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EXPERIMENT1 DETERMINATIONOFDISSOLVEDOXYGENINWATER INTRODUCTION Thedissolvedoxygencontentisanimportantindexwhenconsideringitssuitabilityfortown supply.Agoodcleanpotablewaterwillgivedissolvedoxygenvalueclosetothetheoreticalvaluefor thesaturatedsolutionofoxygeninwater.Whenthereispollutionfromorganicmatterandother tradeeffluents,thedissolvedoxygenisupinvariousbiochemicaloxidationprocessesanditsisonly slowlyreplacedthroughsurfaceabsorption.Suchwaterwillgivealowdissolvedoxygencontent untiloxidationiscompleted.Adequatedissolvedoxygenisnecessaryforthelifeoffishandother aquaticorganisms. Themethodsdescribedbelowforthedeterminationofoxygeninwaterisbasedonthat devisedbyWinkler.Whenmanganesehydroxideisprecipitatedinthewatersampleitisquickly oxidizedtohigherhydratedoxides(probablyinthefourvalentstate)bythedissolveoxygen.Iodine, equivalenttothedissolvedoxygencontent,isthenliberatedonacidificationinthepresenceof iodine,anditmaybetitratedwithstandardthiosulphate.

te. INTERFERENCESANDPRETREATMENT Mostoxidisingandreducingsubstancese.gdissolvedorganicsubstances,nitriteions, highervalencymanganesecompounds,activechlorine,sulphideandsulphiteions,iron(II)andirons interfere. Theinfluenceofthedissolvedorganicsubstancescanbeexcludedbyconversionofthe manganesehydroxidesintooxygensensitivecarbonatesbysubsequentadditionof4cm3 ammoniumhydrogencarbonatesolution. Nitriteinacidicsolutionscatalysestheliberationofiodideandcanbedecomposedby additionofalkalineiodideazidesolution. Iron(III)ionsarerenderedinactiveduringthedeterminationbytheadditionof4cm3 phosphoricacidor2cm3potassiumfluoridesolution. EXPERIMENTAL Collectionofsample Collectthesampleinanarrownecked200300cm3glassbottlehavinganaccuratelyfitting groundglassstopper.Ifthewaterfromatap,passthewaterdownaglasstubetothebottomofthe bottleandallowwatertooverflowfor23minutesbeforeinsertionofthestopper.Whensampling streamwater,displacethewaterinthebottleseveraltimes,beforecollectingthesample.The

watertemperature,weatherconditionsandnatureofthewatersampleatthetimeofsampling shouldberecorded.Avoidinclusionofairbubblesinthesamplebottle. PROCEDUREfortheDeterminationofDissolvedOxygeninWater Carefullyremovethestopperfromthesamplebottleandaddinturn1cm3manganous sulphatesolutionfollowedby1cm3alkalineiodideazidesolution.Whenintroducingvarious reagentsintothefullbottleofsample,thetipsofthepipettesshouldbewellbelowthesurfaceof theliquid.Replacethestoppercarefullyaftereachadditionsoastoavoidinclusionofairbubbles. Thoroughlymixthecontentsbyinversionandrotationuntilaclearsupernatantwaterisobtained. Add1cm3concentratedsulphuricacidwiththetripofthepipettebelowthelevelofsolutionand againreplacethestopper.Mixwellbyrotationuntiltheprecipitatehascompletelydissolved. Pipetteintoa250cm3conicalflask100cm3ofthesolutionandimmediatelytitrateitagainst standardsodiumthiosulphate(0.0125moldm3)usingfreshlypreparedstarchsolutionasthe indicator(addwhensolutionbecomespaleyellow).Carryoutthetitrationinduplicate. StandardisationofSodiumThiosulphate Mix5cm3ofpotassiumiodidesolution(10%w/v)and10cm3ofthedilutesulphuricacid (1:3v/v)andadd2cm3of0.025moldm3potassiumiodatesolutioninthatorderinaglass stopperedflask.Addabout100cm3ofdistilledwater.Titrateimmediatelywithsodium thiosulphatesolutionuntilthecolourispaleyellow.Add2or3dropsofstarchsolution(freshly prepared)andcontinuethetitrationuntilthebluecolourjustdisappears. REPORT Explainthereactioninvolvedinthedeterminationofdissolvedoxygeninwaterusing Winklermethods. Establishtherelationship:10cm3of0.0125moldm3sodiumthiosulphate=1mg02. Reporttheresultinmgdm3andaspercentagesaturation(refertothetableattached) REAGENTS Managanoussulphatesolution Dissolve100gmanaganoussulphate(MnSO4.4H2O)in200cm3distilledwater. Alkalineiodideazidesolution Dissolve100gsodiumhydroxidein100cm3distilledwater.Allowtostandforsomedays,during whichanycarbonatepresentsinkstothebottom.Siphonoffalloftheclearliquid,add30g potassiumiodideand2gsodiumazideandmakeupto200cm3withdistilledwater.Storeinplastic container. SodiumThiosulphate(0.0125moldm3) Dilute125cm30.1moldm3sodiumthiosulphateto1literwithdistilledwater. Potassiumiodidesolution(0.025moldm3)

