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17
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4
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- GravimetricandVolumetricAnalysis
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I\TRODUCTION
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4 Thc tcchniqucsof classicalchemicalanalysiscan bc dividcd into two broad categorics: (l) gravimctric
analysisand (2) volumctricanalysis.The purposeof this cxpcrimcntis to ernployboth mcthodsof analysis
4 to detcrminethc conccntrationof tllSO1 in solutionsthat havc bcen preparedby dilution from a sulfuric
acid solutionofdennite.but unknou,n.conccntration.Fromthe dilutionsthc conccntrationsofthe unknown
-
IIlSC)1solutionmay ihenbe calculated.
-
In gravimetric anal-vsis,the clcmcntto be determinedis isolatcdin a solid compoundof known identity
4 and detiniteconrposition.From thc massof this compound,the analystcan dctcrminethc mass of thc
- clemcnl that !!as prcscntin thc orieinal sample.On thc othcr hand.rhcn thc goal is to deteminc thc
amountof a compoundprcscntin thc originalsample(ratherthan thc amounrof an individualeiement).
- cilhcr one of the ions or onc of thc clementspresentin that compoundis isolatcdin a compoundto bc
a, weighcd.In this cxpcrimcnt,thc amountof sulfuricacidprescntis dctcrminedgravimctricallv
and wcighingBaSOr(s).by rcactionwith BaClr(aq).
bv producing

-
4 l l r S O r( a q )- B a c l r ( a q r) B a S O r ( s+) I H C I ( a q ) tll

4t BaSOI is suitablefbr this gravimetdcdctcrmination bccauscit is prccipilaledreadilyandcomplctcJyfron'r

!t thc solutionbcinganalvzcd.I'urihcrmorc,thc rcsultinSprccipitateis purc and easilyli1tcrcd.it is a solid of
knorvn and dcfinitc composition,and its molar massis sulliciently largethat an apprcciablcand casily
- rvcighcdmassof precipirctc tvill be produccd.

- In volumetric analysis,thc amountofthc specicsprcscntin thc samplcis dctcrmincdbl thc tcchniqueof

-fhe
4 titration. samplcis presentin a solutionof knoun volums.To this solutionof unknownconccntration is
addedanothersolution.calledthc titrant, of kno\\,nconcentration. The litrant is addcdin sucha way that
-t thc volumeaddedat cachpoint is rcadilydqtcrmincd.Tbe solutein thc titrantsolutionis a substance that
- rcactsquicklv and completclywith thc speciesto be dclermincd.lt is also hclpl'ulif an casilyobscnable
changcoccursat thc equivalencepoint of the titration.thc point at which thc amountol tirranrsolute is
t, chemica)lycquivalcnt1othc amountof the speciesbcingdctcrmincd.I1'sucha changcdocsnot occur.olien
an indicator is addedto lhe solutionbcingtitrated.As a resultofthis addition.a color changcoccursin the
-,
rcaciionmixtureat a point in thc titrationvcr./ ncarto (or ideally at) thc cquivalenccpoint.This point of
a color changc is knoun as the end point. In this expcrimcnt.thc amount of H:SO1 is dctcrmined
-t volumetricall-'"by its litrationwith sodiumhydroxidesolution.

-t H]SO1(aq)+ 2 NaOH(aq)--.' NalSO4(aq)

I 2 lllO t2l
-t Sincc no perceptiblcchanscoccursat the equivalence point of this rcaction(r'hcn I molcsof NaOH have
tt been added for everl mole ol' H:SOr originally present).phcnolphthalcinis uscd as an indicator.
Phcnolphthalcin
is colorlessin acidicsolutionand pink in alkalinesolution.
-,
\ I . { T F . R I . \I . S \ \ D C H E } I I C A L S
at
AD 10 mL Vohr pipet;5 mL pipet;25 mL pipct:burctandburetclamp: 100mL r olumctricllask.250 & I 15
mL crlcnmcvcrllask: li ltcr pnpcr: I 0 ml- graduatcdcl lindcr: hol piare.( lf reduccdscalcritrationis uscd.
t) substitutea l0 mL burctand2.00mL pipetfbr thoselisted.)
'D
6 \.4llrsor. 0.20 M BaCll, 0. l0 NI NaOH. | .0 \l HCl.
a)
'D I:ron Lthor.no^ .\ldnuul l& I:\p.rinvntr in Gucra! Chcntstn. Nrnth Edrrion. Thomas G. Greco. I vrnan IL Rickard.
r n d G c r a l d S \ l c i s s .C o p l r i g h 1 ! i ] 0 0 7 b y P e a r s { ) F
n - d u c a n o nI n
. c I ' u b l i s h c db v P r e n t r c eH a l 1 .I n c . A 1 l n g h r sf e s e n e d
-)
,,
'18

