chemical monitoring and management notes distro copy
TRANSCRIPT
CHEMICALMONITORINGANDMANAGEMENTNOTES–ROHANBARAR2016
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ChemicalMonitoringandManagementNotesSection1Muchoftheworkofchemistsinvolvesmonitoringthereactantsandproductsofreactionsandmanagingreactionconditions
• Outlinetheroleofachemistemployedinanamedindustryorenterprise,identifyingthebranchofchemistryundertakenbythechemistandexplainingachemicalprinciplethatthechemistuses
Ø Name:BurhanGemikonakliØ PlaceofWork:Qenos,BotanyNSWØ BranchofChemistry:AnalyticalChemistryØ TypeofManufacture:
• EtheneàEthane(C2H6àC2H4+H2)(cracking)• EthaneàPolyethylene(nC2H4à(C2H4)n)
Ø JobDescription1. Todeterminethenature(qualitative)andamount(quantitative)ofanyimpuritiesintheethene
andpolyethene2. Tomonitorandanalyseproductionwastebeforedischarging3. Toadjustreactionconditionstomaximiseyieldinthecrackingfurnace
Ø ChemicalPrinciple• ManyindustriesuseGLC(GasLiquidChromatography)orGSC(GasSolidChromatography)for
analyticalpurposes.Theseparationisbasedonthesolubilityofthecompoundinthestationaryphase.
• Ifthestationaryphaseispolarthenthepolarsubstancesinthesampleinjectionwillcomeoutlast,as
theyaremostsoluble.• Thepositionofthepeaksonthegraphidentifieswhichcompoundsarepresentinthesample,while
theheightofthepeaksindicatestheamount.• Forexample,ifamixturecontainingasmallamountofethanol,amoderateamountofethane,anda
largeamountofethanewasusedasthesampleinjection,theresultantgraphwouldidentifyethaneasthefirstcompoundtoexit(highpeak),followedbyethane(moderatepeak)andfinallyethanol(lowpeak).
• Asinglepeakonthegraphindicatesapuresample• Ingassolidchromatography,adsorption(moleculesofasubstancecollectonthesurfaceofanother
substance)isused.Thegasthatneedstobeanalysedispassedintothesampleinjector,andthedifferentcomponentsofthegashavedifferentadsorbingstrengthtothesolid.Somecomponentsadsorbstronglyontothesolid,andsomoveasthesolidmovesthroughthecolumn.Thecomponentsthatdonotadsorbwellarecarriedthroughbyaninertgasandexitthecolumnmuchfaster.
• Identifytheneedforcollaborationbetweenchemistsastheycollectandanalysedata
Ø Collaborationbetweenchemists:• Increasesreliability• Decreasestheoccurrenceoferrors,thusincreasesaccuracy• Conditionscanbeadjustedtomaximisetheefficiencyofanindustrialprocess(e.g.taskdelegation,
etc.)
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• Manychemicalproblemsrequireexpertiseandin-depthknowledgefromawiderangeofchemicalbranches
• EXAMPLE:Polymerchemistsworkandcollaboratewithprocessengineerstoadjustreactionconditionssothatmaximumyieldsofpolymercanbeobtained
• Describeanexampleofachemicalreactionsuchascombustion,wherereactantsformdifferentproductsunder
differentconditionsandthuswouldneedmonitoringØ Thecombustionoffossilfuels,suchasoctane,havetobemonitoredonindustriallevels,asinefficient
molesofoxygencanleadtoincompletecombustion,formingtoxiccarbonmonoxideandcarbonsoot,bothofwhichcandamageandpollutetheenvironment
Ø Incompletecombustionalsodoesnotreleaseasmuchenergyascompletecombustion,makingcompletecombustiondesirablefromaneconomicstandpoint
Ø Carbonmonoxideinhibitshumanbloodfromeffectivelycarryingoxygen,andcancausedeathinhighconcentrations
Ø Sootisalsoamajorhealthrisk,asitistoxicandaestheticallydispleasing• 2C8H18(l)+25O2(g)à16CO2(g)+18H2O(g)(CompleteCombustionofOctane)• C8H18(l)+6O2(g)à5C(s)+3CO(g)+9H2O(g)(IncompleteCombustionofOctane)Ø Thusmonitoringisrequiredtoprovideasufficientair-to-fuelratio,sothatcompletecombustiontakes
placeandtheoutputofrequiredproductsishighandthecreationofunwantedsubstancesislowØ NOTE:Ifthefueltooxygenratioistoolow,oxidesofnitrogencanbeformedinstead,whichisa
