consistsoftwoprimaryparts:
Measuringelectrode:Themeasuringelectrodeissometimescalledtheglasselectrode,andisalsoreferred
toasamembraneoractiveelectrode.
Referenceelectrode:Thereferenceelectrodeisalsoreferredtoasastandardelectrode.

Figure4showsthesetwoelectrodes.

ThepHmeasurementiscomprisedoftwohalfcell,orelectrode,
potentials.OnehalfcellisthepHsensitiveglassmeasuringelectrode
andtheotheristhereferenceelectrode.Justasthetwohalfcell
potentialsofabatteryarerequiredtocompleteacircuitsodoesapH
sensor.
Themathematicalexpressionforthisis:

where:
Em=theelectrodepotentialofthemeasuringelectrode
Er=theelectrodepotentialofthereferenceelectrode

Thistypeofmeasurement,inmillivolts,iscalledapotentiometric
measurement.

Sincevoltagemeasuringdevicesonlydeterminedifferencesin
potentials,thereisnomethodfordeterminingthepotentialofa
singleelectrode.Agalvanicmeasurementcircuitisformedby
connectingthemeasuringelectrode(halfcellpotential)andthe
referenceelectrode(halfcellpotential)tothesignalinputofthe
measuringdevice.Atthereferenceelectrode,thereisa
solid/solutioninterface,whereachemicalreactiontakesplace.This
enablesanelectricalcurrenttoflowthroughthemeasuringdevice,
thepHmeter,whichallowsthereadingtobemade(Figure5).

Sincethecurrentthatpassesthroughthehalfcellsandthesolution
beingmeasuredisextremelysmall,thepHmetermusthaveahigh
internalimpedance,soitdoesnot"dragdown"themillivolt
potentialproducedbytheelectrodes.Thislowcurrentflowensures
thatthechemicalcharacteristicsofthesolutionbeingmeasuredremainsunaltered.

Agalvanicpotentialisformedwhenchargeexchangesoccuratthephaseboundariesoftheglassmeasuring
electrode.Ineffect,thepHsensorassemblyformsagalvaniccellusingtwometalconductorsleadwiresofthe
measuringandreferenceelectrodesinterconnectedthroughtheirrespectiveelectrolytesolutionsandthe
 12

media.Sincephaseboundariescannotbemeasuredindividuallyand
therearealwaysmorethantwophaseboundariespresent,thepH
metermeasurestheoverallpotential.Theoverallpotentialis
comprisedofthefollowingelements:
Metalleadoutwireofthemeasuringelectrode
Electrolyteofthemeasuringelectrode
Diffusionpotentialsatsolid/solutioninterfaces
Electrolyteofthereferenceelectrode
Metalleadoutwireofthereferenceelectrode

Themeasuringandreferenceelectrodescanbeinoneoftwoforms:
twophysicallyseparateelectrodes,knownasanelectrodepair;or
theelectrodescanbejoinedtogetherinasingleglassbody
assemblyknownasacombinationelectrode(Figure6).

Theelectrodepairandcombinationelectrodestylesoriginatedmanyyearsagoandcontinuetobewidelyused
today.Inthe1970s,adifferentstylepHsensorwasdevelopedandpatentedspecificallyforcontinuousonline
measurementapplications.ThispHsensorusesadifferentialelectrodetechnique(Figure7)thatemploystwopH
glassmeasuringelectrodes.Oneelectrodeisusedastheactiveormeasuringelectrode,andtheotherisusedas
partofareferenceassembly.ThereferenceassemblyconsistsofapHglassmeasuringelectrodeimmersedina7
pHbuffersolutionwhichismechanicallyisolatedfromthesolutionbeingmeasuredbyadoublejunction"salt
bridge"(see"TheReferenceJunction"subsectiononpage14fordetails).Thesetwohalfcellpotentialsarethen
referencedtoathirdgroundelectrode.

Thedifferentialelectrodetechniqueisexpressedas:

where:
Em=measuringelectrodevoltage
Er =referenceelectrodeassemblyvoltage
Eg=solutiongroundelectrodevoltage

AftercancelingtheEgterm:

OthermajorcomponentsofthedifferentialpHsensorincludethe
sensorcable,atemperaturecompensationdevice,electrolyte
solutions,andreferencejunctions.
Basedonfieldprovenresults,thedifferentialelectrodetechnique
hasshownmarkedadvantagesoverconventionalelectrodepairs
andcombinationelectrodes.Thedoublejunctionsaltbridge(part
ofthereferenceassembly)makesitextremelydifficultforan
appreciableamountofthesolutionbeingmeasuredtomigrateinto
theinnerchamber.Sincetheinnerchamberisfilledwithabuffer,a
100to1dilutionwouldonlyrepresentachangeinmeasuredpHof
0.05pHunits.Similardilutionstotheconventionalreference
electrodeusedinelectrodepairsorcombinationelectrodescould
causeshiftsofupto2.0pHunits.
 13

Another advantage of the differential electrode technique is the third "ground electrode." Since ground loop
currents will pass through only this electrode, and not through the reference electrode, the overall pH signal
outputisunaffectedbythegroundlooppotential.

The Measuring Electrode

Thegalvanicvoltageoutputproducedbyameasuringelectrodewilldependontheionicactivityofthespeciesof
ionswhichtheelectrodewasdesignedtomeasure.InthecaseofpHelectrodes,itisthehydrogenionactivity.

BasedupontheNernstequation,at25C,theoutputofapHmeasuringelectrodeisequalto59.16mVperpH
unit.At7.00pH,whichistheisopotentialpointforaperfectelectrode,theoutputis0mV.AsthesolutionpH
increases(lessacidic),themVpotentialbecomesmorenegative.Conversely,asthesolutionpHdecreases(more
acidic),themVpotentialbecomesmorepositive.

TheglassmeasuringelectrodehasbeenadoptedasthemeasuringelementformostpHsensorsinusetoday.The
measurementispredicatedontheprincipalthatahydratedgellayerformsbetweentheoutersurfaceofthe
glassandtheaqueoussolutionbeingmeasured(Figure8).

Themeasuringelectrodesinternalwireelementhasapotential,E3,withrespecttotheinternalfillsolution
(Figure9).Anotherpotential,E2,existsbetweentheinternalfillsolutionandtheinsidesurfaceoftheglass.