(;ravimctric and \ olumetric Analtsis

EstimatedTime..3.5 :1hours.To savctimc. if the expcrimcntis pcrtbnnsdovcr two laboratoryperiods.the stock

solutionshouldbe storcdin a cleanstoppcredflaskin ihc student's
lockcr'

SAFETY PRECAUI'IONS
Revicu' the saf-etyrulcs.

The original.concentrated H:SOr solulioncan causcchemicalbums il'it comesin contactwilh your skin. An)'
shouldbc promptlvclcancdup so thatothersin the laboraioryarc not accidcntallycxposed.lf
spillsor splashes
you comc in coniactwith this solution.you shouldu'ashthe affectcdarcaibr al leastfite ninutcs \\rtll running
water. inlbm your laboratory instructor.and seek mcdical aitention-An accidentalexposurcto concentrated
HISO] will manillst itsclf afrersometime as a buming sensationon your skin. lf you ticl this scnsation. seek
immediate attention. Delay can lcadto a skin
serious bum.

-l-he
conccntratedacid should be addcd to \r,ater.rolhcr than water to thc concenlralcdacid. Splatteringor
spittingoticn occurswhcn wateris addcdto a conccnirdtcd acid bccauseof thc subslaniialhcal of dilution that
is gcneratcd.You shouldwear gogglcsthroughoutthis proccdure(asu'ell as duringthe resi ol lhc expenment)
and avoid lookingdown into the reactionrnixture.to avoidinadvenentsplashes to ]'our handsor l'acc

Barium ion is a beav,vmctalpoisonand shouldbe handlcdwith car€.Althoughthcreis tlo conclusiveevidence

tllat poisoningoccurson skin contact.all spills shouldbc clcancdup prompti! in order to aloid accidenral
contact.Oncc it is convefted1()bariumsulfatc.hoq,evcr.bariumion poseslittlc hazardbecauscol lhc cxlremc
that has becn usedto hold tsac'lr(aq)shouldbc rinscdwith a small
insolubiiit-vofthe solid rhus. glassg'arc
volumeof dilute H:SO4.This rinseshouldbc disposcdol in lhc mannerdescribcdlbr solutionsin thc disposal
sedion of Pan B.

P R O C E D UR E
A. Dilution of Concentrat€dHzSOr

I . Obtain25 nlL of 6 M H:SOr in a 100 mL or smallcrgraduatcdbeaker.Labcl lhis as the initial solution.

The bcakershouldbc scrupulously cleanto avoidcontamination. Atter use.carcfulll'rinsclhe bcakerwith
xatcr and discardlhc rinsjngs(scethe disposalscctionat the end ofPart A)

2. Pour approximately 50 mL of distilledwatcr in a clean 100mL volumetricflask.Pipct era l-v l{).00ml.

of 6 M II:SO+ into thc fltsk. (Be sureto rinsethe pipct $,ith a small volumcof the suifuricacid solution
first. lf ),ou are unsurc of the proper. safe proccdurc tbr pipcting. consult 1,our instructor befirre
bcginning.)Follow thc sa1'e11- precautionsnotedabove.Add distilled$atcr to ihc calibrationmark o1'thc
volumclric flask. Stopper securcly and inven tcn times to cnsurc thorough miring and unilbrm
conccntntioltthroughoutthe solution.This solutionwill be reterrcdlo as the stock solution.(lt has a
concentration of approximatcl!0.6 M.) it can be transferrcdto a clcanand dry Erlcnmc)srllask anci
stoppercdfor storlge(and labeled S1o.l -5b/!/tior " ). (Rctainthis stocksolutionuntil -v-
ou havccorrlplctcd
the experiment. so that you can makc up more final solution ifneeded.)