respiratoryirritantandcancontributetotheformationofacidrain• N2(g)+O2(g)à2NO(g)• 2NO(g)+O2(g)à2NO2(g)Ø NOTE:Ifthereweresulfurornitrogenimpuritiesintheoctane,combustionwouldleadtotheproduction
ofSO2andNOx.Whenthesedissolveinrainwater,theywillresultintheformationofacidrainwithapH<5.Thiswillresultinanincreaseoftheacidityofwaterwaysandtheburningoftreeleaves.• SO2(g)+H2O(l) H2SO3(aq)• 2H2SO3(aq)+O2(g)à2H2SO4(aq)ßAcidRain
• Gather,processandpresentinformationfromsecondarysourcesabouttheworkofpractisingscientists
identifying:thevarietyofchemicaloccupationsandaspecificchemicaloccupationforamoredetailedstudyØ Chemistswillmonitorandmanageindustrialprocesses.Thishastobedonetoensure:
1. Reactionsproceedefficiently(highyieldandfastproduction)àDevelopmentchemist,Plantchemist2. TherawmaterialsandproductsarepureàAnalyticalchemist,Quality&controlchemist3. TheworkplaceissafeandhealthyàWorkHealth&Safetychemist4. WastesdonotpollutetheenvironmentàEnvironmentalchemist
Ø DifferentTypesofchemicaloccupations• PolymerChemists• NuclearChemists• AgriculturalChemists• PetroleumChemists• Biochemists
• MetallurgicalChemist• PharmaceuticalChemist• Electrochemist• ForensicChemist• EnvironmentalChemist
ChemicalOccupation WorkDone
PharmaceuticalChemist ResearchesanddispensesdrugsformedicinaluseAnalyticalChemist Analysesconcentrationsofchemicalsinwater,food,ores,andmanufacturedproductsand
developspurificationtechniquesBiochemist ResearcheschemicalreactionsinlivingthingsandorganismsIndustrialChemist MonitorsthemanufacturingprocessofchemicalsOrganicChemist Studiesthechemistryofcarboncompounds(Plastics,fibres,syntheticfibres,medicinaldrugs)PolymerChemist Developsnewlongchainmolecules(polymers)suchasplastics,syntheticfibresandadhesivesInorganicChemist Studyofsynthesis,structureandpropertiesformedbymetallicandnon-metallicelementssuch
asnitrogen,sulfur,phosphorusandchlorinePhysicalChemist Useofphysicalandmathematicalmethodstostudythelawsthatgovernnature–ratesof
reactions,structureofcompoundsandthenatureofchemicalbonding
CHEMICALMONITORINGANDMANAGEMENTNOTES–ROHANBARAR2016
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EnvironmentalChemist Monitorwater/airsamplesforpollutantsusinginstrumentalanalysisandotherprocedures.Analyseandassessenvironmentaldata.AdviseexternalbodiessuchastheEnvironmentalProtectionAgency(EPA)
IndustrialChemist EnsurethatchemicalreactionshavehighyieldandrateofreactionDesignmonitoringproceduresandqualitycontroltestingCheckthatrawmaterialsmeetspecificationsMonitorweatherproductsaresufficientlypureEnsurethateffluentsandsolidwastesfromthefactorydonotexceedallowablelimitsofpollutants
Section2Chemicalprocessesinindustryrequiremonitoringandmanagementtomaximiseproduction
• IdentifyanddescribetheindustrialusesofammoniaAmmoniaisaverystrong,pungentandchokinggasthatissolubleinwater.ItisproducedbytheHaberprocessandisanindustriallyimportantchemicalØ Fertilisers
§ Compoundswhichpromotethegrowthofplants,andthusprovidesignificantcommercialbenefitstotheagriculturalandhorticulturalindustries
§ 80%oftheammoniaproducedbyindustryisusedintheproductionoffertilisers§ 2NH3(g)+H2SO4(aq)à(NH4)2SO4(aq)§ NH3(g)+HNO3(aq)àNH4NO3(aq)§ NH4NO3isalsousedasafertiliserasNitrogenisaplantnutrient,anditisanacidicsaltthatwill
increasetheacidityofsoil(goodforsomeplants,liketomatoes)Ø Explosives
§ UsedinbothTNT(Trinitrotoluene)andDynamite(Trinitroglycerin)§ NH3isoxidisedtoHNO3andusedtomakeexplosives
Trinitrotoluene Trinitroglycerin
Ø Fibres§ Nylon-6àUsedforgears,fittings,andbearings
Ø HouseholdCleaners