DependingonthepHofthesolutionbeingmeasured,hydrogenionswillmigrateintooroutofthegellayer.Inan
alkalinesolution,hydrogenionsmigrateoutofthegellayerandanegativechargeisdevelopedontheoutergel
layer.BecausetheelectrodesinternalfillsolutionisataconstantpHvalue,theinternalpotentialremains
constant.Therefore,thepotentialthatismeasuredacrosstheglassmembraneistheresultofthedifference
betweentheinnerandouterelectricalcharge.

Asymmetry Potential

WhenapHelectrodeisimmersedinasolutionwiththesamepHasitsinternalfillsolution,thereshouldnotbea
measurablepotentialacrosstheglassmembrane.Ifsuchapotentialexists,itisknownasanasymmetry
potential(Figure9).Inpractice,thispotentialisusuallyafewmillivoltsorlessforanew,properlystored
electrode.
 14

Factorsthatlimittheabilityoftheionexchangemechanismcause
asymmetrypotential.Thisincludesadehydratedelectrode,usingthe
electrodeinanonaqueoussolution,orpluggingand/orcoatingofthe
glasssurface.Asymmetrypotentialisalsoreferredtoasthedifference
inpotentialsbetweenthemeasuringandreferenceelectrodeswhen
immersedinazerosolution.Thispotentialconstantlychanges
dependingonthepHvalueofthesolution,temperature,ageofthe
measuringelectrode,anditstypeofglassformulation.

CalibrationofthepHsensor,withthemeasuringinstrument,will
compensateforanyasymmetrypotential(s).Propercleaningofthe
electrodeandreferencejunctionpriortocalibrationisessential.Long
termusageofthesensorbetweencalibrationswillshowchangingpHas
afunctionoftheasymmetrypotential(s)incombinationwithactual
changesofthepHvalue.Oncetheasymmetrypotentialhasincreased
beyondtheinstrumentcompensationcapabilitythroughcalibration,
thesensormustberenewed,ifpossible.Ifchangingtheinternalfill
solutionand/orjunctiondoesnotreducetheasymmetrypotential,the
sensorisbeyondrefurbishingandmustbereplaced.

Sodium Ion Error

AlthoughthepHglassmeasuringelectroderespondsveryselectivelytohydrogenions,thereisasmall
interferencecausedbysimilarionssuchaslithium,sodium,andpotassium.Theamountofthisinterference
decreaseswithincreasingionsize.Sincelithiumionsarenormallynotinsolutions,andpotassiumionscausevery
littleinterference,sodiumionspresentthemostsignificantinterference.

Sodiumionerror,alsoreferredtoasalkalineerror,istheresultofalkaliions,particularlysodiumions,
penetratingtheglasselectrodesiliconoxygenmolecularstructureandcreatingapotentialdifferencebetween
theouterandinnersurfacesoftheelectrode.Hydrogenionsarereplacedwithsodiumions,decreasingthe
hydrogenionactivity,therebyartificiallysuppressingthetruepHvalue.ThisisthereasonpHissometimes
referredtoasameasureofthehydrogenionactivityandnothydrogenionconcentration.

Sodiumioninterferenceoccurswhenthehydrogenionconcentrationisverylowandthesodiumion
concentrationisveryhigh.Temperaturealsodirectlyaffectsthiserror.Asthetemperatureoftheprocess
increases,sodoesthesodiumionerror.

Dependingontheexactglassformulation,sodiumioninterferencemaytakeeffectatahigherorlowerpH.There
isnoglassformulationcurrentlyavailablethathaszerosodiumionerror.Sincesomeerrorwillalwaysexist,itis
importantthattheerrorbeconsistentandrepeatable.Withmanyglassformulations,thisisnotpossiblesince
theelectrodebecomessensitizedtotheenvironmentitwasexposedtopriortoexperiencinghighpHlevels.For
example,theexactpointatwhichthesodiumionerrorofanelectrodeoccursmaybe11.50pH,afterimmersion
intapwater,but12.50pHafterimmersioninanalkalinesolution.

Controlled molecular etching of special glass formulations can keep sodium error consistent and repeatable.
This is accomplished by stripping away one molecular layer at a time. This special characteristic provides a
consistentamountoflithiumionsavailableforexchangewiththehydrogenionstoproduceasimilarmillivolt
potentialforasimilarcondition.

 15

Acid Error

AciderroraffectsthelowendofthepHmeasuringscale.AspHdecreasesandtheaciderrorbegins,water
activityisreducedduetohigherconcentrationsofaciddisplacingwatermolecules.Thethicknessofthehydrated
gellayerbecomesthinnerduetoacidstripping.ThiseffecthasanegativeinfluenceonthemVoutput,thereby
causingthemeasuredpHvaluetoremainhigherthanthetheoreticalpHvalue.Theaciderrorchangesverylittle
withtemperature.Overtime,anupwarddriftofpHinacidicsolutionsisindicativeofaciderror.

Sinceaciderrorisusuallyobservedbelow1.00pHandmostprocessapplicationsarewellabovethat,itisfairly
uncommon.Processmonitoringequipmentisusuallysettorespondtoasetpointatwhichappropriateactionis
takentoreturnthepHtothesetpointvaluewhenthepHrisesaboveorfallsbelowit.Forexample,the
controllerwilladdcaustictoasolutionthatisbelowthesetpoint.ItdoesnotmatterthatthetruepHvalueis
0.91pHandisnotaccurate,sincethecontrollerwillbecallingforcausticadditionuntilthesetpointisreached.

Temperature Effects

TemperatureaffectsthepHmeasurementintwoways.ThefirstisachangeinpHduetochangesindissociation
constantsoftheionsinthesolutionbeingmeasured.Thisimpliesthatassolutionstemperaturechanges,thepH
valuealsochanges.Presentlyavailableinstrumentationcannotaccountforthischangebecausethedissociation
constantsvaryfromsolutiontosolution.

ThesecondreasontemperatureaffectsthepHmeasurement,isglasselectroderesistance.Sincetheglass
measuringelectrodeisanionicconductor,itstandstoreasonthattheresistanceoftheglasswillchangeasthe
solutiontemperaturechanges.Astemperaturerises,resistanceacrosstheglassbulbdecreases.Thischangein
resistanceversustemperatureisconstantandcanbecalculateddependingonthespecifictypeofglass
formulationoftheelectrode.

Inpracticalterms,electroderesistancedropstenfoldforevery30Criseintemperature.Forexample,an
electrodewitha100megohmresistanceat25Cwilldecreaseto10megohmat55C.Assumingthatthe
theoreticalpHofthesolutionisconstant,thechangingelectroderesistancewillincorrectlyaffectthepH
reading,requiringtheuseoftemperaturecompensationinthemeasurementcircuit.

