EXPERIMENT11 STANDARDIZATIONOFASODIUMHYDROXIDESOLUTION WITHAPRIMARYSTANDARD PURPOSE: Tostandardizeasolutionofsodiumhydroxidebytitrationwithaprimarystandard,potassium hydrogenphthalate(KHC8H4O4) PRINCIPLES: Acidbasereactionsinaqueoussolutionrepresentoneofthemostimportanttypesofchemical reactions. Formanyyearsacidsweredescribedasthosesubstancesthattastesour,turnbluelitmuspaper red,reactwithmetalstoproducehydrogengas,reactwithcarbonatesandbicarbonatesto producecarbondioxide,andreactwithbasestoformwaterandsalt. Similarly,basesweredescribedastastingbitter,feelingsoapyorslipperytotouch,turningred litmuspaperblue,andreactingwithacidstoproducewaterandasalt.

In1887,SwedishchemistSvanteArrheniusshowedthatsomecompoundscontaininghydrogen atomscouldionizeinwatertoformhydrogenions. ThesesubstancesarenowknownasArrheniusacids. AccordingtoArrhenius,asolutioncontainingexcesshydrogenionsisanacidsolution,andthe morehydrogenionspresent,themoreacidicthesolution. + Morerecentstudiesindicatethatthehydrogenion(H ),orprotoninaqueoussolutionis + hydrated,producingnewspeciescalledthehydroniumion,H3O :

+ + H (aq)+H2O(l) H3O (aq) + + PurewateralreadycontainssmallquantitiesoftheH ion(proton),H3O (hydroniumion) duetotheselfionizationreactionofwater,writteneitheras:

H2O(l) or H2O(l)+ H2O(l)

+ H (aq)

- + OH (aq)

+ H3O (aq) +

- OH (aq)

+ Acidsubstancesmayalsobedefinedasproton(H )donorswithinthecontextofagiven reaction,accordingtothedescriptionofBronstedandLowry(1932)

HCl(aq)+H2O(l)

+ - H3O (aq)+ Cl (aq)

TheseareknownasBronstedLowryacids. Wheneversolutionsofaqueousacidsarediscussed,theacidspeciesinthesolutionisthe hydroniumion. Arrheniusbasesaredefinedmostsimplyassubstancesthatgeneratehydroxideionsinsolution: NaOH(aq)

+ Na (aq)

- OH (aq)

BronstedandLowryexpandedthedefinitionofabasetoincludeanyspeciesthatcanaccepta + proton(H ) SuchsubstancesarenowcalledBronstedLowrybases. 1

EXPERIMENT11 STANDARDIZATIONOFASODIUMHYDROXIDESOLUTION WITHAPRIMARYSTANDARD Thus,accordingtoBronstedLowry,allhydroxidesarebases,asarecarbonates,bicarbonates, acetatesandammonia: - + OH (aq) + H (aq) H2O(l) 2- + CO3 (aq) + H (aq) HCO3-(aq) + HCO3-(aq) + H (aq) H2CO3(aq) + C2H3O2-(aq) + H (aq) HC2H3O2(aq) + NH3(aq) + H (aq) NH4+(aq) ThereactionbetweenanArrheniusacidandanArrheniusbase,orbetweenaBronsteadLowry acidbasepairiscalledaneutralizationreaction. + Inacompleteneutralizationinaqueoussolution,theH3O ionsreactwithanequalnumberof OH- ions. + + TheneutralizationofanacidreleasingoneH ion(orH3O ion)performulaunit(monoprotic acid)withabasereleasingoneOH- ionperformulaunit(monohydroxyormonobasicbase) exhibitsasimplestoichiometry. Anexampleofsuchareactionisillustratedbytheequationdescribingthereactionof hydrochloricacid(astrongacid)with sodiumhydroxide(astrongbase): HCl(aq) + NaOH(aq) NaCl(aq) + H2O Thecorrespondingnetionicequationforthisneutralizationreactionis: + - H (aq) + OH (aq) H2O(l) SinceHCl(aq)isastrongmonoproticacid: + NumberofmolesofH = SinceNaOH(aq)isastrongmonohydroxybase: - Numberofmolesof OH =

Numberofmolesofacid=na

Numberofmolesofbase=nb

+ Since1moleofH usesupcompletely1moleofOH- ,itfollowsthatthecomplete neutralizationrequiresthatthenumberofmolesofacid(na)beequaltothenumberofmolesof base(nb): na =nb Thisrelationshipcanbecombinedwiththedefinitionofmolarity:

na =MaxVa Ma =Molarityoftheacid Va =Volumeofacid Itfollowsthat:

and

nb =MaxVb Mb =Molarityofthebase Vb =Volumeofbase

Ma xVa =Mb xVb

Thelastrelationshipapplieswhenevertheacidandbasereactina1:1moleratio.

