10

DeterminationoftheKaValueand
MolarMassofanUnknownWeakAcid

Introduction
Inthisexperimentyouwilltitrateamonoproticweakacidwithastrongbase,and
measurethetitrationcurvewithapHmeter.Byanalyzingthetitrationdata,youwillbe
abletodeterminetheionizationconstantKafortheweakacid,aswellasitsmolarmass.
Weakacidsreactwithwatertoproducesmallconcentrationsofions.Thedegree
ofionizationisdescribedbytheequilibriumconstantKa.
+ [H3O + ][A ]
HA(aq)+H2O(l) H3O (aq)+A (aq) Ka=
[HA]
ThevalueofKa canbedeterminedexperimentallybymeasuringtheconcentrationsof
+
H3O ,A ,andHAatequilibrium.
TodetermineKa,itmayseemstraightforwardtoputameasuredamountofHA
intoameasuredamountofpurewaterandmeasurethepH.FromthepH,youcouldfind
+
[H3O ],whichshouldbeequalto[A ]becauseoftheonetoonestoichiometry. By
subtractionyoucouldfindtheremaining[HA],andthecalculateK a.However,thereare
twoflawsinthisapproach. First,youwouldneedtoknowtheinitialconcentrationof
HA,soyouwouldhavetodoanotherexperimenttofinditsmolarmass.Second,truly
purewaterisnotavailableinourlaboratories. Ourwaterhasbeendeionized,which
meansithasbeenpassedthroughacolumnthatreplacesmetalionimpurities(suchas
+ 2+ 3+ +
Na ,Ca ,andFe )withH3O ions.Onsomedays,ourdeionizedwaterhasapHas
+ 5
low as 4! Since weak acids produce very low H 3O concentrations (~10 M for
example),startingwithpH4waterwouldbedisastrous.Yourresultwouldbeoffbya
factorof100!
Inthisexperiment,youwillprepareasolutionwhosepHisresistanttoimpurities
bytitratingtheweakacid(wellcallitHA)withastrongbase.

HA(aq)+OH (aq)H2O(l)+A (aq)

Chemistry1BExperiment10 41
Thisreactionhasaverylargeequilibriumconstantandgoestocompletion.Everymole

ofaddedOH ionsconvertsonemoleofHAtoonemoleofitsconjugatebase,A .

Attheequivalencepointofatitration,exactlyenoughOH ionshavebeenadded
toreactwithalloftheHAmoleculesthatwereoriginallypresent.Aroundthispoint,the
pHofthemixtureincreasessuddenlyanddramatically.TherapidincreaseinpHcanbe
detectedusinganindicator(suchasphenolphthalein)orwithapHmeter.Ifyoumeasure

theamountofOH neededtoreachtheequivalencepoint,youalsoknowthemolesof
HAthatwerepresentoriginally.

Thehalfwaypointofatitrationishalfwaytotheequivalencepoint.EnoughOH
ionshavebeenaddedtoreactwithexactlyhalfoftheHAmoleculesthatwereoriginally

present,convertingthemintoA .Atthispoint,thereareequalamountsofHAandA in
thesolution.Atthehalfwaypoint,theKaexpressionsimplifiesto:
+
Ka= [H 3O ][A ] =[H3O ]when[HA]=[A ]
+
[HA]
+
IfyoumeasurethepHatthehalfwaypoint,youcaneasilycalculate[H 3O ]andKafor
theacid.
Thehalfwaypointliesinthemiddleofthebufferregionofthetitrationcurve.In

the buffer region, there are appreciable concentrations of both HA and A ion the
solution. Whiletheconcentrationsareequalatthehalfwaypoint,theyarewithinthe
sameorderofmagnitudethroughoutthebufferregion. Inthebufferregion,thepHis

insensitivetoacidicimpuritiesinourlaboratorywater,becauseA isavailabletoreact
withthem.
+
A (aq)+H3O (aq)HA(aq)+H2O(l)
Thus,apHmeasurementatthehalfwaypointofyourtitrationshouldmostaccurately
reflectthestrengthofyourunknownacid.Buffersolutionshaveasimilarresistanceto
pHchangesfromsmallamountsofbasicimpurities,becauseHAisavailabletoreact
withthem.