Dryanalyticalgradepotassiumiodateat120oC.Dissolve5.35gindistilledwateranddiluteto exactly1litre.Thissolutionisstableforlongperiodsifstoredinaglassstopperbottle. Potassiumiodidesolution(10%W/v) Dissolve10gKIin100cm3distilledwater. Potassiumfluoridesolution(10%W/V) Dissolve10gpotassiumfluorideindistilledwaterandmakeupto100cm3 Ammoniumhydrogencarbonatesolution Dissolve70gammoniumhydrogencarbonatein185cm3distilledwater. Phosphoricacid(85%V/V) Temperature o C O2content mgKg1 10 11.2 15 10.2 20 9.1 25 8.3 30 7.6 35 7.1

OXYGENCONTENTINAIRSATURATEDWATER

EXPERIMENT2 DETERMINATIONOFCHEMICALOXYGENDEMANDOFWATER INTRODUCTION Thechemicaloxygendemandgivesinformationontheoxygenrequiredbyawaterof oxidationofalmostallwatersolubleorganicsubstance,theexceptionsbeinganumberof compoundscontainingnitrogenandonlyveryslightlysolublehydrocarbons. Thefollowingmethodisusedtodeterminethequantityoforganicmaterialinasamplewhichmay beoxidisedchemically.Thesampleisrefluxedwithanaccuratelyknownamountofapotassium dichromateinalargeexcessofsulphuricacidfordefinitetime.Mostorganicsubstancesare completelyoxidisedandtheremainingdichromateisdeterminedbytitrationwithferrous ammoniumsulphate.Silversulphateisaddedasacatalystfortheoxidationandmercuricsulphate isaddedtoovercomechlorideinterference. Themethodshasatheoreticalrangeof0500mgdm3chemicaloxygendemand(COD)when usinga5cm3sampleandissuitableforhighlypollutedwater.Itshouldbenotedthatifalarger sampleisusedorganicmattermaynotbeoxidisedtothesameextentbythemoredilutereagents. EXPERIMENTAL (Allapparatusshouldbewashedinchromicacidbeforeusedandshouldbefreeofdust.Theground glassjointsshouldfreegrease). CollectionofSample Collectthesampleinanarrownecked200300cm3glassbottlehavinganaccuratelyfitting groundglassstopper.Whensamplingstreamwater,displacethewaterinthebottleseveraltimes beforecollectingthesample.Avoidcontamination. ProcedureforDeterminationofChemicalOxygenDemand Introduce10.0cm3ofthewatersampleinto100cm3roundbottomedflask,andadd2cm3 potassiumdichromate,2.5cm3mercuricsulphatesolution,1015mlconcentratedsulphuricacid containingsilversulphate,andanantibumpingrod.Heattogentle,butsteadyboilingoveran electrichotplateorheatingmantleandunderarefluxcondenser.Afterexactly45minutesboiling, allowtocoolbriefly,wash20cm3distilledwaterthroughthecondenserintotheflaskandthecool completelyincoldwater.Add2dropsofferroinsolutionandtitratetheexcesspotassium dichromatewithammoniumiron(II)sulphateuntilthecolourchangesfrombluishgreentoreddish brown. Determineablankwith10.0cm3distilledwaterunderexactlythesameconditions. StandardizationofAmmoniumIron(II)Sulphate

Add10cm3concentratedsulphuricacidcarefullyto20cm3waterandcool.Add2cm3 potassiumdichromateandtitratewithammoniumiron(II)sulphateusingdropsofferroinas indicator.Thecolourchangesfrombluishgreentoreddishbrown. REAGENTS StandardPotassiumDichromate(K2Cr2O7)(0.025moldm3) Dissolve7.3548gARpotassiumdichromateindistilledwater,andmakeupto1litre.Drythe potassiumdichromatefortwohoursinadryingchamberat1050Cbeforeweighingout. AmmoniumIron(II)Sulphate(NH4)2SO4.FeSO4.6H2O(0.0125moldm3) Carefullyadd20cm3concentratedsulphuricacidto200cm3water,mix,andcool.Dissolve4.902g ammoniumiron(II)sulphateinthecooledacidandmakeupto1litre. Mercuricsulphate Dissolve5gmmercuricsulphateinamixtureof25cm3concentratedsulphuricacidand225cm3 water. SilverSulphate/Sulphuricacid Dissolve5gsilversulphatein500cm3ARconcentratedsulphuricacidbymixing. FerroinIndicator Dissolved0.695gFeSO4.7H2Oindistilledwater(100cm3),add1,10phenanthrolinemonohydrate( 1.485g)andshakeuntildissolved.