Atypicalglasselectrodeat25Ccanhavearesistanceof100megohms.Typicalrangescanvaryfrom20to800
megohms.Incontrast,theresistancerangeforreferenceelectrodesvariesfrom100to5000ohms.

Theresistancevalueofthemeasuringelectrodeisbasedon
anumberofinfluences:solutiontemperature,glass
formulation,glassthickness,theshapeofthemeasuring
electrodetip(Figure10),itssurfacemeasuringarea,andthe
physicalstateofthehydratedgellayer.

Althoughtemperaturewillnotaffecttheelectrodes
responsespeed,thethicknessoftheglasswill.Athicker
glasswillbemoredurable,butitalsohasmoreresistance,a
noisiersignalandalongerresponsetime.Athinnerglasswill
havelessresistanceandaquickerresponsetime,butwillbe
morefragile.

 16

Withhighelectroderesistancecomestheimpactofcapacitance
couplingandelectricalnoise(Figure11).Theleadwireexitingthe
measuringelectrodeispronetopickingupspuriouselectrical
signalsaneffectknownashandcapacitance.Similarto
extendingaradioantennaforpullingindistantstations,the
longertheelectrodeleadwirelength,themorepronethe
electrodeistopickingupinterference.Inthecaseofhand
capacitance,merelywavingahandnexttothecablewillcause
themeasuringinstrumentdisplaytochangeerratically.

Shieldingtheelectrodeandusinghighqualitycableinthe
manufacturingprocesscanminimizetheeffectsofelectrical
noise.Shieldingisusuallyaccomplishedbyincorporatinga
metallicbandwithintheglassmeasuringelectrodebody.This
bandextendsfromthebaseofwherethebulbiscoupledto
theelectrodebody,uptheshaft,andbacktowherethecable
exitsthebody.Whentheelectrodeisimmersedinthesolution,
thebandeffectivelyshieldsthemeasuringelementfromstray
interferencethroughthesolution.Combinationelectrodesareinherentlyshieldedbythereferencefillsolution
thatsurroundstheentiremeasuringelement.

Whentakingmeasurements,itisbesttoimmerseamajorityofthemetalband(themeasuringelectrodeshaft)
intothesolution.However,theareawheretheelectrodeshaftjoinsacaporcableconnectionshouldnotbe
immersed.Asforshieldingtheglassbulb,thesolutionbeingmeasuredactsastheshield.

Mostinstrumentspresentlymanufacturedcompensateforelectroderesistancechangesresultingfromsolution
temperaturefluctuations.Thiscompensationisalmostalwaysaccomplishedautomaticallyusingatemperature
sensitivedeviceaspartofthemeasuringcircuit.Inothercases,itisaccomplishedmanuallywithanadjustment
tothefeedbackcircuitoftheinstrumentselectronics.Onanaloginstruments,thisisachievedbysettingadial
tothecorrecttemperaturesetting.Formicroprocessorbasedinstruments,atemperaturevaluecorresponding
totheactualtemperatureofthesolutionbeingmeasuredismanuallyentered.

The Reference Electrode

Theglassmeasuringelectrodeissignificant,butonlyaspartoftheoverallsystemusedtomeasurepH.Itshalf
cellpotentialmustbecombinedwiththeotherhalfcellpotentialofthereferenceelectrodetocompletethe
measurementcircuit.Bothoftheseelements,whensubmersedintoasolution,generateapHmeasurement
whenconnectedtoameasuringdevice.Forthemeasuringelectrodetoprovideanaccuratemeasurement,the
referenceelectrodemusthaveaconstantandstablepotential.Anydeviationinitspotentialwillcausetheoverall
potentialtochange,therebycausingthepHreadingatthemeasuringdevicetoalsochange.

Thereferenceelectrodeconsistsofasilverwirecoatedwithsilverchloridethatisimmersedinanelectrolyte
solution.Thiswiremustbeelectricallyconnectedwiththesolutionbeingmeasured.Thisisaccomplishedthrough
aporousjunction,commonlycalledasaltbridge,whichphysicallyisolatestheelectrolyteandwirefromthe
solutionbeingmeasured.Theelectrolytesolutionmusthaveahighionicstrengthtominimizeresistanceandnot
affectthesolutionbeingmeasured,andmustremainstableoverlargetemperatureswings.Potassiumchloride
(KCl)solutionsthatare3.0molar,3.5molar,orsaturatedhavebeenusedsuccessfullyformanyyears.This
referencewireandelectrolytecombinationisthesilver/silverchloridereferencesystem.Othertypesof
referencesystemsarealsomanufacturedforspecificmeasurementneeds.Thesealternatereferencesystems
consistofcalomel,thalamidormercury.
 17

The Reference Junction

Thereferencejunctionislocatedatthemeasuringendofthereferenceelectrode(orreferenceelectrode
assemblyforadifferentialpHsensor).Thereferencejunctionisalsoreferredtoasa"saltbridge,"liquidjunction,
orfrit.Itspurposeistointerfacephysicallyandelectricallywiththeinternalelectrolyteandthesolutionbeing
measured.Thisreferencejunctioncompletesthecurrentpathfromtheglassmeasuringelectrodetothe
referenceelectrode.

Thereferencejunctionmustbechemicallyinert,soitdoesnottointerferewiththeionexchangeprocessbut
allowssmallamountsofelectrolytetoflowthroughit,whilemaintainingaconsistentlowresistancevalue.The
referencejunctionisconstructedofporousmaterialssuchaswood,Teflon,Kynar,ceramic,ormoreexotic
materialssuchasasbestosorquartzfibers.Thereisalsoagroundglasssleevejunctionthat,justasthename
implies,usestwogroundglasssurfacesmatedtooneanother.Thesetwosurfacesarefittightlytogether,but
theyallowelectrolytetopermeatebetweenthem.Thesizeofthejunctionmaterialusuallycorrespondstothe
sizeofthereferencewire,anditisusuallycylindrical.Itsdiameteristypically1/16inchto1/8inchanditslength
isbetween1/8inchand1/2inch.Annularjunctions,whichsurroundthereferenceelectrode,arealsoused.They
areavailableinawiderangeofmaterialsandsizes.