HA(aq)+OH (aq)H2O(l)+A (aq)

ExampletoshowhowthepHofbuffersolutionsisinsensitivetosmallamountsofimpurity:

Supposeatthehalfwaypointofthetitration,yoursolutionhas[HA]=[A ]=0.04M.
+
ThepH4laboratorywaterhas[H3O ]=0.0001M.

AftertheimpurityreactswithA ,

[A ]=0.04M0.0001M=0.0399M,
[HA]=0.04M+0.0001M=0.0401M,so
+ K a [HA] K a (0.0401)
[H3O ]= [A ] = (0.0399) =1.005Ka(<1%different),and

pH=log(1.005Ka)=Ka0.002(offbyonly0.002pHunits).

42 Chemistry1BExperiment10
Procedure
SAFETYPRECAUTIONS:WearyourSAFETYGOGGLES.Ifyouspillanyacidor
baseonyourskinorclothing,washitoffimmediatelywithcopiousamountsof
runningwater.
WASTEDISPOSAL: PourtheexcessNaOHandbuffersolutionsdownthedrain,
followedbyplentyofrunningwater.Emptythetitratedsolutionsandtheremainderof
yourunknownacidsolutionintotheINORGANICWASTEcontainersinthefumehood.

PartI.Preparingasolutionofyourunknownweakacid
Obtainavialcontaininganunknownweakacid.Yourunknownwillbeasolid.
Recordtheunknownnumber.
Obtain a 100.0mL volumetric flask and a powder funnel. Weigh the vial
containingtheunknownontheanalyticalbalance,andrecorditsmassto0.001g.Place
thefunnelintheneckofthevolumetricflask.Gentlytapbetween1.9and2.1gramsof
theunknownintothefunnel.(Youwillneedtocheckthemassofthevialseveraltimes
toseehowmuchyouhaveadded.)Reweighthevial,andrecorditsfinalmassto0.001
g.Thedifferenceinmassisthemassofunknownacidinyourflask.
Useajetofdeionizedwaterfromawashbottletorinsealltheacidfromthe
funnelintothevolumetricflask. Filltheflaskaboutthreequartersfullwithdeionized
water.Swirluntilalltheaciddissolves.(Thismaytakeawhile.)Thenadddeionized
waterjustuptothe100.0mLmark.Inverttheflaskseveraltimesforthefinalmixing.
Theconcentrationofthesolutionyouhavejustpreparedissomewhereinthe
range0.09M0.2M.

PartII.Performingatrialtitrationusingphenolphthaleinindicator
Obtain about 100 mL of standardized NaOH solution in a clean dry flask or
beaker. RecordtheexactconcentrationoftheNaOHsolution. Itisbesttokeepthis
solutioncoveredwhenyouarenotusingit. Rinseoutaburetthreetimeswith5mL
portionsoftheNaOHsolution. Tilttheburetbackandforth,sothesolutiontouches
everypartoftheinsidewalls,andremembertorunsomesolutionthroughthetip.Then
filltheburettojustunderthe0.00mLmarkwiththeNaOHsolution. Supportitona
ringstandusingaburetclamp.
Rinseouta25.00mLpipetthreetimeswithsmallportionsofyourunknownacid
solution.Pipetexactly25.00mLofyourunknownacidsolutionintoacleanErlenmeyer
flask.(Thisflaskdoesnothavetobedry.)Add3dropsofphenolphthaleinindicator.
Placetheflaskundertheburet,andplaceapieceofwhitepaperundertheflask.
Read the NaOH buret and record the reading to 0.01 mL. Titrate the acid
solutionwithNaOH,swirlingtheflaskconstantly.Theendpointisthefirstsignofpink
colorthatpersistsforatleast60secondsbeforefadingaway.Asyouneartheendpoint,

Chemistry1BExperiment10 43
addtheNaOHdropbydrop.Attheendpoint,readtheNaOHburetandrecordthereading
to0.01mL.Theendpointisveryclosetotheequivalencepointofthetitration.
PreparingforthepHmeasurements:Thetrialtitrationhasprovidedinformation
thatwillhelpyoumeasurethetitrationcurveproperly.ThepHchangesrapidlynearthe
beginningofthetitrationandneartheequivalencepoint.Youwillneedcloselyspaced
pH measurements in these regions. From the trial titration, you know how many
millilitersofNaOHsolutionareneededtoreachtheendpoint. Calculate10%,90%,
110%,and120%ofthisvolume.