EXPERIMENT3 COMPLEXOMETRICTITRATIONOFMETALION INTRODUCTION Thetitrationofmetalsbychelatingagents(complexometrictitrations)developedrapidly aftertheinitialworkbyschwarzenbachabout30yearsago.Themostimportantmoleculeinthis fieldisthedisodiumsaltofethylenediamainetraaceticacid(EDTA).EDTAformsstablecomplexes withalmostallmetals(ina1:1molecularratio)thereactionquicklyproceedingnearenoughto completionforallpracticalpurposeifasuitablepHismaintained. BecauseofitswideapplicabilityEDTAlacksselectivity.ControlofpHbybuffersolutions maysometimesbeusedtoenablemetalsinmixturetobetitratedindividuallyandsuccessfullyin thesamesolution.Maskingagentsarealsofrequentlyused,forexamplepotassiumcyanide stabilisessilver,cadmium,mercury,iron(II),zinc,cobaltandnickelagainstEDTAcomplexformation permittingthetitrationoflead,manganeseandthealkalineearthsinthepresence.Potassium iodidelikewiseusedinthemaskingofmercuryinthedeterminationofcadmium. BismuthformsastrongcomplexwithEDTAwhichpersistseveninquitestrongmineralacid (ph13).Consequentlytheselectivityofdeterminationofbismuthisquitegood.Thebismuth/EDTA complexisalsocolourlesssothatquitelargeamountsmaybedeterminedwithoutthedifficulties associatedwithintensityofcolour. CadmiummaybedeterminedbyEDTAtitrationinweaklyacidic,nearneutraloralkaline media. Mercury(I)disproportionateuponreactionwithEDTAHgoandtheHg(II)EDTAcomplex; consequentlynousehasbeenmadeofHg(I)incomplexometrictitrationwithEDTA.Themercury (II)complexis,however,verycomplexandcanbeutilizedoveraverygreatpHrange.Themasking actionofiodideionforHg(II)isvirtuallyspecificinEDTAtitrimetry. LeadmaybetitratedwithEDTAoverseveralpHrangesusingavarietyofindicators.Inacidicmedia (pH46),xylenolorangeissuitableindicator. Bismuthandleadmaybedeterminedtogetherinonesolutionusingthesameindicator.The bismuthisfirstdeterminedatpH12,thenleadatpH56usingxylenolorangeasindicatoreach time. CadmiumandmercuryaredeterminedtogetherwithEDTAsolutionanderiochromeblackT asindicator.Potassiumiodideisaddedtothetitratedsolution.Inthis,themercurychelateis convertedintopotassiummercuryiodide,liberatingEDTA.TheliberatingEDTAmaybetitratedwith standardzincsolution.

EXPERIMENTAL StandardisationofEDTA Weightoutaccuratelyabout0.15gofzincmetal(granulatedzinc),anddissolveinafew dropsof1:1nitricacid.Rinsethewatchglassandtheresultingsolutionquantitativelyinto250cm3 standardflask,makeuptothemarkwithdistilledwaterandmixwell. Measureout25cm3oftheaboutzincsolutionanddilutetoabout100cm3flask,add1or2 dropsofxylenolorangeindicatorsolutionanddilutetoabout100cm3withdistilledwater.Add hexaminesolution(10%w/v)unitthecolourbecomeredpurple,andadd12cm3more.Titrate thesolutionwithEDTA.Attheendpointcolourchangestoayelloworange CarryoutthestandardisationintriplicateandcalculatethemolarityoftheEDTAsolution. PROCEDUREforDeterminationofBismuthandLead Pipette10cm3ofsamplesolutionintoa250cm3conicalflask.Add1or2dropsxylenol orangeindicatorsolutionanddilutetoabout100cm3withdistilledwater.Titratewithstandard EDTAsolutionuntilthecolourchangesfromredpurpletoclearorangeyellow. Addhexaminesolution(10%w/v)untilthecolourbecomesredpurple,add12cm3more. ContinuethetitrationwithstandardEDTAsolutionuntilaclearorangeyellowcolourisobtainagain. Carryoutthedeterminationintriplicateandthecalculationofconcentrationsofthemetal ionsingdm3. PROCEDUREforDeterminationofCadmiumandMercury Pipette10cm3ofsamplesolutioninto250cm3conicalflask.Addtheaccuratelymeasuredexcessof standardEDTAsolution(35cm3willbesufficientinthiscase).Afterabout5minutes,add5cm3of ammoniaammoniachloridebuffer(pH10)andsomesolochromeblackT/KCIindicatormixure.Back titratetheexcessEDTAsolutionwithstandardzincsolution(fromtheEDTAstandardization)until thecolourchangesviabluetopurple. Add12gofpotassiumiodidetothetitratedsample.TitratetheliberatedEDTAwiththe standardzincsolutionintothepinkredcolourisobtainedagain. Carryoutthedeterminationintriplicateandcalculatetheconcentrationsofthementalions 3 ingdm . REPORT Explainthereactionsinvolvedusingequationsandaconsiderationofthestabilitycontents. Reporttheconcentrationofthemetalionsinthemixturesingdm3.

