y.

com/)

(http://www.odinity.com)

StudentSweepstakes(http://www.odinity.com/chemistry/)

ypal.com/cgibin/webscr?cmd=_sxclick&hosted_button_id=LWUCKL4RKN72G)

FreeTitrationGuide
NewGuideABCofBasicTitrationbyMETTLERTOLEDO.Downloaditnow!Go
tomt.com/ABCTitrationGuide

Determination of Mn in Steel
OrganicChemistryLabs
(http://www.odinity.com/category/science/organicchemistry
lab/)
13870Views 3040Words

By:JunoKimandNicole
Introduction
Thegoalofthisexperimentwastodeterminethe
masspercentofmanganeseinanunknownsteelsample
usingmethodsofvisiblespectroscopyandvolumetric
analysis.Thetwomethodswerethenanalyzedand
comparedtodecidethebettermethodfordeterminingthe
compositionofMnintheunknownsteel.Inbothmethods,the
unknownsteelwasdigestedinhotconcentratedNitricacid,
HNO3,andanalyzedfortransitionmetals.Anaccurate
analysisofsteelcompositionisimportantbecausethemass
percentofcarbonandtransitionmetalsinthesteeldetermine
itspropertiessuchasstrength,conductivity,abilitytobe
alteredbyheat,andcorrosivenessthatultimatelydecidethe
steelsusage.Analloyisamixtureoftwoormoreelements,
oneofthembeingametal,andsteelisanalloyofiron

containingsmallamountsoftransitionmetals.Addingcarbon
toironcreatessteelwhichhasversatileusesforitsgeneral
properties.
Pertainingtothislab,knowingthecompositionofsteel
revealsthebestformofusage.Forexamplestructuralsteels
containalloyingelementslikeMnthatcanbeusedto
producecomplexstructuresandmachinepartswhiletool
steelshavehighercarbonmasspercentageandcontain
alloyingelementssuchaschromium.Comparedtoiron,steel
istougherwithhighstrengthandhastheabilitytogreatly
alterformthroughheattreatment.AddingChromiumtosteel
producesstainlesssteelthatresistscorrosionandadding
silicontosteelcreatessiliconsteelusedforelectronic
purposes.Thecompositionofsteelmustbedeterminedand
doublecheckedpriortoitsintendedusetoavoid
consequencesaslargeasabridgecollapsingduetotheuse
ofinadequatesteel.Themethodsofdeterminingthe
compositionofsteelcanalsobeusedtoanalyzethestrength
anddurabilityofalreadystandingstructuresthathavebeen
subjecttocorrosionandweatheringaswell.Themain
objectiveoftheexperimentwastodeterminethemanganese
compositionofthesteelunknownbythemethodsofstandard
additions,involvingvisiblespectroscopy,andvolumetric
analysis,involvingbacktitration.
ExperimentalMethods
I.StandardAddition
Thestandardadditionmethodusedvisiblespectroscopyto
determinetheconcentrationof
manganeseintheunknownsteelsample.Standardaddition
isusedtoaccountforthepotentiallyinterferingionsfrom
othertransitionmetals.2Tostartwith,thesampleofunknown
steelwasdigestedinhotnitricacid.Precisely1.0437gof
steelunknownand50mLof4Mnitricacid,HNO3,were
addedtoa250mLbeakerandbroughttoagentleboil.The