PartIII.Determiningthetitrationcurve
ObtainapHmeterandsetitupatyourbench.CalibratethepHmeteraccording
totheinstructions forthat particular pH meter. Becarefulwiththeglasstipofthe
electrode,asitisverydelicateandveryexpensive.Donotletitdryout,andremember
torinseitwithdeionizedwaterwhentransferringitfromonesolutiontoanother.
RefilltheburetwithNaOHsolutiontojustunderthe0.00mLmark.Recordthe
initialreadingoftheburetto0.01mL.Pipetexactly25.00mLofyourunknownacid
solutionintoaclean,dry150mLbeaker. Add3dropsofphenolphthaleinindicator.
MeasurethepHofthesolution.
YouwillnowaddsmallamountsofNaOHtoyourunknownacidsolution.After
everyaddition,youshouldstirthemixturewiththepHelectrode,readthepH,andread
theburetto0.01mL.
Atthebeginningofthetitration(010%ofthewaytotheendpoint),takereadings
afterevery5dropsofNaOHadded.
Inthemiddleofthetitration(1090%ofthewaytotheendpoint),takereadings
aftereverymilliliterofNaOHadded.
Neartheendpointofthetitration(90110%ofthewaytotheendpoint),startby
takingreadingsafterevery5dropsofNaOHadded. WhenthepHstartstochangeby
morethan0.2pHunitsbetweenadditions,takeareadingaftereverydropofNaOH
added. Atanequaldistanceontheoppositesideoftheendpoint,youmayagaintake
readingsafterevery5dropsofNaOHadded.
Beyondtheendpointofthetitration(110120%ofwaytotheendpoint),take
readingsaftereverymilliliterofNaOHadded.
Aftercompletingtheexperiment,remembertorinseouttheburet,pipet,powder
funnel,andvolumetricflaskwithtapwaterandreturnthemtotheappropriateboxesin
thefumehood.TurnoffthepHmeter,rinseofftheelectrodeandreplaceitsprotective
cover,andreturnthepHmetertothefumehood.

44 Chemistry1BExperiment10
Calculations
MakeatableofthepHmeasurementsandthemillilitersofNaOHsolutionadded
inPartC. (TofindthemillilitersofNaOHaddedateachdatapoint,youwillneedto
subtracttheinitialburetreadingfromeachoftheotherburetreadings.)
Prepareatitrationcurvefromyourdata.Thatis,makeafullpagegraphwithpH
ontheyaxisandvolumeofNaOHaddedonthexaxis.Drawasmoothcurvethrough
alltheplottedpoints.Onyourtitrationcurve,indicatetheexact equivalencepointand
halfwaypoint,asdescribedonthenexttwopages.
Anexampleofatitrationcurveisshowbelow.Yourtitrationcurvewillnotlook
exactly the same as this one, because you are using a different acid, and different
concentrationsofacidandNaOH.

Titration of Acetic Acid with NaOH

14

12

10 Equivalence point
pH = 8.72
24.87 mL
pH

8
Halfway Point
pH = 4.474
6 12.435 mL

4
Buffer Region

2
0 5 10 15 20 25 30
Volume of NaOH added (mL)