REAGENTS EthylenediamintetraaceticAcid(approx.0.01moldm3) Dissolve3.72gofethylenediaminetetraaceticacidinavolumetricflaksindistilledwaterandmake uptovolumeof1litre. XylenolorangeIndicator(0.1%w/v) Dissolve0.1xylenolorangein100cm3distilledwater. SolochromeBlackT/KCIIndicatormixture Mix1partofsolochromeblackTwith99partofpotassiumchloride(byweight)andstoreinbottle. Hexaminesolution(10%w/v) AmmoniaAmmoniaChloridesolution(pH10buffersolution) Dissolve54gammoniumchlorideinabout200cm3distilledwater.Add350cm3ammoniasolution (0.89)andmakeupto1litrewithdistilledwater. QUESTIONS 1) WhyshouldheatingassistanEDTAreaction? 2) WouldyouexpectpositiveornegativeerrorsinthedeterminationofCdandHg(orno error)?Ifso,why? 3) WhatwouldhappeninatitrationofmetalMwithEDTAwithindicatorHxIninthe presenceofametalionNthatformedanindicatorcomplexNinthatwasmorestable thanthecomplexNYandthecomplexMin. 4) TheformationcontentsforBiEDTAare1x1023and1.1x1018respectively.Inamixture ofbismuthandleadion(0.02moldm3forbothions)predictthepHatwhicheachof thementalioncanbedeterminedquantitativelyusingEDTAtitrations.(Attemptthis questionbeforeyoustarttheexperiment) REFERENCE 1) J.SFritz&G.HSchenk,Jr.,QuantitativeAnalyticalChemistry,2nded.,Allynandbacon Inc.,Boston1973,p.211 2) D.ASkoog&D.M.West,FundamentalsofAnalyticalChemistry,2nded.Holt,Rinehart andWinstoninc.,NewYork,1969,p.338 3) T.SWest,ComplexometrywithEDTAandrelatedReagents,3rdEd.,BDHChemicalsLtd, Poole,1969

EXPERIMENT4 ABSORPTIOMETRIC(UV)ANALYSISOFAPCTABLETS INTRODUCTIONS TheAPCtabletisacommonpharmaceuticalpreparationconsistingofamixtureofaspirin, phenacetin,andcaffeine.AcommonsizeAPCtabletcontains3.5grainsaspirin,2.5grains phenacetin,and0.5graincaffeine,plusperhapsasmallamountofstarchorotherinertmaterialas binder.(1grainisapproximately65mg).Eachofthesesubstanceshascharacteristicabsorptionin theultraviolet,theprinciplemaximalyingat277nmforaspirin,275nmforcaffeineand250nmfor phenacetin(allchloroformsolution). Themethodofanalysiscallsforthepartitionofthedissolvedsamplebetweenchloroform and4percentaqueoussodiumbicarbonate,theaspirinalonepassedintotheaqueouslayer.The phenacetinandcaffeineareanalyzedsimultaneouslyinchloroform.Theaspirinsolutionisacidified, extractedbackintochloroformanddeterminedspectrophometrically. EXPERIMENTAL GrindonepreweighedAPCtabletintofinepowder.Weighaccurately0.10gofthefinely grindedtabletintoa100cm3beakerandadd20cm3ofchloroform.Transferthecontents quantitativelyintoa125cm3separatoryfunnel,rinsingthebeakerwithalittlemorechloroformif necessary. Extractthechloroformsolutionwithtwo15cm3portionsofchilled4.0percentsodium bicarbonatesolutionandthenwithone10cm3portionofchloroform.Washthecombinedaqueous extracts*withtwo10cm3portionsofchloroformextractstotheoriginalchloroformsolution. Filterthechloroformsolutionthroughafilterpaper(toremovetracesofwater)previouslywetted withchloroformintoa50cm3volumetricflaskanddilutetothemarkwithchloroform.Futher dilute1cm3aliquotwithchloroform. Acidifytheaqueousextract*immediately(topreventhydrolysisoftheaspirin),stillinthe separatoryfunnel,with10cm3of1moldm3sulphuricacid.Theacidmustbeaddedslowlyin smallportions.Allowcompleteevolutionofcarbondioxide.Mixwellbyrepeatedinversion.ThepH ofthesolutionshouldbebetween1to2(pHtestpaper).Extracttheacidifiedsolutionwithfour10 cm3portionofchloroform,andfilterthechloroformextractsthroughachloroformwettedfilter paperinto50cm3volumetricflask.Dilutetovolume,andfurtherdilute1cm3aliquotto25cm3 withchloroform. Standardsolutionsinchloroform,containingrespectivelyabout75mgaspirin,10mgof phenacetin,and10mgofcaffeineperlitreareprovided.