3. Rinsethe volumetricflaskwith scvcralDortionsoldistillcd *'ater. Discardthc nnse$aicr'

,1.Pipet 25.00 mL of rhe srocksolutioninto the 100ml- r'olumctricllask. I-histl|tsk must bc cleanbut not
necessarily dry: you will bc addingdistillcdwaterto its conlcnts.Add distillcdrvatcr.stirling it in ordcr
to mix thoroughiyaiter eachaddition.to fill thc flaskto the calibraiionmark.Stoppcrsccurcl,'- and invcn
tcn times to cnsurethoroughmixing. Ihis final solution has a conccnlntion of 0.15
approxinlalclv M. Il
shouldbe storcdin a stoppercd. clean.and dry 125 nt- Ilrlcnmelcr llask (labcled"Finol Solution ) f,\r
filrther usc. lCarel l! Pipetingfrcm u wtlumctricflusk tan fu hu:urdous )

DISPOSAL
llxcess acid: Add phcnolphthalcin and ncutralizc\\ilh I Nl NIOH (first appcaranccoi pemlanentPrnk
color).Flushthc resullingsall solutiondown thc sink with runnllrg$atcr.
-
!-t
19
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Gravimetric and Volumetric Analvsis
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-l B. Gravimetric Determinationof Sulfate lon
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l2 ml- of 0.2 M BaCl:(aq)in a clcan,dry. sloppcredl2-5mL Erlcnmcyerllask.
| . Obtainapproxirnatcly
s
-) 2. Obtaina piccc of filter paperand dctermincits mirssto thc nearestmg (-0.001 s). with pcncil (not inkl)
uritc an idcnrilyingmark (/ or f)on the outsidccdgeof thc filter paper.Fold the filtcr paperin quaners.
s ntakea conc.andplaccit in a funneL.Moistenit \\ith distillcdwarcrso thar it adhercsto the walls ofthc

s funnel.

- 3. Using a l0 mL graduatcdcl,linder.transf'er5.0 mL of the 0.2 M BaCl: obtaincdin stcp 1 into a 50 rnl

bcakcr.This providcsa slight exccssof bariumion. On a hot platcwarm this solutionto ncarboiling{iur
- aboutl5 minutcs).Do not allow it 10boil or heatto dryncss.
-
-1.Whilc tbe abovesolutionis heating.pipct 5.00 ml- of the final solutionof H:SOj into a 50 mL bcakcr.
- Add 5 mL of 1.0 M HCI (use a graduatedcylindcr) to this solutioo.This rddcd acid rvrl) hclp to lbrm
,) large.filtcrablepaniclesof precipitate.Heatthis solutionlo nearboiling(aboutl0 minuleson a hot platc).
Do not hcatto dryness.
ta
s 5. \Vhileboth solutions(steps3 and 4) arc still hot. slowly add the BaCl:(aq)into the bcakerof HrSOr(aq).
$ ith r lg{z"orl.r.r/lrring. Add .r1orr'lr'so that largc particles of prccipilatc will fbnn. Rrlsc the stimng rod
- $ ith 1'ourwashbottlcbctbrcrcmovingit fiom tlrebcakcr.

s 6 Io t'ufihcrpromotcthc lbnnatiolrof large particlesof prccipitatc.1-oushould$arm thc mi\turc in lhc

- hcakcrto ncarboilingon a hot platcand kecp it at this tcmpcraturcibr :0 minutcs.Do nol ireatto dryrless.

s Strroccasionall,u-. proccduredissolrestlrc smdllerpiLnicles

thenallolv it ro ccxrlslorvly.This r/igcslir.rir
solid.which later$'ill rcprecipitatcon thc rcInainingparticlcswhcn the mr\turecools.
of

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7. Usc the stirringrod m dircct thc liquid. and pour thc mixturc tiom thc bcakcronto thc filtcr papcrin thc
s funncl.Washthc prccipitatctiom the beakcr*ith rcpcatcd5 rnl- alicluolsol distillcdwalcr.Makc \ure lc)
- alsorvashot'f thc stirringrod so thal all solid is quantitativcl-v 1lf solneol'lhc finc pr.ccipitate
transi'cncd.
passcsthrough thc t-rhcr papcr. rc-tiitqr thc liltrate through the same lllter paper. Makc surc to
- quanritativclytranst'er irll of thc ijltratc to thc funnel.)Carelully transterthc wct fllter papcr fiom the
funnclonto a cleandry p.rpcrtorl,cl.anclplaceit in,"-ourlockerto dry until the ncxt laboratonpcriod.Bc
-
lcry carcf'ulr.viththis transf'cr.sincc*ct filtcf piipcrn'raytcar. Ifa dryinuoven is availablc.placcthc uct
- flhcr on a largewatchglassand dry in a I l0'C--ovenfor I lo 2 hours.