Forcurrenttoflow,thejunctionmustbeabletoconductelectrons.Thiscurrentflowisestablishedbyallowing
electrolytesolution(andtosomedetriment,thesolutionbeingmeasured)topenetratethestructureofthe
junction.Thejunctionisdesignedtoenablesmallamountsofthereferenceelectrodeelectrolytetoleachout,or
flow,throughitintothesolutionbeingmeasured.Astheelectrolyteflowsoutthroughthejunction,itprevents
thesolutionbeingmeasuredfromflowingbackintothereferencesystemandcontaminatingtheKClsolution,or
attackingthesilverandsilverchloride(Ag/AgCl)wire.

However,therearetimeswhenthesolutionbeingmeasureddoespenetratethejunctionandcontaminatethe
referencesystem.Thesolutionbeingmeasuredmaybeundersufficientpressuretoforceitbackthroughthe
junctionintothereferencesystem.Withreplaceablejunctions,anincorrectlyinstalledjunction(missingOring,
tornOring,orcrossthreading)willallowthesolutionbeingmeasuredtoflowunimpededpastthejunction.
Measuringasolutionthattendstocoatorplugthejunctionisalsodetrimental,sinceitstopstheelectrolyte
flowandincreasestheresistanceofthejunction.

Theoretically,theresistanceofthejunctionandthechemicalmakeupofthereferencesystemareassumedto
beconstantduringcalibrationandmeasuring.However,duetojunctioncontamination,junctionplugging,
electrolytedilution,andchemicalattackofthesilver/silverchloridewire,theresistanceisalwayschanging,asis
thechemicalcompositionofthewholereferenceelectrode.Consequently,thishighlightstheimportanceof
frequentlycalibratingtocompensateforthesefactors.

Junction Potentials

WhencomparingpHreadingsbetweentwoormorepHsensors,thereareusuallydifferencesbetweenthe
readings.Thecomparisonsmaybebetweenaprocesssolutionreadingandagrabsamplereading.Inthiscase,
thedifferencesareusuallycausedbytheprocessreadingbeingunderpressure,whilethelaboratoryreadingis
not.Gasesarenormallyentrained(dissolved)intheprocesssolution,butdissipatefromthegrabsampleandno
longeraffectthepHreading.Additionally,thegrabsampleandprocesssolutiontemperaturesmaybefarenough
aparttoaffectthepHreading.

Usingsensorsofdifferenttypescanalsocausedifferencesinreadings.Typically,combinationelectrodesor
differentialpHsensorsforprocessmeasurementandelectrodepairsforlaboratorymeasurement,orany
 18

combinationthereofcanbethecause.Thesensorfortheprocessreadingisusuallyasealeddevice,whereasthe
laboratoryelectrodepairisopentotheatmospheretoenablerefillingofelectrolyte.Sealedreferenceswill
usuallyproducedifferentzeropointsthanthoseoflaboratoryrefillableelectrodes,resultingindifferentpH
readings.

DifferencesinreadingsmaynotnecessarilybeduetoactualpHdifferences.Effectsofjunctionpotential,
electricalgrounding,electrodemembranecoating,anddissociationconstantsofthesolutionbeingmeasuredcan
greatlyaffectthemillivoltoutputofthemeasuringandreferenceelectrodes.Additionally,chemicalcompounds
orparticulatematterinthesolutioncandisablethereferenceelectrodeorjunction.Theprocesscanalso
contaminatethesilver/silverchloridereferencesystem.Sulfurcompounds,heavymetals,andstrongoxidizing
andreducingagentscanattackthesilver/silverchloridereferencesystem.Theresultantreactionofthisattack
willformsilvercomplexesorprecipitateelementalsilverthatcanblocktheporesofthejunctionorproduce
oxidationreductionpotentialsacrossthejunction.Ineithercase,thisresultsinanoffsetreferencepotential.

Gel-filled reference Electrode

Thegelfilledreferenceelectrodeusesagellingagentaddedtothereferenceelectrolytesolution.Thepurposeis
toslowdowntheeffectsofcontaminationonthereferenceelectrolytebyprocessmigrationthroughtheporous
junction.Itisalsomoredifficultforthisgelledelectrolytetobeforcedoutofthereferencesystemcavitywhile
theprocessundergoesperiodsoftemperatureandpressurecycling.Thegeltendstolastlongerthan
conventionalelectrolytesolutionundernormalcircumstances.Highertemperaturesandprocessesthatattackor
stripthegellingagentwhenitismigratingthroughtheporousjunctionwilltendtobreakdownthegellingagent.

Buffers

Thetermbufferisdefinedas"asubstancethatabsorbsanimpact,protectsagainstashock,resistschange,or
maintainsarelativeacid/baseconcentrationwithinaspecificrange."

WithregardtopH,buffersaresolutionsinwhichthepHremainsunchangedwhensmallamountsofanacidora
baseareadded.Abufferisasolutionofaweakacidorbaseandoneofitssalts,thatmustresistachangeinits
pHvalue.AbufferedsolutioncontainschemicalsthatwillnotreadilyallowachangeinpHvaluewhenitisbeing
neutralizedorchangedbydilution.

Anexampleofapoorbuffersolutionistrisodiumphosphate.A0.06%solutionatroomtemperaturehasapHof
12.0.Asolutionwithhalfasmuchconcentration(0.03%)hasapHofabout11.7,whileasolutionwithtwiceas
muchconcentration(1.2%)hasapHof12.5.Itisevidentthatanincreaseordecreaseinsolutionconcentration
willalsoincreaseordecreasethepH.

Anexampleofagoodbufferisasolutionofsodiumsesquicarbonate.ThepHvalueforthissolution,inthesame
concentrationsandwiththesametemperatureasthepreviousexample,remainsconsistent.Thisbuffer
indicatesthatitisamorestablesolution.

Calibration

pHelectrodesmustbecalibratedfromtimetotimetomaintainmeasurementaccuracy.Itisafactthatthe
performanceofapHsensordegradesovertime.Thetimeperiodandrelatedlossofsensorperformancevaries
considerablywitheachapplicationanditsuniqueconditions.

 19

Specifically,calibrationisperformedtocompensateforchangesinpotentialwithinthemeasuringandreference
electrodes,aswellasanychangeofpotentialbetweenthem.Theelectrodesareusuallymatchedatthefactory
sothatthemeasuringelectrodeandreferenceelectrode,whenputinazerosolution,(7.0pHbuffer)providea
zeromVoutput.