Measuretheabsorbanceofstandardandunknownaspirinsolutionat277nmin1cmsilica cuverts.Correctforopticalinequalitiesinthecuvertsbyinterchangingtheblankandsolutionin eachcaseandaveragingtheresults. Withsimilarprecautions,measuretheabsorbanceofstandardsandunknowncontaining phenacetinandcaffeineatboth250nmand275nm. REPORT CalculatethequantityofaspirinbydirectapplicationofBeerslaw,andofphenacetinand caffeinebymeanofsimultaneousequations.Reporttheresultsintermsofmilligramsofeach constituentpertableandalsoasapercentageofthetotalweight. REAGENTS Spectrogradechloroform Usedchloroformsolutionsshouldbereturnedabottle,designatedforthepurpose(fortherecovery ofsolvent). Sodiumbicarbonatesolution(4%w/v) Dissolve4.0gsodiumbicarbonatein100cm3distilledwater.Addafewdropsconcentrated hydrochloricacidtoeachlitreofsolution. Sulphuricacid(1.0moldm3)

EXPERIMENTS5 SPECTROPHOTOMETRICDETERMINATIONOFMANGANESEINSTEEL INTRODUCTION Plaincarbonsteelcontainsacertainamountofcarbon,silicon,sulphur,phosphorusand manganese.Forspecialpurpose,varyingamountofotherelementssuchaschromium,vanadium, molybdenum,tungsten,titanium,nickel,cobalt,zirconiumandcopperareadded.Thephysical propertiesofsteeldependhighlyonthecontentoftheseelements.Thus,thequantitativeanalysis oftheseelementsisofgreatpracticalimportance. Inthisexperiments,manganeseisdeterminedspectrophotometricallyasthepurple colouredpermanganateion,MnO4.Thisiscommonlyusedandaccuratemethodofdetermining thelowconcentrationsofmanganeseissteel.Thesteelisdissolvedinnitricacidtogiveasolutionof manganese(II)ions.Theperiodateion,addedasthepotassiumsalt,KIO4,readilyoxidizes managanese(II)topermanganateaccordingtotheequation + 5IO4 + 3H2O = 2MnO4 + 5IO3 + 6H+ 2Mn2+ Thecalibrationcurveisdeterminedbymeasuringtheabsorbanceofaseriesofstandardised permanganatesolutionprepared.Thepermanganatecanbeaccuratelystandardisedusinga primarystandard,sodiumoxalate.TheOxalateanion,C2042,reducepermanganatetomanganese (II)inacidsolutionat60700Caccordingtotheequation 16H+ = 2Mn2+ + 10CO2 + 8H2O 2MnO4+ 5C2O42 + EXPERIMENTAL StandardisationofPermanganatewithOxalate Anapproximately1.000gMndm3solutionwillbesupplied.Standardisethissolutionwith oxalatesolutionasfollows;weighoutaccuratelyabout1.6gofsodiumoxalateandmakeupto250 cm3instandardflaks.Acidifya25cm3aliquotwith5cm3of5moldm3sulphuricacid,warmthe mixtureto60700Candtitratewithpotassiumpermanganateuntilafaintpinkcolorationwhich persistsforatleast30seconds.Fromthemeanofthreeconcordanttitrationscalculatethe concentrationofthepotassiumpermanganatesolution. DeterminationoftheCalibrationcurve

Accuratelydilutethestandardpotassiumpermanganatesolutionandprepareaseriesoffive standardssoastogiveanabsorbancerangebetween0.1to0.9.Measuretheabsorbanceofthese fivesolutionsusingaspectrophotometersetat525nm.Usewaterasreferencesolution. PROCEDUREfortheCalibrationcurve Accuratelyweighoutduplicatesample(approx.0.2g)ofthesteelsampleprovidedinto150 cm3beakers. Coverthebeakerwithwatchglass;add30cm3of1:1nitricacid.Warmtodissolvethe alloy(addfurthernitricacidifnecessary)andthenheattogentleboilingforafewminutestoexpel oxidesofnitrogen.Cautiouslyaddabout1gofammoniumperoxydisulphateandboilfor1015 minutes.Ifthesolutionispinkorcontainsbrownoxideofmanganese,addabout100.1gof sodiumbisulphateandheatforfurther5minutes.Cool,rinsedownthewatchglassandtransfer thesolutionquantitativelytoa100cm3volumetricflaskanddilutetothemarkwithdistilledwater. Makeuptothemarkandmixwell. Pipettetwo25cm3aliquotsofthesamplesolutionintosmallbeakers,add5cm3of phosphoricacid.Tooneofthetwoaliquotsadd0.5gofKIO4andboilthesolutionfor5minutes. Thesecondaliquotisnottreatedwithperiodateandwillserveastheblank.Cooltoroom temperature,transfereachaliquotquantitativelytoa50cm3volumetricflaskanddilutetothemark withdistilledwater. Measuretheabsorbanceofthesolutionandtheblankusingdistilledwaterasthereference solution. REPORTS Prepareacalibrationcurvefromthedataobtainedbyplottingabsorbanceversus concentration. Fromthemeasuredabsorbancevaluesoftheunknownsampleduplicates,determinethe concentrationofMnO4fromthecalibrationcurveaftermakingcorrectionduetosampleblank. Expressthefinalresultaspercentageofmanganeseinsteelturnings. REAGENTS PotassiumPermanganateSolution(1.00gMndm3) Dissolve2.877gpotassiumpermanganatein1literofdistilledwater. SulphuricAcid(5moldm3)

QUESTIONS 1) Whatisthepurposeofusingthefollowingchemicalsinthisexperiment?Briefdiscuss themwiththechemicalreactioninvolved. a) Nitricacid b) Bisulphite c) Phosphoricacid d) Peroxydisulphate 2) Couldwaterbeusedasablankinthemeasurementoftheabsorbanceofthestandard solutions? 3) Themeasurementoftheabsorbanceduetothesampleblankisessential Commentontheabovestatement.