EXPERIMENT11 STANDARDIZATIONOFASODIUMHYDROXIDESOLUTION WITHAPRIMARYSTANDARD Thestoichiometrybecomesmorecomplexwhentheacidandbasereleaseunequalnumberof + H3O andOH- ions.Theneutralizationofsulfuricacidwithsodiumhydroxideisexpressedby thebalancedchemicalequation: H2SO4(aq) + 2NaOH(aq) Na2SO4(aq) + 2H2O(l) The1:2moleratiooftheacidtothebaseinthebalancedequationindicatesthattwiceasmany molesofbaseareneededthanofacid: 2na =nb 2(Ma xVa)=Mb xVb InthisexperimentyoursolutionofNaOHwillbestandardizedbytitratingagainstaverypure sampleofpotassiumhydrogenphthalate,KHC8H4O4,ofknownmass. Potassiumhydrogenphthalate(thereafterabbreviatedasKHP)isasolublesalt,andassuchis completelydissociatedinaqueoussolution: + - KHP(aq) K (aq) + HP (aq) Thehydrogenphthalateion,HP-(aq)isaweakacidanditundergoespartialionization: - + 2- HP (aq) + H2O(l) H3O (aq) + P (aq) TheadditionofNaOHtothisequilibriumsystemwillcausetheOH- tocombinewiththe + H3O ionstoformwater: - + OH (aq)+H3O (aq) H2O(l) + ThedecreaseintheconcentrationofH3O ionswillcausetheequilibriumsystemtoshifttothe rightandassuchmoreoftheweakacid(hydrogenphthalateion,HP-)willionize. + SuccessiveadditionsofNaOHwillcontinuallyremoveH3O ions,shifttheequilibriumtothe rightandforcetheweakacidintocompleteionization. Thissituationcanbesummarizedintheequilibriumtablebelow: - + 2- HP (aq)+ H2O(l) H3O (aq)+ P (aq) - addOH

+ Stress:[H3O ]decreases

2H2O

Equilibriumshift: Thenetresultisthecompleteneutralizationofpotassiumhydrogenphthalate(KHP)bythe NaOHsolution,asshownbytheequationsbelow: KHP(aq) + NaOH(aq) KNaP + H2O(l) NetIonicEquation: - - HP (aq) + OH (aq) P2-(aq)

H2O(l)

NumberofmolesofKHP =NumberofmolesofHP- =NumberofmolesNaOH=MbxVb NumberofmolesofKHP=MbxVb 3

EXPERIMENT11 STANDARDIZATIONOFASODIUMHYDROXIDESOLUTION WITHAPRIMARYSTANDARD Ifonemeasuresthevolume(inliters)ofbase,Vb,requiredtoneutralizeaknownmassofKHP, itispossibletocalculatethemolarity(Mb)ofthebasebecausethemolarmassofKHPisknown. TheexactmolarityoftheNaOHsolutioniscalculatedfromthemassofKHP,itsmolarmass, andthevolumeoftheNaOHsolutionrequiredtoreactcompletelywiththeKHP,asdetermined byatitration. Theentireprocedurebywhichweobtainthemolarityofasolutionofonesubstance(NaOH) fromanaccuratelyknownamountofanothersubstance(KHP)iscalledstandardization. SampleCalculation: WhatisthemolarityofaNaOHsolutionif35.75mLofitisrequiredtoneutralize1.0705gof potassiumhydrogenphthalate(KHP).? ThemolarmassofKHPis204.2g/mol 1moleKHP NumberofmolesofKHP =1.0705gx =5.2424x10 -3 moles 204.2gKHP NumberofmolesofKHP =NumberofmolesNaOH=5.2424x10 -3 moles NumberofmolesNaOH=MbxVb 5.2424x10 -3 moles Mb = = 0.1466M 0.03575L PROCEDURE: 1. Preparationofapproximately0.100Msodiumhydroxidesolution (a) Measure8.4mLof6Msodiumhydroxidesolutionina10mLgraduatedcylinder. (b)Pourthesolutionintoaclean500mLplasticbottle (c) Dilutethissolutiontoapproximately500mLwithdeionizedwater.Thevolumeofthe sodiumhydroxidesolutiondoesnothavetobeknownaccurately. (d)Stopperfirmlytheplasticbottleandmixthesolutionthoroughlybyinvertingtheplastic bottleatleasttentimes.Pleasenotetheinsufficientmixingof solutionsisacommon sourceoferrorintitrations. KEEPTHEBOTTLEOFNaOHSOLUTIONSTOPPEREDATALLTIMES! (e) Placealabelontheplasticbottlewithindicatingyournameandthecontents (0.1MNaOH) (f) ThissolutionwillbetitratedinthenextpartoftheexperimentagainstKHPtodetermine itsexactMolarity 2. StandardizationoftheSodiumHydroxideSolution (a) Prepareabout400 500mLofCO2 freewaterbyboilingforabout5minutesthe deionizedwater. (b)Usingtheanalyticalbalance,accuratelyweigh(fromavial)between0.4gand0.6g sampleofpurepotassiumhydrogenphthalateintoaclean250mLErlenmeyerflask Theflaskdoesnothavetobedry. Note: ONLYTHECAPPEDVIALWILLBEPLACEDONTHEANALYTICAL BALANCE,BUTNOTTHEFLASK. Yourinstructorwilldemonstratehowtobestestimatethemassofsaltthatmustbe removedfromthevial. 4