Differencesorchangesinpotentialcanbecausedbyoneormoreofthefollowingfactors:

Contaminationofthereferenceelectrolytesolution.Thesolutionbeingmeasuredisallowedtomigrate
throughthejunction,enteringtheelectrolytecavity,therebychangingitscompositionandalteringits
electrochemicalreaction

Electrolyteevaporationordepletion.Asthesolutionbeingmeasuredentersthereferenceelectrolyte
cavity,theelectrolyteisdisplaced.Undertherightcombinationoftemperatureandpressureconditions,
theelectrolyte,processsolution,oramixtureofbothcanbedrawnoutofthecavity.Asthelevelchanges,
sodoesthepotentialoutput,untilfinally,theleveldropsbelowthesilver/silverchloridewiretocausean
openmeasuringcircuit.

Chemicalattackofthesilver/silverchloridewire.Asthesolutionbeingmeasuredentersthereference
electrolytecavity,certainchangesmayoccurthatpoisonthesilver/silverchloridewire.Thisphysicaland
chemicalattackonthewirechangesitspropertiessothatthewholereferencesystemnolongerproduces
thesameoutputasitdidpriortotheattack.Insomecases,thischangeinoutputwillremainconstant,
whileinothersitmaybeconstantlydegeneratingovertime.

Junctionpotential.Whenexposedtothesolutionbeingmeasured,thereferencejunctionmaybecome
contaminatedorplugged.Thischangestheresistanceofthereferenceelectrode,therebychangingits
output.

Agingofthemeasuringelectrode.Astheglassmeasuringelectrodeisexposedtothesolutionbeing
measured,theelectrodeiscontinuouslyattacked.Thegellayerthatisformedattheelectrodetipundergoes
continuouschange,whichultimatelyaltersitsoutput.This"aging"iscontinuous.Theglassmeasuring
electrodeneverbecomesstable.Asagingprogresses,thegellayerbecomesthicker,therebyaffectingits
output.

Takingintoaccountanyoneofthesefactors,letalonethepossibilityoftwoormoreoftheseconditions
occurring,itiseasytoseewhyapHsensormustberecalibratedinapHbuffersolutiontomaintainmeasurement
accuracy.

Calibrationalsoinvolvescheckingtheslopeofthemeasuringelectrode.Slopedefinestheabilityofthemeasuring
electrodetochangeitsoutputby59.16mVperpHunitat25C.Forpreviouslystatedreasons,virtuallyallpH
instrumentsuseaslopeadjustmenttocompensateforthemeasuringelectrodesinabilitytoaccuratelyproduce
itsoutputsignal.Theslopeadjustmentismadeusingabufferthathasavalueatleast3pHunitsfromthezero
buffer(7.0pH).

BuffersareusedwhencalibratingpHsensorstocompensateforanyinherentoffsetsofthesensor.Typically,4
pHand7pHbuffersareusedtoperformthecalibration.Forbestcalibrationaccuracy,usebufferswithvalues
thatareclosetothenormalpHvalueofthesolutionbeingmeasured.Forexample,ifthesolutionbeing
measuredisnormally2pH,itisbesttouse4pHand7pHbuffersratherthan7pHand10pHbuffers.Ideally,one
ofthebuffervaluesforthisexampleshouldbe2pH.

 20

AdheretothestandardpracticeofusingcalibrationbuffersthatareatleastthreepHunitsapart.Thisdifference
isintendedtoprovidetheelectrodewithsufficientchange,enablingitsslopetobeplottedoverawidearea.
Whenadjustingthezeroandslope,carefullyfollowtheequipmentmanufacturersinstructionstoavoid
inaccurateresults.Whencalibratinganinstrumentwithouttemperaturecompensationcapability,the
temperaturesofthebuffersneedtobeknown.

Figure12indicateshowthevalueofapHbufferisaffectedby
changesintemperature.

Forinstrumentswithautomatictemperaturecompensation,the
propercalibrationtechniqueistoallowthesensorandbuffer
temperaturestoequalize,andtorinsethesensorindistilled
waterbetweenbuffers.Thiswillremoveresidualcontaminants
fromthesensor,preventbuffercontaminationcarryover,and
prolongthebuffersolution.Neverreusebuffersbypouringthe
usedbufferportionbackintothebottles.Alwaysdiscardbuffers
immediatelyafteruse.

ThefollowinggraphsshowthetemperatureversuspHcurveinamorerepresentativeform:

 21

NOTE:pH10bufferisalsoreadilyavailable,butitisnotasstableaspH7andpH4buffers,particularlyat
extremetemperatures.WhenpH10bufferisexposedtoair,itabsorbscarbondioxide.Asthisoccurs,thebuffer
becomesmoreacidicandisnolongerdependableasacalibrationreferencesolution.Evenwhenstoredin
sealedplasticbottles,thecarbondioxidemoleculespermeatetheplasticbottleandovertime,thiswillcause
thesamereaction.

 22

Chapter 5 CARE OF pH ELECTRODES

Dehydration

Leftoutofsolution,thepHglassmembranewillbecomedehydrated.Afterthishappens,thepHsensorwillhave
slowerresponseandahigherthannormalimpedancewhenitisputbackintooperation.Repeateddehydration
andreusewilldramaticallyreducethenormalservicelifeofthepHsensor.Prolongeddehydrationwillcausethe
glassmembranetofailcompletely.

Ifthereferenceelectrodebecomesdehydrated,itwillnolongeroperateproperly.Theelectrolytewillleachout
oftheelectrodecavity,throughthejunction(s),formingsaltcrystalsonthejunctionsurface.Overtime,leaching
willweakentheelectrolytepotential,andmayalsocauseaphenomenonknownasabridgingeffect.Bothof
theseconditionswillincreasetheoutputimpedance,makingthereferenceelectrodeoutputunstable.With
continueddehydration,theimpedancewillrisetoalevelthatbecomesunusabletothepHmeter.

Factors Detrimental to Electrode Life

ApHelectrodeoperatessimilarlytoahydrogenelectrodewithintherangeof0.0012.00pH(wherethealkali
erroraffectsthereading).Thisisknownasasodiumionerror(discussedearlierinChapter4ThepHSensor).
Withinthisrange,theoutputslopeoftheelectrodecorrespondstothetheoretical59.16mVasdefinedbythe
Nernstequation.

Aswithallglass,pHglassissusceptibletochemicalattack.Temperaturechangescanaltertherateofthisattack.
Forevery30Criseintemperature,therateofattackincreasestenfold.Accordingly,processsolutionswith
elevatedtemperaturesshortenelectrodelife.Strongacidsandstrongalkalinesolutions,toagreaterextent,
attacktheglassmembrane.Evenneutralsolutionsthatcontainhighconcentrationsofalkaliions,sodiumionsin
particular,attacktheglass.UsingapHsensorwithaglassformulationthatisinappropriatefortheapplication
mayrenderthesensorinoperableafteronlyashorttimewithoutanyvisibleglassdefects.