EXPERIMENT6 DETERMINATIONOFPHOSPHATEINWATER INTRODUCTION Phosphateswhichareaddedtoboilerfeedtopreventscalingmaybeanalysedbya varietyofmethodsbutnormallythesedetermineonlytheorthophosphate. Pyrophosphateisreadilyconvertedtoorthophosphatebyboilinginacidicsolutionbut metaphosphaterequiresabout20minutesboilingin10%sulphuricacidtoget satisfactoryconversiontoorthophosphate.Calgonorsodiumhexametaphosphate whichisfrequentlyusedisnormallyhydrolysedintheboilerbuthydrolysisbyboilingin acidicsolutionmaybenecessaryparticularlyifthesampleisremovedsoonafterthe additionofcalgon. Themethoddescribedhereconsistsofaddingammoniummolybdatetoanacid solutionofthephosphate.Theammoniumphosphomolybdateformedisthenreduced tothebluecoloredloweroxidationstatemolybdenumcompoundbyreactionwith ascorbicacidat1000C.Theresultingcolorsarecomparedwithaseriesofstandards preparedfromphosphatesolutionofknowconcentrationinacolorimeteror spectrometer. EXPERIMENTAL PreparationofCalibrationCurves PrepareaseriesofstandardsolutionbymeasuringtheappropriatevolumeofP2O5 stocksolution(10mgdm3)aslistedintable1intoeachofaseriesof100cm3beakers anddiluteeachsampletoabout40cm3.Addtoeachsolution4.0cm3ammonium molybdatesulphuricacidreagent,mix,andthenadd0.1gascorbicacid.Coverwitha watchglass,heattoboiling,boilfor1minute,coolquickly,andtransferthesolution quantitativelyintoa50cm3volumetricflaksusingdistilledwatertocompletethe transfer.Dilutetothe50cm3markandmixwell. Measuretheopticaldensities(orabsorbance)oftheblankandstandardsolutionat 810nm. TABLE1

SolutionNo. 1 2 3 4 5 6

VolumeofP2O5stock solutionused,cm3 1 2 3 4 5 10

Concentrationmgdm3 P2O5 0.2 0.4 0.6 0.8 1.0 2.0

PROCEDUREAnalysisofBoilerWaterSamples Filterthetestsamplethroughafinefilterpaper.Sludgeinthetestsolutionmay containphosphateandgiverisetoincorrectphosphatevalues. Measure20cm3ofthesampleintoa100cm3beaker,neutralisethesolutionwith 0.5moldm3sulphuricacidanddilutetoabout40cm3.Addammoniummolybdate sulphuricacidreagent,ascorbicacid,andtreatinthesamemannersamplesusedinthe preparationofthecalibrationcurve.Measuretheopticaldensity. Wherethesampleisintheformofhexametaphosphate,neutralizethe20cm3 samplewith0.5moldm3sulphuricacid1cm3conc.Hydrochloricacidandevaporate justtodryness.Thendiluteto40cm3andproceedasbefore. Report CalculatetheconcentrationofP2O5inthetestsample.Explainthereactions involvedusingchemicalequations. REAGENTS AmmoniumMolybdatesulphuricAcid Dissolve10gammoniummolybdateindistilledwateranddiluteto100cm3.Carefully addthissolutiontoacoldmixtureofconcentratedsulphuricacid(150cm3)andwater (150cm3).Protectthesolutionfromlightinaplasticbottle. AscorbicAcids Asrequireddissolve1gascorbicacidin10cm3distilledwater.Add1cm3ofthis solutionfor0.1ascorbicacid. StockPhosphateSolution Dissolve0.7669gofpotassiumdihydrogenorthophosphateindistilledwateranddilute to1liter. StandardPhosphateSolution(10mgdm3P2O5) Dilute25cm3oftheabovestocksolutionto1literwithdistilledwater.

