7/1/2015 Lab6:Hardness

Lab6:

Hardness

ReadingAssignment
ReadChapter14inSimplifiedProceduresforWaterExamination.

Introduction
Thislabisconcernedwithhardness,whichistheamountofdivalentmetalliccationsinthewater.Theprimarycausesof
hardnessarecalcium(Ca+2)andmagnesium(Mg+2)ions,butothermetalssuchasstrontium,ferrousiron,manganous,
aluminum,andferricironcanalsocontributetohardness.Ofthese,ferricironandaluminumionstendtohavelittleeffecton
hardnessinnaturalwaterssincetheyarenotverysolubleinwateratnaturalpHlevels.

Sincethehardnessinwaterprimarilyoriginatesfromcontactwiththesoilandwithrockformations,hardwaterstendto
originateinareaswheretopsoilisthickandlimestoneformationsarepresent.Softwaters(thosecontainingrelativelylittle
hardness)originateinareaswherethetopsoilisthinandlimestoneformationsaresparseorabsent.

Inorderforhardnesstoenterwaterfromtherocksandsoil,thewatermustbesomewhatacidic.Rainwaterusuallyhasa
neutralpHandisincapableofdissolvingmostsolidsinrocksandsoil,butcarbondioxideisreleasedintothewaterbybacterial
actionasthewaterpercolatesdownthroughthesoil.Thiscarbondioxideformscarbonicacidandmakesthewateracidicand
thusabletodissolvebasicmaterials,suchaslimestone.Sincelimestoneisprimarilycomposedofcalciumcarbonate,calcium
isusuallythelargestcauseofhardnessinwater.Butmostlimestonealsohassomeimpuritiessuchassulfates,chlorides,and
silicateswhichcanalsopassintosolutionasthecarbonatesdissolveawayaroundthem.

ItiseasytoconfusehardnesswithalkalinitybecausebotharemeasuredinppmCaCO3andbothoftenenterthewaterfrom
limestone.Infact,whenlimestoneistheonlycauseofhardnessandalkalinityinwater,theamountofalkalinityandhardness
inthewatershouldbeaboutthesame.Toseewhy,considerthefollowingchemicalequation:

CaCO3 Ca+2+CO32

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Whencalciumcarbonatefromlimestoneisdissolvedinwater,itionizesintoitsconstituentcomponentscalciumionsand
carbonateions.Thecalciumionscausehardnessinwaterwhilethecarbonateionscausealkalinity.

Despitethesimilaritiesincauseandmeasurement,hardnessandalkalinityhaveverydifferenteffectsonwater.Asyouknow,
alkalinityisabuffer,keepingthepHofwaterrelativelystable.HardnessdoesnotaffectthepHofwaterinstead,itreactswith
soapinwatertoformprecipitates("soapscum")andwithcertainanionsinwatertoformscale.Hardnesscanalsodamage
someindustrialprocessesandcanresultinundesirabletasteindrinkingwater.

Themostaccuratemethodofmeasuringhardnessistohavethewatertestedinalaboratoryfortheamountsofcalciumand
magnesium.However,inmostcases,watertreatmentlabswillnothavetheequipmenttomaketheseanalyses.Below,we
haveexplainedatitrationprocedurethatcanbeusedtoapproximatehardnessinmostlabs.Inthistitration,abufferisaddedto
changethewatertotheappropriatepH,thenEDTAisslowlyaddedtothesample.EDTAreactswithcalciumandmagnesium
inthewater,removingthemfromsolution.Whenallofthecalciumandmagnesiumhavebeenusedup,theindicatorchanges
colorandyoucancalculatetheamountofhardnessthatwaspresentinthesamplewater.

Equipment
beakers
rubbertippedstirringrod,ormagneticstirrerandstirbar
25or50mLburette,graduatedin0.1mL
burettesupport

Reagents
distilledwater
buffersolution
indicator
EDTAtitrant

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7/1/2015 Lab6:Hardness

LaboratoryProcedure
1. Forwaterwithrelativelyhighhardness,youshouldput25.0mLofsamplewaterinabeakeranddiluteittoabout50mL
byaddingdistilledwater.Ifthewaterisrelativelysoft,youcanusealargersamplesizeof100to1000mLwithout
dilution.Recordtheamountofsampleused.
2. Add1to2mLofbuffersolutiontothebeaker(ormoreifyouusealargerwatersample.)ThiswillchangethepHofthe
samplewatertoabout10.0to10.1.Stir.
3. Add1to2dropsofindicatorsolutiontothebeaker(ormoreifyouusealargerwatersample.)Stir.
4. TitratewithEDTAtitrant,stirringatintervals,untiltheindicatorchangescolor.Thecolorwillchangefromreddishto
blue,althoughincandescentlightstendtogivethefinalsolutionareddishtinge.
5. RecordtheamountofEDTAtitrantwhichwasrequiredtoreachtheendpoint.
6. Calculateandrecordtheamountofhardness(asppmCaCO3)inthewaterusingthefollowingformula:

Data

WaterSource SampleSize(mL) MolarityofTitrant(M) AmountofTitrant(mL) Hardness(ppmCaCO3)

VirtualLab
Theprocedureoutlinedonthispageisamanualtitrationprocedure.Youshouldalsoviewthevirtuallabwhichshowshowto
testalkalinityusingatitrator.Thereisanassignmentthatneedstobecompletedconcerningthevirtuallab,sopleaseprintthe
assignmentfirstandthenanswerthequestionsasyouperformthelab.Onceyouhavetheassignmentcompleted,loginand

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7/1/2015 Lab6:Hardness

completetheassignmentonlinetobeentereddirectlyintothedatabase.

Sources
AmericanPublicHealthAssociation,AmericanWaterWorksAssociation,andWaterEnvironmentFederation.1998.
StandardMethodsfortheExaminationofWaterandWastewater.AmericanPublicHealthAssociation,Washington,D.C.

DeJess,M.A.2004.Experiment6:EDTADeterminationofTotalWaterHardness.UTChemistry,AnalyticalChemistry
Laboratory,Chemistry319.

Wurts,W.A.andR.M.Durborow.December1992."InteractionsofpH,CarbonDioxide,Alkalinity,andHardnessinFish
Ponds."SouthernRegionalAquacultureCenter.

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