Hydrofluoricacid(HF)willreadilypoisontheglassmembranewhenthepHisbelow6.00.Thegreaterthefluoride
ionconcentration,thefastertheelectrodewillfail.Thefluoridestripsawaythegellayeroftheglassmembrane
renderingitinoperative.

AspecialelectrodemanufacturedfromantimonyisavailableformeasuringpHinsolutionscontainingHF.The
antimonyelectrodeexhibitssimilarpropertiestoglasselectrodeswithincertainlimits.Onedrawbackisthatthe
repeatabilityandspeedofresponseforanantimonyelectrodeisinferiortothatofaglasselectrode.Also,
antimonyelectrodesareonlylinearbetween3.0and8.0pH,andshouldonlybespecifiedwhenthepresenceof
hydrofluoricaciddictatestheiruse.

Transportation

Freezing,extremeheat,vibration,andmechanicalshockmustbeavoidedwhentransportingelectrodes,whether
withinafacility,orfromonefacilitytoanother.Alwaystrytoreusetheoriginalboxandpackingmaterialsto
transportelectrodes.

Whenshippingtheelectrodeusingmotorfreight,selectacarrierthatwillguaranteethatthepackagewillnotbe
exposedtoextremetemperatures.Usuallysendingtheelectrodebyanovernightdeliveryserviceensuresthat
thepackagewillnotbeexposedtotheelementslongenoughtodamagetheelectrode.
 23

Storage

pHsensors(electrodepairs,combinationelectrodes,anddifferentialstyles)shouldbestoredinambient
conditionsbetween10and30C.Protectivecapsandsolutionstoragecapsshouldbekeptintactandinstalledon
theendofthesensorasprovidedbythemanufacturer.

Thebestsolutionforstoragepurposesisa3to3.5MKClsolution.Thissolutionprovidesaneutraltoslightly
acidicenvironmentfortheglasselectrode,andwillnotimposeamemoryontheglass,muchasNiCadbatteries
canhavememoriesimposeduponthemwhentheyarenotfullydischargedpriortorecharging.ShouldKCl
solutionbeunavailable,appropriatesubstitutesinorderofpreferenceare:

1. pH4buffer
2. Distilledwater
3. Tapwater

Undertheseconditions,theglassmeasuringandreferenceelectrodescanbestoredforthreetofiveyears.

NOTE:Periodicallychecktoverifythatthestoragesolutionhasnotevaporated.

 24

Chapter 6 COMMON APPLICATIONS

Cooling Tower Control

ThepurposeofacoolingtoweristocooldownindustrialprocessesandprovidecooledwaterforHVACcontrol.
Thecooledprocesswaterisdirectedthroughtheprocess,whereitabsorbsheat,andisthensentbacktothe
towertoberecooled.Largeamountsofwaterarerequiredasevaporationoccursduringthecoolingcycle.Since
waterisanexpensivecommodity,primaryconcernsareefficienciesincoolingtowerdesignandchemical
treatmentofthewaterbeingused.

Hotwaterenteringthecoolingtowerissprayedthroughcoolerairtospeedevaporation.Forefficientcooling,it
isveryimportanttomaintainalargesurfaceareaforexposingthewatertotheairforanextendedperiodof
time.Theseheattransfersurfacesmustbeprotectedfromcorrosionandscale.Afterthewateriscooled,itis
collectedinasumpandpumpedbackthroughtheprocesspiping.

Propercontrolofanumberofparameterswillkeepthetoweroperatingefficientlyandpreventdamagetovital
partsfromscale,corrosion,andbiologicalgrowth.Asairflowsthroughthetower,airbornecontaminantsare
pickedupbythewater/airinterface.Thesecontaminantswouldbecarriedthroughthesystemiftheywerenot
controlledpriortodistribution.

pHisoneofmanyparametersthatcontrolsthewaterchemistryofthetower.MaintainingapHlevelbetween
6.0and7.0isfairlycommon.DependingonthepHofthewatersupplytothetowerlake,stream,ormunicipal
watersupplyeitheranacidorcausticcontrolschemeisusedtomaintainthepHinthisrange.

Food Processing

Canningplantsusecausticsoda(NaOH)intheirfruitandvegetablepeelingoperations.Priortodisposalofthe
wastes,thepHmustbeneutralized.UsuallythisisaccomplishedusingCO2(carbondioxide)asareagent.TheCO2
isinjectedintostainlesssteelpipelinestolowerthecausticwaste,typicallyfromapHof12.7to9.5.Theamount
ofCO2reagentaddedtothepeelingwastesisdeterminedbytheresultantpHvalueofthewastestreamatthe
plantdischargepoint.

Theneutralizedwastematerialisrecycledandusedasbothwetanddryanimalfeedforsurroundingfarms.

Coal Industry

Waterrunofffromcoalminingoperationsisacidicandmustbecollectedandtreatedpriortocontactwith
surroundingwatersheds.AnhydrousammoniaistypicallyusedasareagenttoincreasethepH.Valuesofcoal
runoffwaterhavebeenknowntobeaslowas2.05pH.

Underatmosphericconditions,anhydrousammoniaisavapor.Storedinatankunderpressure,itisaliquid.
Speciallyengineeredsystemscanfeedeitherliquidorvaporousanhydrousammonia.Dependingonthesystem
designcriteria,eachformhasitsparticularadvantagesanddisadvantages.Whenfeedinganhydrousammonia
invaporform,anelectricallyheatedvaporizermustbeused.Ammoniaiseasiertomeasureandcontrolif
appliedasavapor.

 25

Runoffwateriscollectedorpooled.ThepHofthiseffluentismeasuredandthencomparedtothecontrol
setpoint.IfthepHisbelowtheacceptablelevel,thepHcontrollercontrolsavalvetoallowthereagenttobe
addedtotheeffluentandmixeduntiltheoptimumpHvalueisreached.Afterthecollectedwateris
appropriatelytreated,itisdischarged.

Plating Waste Treatment

Theplatingindustryproduceswastesofcyanides,chromates,acids,andalkalicleaners.Eachmustbetreated
priortodischarge.Typically,pHandOxidationReductionPotential(ORP)measurementandcontrolareusedin
combinationtoneutralizeanddetoxifythesesolutions.Themajorityofapplicationsinvolvebatchtreatmentin
holdingtankswithgoodmixing.