Chemistry1BExperiment10 45
 Equivalence point. The equivalence point of the titration is the point when

exactlyenoughOH ionshavebeenaddedtoreactwithalloftheHAthatwasoriginally
present.ItisthepointofinflectioninthepartofthetitrationcurvewherethepHshoots
straightup.Theendpointofthetitrationisthepointwheretheindicatorchangescolor.
Whiletheendpointisveryclosetotheequivalencepoint,theyarenotexactlythesame.
TofindtheexactvolumeofNaOHneededtoreachtheequivalencepoint,replot
thesmallregionofthetitrationcurvearoundthispoint.Drawatangentlinethattouches
thesteepestpartofthetitrationcurve. Findthetwopointswherethetitrationcurve
deviatesfromthetangentline.Theequivalencepointisexactlyhalfwaybetweenthese
twopoints.
Inyourexperiment,whatvolumeofNaOHwasneededtoreachtheequivalance
point?WhatwasthepHatthispoint?
Howclosewastheendpointtotheequivalencepointinyourexperiment?

Near the Equivalence Point

12

11
Tangent line

10
pH

9
Equivalence point
is the Places where the titration curve
midpoint of the tangent line deviates from the tangent line

24.87 mL

6
24 24.5 25 25.5 26
Volume of NaOH added (mL)

46 Chemistry1BExperiment10

Halfwaypoint.ThehalfwaypointofthetitrationisthepointwhenenoughOH
ionshavebeenaddedtoreactwithexactlyhalfoftheHAthatwasoriginallypresent.If
youknowthevolumeofNaOHneededtoreachtheequivalencepoint,simplydivideitby
twoforthevolumeofNaOHneededtoreachthehalfwaypoint.
TofindtheexactpHatthehalfwaypointofyourtitration,replottheregionofthe
titrationcurvearoundthispoint,usinganexpandedpHscale. Thisallowsaprecise
interpolationofthepH.
Inyourexperiment,whatwasthepHatthehalfwaypoint?

Near the Halfway Point

5.1

4.9

4.8
pH = 4.744
pH

4.7

4.6

4.5

4.4 0.5 x 24.87 mL =

12.435 mL
4.3
8 9 10 11 12 13 14 15 16
Volume of NaOH added (mL)

Chemistry1BExperiment10 47
PropertiesofYourUnknownAcid
Nowthatyouhaveproperlylocatedtheequivalencepointandthehalfwaypoint
on your titration curve, you are ready to use it to determine the properties of your
unknownacid.
1. WhatisthevalueofKaforyourunknownacid?
2. Whatwastheconcentrationoftheunknownacidsolutionyouprepared?(Use
yourtitrationdataandthemolarityofthestandardizedNaOHsolution.)
3. Whatisthemolarmassofyourunknownacid?(Usethemassandmolesof
thesampleinyourexperiment.)
Notethattheunknownweakacidisnotoneoftheonesintabulatedinyourtextbook,so
youwillnotbeabletoidentifyit.

CheckingYourResultsforConsistency
Using your experimental Ka value, the concentration of your unknown acid
solutionandtheconcentrationofthestandardizedNaOHsolution,calculatethepHofthe
followingpointsonyourtitrationcurve:
1. ThebeginningofthetitrationbeforeanyNaOHwasadded.
2. 25%ofthewaytotheequivalencepoint
3. 75%ofthewaytotheequivalencepoint
4. Theequivalencepoint
5. 120%ofthewaytotheequivalencepoint
ComparethecalculatedpHvaluestothepHthevaluesonyourgraph.Somepointswill
agreebetterthanothers.Whatarethereasonsforthis?

48 Chemistry1BExperiment10
PrelabQuestion
Thetitration curvebelow was obtainedbytitrating 25.00mLofaboricacid
solutionwitha1.000MNaOHsolution.Usetheinformationgivenonthetitrationcurve
toanswerthefollowingquestions:
1. WhatisthevalueofKaforboricacid?
2. Isboricacidastrongerorweakeracidthanaceticacid?
3. Whatwastheconcentrationoftheoriginalboricacidsolution?

Titration of Boric Acid with NaOH

14

12 pH = 11.40
20.00 mL

10 pH = 9.137
10.00 mL
pH

pH = 4.17
0.00 mL
4
0 5 10 15 20 25
Volume of NaOH added (mL)

Answers:(1)7.291010;(2)weaker;(3)0.8000M.Showyourworkandexplainyourreasoning.

Chemistry1BExperiment10 49