beakerwascoveredwiththewatchglasstoavoidlosingits
contentsthroughsplattering.Ittookclosetoanhourforallof
theunknownsteeltodissolvesoexcess4MHNO3was
addedduringthedigestiontodisplacetheevaporatedliquid
andkeepthevolumecloseto50mL.Afterdigestion,1.0gof
ammoniumperoxydisulfate,[(NH4)2S2O8],wasslowlyadded
tothebeakerandputtoboilfor15minutes.Duringtheboil,
peroxydisulfateoxidizesanycarboninthesampleinthe
reactionshownbelow:
2S2O82+C+2H2O>CO2+4SO42+4H+
Followingtheprocedure,0.1gofsodiumbisulfate(NaHSO3)
wasaddedwhileheatingandtheresultingsolutionwasleftto
cooltoroomtemperatureandtransferredtoa250mL
volumetricflaskwhereitwasdilutedwithdistilledwatertothe
mark.NotethatNaHSO3solutionwasaddedtoreduceany
permanganatethatmayhaveformedthroughthisreaction:
5HSO3+2MnO4+H+>2Mn2++5SO42+3H2O
Followingthesteeldigestion,thestandardMn
solutionwasprepared.Forthat100mgofMnwasdissolved
in10mLof4MHNO3andputtoboiltoremovenitrogen
oxides.TheresultingsolutionwasdilutedtothemarkwithDI
waterina1Lvolumetricflask.
Afterthenecessarysolutionswereprepared,standard
additionstookplace.Totalofsevensampleswereprepared
forthespectroscopyandineachsample20mLaliquotofthe
digestedsteelwasputintoa250mLbeaker.Then5mLof
85%phosphoricacidwasaddedtoeliminateiron(III)asa
sourceofinterferencewhentakingthespectroscopy.
SamplesofstandardMn2+andsolidpotassiumperiodate
wereaddedtothebeakeraccordingthetableIprovided
below:
TableI:CalibrationStandardSampleVolumes

Sample

Steel

H3PO4

Standard

KIO4

Mn

1blank

20mL

5mL

0mL

0g

20mL

5mL

0mL

0.4g

20mL

5mL

1mL

0.4g

20mL

5mL

2mL

0.4g

20mL

5mL

3mL

0.4g

20mL

5mL

4mL

0.4g

20mL

5mL

5mL

0.4g

Uponheating,KIO4oxidizesMn2+toapermanganateionin
thereactiongivenbelow:
2Mn2++5IO4+3H2O>2MnO4+5IO3+6H+
Eachofthesampleswereboiledfor5minutesandcooled
beforebeingdilutedina50mLvolumetricflask.Then,using
theUVVisiblespectrometer,absorbanceatthemax
wavelengthforpermanganateionwasmeasured.Themax
wavelengthforthepermanganateionis525nmandthe
analyzersaredesignedtomeasuretheabsorbanceina
particularwavelengthband1.Smallaliquotsofeachsample
wereaddedtoacuvettetomeasuretheabsorbanceanda
lineargraphwasexpectedwithnoabsorbancevaluegreater
than1.0foranyofthesamples.Attheend,theabsorbance
oftheblanksolution,containingnoMnorKIO4,was
deductedfromtheothersamplesabsorbancevalues.The

lineofbestfitfortheplotofconcentrationofaddedMn2+vs.
theabsorbancewasdrawntofindthexinterceptwhich
representedtheconcentrationofMnintheunknownsteel
sample.TheconcentrationofaddedMn2+wascalculatedby
usingtheconcentrationofthestandardMnsolutionasshown
below:
100.0ppm*(mLofMnadded/50mL)=concentrationofMn
inppm
II.VolumetricAnalysis
DeterminationofMnintheunknownsteelthrough
volumetricanalysisinvolvedtitrations.Astandardpotassium
permanganate(KMnO4),standardFerrousAmmonium
Sulfate(Fe(NH4)2(SO4)2),andanunknownsteelsample
werepreparedinlabforthetitrationoftheunknownsteel
sample.
TheKMnO4solutionwaspreparedbyglassfiltering100mL
of0.1MKMnO4solutionthroughasinteredglassfilter.The
resultingsolutionwasthentransferredtoa1Lvolumetric
flaskanddilutedtothemarkwithDIwater.Tostandardize
thissolution,solidsodiumoxalatewasputtodryinanoven
foranhour.Thenthree100mgsamplesofdriedsodium
oxalateweretransferredto250mLbeakersalongwith100
mLof0.9Msulfuricacid(H2SO4)andheated.Whileheating,
aburettewasfilledwiththepermanganatesolutionandits
initialvolumewasrecorded.Asingledropofthe
permanganatesolutionwasaddedtoeachofthebeakers
whileheatingandthetitrationscommencedoncethepink
colorfromthepermanganatedisappeared.The
reappearanceofthepinkcolormarkedtheendoftitrations.
Thereactionofpermanganatewithoxalateisasfollows:
2MnO4+5C2O42+16H+>2Mn2++10CO2+8H2O