EXPERIMENT11 STANDARDIZATIONOFASODIUMHYDROXIDESOLUTION WITHAPRIMARYSTANDARD (c) Addabout100mLofCO2 free,deionizedwatertotheflask,andwarmgentlywith swirlinguntilthesaltiscompletelydissolved. (d)Addtwodropsofphenolphthaleinindicatortothesolutionintheflask. (e) Rinseapreviouslycleanedburetwithatleastfour5mLportionsoftheapproximately 0.1Msodiumhydroxidesolutionthatyouhaveprepared.Discardeachportion. (f) Completelyfilltheburetwiththesodiumhydroxidesolutionandremovetheairfromthe burettipbyrunningoutsomeofthesolutionintoanemptybeaker. Makesurethatthelowerpartofthemeniscusisatzeromarkorslightlylower. Removeanyhangingdropfromtheburettipbytouchingittothesideofthebeakerused forwashings. Allowtheburettostandforatleast30secondsbeforereadingtheexactpositionofthe meniscus. Recordtheinitialburetreading. (g)SlowlyaddtheNaOHsolutiontoyourflaskofKHPsolutionwhilegentlyswirlingthe contentsoftheflask(amagneticstirrerifavailablemaybeusedformechanicalmixing) AstheNaOHsolutionisadded,apinkcolorappearswherethedropsofthebasecome incontactwiththesolution.Thecolordisappearswithswirling. Astheendpointisapproached,thecolordisappearsmoreslowly,atwhichtimethe sodiumhydroxidesolutionshouldbeaddeddropbydrop. (h)Theendpointisreachedwhenonedropofthesodiumhydroxidesolutionturnstheentire solutionintheflaskfromcolorlesstopink. Thesolutionshouldremainpinkwhenitisswirledandafterthatshouldmaintainitsfaint pinkcolorforatleast30seconds. (i)Discardthesolutionandwashouttheflaskwithplentyoftapwater.RinsewithD.I.water (j)Repeattheproceduredescribedabovewithatleastthreemoresamples. (k)Fromthedatayouobtaininatleastthreegoodtitrations,calculatethemolarityofthe NaOHsolutionandwritethismolarityonthelabelpreviouslyplacedonthebottle. DONOTDISCARDTHESTANDARDIZEDSOLUTIONOFNaOHSINCEIT WILLBEUSEDINTHENEXTEXPERIMENT. AFTERYOUMADESURETHATTHEBOTTLEOFNaOHSOLUTIONIS TIGHTLYSTOPPERED,PLACEITINYOURLOCKER.

EXPERIMENT11 STANDARDIZATIONOFASODIUMHYDROXIDESOLUTION WITHAPRIMARYSTANDARD REPORTFORM NAME:__________________________ MolarMassofPotassiumHydrogenPhthalate:204.2g/mol st nd rd th th 1 Titration 2 Titration 3 Titration 4 Titration 5 Titration (g) (g) (g) (g) (g) Initialmassof KHP+vial: Finalmassof KHP+vial: MassofKHP used: st nd rd th th 1 Titration 2 Titration 3 Titration 4 Titration 5 Titration (mL) (mL) (mL) (mL) (mL) FinalBuret reading: InitialBuret reading: mLofNaoH used: LofNaOH used st nd rd th th 1 Titration 2 Titration 3 Titration 4 Titration 5 Titration Molesof KHP Molesof NaOH Volumeof NaOH(L) Molarityof NaOH (moles/L) Average Molarity ofNaOH Deviation* di Mean Deviation,d* RelativeMean* Deviation,RMD *Seenextpageforexplanationofterms

EXPERIMENT11 STANDARDIZATIONOFASODIUMHYDROXIDESOLUTION WITHAPRIMARYSTANDARD Deviation, di = isthedifferencebetweentheAverageMolarityandanyIndividual MolarityValue = isexpressedasanabsolutevalue(nosign) di=AverageMolarityIndividualMolarityValue NOTE: Ifoneindividualdeviationismuchlargerthantheothers,thisisa possibleindicationofabadtitration. Youmaychosenottoexcludethistitrationfromthecalculationof theAverageMolarity.

MeanDeviation,d

istheaveragedeviationbasedonallindividualdeviations, di

RelativeMeanDeviation

MeanDeviation =RMD= x1000(partsperthousand) AverageMolarity

NOTE: 1. ThelowertheRMD,thebettertheexperimentaldata. 2. GoodStudentWorkshouldhaveanRMDoflessthan5ppt(partsperthousand) 3. Itispermittedtodiscardoneorseveralbadtitrations. However,foracceptablelabwork,theAverageMolarityshouldbebasedonatleast threegoodtitrations.

CONCLUSION: Forqualitylaboratorywork,thefollowing2conditionsmustbesatisfied: 1. 2. TheresultsofatleastthreetitrationsshouldbeincludedinthecalculationoftheAverage Molarity,and ThethreetitrationsandthecorrespondingAverageMolarityshouldyieldacalculated RMDvaluethatislessthan5.