EXPERIMENT7 ANALYSISOFTRACEMETALSBYFLAMEEMISSIONANDATOMICABSORPTION SRECTROPHOTOMETRY INTRODUCTION Thisexperimentisdesignedtoacquaintinstudentwiththetechniquesofatomic emissionandabsorptionspectroscopyfortheanalysisofmetals.Theuseofa multipurposeemissionabsorptioninstrumentisillustratedforthedeterminationofthe sodiumbyemissionandmagnesiumbyabsorption.Theeffectofionizationinterference onthedeterminationofsodiumandchemicalinterferenceontheestimationof magnesiumareinvestigated. EXPERIMENTAL PROCEDUREforEmissionAnalysisofSodiumIon Usingeitheraburetteorpipette,makeupin50cm3volumetricflaskthesolutionslisted intable1. TABLE1 Concentration(mgdm3) SolutionNo 1 2 3 4 5 6 7 8 9 10 11 Na+ 1 5 10 30 50 0 1 5 10 30 50 K+ 0 0 0 0 0 200 200 200 200 200 200

Turntheinstrumenton,ignitetheflame,andallowtheinstrumenttowarmupforabout 1015minutes.Settheinstrumentaccordinglytoinstructionsgivenintheoperation manual.Setthemonochromatorat589.0wavelengthandsetemissionto100%with the50mgdm3Nasolutionand0%withdistilledwater.Measuretheemission intensitiesofsolution111,risingtheburnerbetweenmeasurementsbyaspirating distilledwater. TabwaterandunknownNasampleswereaspiratedlikewise.Also,tabwaterand unknownsodiumsampleswithaddedpotassium(2000mgdm3)weredeterminedfor

thesodiumcontents.ThetabwaterandunknownNasamplesolutionshouldbediluted by5timnes. REPORT Plottheemissionintensityversusconcentrationofsodiumionfromthe experimentaldata. Calculatethesodiumionconcentrationinthetabwaterandunknownsodium samplesinthemgdm3. Comparethedateobtainedwithandwithouttheaddedpotassium.Comparethe results. PROCEDUREforAbsorptionAnalysisofMegnessiumIon Usingeitherapipetteorburette,makeupin50cm3volumetricflaskthesolution listedinthetable2.UseMgSO4,stocksolution,and0.5moldm3hydrochloricacidfor dilution. TABLE2 Concentration(mgdm3) SolutionNo 1 2 3 4 5 6 7 8 9 10 11 Mg2+ 0.2 0.5 1.0 1.5 2.0 0.0 0.2 0.5 1.0 1.5 2.0 La3+ 0 0 0 0 0 1000 1000 1000 1000 1000 1000

Optimizetheinstrumentconditionsaccordingtotheoperationmanual.Setthe monochromatoratthe285.2nmwavelengthandsetthezeroabsorptionbyaspirating 0.5moldm3hydrochloricacidinfoflame.Usingsolutionno5(2mgdm3)adjustby

rotatingtheburnerheadsoastogetanabsorbanceofabout0.8only.Measurethe absorbanceofthissolution111,rinsingtheburnerbetweenmeasurementsby aspirating0.5moldm3hydrochloricacid. Dissolveabout0.1g(accuratelyweighted)ofthecementsamplein10cm3 concentratedhydrochloricacidanddilute250cm3inavolumetricflask.Furtherdilution maybenecessaryinorderthattheabsorbanceiswithintherangeofthecalibration curve. Watersampleandcementsamplesolutionwithandwithoutaddedlanthanumsare aspiratedinordertodeterminethemagnesiumconcentrations.TheMgsolution shouldonlybediluted5timesinbothcases. REPORT Plottheabsorbanceversusconcentrationinthetapwaterandcementsampleby comparisonwithcalibrationcurve.ExpressmagnesiumaspercentageMg0inthe cementsample. Comparetheresultsobtainedwithandwithoutaddedlanthanumion. REAGENTS SodiumStockSolution(1000mgdm3) Dissolve2.543gARsodiumchloridein1literofdistilledwater. PotassiumStockSolution(5000mgdm3) Dissolve9.534gpotassiumchloridein1literdistilledwater. MagnesiumstockSolution(500mgdm3) Dissolve5.069gMgS04.7H20(ortheequivalentforotherhydrate)in0.5moldm3 hydrochloricacid,andmakeupto1liter. LanthanumStocksolution(5000mgdm3) Dissolve11.700gLa(N03)3in0.5moldm3hydrochloricacidanddiluteto1liter. HydrochloricAcid(0.5moldm3)

QUESTIONS 1) Whyisflameemissionamoresensitivetechniqueforsomecations,mainlythe alkalineandearthalkalications,whileatomicabsorptionhasgreatersensitivityfor othercations,suchasthetransactionmetalions? 2) WhatdifficultieswouldyouanticipateintheanalysisofthemixtureofNa+andK+? 3) ExplainwhyASSissoselective,i.ewhydoetherelementsnotusuallyinterfereinthe analysis? 4) Whydoesthedeviationfromlinearityofabsorptionversusconcentrationincrease withincreasingconcentration?