Usingstoichiometry,theconcentrationofMnO4inthe
solutionwascalculatedusingtheformula:
0.100gC2O4*(1mol/88.01928gC2O4)*(2molMnO4/5
molC2O4)*(1/LofMnO4used)
TakingtheaverageofthethreetrialsyieldedaMnO4
concentrationof0.0148Minthestandardsolution.
ForthepreparationofstandardFe(NH4)2(SO4)2solution,
about12gramsofferrousammoniumsulfatehexahydrate
wereaddedtoa1Lvolumetricflaskanddissolvedin1:20
sulfuricacid(H2SO4).Thesolutionwasdilutedtothemark
with1:20H2SO4.Forthestandardizationprocess,25mLof
1:30nitricacid(HNO3)wasaddedtoa250mLErlenmeyer
flaskusingavolumetricpipette.Then25mLof
Fe(NH4)2(SO4)2wasaddedandtheresultingsolutionwas
titratedwithKMnO4untilthepalepinkendpoint.Theferrous
ionsreactwithMnO4intheredoxreactiongivenbelow:
MnO4+5Fe2++8H+>Mn2++5Fe3++4H2O
Usingstoichiometry,theconcentrationoftheferrousion,
Fe2+,wascalculatedusingtheformula:
(VolumeofKMnO4used)*0.0148MKMnO4*(5MFe2+/1M
MnO4)*(1/volumeofsample)
Takingtheaverageconcentrationsoffourtrialsyieldeda
Fe2+concentrationof0.0466Minthestandardsolution.
Forthepreparationofsteelunknownsample,0.2351gofthe
unknownsteelsamplewasaddedtoa250mLbeaker.The
manualstatesawholegramoftheunknownsteelshouldbe
used,butafterafewfailedtrialswiththefirstmethod,only
0.2351goftheunknownsteelwasleftforanalysis.Then50

mLofnitrousacidfree1:3HNO3wasaddedtothebeaker
andthecontentswereputtoagentleboilunderawatch
glasscover.Onceallthesteeldissolved,thebeakerwas
removedfromheatand0.5gofsodiumbismuthate(NaBiO3)
wasadded.AftertheadditionofNaBiO3,thecontentswere
boiledforanotherfiveminuteswhichafter,thesolution
turnedpurplesotherewasnoneedtoaddadditionalgrams
ofNaBiO3.Theresultingpurplesolutionwasremovedfrom
heatanddropsofsodiumsulfite(NaSO3)wereaddeduntil
thepurplecolordisappeared(3dropsused).Thenthe
solutionwasputtoboilandbecamerustorangeincolorafter
5minutes.Thebeakerwascooledinanicebathandallowed
tochillandafter,0.7gofNaBiO3wasaddedtoformasolid
NaBiO3insideapurplesolution.Thereactionofbismuthate
withmanganeseionisshownbelow:
2Mn2++5BiO3+14H+>2MnO4+5Bi3++7H2O
Totransferthesolution,asinteredglassfilterwasused
insteadoffilterpaperwhichtheMncouldreactwith.Thefilter
waswashedwith1:30HNO3andthesolutioninsidethe
beakerwasfilteredintoaflask.Afterfiltration4mLof85%
phosphoricacid(H3PO4)wasaddedtothefiltrateand
mixed.Theresultingsolutionwasthentransferredtoa100
mLvolumetricflaskanddilutedtothemarkwith1:30HNO3.
Afterthenecessarysolutionswereprepared,thetitrationof
theunknownsteel64commenced.25mLofthe
(Fe(NH4)2(SO4)2)solutionaswellas25mLofthesteel
unknownsolutionwereaddedtoanErlenmeyerflaskusinga
volumetricpipette.Thepurplecolordisappearedasthesteel
unknownreactedwiththeferrousions.Thenthesolutionwas
backtitratedtothepinkendpointwiththestandardKMnO4
solution.Inthisbacktitration,anexcessofstandard
(Fe(NH4)2(SO4)2)wasaddedtothesteelunknown,turning
thecolorclearastheferrousionsreacted.Thentheexcess

(Fe(NH4)2(SO4)2)wastitratedwiththestandardKMnO4until
theendpointwhichwassignaledbythereemergenceofthe
palepinkcolor.OncealltheFe2+ionshavereacted,MnO4
remainedinthesolutiontosignaltheendofthebacktitration
withthepalepinkendpoint.Thenetionicequationis:
MnO4+5Fe2++8H+>Mn2++5Fe3++4H2O
ThepercentageMninthesteelunknownwascalculatedby
theformulabelow:

Results
Theresultsfromthetwodifferentmethodswere
synchronized.TheMncontentsofalltheunknownsvaryfrom
0.10%to1.00%sobothmethodsgaveanacceptableresult.
TheBeerslawstatesthatabsorbanceisproportionalto
concentration.ThecalibrationplotofUVVissupportsthe
law.Beerslaw:
A=lc
Arepresentsabsorbancewithnounits.isthemolar
absorptioncoefficientwithunitsLmol1cm1.lrepresentsthe
pathlengthofthecuvetteandcistheconcentrationofthe
compoundinsolutionexpressedinmolL1.Anotherformof
BeerLambertslawis:
I=I010^cL3
Iisthetransmittedintensity,varyingwiththelengthLand
I0theincidentintensity.2UVandvisiblespectraareplotsof
absorbanceagainstthewavelengthinnanometers.Its

absorbanceisrelatedtoconcentrationbytheBeerLamberts
law.4
A=log(I0/I)=lc4
Discussion
TheweightpercentageofMnintheunknownsteel
samplewascalculatedas.51%with95%confidenceinterval
of0.71fromthevisualspectroscopymethod.Theabsorption
oftheblanksamplecontainingnostandardMnorKIO4was
measuredtobe0.0395.Themeasurementofthesecond
sampleyieldedabsorptionvalueof0.4020.Aftersubtracting
theblankabsorptionvaluethefirstsamplesabsorptionwas
0.3625.Thiswasalothigherthan0.1absorptionvaluethe
secondsampleshouldbeatsotheabsorptionvaluesalong
withthesteelsamplevolumewereadjustedthroughdivision
by4.The95%confidenceintervalvalueof0.71isveryhigh.
Thecauseoferrorinthismethodmostlikelyresultedfrom
thefactthatthesteelunknownsolutionhadsmall
precipitatesthatwouldnotdissolve.Sucherrormaybe
alleviatedbylettingthesolutionsitforaperiodoftimeuntil
theprecipitatesfalltothebottomoftheflask.Thensamples
couldbetakenfromthetopofthesolutionwithoutany
precipitateusingapipette.Thesteelunknownsampletook
45minuteslongerthananticipatedtodigestduringthelab
andevenafterthedigestionthereweresomeparticlesleftin
thesolution.Thiscouldbefromimpuritiesoftheunknown
steelsample.Thedigestionprocesscouldbespedupnext
timebypreparingahotHNO3todigestthesteelunknown.

FreeTitration
0.51%intheunknownsteelwiththe95%confidenceinterval
Guide
of0.16.Forthisexperiment,judgingfromthelowervaluefor
ThevolumetricanalysisalsogaveaMnconcentrationof

theconfidenceinterval,thismethodofbacktitrationgave
morereliableconcentrationofMninthesteel#64.Notethat

NewGuideABCof
insteadofusing1goftheunknownsteelsample,only

0.2351gwasusedbecausethatiswhatwasleftavailable.
BasicTitrationby

METTLERTOLEDO.

METTLERTOLEDO.
Downloaditnow!

ThevolumesofKMnO4usedtobacktitratethemixtureof25
mLunknownsteelsolutionand25mL(Fe(NH4)2(SO4)2)
wereveryconsistentandconsequently,theyyielded
consistentMnweightpercentagevaluesinthethreetrials.
TheweightpercentagesofMnforthethreetrialswerefound
tobe0.52%,0.51%,and0.50%withthelowvarianceof