- S. If timc-allows.repcatslcpsI throughI ibr a sccondiletermination.

-
thathasbccn uscdlbr BaCl:(aq)rvith smallportionsof H1O.Discardthcscrinsingsin
9. Rinscall glassware
-a thc mannerindicatcdtbr solutionsin tlredisposalscction.
ta 10. During the ncxl laboratorypcriod. dctermincthc massof filter paperand tlaSOr(s)10 thq ncarcstnrg.
-a Subtracttbe rccordcdnrassol the filtcr papcrto dctcmlinethe massof thc prccipilatc.
fa
DISPoSAL
fa
Solid BaSO.r:Putprccrpitate and tilter paperinto a waslcbotllc lirbclcdtbr solids.
fa Filtrate and unusedllaclz solution: Add6N{H]SO1 lo precipilateall fte bariumas BaSO.r and tlltcrintoa
fa labclcduastc bonlc.Thc solid uill bc disposcdin the sainemann!-ras thatabovc.and the acid solution*rll
be ncutralized,rrdisposcdin a labclcdrvastcbottls.
aa
fa
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-
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-
ta
20
(;ravimetric and Volumetric Anallsis

C. Volumetric Determinationof Acid Concentration

0.100M .\-aOIIsoluuon.
L Obtaina clean50 n1Lburet.Rinsc it t\\,iccwith 5 rnl- ponionsof standardizcd
Make surcto run somcol tlrisrinse solutionthrough lhc burct tip

2. Fill thc burcrwith 0.100M NaOH. Do not fill ihe burctlo lhc 0.00 mL nark. lnstcad.fill the burctncariy-
to this mark. nrakingsurcthat the tip is llllcd. and rcad the liquid lcvcl (to one digil be-vondthc tincst
graduation: cstimaiethe lastdigit).

3. Using a suctiondeviccandcareful.sale proccdure.pipct 10.00nL oflhc final solutioninlo a clean150

mL Erlenmcyerflask.Add ttvo or threedropsof phenoiphthalcinindicatorsolutlon

4. Tjtratclhis samplcof the tinal solutionwith 0. 100M NaOH(aq)until a /l?irl pink color persistsibr over
l5 scconds.Swirl the solutionin thc tlask as you tilratc.Washdo$n thc walls of tlretlaskrvith dLstilled
qatcr tiom ),ourq,ashbottlclo cnsurcihat any splattered acid or baseis rctumedlo thc titralionmixture.
A half drop of 0. 100 M NaOH(aq)can bc addedby "hanging"a partialdrop on thc burct tip. touching
this drop 10 thc insideof rhe ilask. and then washingthc drop into the solutionwith dislilled $'ater.
Rccordrhc volumc(lo -0.01 mt-) ofthc baseused.

5. Rcpcatsteps2 through.l with a secondpodion of the iinal solutron.unlil thc volumco1'titrantusedin

titrationsagrccswithin Iot,.
succcssive

DISPoSAL
Titration solutions: Sincclhcscare virtually nculralsalt solutions.they may bc ilushcddo\l'nthc sn]k$ rth
running$alcr.
Unused HrSOr and \aOH; Pur in a labcledwastcbottle.or mix unuscdacid and basctn a largcbcaker.
Add phenolphthalein and ncutralizc\\,,ithI M II.SOi (thc first disappcarancc
of pLnkcolor)or NaOH {tlrst
appearancc of pcmanentpirk color).Flushthe rcsultingsaltsolutiondo\rn thc sink \\'ithrunnlnqlvalcr.