Treatingtoxicsolutionsbeforetheybecomepartoftheeffluentflowispreferabletofinalstagetreatment.
Cyanideandchromatewastesarejusttwoexamplesthatusethisscheme.Inthisscenario,atankwiththe
treatmentchemicalsisdownstreamfromtheplatingtank.Ratherthanbeingrinsedfromthepartsandtreated
later,carryoverchemicalsaretreatedwithinthistank.

Chlorineorsodiumhypochloriteisusedtooxidizecyanidetoalesstoxiccyanate.Propercaremustbetakento
maintainanalkalinepHsothatthepHofthesolutiondoesnotfall,producingdeadlycyanidegas.Causticis
addedtotheprocessthroughasolenoidvalvecontrolledbythepHmeasurementsystem.ThepHduringthis
treatmentphasemustbecloselymaintainedbetween9.98and10.02pH.ThereactionisfurtheredwhentheORP
value,monitoredbyanORPmeasurementsystem,reachesapredeterminedpointforaspecifiedtime.

Thefinalstepinvolveseitherpumpingthesolutiontoanothertanktoextracttheheavymetals,oraddingacidto
thesolutiontogetafinal7.5to8.0pHlevel.Thisprocessstartstheoxidationofthecyanate.AfterproperpH
adjustment,thecyanateisoxidizedtocarbondioxide,nitrogen,andwaterbyaddingchlorineorhypochlorite.
Again,propermonitoringofORPduringthisstepensuresacompletedreaction.

Ultrapure Water

ThemeasurementofpHinultrapurewaterrequiressomespecialconsiderations.Becauseofitsunique
properties,ultrapurewaterhasbeencalledtheworldsgreatestsolvent.Itspurityandsolventpropertiesprevent
corrosionofwettedpartsinboilersinpowergeneratingplants.Itisusedasacleanertowashcontaminantsfrom
electronicmicrochipsintheelectronicsindustry,anditprovidesthebaseforinjectablemedicinesinthe
pharmaceuticalindustry.

Chemicallypurewaterconsistsoftwoatomsofhydrogenandoneatomofoxygen.Itisodorlessandcolorless.
ItalianscientistStanislaoCannizzarrodefinedthechemicalformulaofthewatermolecule,H20,in1860.
Absolutelypurewaterdoesnotlastlongbecauseitdissolvesnearlyeverythingitcomesintocontactwith,
therebyretainingsomeofthepropertiesofthecontactedmaterial.Itreadilyabsorbscarbondioxidewhen
exposedtotheatmosphere.Itisverydifficulttomakepurewatereventhroughrepeateddistillations.

Whenheated,waterboilsproducingsteam(watervapor)asabyproduct.Consideredpure,steamquicklyabsorbs
atmosphericelementssuchascarbondioxidethatquicklychangethewatertosomethingotherthanultrapure
water.Becauseultrapurewaterhasnobuffercapacity,theslightestcontaminationwillchangeitspHvalue.

Purewaterisaverygoodelectricalinsulator.Thismakesitespeciallydifficulttoconductelectronsbetweenthe
measuringandreferenceelectrodesofapHsensor.WithinthepHelectrodemeasuringcircuit,thiscausesa
highresistancethatispronetoelectricalnoise,slowelectroderesponse,handcapacitanceeffects,andstatic
 26

buildup.Thisstaticbuildupisevenmoreprevalentwhenpurewaterflowsthroughplasticpiping.Acommon
phenomenonstemmingfromthisbuildupofstaticchargeisreferredtoasastreamingcurrentpotential.This
potentialwillaffectthepHreadingbyprovidingfalseelectricalpotentialstothemeasuringandreference
electrodes.Thesepotentialscancauseavariableorconstantvoltageoffsettobeappliedtotheelectrodes,
makingthepHmeasurementmeaningless.Afterrepeatedexposuretoultrapurewater,thereferencejunction
willexhibitahighresistanceduetoitsinsulatingproperties,causingdriftandunstablecalibration.

Electrodesformeasuringultrapurewaterarespecializedandareusuallymatedwithametal,groundedflow
assembly.Themetalflowassemblyhelpsshieldthereadingfromelectricalnoiseandhandcapacitance.Aslow
processflowratethroughtheassemblyalsoprovidesampleresidencetimeforthemeasurementtooccurand,
tosomedegree,eliminatesstreamingcurrentpotentials.

Theelectrodeassemblieshavegelfilledreferencesorflowingjunctionssoafastandefficientpotentialis
establishedbetweenthejunctionandthesolutionbeingmeasured.Theelectrolytepassingthroughthejunction
providesthispotentialwithaminimalchanceofjunctionpluggingorfouling.Theonlydrawbackofthisdesign
maybethecontaminationoftheprocesssolutionwiththeelectrolyte.Puttingtheentiremeasuringloopintoa
bypassassemblyandthendirectingthesampledischargetodrainwillkeepaconstantpressureonthemeasuring
electrode.Thiswillalsonegatetheproblemofsendingaprocesssample,contaminatedwithKClelectrolyte,back
intotheprocess.

 27

BIBLIOGRAPHY

Arthur,RobertM.1982.ApplicationofOnlineAnalyticalInstrumentationtoProcessControl.Arthur
Technology.Bates,RogerG.1973.DeterminationofpH,TheoryandPractice.
Beckman1983.TheBeckmanHandbookofAppliedElectrochemistry.BeckmanInstruments,Inc.
Chemtrix.pHinPlainLanguage.Chemtrix,Inc.
Gray,DavidM.1994.OnlineHighPuritypHMeasurement.LeedsandNorthrup.
Ingold,1989.PracticeandTheoryofpHMeasurement.IngoldMesstechnikAG.
McMillan,GregoryK.1994.pHMeasurementandControl;SecondEdition.InstrumentSocietyofAmerica.
Merriman,DaleC.1993.ReferenceJunctionPotentialDifferencesBetweenLaboratoryandProcess
Instrumentation.InstrumentSocietyofAmerica.
Moore,RalphL.1978.NeutralizationofWasteWaterbypHControl.InstrumentSocietyofAmerica.
SchottGerate.ElectrodesandAccessoriesforTechnicalService.SchottCorporation.