www.mt.com/ABC-TitrationGuide

0.02.Thestandarddeviation,0.1414,wascalculatedby
squarerootingthevariance.Thestandarderror,whichwas
multipliedby1.96togive95%confidencemarginoferror,
wascalculatedbydividingthestandarddeviationbythe
squarerootofthenumberoftrials.Theconfidenceinterval,
calculatedas0.16,isstillhighconsideringthepreciseMn
percentagevalues.Thiscouldbeamendedbyincreasingthe
numberoftrialswhichwouldbringdownthevalues
(assumingthesame,preciseMnpercentagesare
calculated).
Comparingthetwo,bothmethodsgaveaveryprecise
concentrationofMnintheunknownsteel.Thevolumetric
analysishadamuchlowervalueforitsconfidenceintervalso
forthisexperimentthebacktitrationprovedtobethebetter
method.Thevisualspectroscopymethodwaseasierina
sensethattheUVVisiblespectrometermeasuredthe
absorbanceforeachofthepreparedcuvettesamplesleftto
begraphedandanalyzed.Howevertheslightproblemwith
thismethodisthefactthatitreliesonthelineofbestfitto
findtheconcentrationofMninthesample,makingitmore
pronetoerrorsbyinaccuratemeasurements.
Thevolumetricanalysisinvolvedpreparingtwostandard
solutionsandanunknownsteelsolutionbeforethetitrationof

FreeTitration
controlbecausethestandardsolutionsweremadeinlaband
Guide
theirconcentrationswerecalculatedusingstoichiometryfrom
thesteelunknown.Thismethodgavetheexperimentmore

theredoxequations.Itwasalsoeasytotellifacertain
titrationhasgonewrongbylookingatthevolumetricdata

NewGuideABCof
andnoticinganoutlieramongthevolumesusedforthesame
titration.Inthismethoditwascriticaltokeeptheprepared
BasicTitrationby
solutionsfrombeingaffectedbyimpurities.Thatwas

METTLERTOLEDO.

METTLERTOLEDO.
Downloaditnow!
solutionsintobeakersanddrawingsamplesfromthe

achievedbytransferringsmallamountsofthestandard
beakers.Thatpreventedthestandardsolutionsfrombeing
contaminatedthroughmultiplealiquotsdrawnbyapipette.
Conclusion:

www.mt.com/ABC-TitrationGuide

Thepurposeoftheexperimentwastofindtheconcentration
ofMninanunknownsteelsamplethroughthemethodof
standardadditions,involvingvisiblespectroscopy,and
volumetricanalysis,wheretheconcentrationwascalculated
throughbacktitration.Thevolumetricanalysisprovedtobea
bettermethodsincethestandardadditionmethods
calibrationplotoftheUVVisiblespectrometeryieldedafaulty
0.71marginoferrorundera95%confidencelevel.Such
marginoferrorisunacceptableconsideringtheMn
concentrationfallsoutsideprobablerangebetween0.1%and
1%afterjustonestandarddeviationawayfromthemean.
Afterbacktitrations,theMnconcentrationintheunknown
steelwasfoundtobe0.51%with0.16marginoferrorunder
a95%confidence.AddingMntosteelincreasesthesteels
toughnessandstrengthandanalysisoftheconcentrationof
Mnorothertransitionmetalsinsteelaswellascarboncan
revealthepropertiesofthesteelanditspracticalusage.

References
1Laverman,L.E.ExperimentsinAnalytical,Physicaland

InorganicChemistry,3rdEditionp.

FreeTitration
Guide
Green,DonW.,Perry,RobertH.PerrysChemical

14.
2

EngineersHandbook,8thEdition
McGrawHill:NewYork,2008,p.862.
NewGuideABCof

BasicTitrationby
METTLERTOLEDO.

METTLERTOLEDO.
Downloaditnow!

3Atkins,Peter.,Paula,Juliode.PhysicalChemistry,9th

EditionW.H.FreemanandCompany:
NewYork,2010,p.490.

4Mohrig,J.M.,Hammond,C.N.,Schatz,P.F.Techniquesin
rdEditionW.
OrganicChemistry,3
www.mt.com/ABC-Titration-

Guide
H.FreemanandCompany:NewYork,2010,p.429.

Explore It Now

FreeTitration
Guide
NewGuideABCof
BasicTitrationby
METTLERTOLEDO.

METTLERTOLEDO.
Downloaditnow!

www.mt.com/ABC-TitrationGuide

Home(http://www.odinity.com/) Contact(http://www.odinity.com/contact/)
SiteMap(http://www.odinity.com/sitemap/)
PrivacyPolicy(http://www.odinity.com/privacypolicy/)
Terms&Conditions(http://www.odinity.com/termsconditions/)
Copyright2014Odinity.com

FreeTitration
Guide
NewGuideABCof
BasicTitrationby
METTLERTOLEDO.

(http://www.twitter.com/odinity)
(http://facebook.com/odinity)
()