EXPERIMENT8 SOLVENTEXTRECTIONOFCOPPER(II)COMPLEX INTRODUCTION Atypicalseparationofmetalionsbysolventextractionconsistsofextractingoneofthe metalionsfromaqueoussolutionintoanorganicsolvent.Conditionsmustbefoundwhichwill permitquantitativetransferofthemetalionfromanaqueoustotheorganicphaseandwhichwill avoidtransferofappreciableamountsoftheothermetalionspresent.Ausefulwayof characterizingthedegreeoftransferofametalionistodeterminethedistributioncoefficient,Dm. ThisexperimentinvolvesthedeterminationofDmfortheextractionofCu(II)with8hydrochloric acidintochloroform.TheeffectofpHontheextractionprocessisinvestigatedandthevalueofy (thenumberofligandsbondedtothemental).pH1/2(thepHatwhich50%ofmetalisextracted) andthecompletenessoftheextractionprocessareevaluated. EXPERIMENTAL 1) Pipetteexactly1.0cm3ofstandardCu(II)solutionto125cm3separatoryfunnel.Add49 cm3(usemeasuringcylinder)ofdistilledwaterandabout25dropsof1moldm3HCI.Then add1.0cm3of0.10moldm38hydropxyquinolinesolutionand19.0cm3ofpure chloroform.Stopperthefunnel,graspitbythestopperandstopcock,andshake(avoid vigorousshaking!)forabout2minutesbytiltingthefunnel.Allowedthefunneltostandfora fewminutesandrepeatthe2minutesshakingforafurtherfourtimes.Nowallowthelayers toseparateandbecomeclear.Carefullydrainoffthechloroformlayerthroughapieceof cottonwool(orfilterpaper)barelymoistenedwithchloroformdirectlyintoglasscellsand measuretheopticalintensityoftheextractat450nmusingUnicamSP600 spectrophotometer.Asreagentblankuse1.0cm3of(0.1moldm38hydroxyquinolinein chloroform)dilutedto20cm3. Carefullypourtheaqueouslayerintoa50cm3beakerandmeasurethepHofthe solutionaccuratelyusingapHmeter. 2) Repeatstep1with23,20,17,14,11,8,5and0dropof0.1moldm3HCI 3) TheopticaldensitydataobtainedcanbeconvertedtoamountofCu(II)presentinthe chloroformphasebyjustreadingitfromagivencalibrationcurvepreviouslyprepared. REPORT 1) Calculatetheamountofcopper(II)intheorganicandaqueousphasesandthencalculatethe distributioncoefficient,Dm,foreachextraction.PlotDmagainstpHdeterminethenumber ofligandsthatreactwitheachCu(II)metalion. 2) Calculatethepercentageofextraction(%E)fromthedataobtained. 3) DeterminepH1/2valueforCu(II)8hydroxquinolatecomplex. REAGENTS HydrochloricAcid(1.0moldm3)

StandardCopperSulphateSolution(0.5mgcm3Cu(II)) Dissolved3.932gCuS04.5H20in2litreofdistilledwater 8hydroxyquinolineSolution(0.1moldm3) Dissolve1.452gofsaltinchloroformandmake100cm3 QUESTIONS 1) Whydoyoudraintheextractthroughapieceofcottonwool(orfilterpaper)? 2) SuggestanothermethodsofobtainingthevalueofDm. 3) Usingchemicalequation,explainthereaction(s)involvedintheextractionofCu(II).Draw thestructureofthecopperhydroxyquinolinatecomplex.

EXPERIMEN9 DETERMINATIONOFFLUORIDEUSINGSPECIFICIONELECTRODE INTRODUCTION AconventionalglasselectrodeusedinthemeasurementofpHdevelopselectricalpotentialin responsetotheactivityofthehydrogenioninasolution.Aspecificionelectrodeisdesignedto developapotentialinresponsetotheactivityoftheionforwhichitisselective.Indilutesolution theactivityofanionapproachesconcentrationandthussuchelectrodesareusefulfordetermining theconcentrationofionundertheseconditions.Thisisparticularlysowhenelectroderesponseis comparedwithacalibrationgraphusingsolutionofknownconcentration.Thespecificionelectrode mayalsobeusedasindicatorelectrodetodetecttheendpointofatitration.Awiderangespecific ionelectrodeisnowavailable.Theseincludeelectrodesspecificforbromide,cadmium,chloride, cupric,cyanide,fluoride,iodide,lead,nitrateandsodiumions. Thesensingelementintheelectrodeisaspeciallytreatedcrystaloflanthanumfluoride,butthe electrodemustbeusedinconjunctionwithareferenceelectrodesuchascalomelelectrode.The referenceelectrodemaybeseparatebutthefluorideelectrodeisavailableasacombination electrodewiththereferencebuiltintotheelectrode.Therelationshipbetweenionactivityand electrodepotentialislogarithmic. RT E=EA2.3logaf(Eaisaconstant) Whereafistheactivityofthefluorideioninthesamplesolution.Whensensingananionthe electrodepotentialbecomesmorenegativewithincreasingionicactivity.At250Ctheelectrode potentialchangesby59.1mvforatenfoldchangeinionicactivityiftheionbeingmeasuredis monovalent.Thelowerlimitofdetectionisdeterminationbythesolubilityoftheelectrodesensing element.