 28

GLOSSARY
Activity:Athermodynamictermfortheapparentoractiveconcentrationofafreeioninsolution.Itisrelatedto
concentrationbytheactivitycoefficient.
AsymmetryPotential:Thepotentialdevelopedacrosstheglassmembraneofthemeasuringelectrodewith
identicalsolutionsonbothsides.AlsoatermusedwhencomparingmeasuringelectrodepotentialinpH7buffer.
ATC:Automatictemperaturecompensation.
BNC:Aquickdisconnectelectricalconnectorusedtointerconnectand/orterminatecoaxialcables.
BufferCapacity:AmeasureoftheabilityofthesolutiontoresistpHchangewhenastrongacidorbaseisadded.
Buffer:Anysubstanceorcombinationofsubstanceswhich,whendissolvedinwater,producesasolutionthat
resistsachangeinitshydrogenionconcentrationwhenacidoralkaliisadded.
Calibration:Theprocessofadjustinganinstrumentorcompilingadeviationchartsothatitsreadingcanbe
correlatedtotheactualvaluebeingmeasured.
Conductance:Themeasureoftheabilityofasolutiontocarryanelectricalcurrent.
DissociationConstant:Avaluewhichquantitativelyexpressestheextenttowhichsubstancesdissociatein
solution.ThesmallerthevalueofKis,thelessdissociationofthespeciesinsolution.Thisvaluevarieswith
temperature,ionicstrength,andthenatureofthesolvent.
Drift:Achangeofareadingorasetpointvalueoveraperiodoftimeduetoseveralfactorsincludingchangein
ambienttemperature,time,andthelinevoltage.
ElectrodePotential:Thedifferenceinpotentialestablishedbetweenanelectrodeandasolutioninwhichitis
immersed.
Electrolyte:Anysubstanceinasolutionthatwillconductanelectriccurrent.Acids,bases,andsaltsarecommon
electrolytes.
FillingSolution:Asolutionofdefinedcomposition,alsocalledanelectrolyte,thatprovidesachemicalreaction
aswellasanelectricalpotentialbetweenaninternalelementandtheprocessbeingmeasured.Anexampleis
thesolutionsealedinsideapHglassbulb,typicallyKCl.Afillingsolutionnormallyisabufferedchloride,which
providesastablepotentialandaspecificzeropotentialpoint.Inareferenceelectrode,theelectrolyte,also
calledthereferencefillingsolution,surroundsthesilver/silverchloridewireandperiodicallyrequires
replenishing.
HydrogenIonActivity:Activityofthehydrogenioninsolution.Itisrelatedtohydrogenionconcentration(CH+)
bytheactivitycoefficientforhydrogen(H+).
Impedance:Thetotalopposition(resistiveplusreactive)toelectricalflow.
InputResistance(Impedance):TheinputresistanceofapHmeteristheresistancebetweenthemeasuring
electrodeterminalandthereferenceelectrodeterminal.Avoltagedivisionbetweenthetotalelectrode
resistanceandtheinputresistancealwaysaffectsthepotentialofapHmeasuringelectrodecircuit.
InternalReferenceElectrodeWire:Thesilver/silverchloridewireusedinareferenceelectrode.

IsopotentialPoint:Apotentialwhichisnotaffectedbytemperaturechanges.ItisthepHvalueatwhichdE/dt
foragivenmeasuring/referenceelectrodesystemiszero.Theoretically,foraglassmeasuringelectrodeandSHE
referenceelectrode,thispotentialexistswhenimmersedinpH7buffer.
 29

LogarithmicScale:Amethodofdisplayingdata(inpowersoften)toyieldmaximumrangewhilekeeping
resolutionatthelowendofthescale.
Membrane:ThepHsensitiveglassbulbisthemembraneacrosswhichapotentialdifferenceisdevelopedfrom
anionexchangereaction.Themembraneseparatestheelectrolyteinthemeasuringelectrodefromthe
solutionbeingmeasured.
Millivolt(mV):Aunitofelectromotiveforce.Itisthedifferenceinpotentialrequiredtomakeacurrentof1
millampereflowthrougharesistanceof1ohm.Onemillivoltequalsonethousandthofavolt.
Molality:Ameasureofconcentrationexpressedinmolesperkilogramofsolvent.
Molarity:Ameasureofconcentrationexpressedinmolesperliterofsolution.
NernstEquation:Amathematicaldescriptionofelectrodebehaviorinwhich:Eisthetotalpotential,inmillivolts,
developedbetweenthemeasuringandreferenceelectrodes;Exvarieswiththechoiceofelectrodes,
temperature,andpressure;2.3RT/nFistheNernstfactor(RandFareconstants,nisthechargeontheion
includingsign,andTisthetemperatureindegreesKelvin);andaiistheactivityoftheiontowhichtheelectrode
isresponding.
NernstFactor(Slope):Theterm2.3RT/nFintheNernstequation,whenT=25C,isequalto59.16mVwhenn=
1,and29.58mVwhenn=2.Thetermnisthesignofthechargeontheion.TheNernstfactorvarieswith
temperature.
pHJunctions:Thejunctionofareferenceelectrodeorcombinationelectrode,typicallyaliquidjunction,isa
permeablemembranethroughwhichtheelectrolytemigrates.
SaltBridge:Thesaltbridgeofareferenceelectrodeisthatpartoftheelectrodewhichisincontactwiththe
electrolyte,establishingtheelectrolyticconnectionbetweenthereferencesystemandthesolutionbeing
measured.An"auxiliary"saltbridgeisaglasstubeopenatoneendforelectrolytefilling,andconnectedtothe
referenceelectrodecavityattheotherend.Thistypeofsaltbridge,usedforspecialapplications,increasesthe
electrolytecapacity.
Span:Thedifferencebetweentheupperandlowerlimitsofarangeexpressedinthesameunitsastherange.
Stability:Thequalityofaninstrumentorsensortomaintainaconsistentoutputwhenaconstantinputis
applied.
Standardization:Aprocess,alsoknownascalibration,ofequalizingthemeasuringelectrodeandreference
electrodemillivoltoutputpotentialsinonestandardizingsolution(buffer)sothatpotentialsdevelopedin
unknownsolutionscanbeinterpretedaspHvalues.
Thermistor:Atemperaturesensingelementcomposedofsinteredsemiconductormaterialwhichexhibitsa
largechangeinresistanceproportionaltoasmallchangeintemperature.Thermistorsusuallyhavenegative
temperaturecoefficients.

LITG004
HachCompany,2010.Allrightsreserved.
Intheinterestofimprovingandupdatingitsequipment,HachCompanyreservestherighttoalterspecificationstoequipmentatanytime.