§ CloudyAmmonia§ NH3(g)+H2O(l) NH4OH(aq)ßAlkalithatwilldissolveinoilandproteins
Ø CationicDetergents§ Cationicdetergentsareusedinfabricsoftenersandhairconditioners§ Longhydrocarbonchain,followedbyNbondedto3CH3groups,cappedwithaCl-ion
• Identifythatammoniacanbesynthesisedfromitscomponentgases,nitrogenandhydrogen
Ø Ammoniaisproducedindustriallyfromitscomponentgassesinanexothermic,catalyticandreversiblereaction(HaberProcess)
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Ø N2fromtheairisconvertedtonitrogencompounds(nitrogenfixation)bylightningorbythenitrogenfixingbacteriaintheroodnodulesoflegumessuchasbeansandsnowpeas.N2isverystableduetoitsstrongcovalenttriplebond,whichmustbebroken.
Ø IntheHaberprocess,N2isobtainedfromtheatmospherewhileH2isobtainedfrommethanegas(CH4)withaNickelcatalyst
2CH4(g)+O2(g)à2CO2(g)+4H2(g)
TheN2andH2gassescanthenbesenttotheHaberProcess
• Describethatsynthesisofammoniaoccursasareversiblereactionthatwillreachequilibrium
Ø ThesynthesisofammoniaisareversiblereactionthatwillreachequilibriumØ Theforwardreactionisexothermic,andreleases92kJofenergypermoleØ TherateoftheforwardreactionandreversereactionareequalwhenthesystemreachesequilibriumØ TheconcentrationswillremainconstantafterequilibriumisreachedØ ThisreactionissubjecttoLeChatelier’sPrinciple*,andcanbeinfluencedthroughchangesin
concentration,pressure,volumeandtemperature.*Whenanysystematequilibriumissubjectedtochangeintheconcentrationofreactantsandproducts,temperature,volume,orpressure,thenthesystemreadjustsitselftopartiallycounteracttheeffectoftheappliedchangeandanewequilibriumisestablished.
• Identifythereactionofhydrogenwithnitrogenasexothermic
Ø ThereactionbetweennitrogenandhydrogengasisexothermicØ Ø Theenergyabsorbedtobreakthetriplecovalentbondbetweennitrogenandthesinglecovalentbond
betweenhydrogenISLESSTHANtheenergyreleasedinformingthebondsinammonia.Therefore,theforwardreactionisexothermicasheatisreleased.
• Explainwhytherateofreactionisincreasedbyhighertemperatures
Ø Temperature=RateofReactionØ Particleshavehigherkineticenergiesandmoremoleculeshavesufficientenergytoovercomethe
activationenergybarriertobreakthecovalentbondswithindiatomicN2andH2Ø Increasednumberofparticlecollisionsbetweenreactantmoleculesperunitvolumeperunitoftime,
hencegreaterreactionrateØ NOTE:Thereactionrateisincreasedforboththeforwardandreversereaction
• ExplainwhytheyieldofproductintheHaberprocessisreducedathighertemperaturesusingLeChatelier’s
principleØ ByLCP,increasesintemperaturefavourthereverse(backward)endothermicreactionandsothe
equilibriumshiftslefttoreducethisstressandconsumetheexcessheatandhencereducesyieldofammonia
• ExplainwhytheHaberprocessisbasedonadelicatebalancingactinvolvingreactionenergy,reactionrateand
equilibriumØ BalancingactbetweenyieldofNH3andtherateandyieldatwhichNH3canbeformedthatisboth
reasonableandeconomicallyfeasible
CHEMICALMONITORINGANDMANAGEMENTNOTES–ROHANBARAR2016
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§ Compromisebetweencost,safety,reactionenergy,reactionrateandthepositionofequilibrium(yield)
§ Theconditionsrequiredtomaximisethesefactorsareoftenconflicting§ Catalyst:Themagnetite(Fe3O4)catalystisusedasitprovidesanalternatereactionpathwaywith
aloweractivationenergy,allowingthereactionratetoremainhighdespitemoderatetemperatures(providesasurfaceforthereaction)
§ Temperature:LCPpredictsthatlowertemperatureswillproduceahigheryieldofammoniaatequilibrium,asitisanexothermicreaction.Iftemperatureistoolow,therateofreactionbecomesuneconomicallyslow(collisionsreducethuslowerrateofreaction),thusacompromisetemperatureof450–500degreesisused.