D, ReducedScaleVolumetric Detcrmination of Acid Concentration

As an altemativcto thc titrationin Part C. a l0 mL buretmay bc used. Ihis shouldbe rinscd$ith snlall
poftionsol'0.100M NaOH. Iripcr2.00 mL ofthe final IlrSOr solutioninto a 25 mL volumctricilask.Titratc
thc solutionby thc proccdurcdescribcdin PartC.
2
,
a 21

4 Grarimetric and Volumetric AnNlrsis

a Reporl Namc
D Scction
Crarimetric and Yolumetric Analvsis
a DATA
4 B. Gravimetric Determinationof SulfateI o n
a Trial I l rial 2 Triai i Trial 4
4 Massol'BaSOrandilltcr paper,g
a Vass of filtcr paper.g
a
4 Nlassof BaSOIprecipitatc.
g

t Millimolcsof tsaSOr

a \,lillimolcsof HISOrthatrcacted
4 Volumcoi flnal solutionrcacted.mL
a
D IHlSOs].final solution.M

a IH:SOI]. stocksolution.\,1*
a IH]SOrl. initialsolution.Nl*
a AvcragclllrSOrl. initial soln. M
a
a c. volumetric Dcterminationof Acid Concentration

a Molariw of NaOH(aq
)
'Irial
I Trial 2 l rial i Trial -l
t lnitial NaOH burctrcading.mL
,
a Final NaOll burctreading.nr[-

t Volunrcof NaOHlaq)used.ml-

) Millimoles of \iaOl I
a Millimolcsoi HlSO3titrated
t
\ o l u r n co f l l n l l \ ( ' l u l t . r lnl r c t ' i J . m l
)
a IH1S()1].tinal solution.M
J' l l l r S O r l .s t o c ks o l u t i o nM. *
)
lHrSOrl. inrtialsolution.M*
a AveragcfHlSO.l. inirialsoln. M
)
a * Calculatcdbv takingthc successivc
dilutiousinto account.

a SampleCalculations
a
a
a
a
)
 !
!
22
!
Gravimetric and Volumelric Analvsis
!
!
Report Name Scction
!
QUlrsTroNs !
L Calculatethe conccntralions ofHlSOa fbr the initial solutionliom vour rcsultsfbr llartsB andC. Which a
r c s u l tB. o r ( . i s l i k c l l r L , h c n r o r c p r c c r lte\ p. 'l a r n .
!
!
!
!
a
2. There is an inhcrcnt flaw in the clrying proccdurc fbr thc gravimetric detcrminationthat causesthe mcasured !
massofBaSOato bc crroncouslyhigh. What is ir and how couldrheproccdurcbe improvcd?
!
t
!
C
!
3. Ifthc volumetricprocedurc
l,icldsmorc accuratcresults.why pcrlbrmthc gravimetricproccdureat all'l
!
!
t
J
t
4. If the BaSOIresiduewasbakcdin an ovcn at 100"Clbr severalhoursratherlhanair drying,what cliect
rvouldlhis havcon its nrassanclhow would the initial concentralion
!
ofHISOq bc afl'ccted(highcr.lo$er. or
no chanee)?ExDIain. !
J
t
t
!
C
,5.ll a 20.00ml- pipetrvasunkno*ingly uscdin pipctingihe flnal solutionin PartC. holv would thc calcularcd
initial concentration
ofH:SOr bc affecrcd(higher.lou'cr.orno chanee)'lExplain. a
a
!
!
G
f
t
t
;
f
t
!
4
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- 23

4 Gravimetric and Volumctric .tnrl\ris

4
Prelah Name Section
4
4
Gravimetric and ! olumetricAnalysis
4

) l. \\'haris thc principalpurposeofthis experinenr'l

4
)
4
4 I \\'rrtea balanccdcquationfbrthe reactionusedin lhc grrrr.imclric
analysispan of this cxperinrent.

4
4
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! I \\hal inusrbedoncwrththcsolrdbaiumsulfate
rvaste?
-,

-
)
J'
I -l l{) lX)rnl r,trnpr,)rimatclv
6 Nfsulfuricacidis trans
l'errcdto a I 00-mLvolutnetric llaskanddilurc'd
to rhc
rnlrkrritirdistillcJ$atcrandmixed.Then10.00rnl.ofthissolution is dilutedfurthcrro 100mL. Whatis
)
t l r c r r r r . h r i n . r l r h r sh s r s o l u t r o n . '
-
)
-
)
4
-
j ll).ll{, IrrL ol thc flnll acid solution is rcactcd with crcess barium chloridc to producc a prccipitate ofbarium
I
\ t r l l J t c( F h l r l l - ! n r o l ) .T h c d n s o l i d r v e r g h s0 . 3 9 7g . U s c t h i s r n a s sa D d t h c d i l u r i o n I o l u m e s r o c a l c u l a t c
- lhc actual molarity ol'thc sulluric acid in thc initial solurrou.

,D
a,
,D
a,
a
a
a
a
a
a
t
D