§ Pressure:LCPpredictsthatlowertemperatureswillproduceahigheryieldofammoniaatequilibrium,astherearefewermolesofgasontheproductssidethanthereactantsside.Increasingpressurewillalsoincreasereactionrate.However,havingthepressureveryhighisexpensivetomaintain(duetotherequiredthicknessofthereactionvessel).Safetyfactorswiththeuseofhighpressurevesselsmustalsobeconsidered.Acompromisepressureof200to300atmospheresisused.
§ RemovingAmmonia:Ammoniaisproducedisseparatedfromunreactednitrogenandhydrogenbyliquefyingitunderpressure/cooling.Theunreactednitrogenandhydrogenarethenrecirculatedintothereactionchambertobeusedagain.Thisisdonedespitethecostsofthisprocess,becauseremovingammoniapreventsthereactionreachingequilibrium(Yield=98%)
§ Individualplantsdecideonprofitability:slow(highyield)orfast(loweryield)Ø COMPROMISE:Carriedoutat450degreesCelsiusandat250atmospheresofpressurewithFe3O4catalyst
• Explainthattheuseofacatalystwilllowerthereactiontemperaturerequiredandidentifythecatalyst(s)usedin
theHaberprocessØ Magnetite(Fe3O4)isusedasacatalyst.Theironinmagnetite
providesasurfaceforthegasphasereaction.(Itdoesthisbyadsorbingthereactingmoleculestoitssurface,whichdistortsandweakenstheirbondssotheycanbemoreeasilybroken)
Ø Theheterogeneouscatalysttakespartinthereactionbutdoesnotget‘usedup’.Therefore,onlyasmallamountofmagnetiteisrequiredtoincreasetherateofreactionbyloweringtheactivationenergy(andthusallowingforlowertemperatures).
Ø ItisimportanttonotethatthecatalystdoesNOTreducetheconcentrationoramountofNH3produced–itsimplyincreasestherateoftheforwardandreversereaction.Thismeansthatequilibriumisestablishedfaster.
Ø Thecatalysthasalifeof5–10years
• AnalysetheimpactofincreasedpressureonthesysteminvolvedintheHaberprocessØ (LCP)Whenpressureisincreasedbyloweringthevolume,theequilibriumwillshifttothesidewithless
gasmolecules.Therefore,theyieldofNH3willincrease.Ø Haberprocessiscarriedoutat250atmospheres(25,000kPa)Ø NOTE:Ifpressureisincreasedbyaddinganinertgasthereisnochangeinconcentrationsortothe
reactionØ NOTE:Whenthepressureisincreased,therateofreactionofboththeforwardandbackwardreaction
increase.Thisisbecausethegreaterconcentrationofgasparticlesincreasesthefrequencyofsuccessfulcollisions.
• ExplainwhymonitoringofthereactionvesselusedintheHaberprocessiscrucialanddiscussthemonitoring
requiredØ Whythereactionvesselhastobemonitored/maintained:
§ TheNitrogentoHydrogenratiomustbe1:3toavoidthebuild-upofonereactant§ Temperatureis450degreesandpressureis250atmospherestogetaneconomicalyieldof
ammonia§ Nooxygenispresentashydrogenisaflammablegaswhichwillexplodeundersuchconditions
CHEMICALMONITORINGANDMANAGEMENTNOTES–ROHANBARAR2016
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§ Carbonmonoxideandsulfurcompoundswill‘poison’thecatalyst§ Nobuild-upofargon(fromatmosphere)whichwillincreasethepressureunnecessarilyand
decreasetheefficiencyoftheprocess§ Highpressurereactionsaredangerousandcancausedamageandharm,thusthereaction
pressuremustconstantlybemonitoredØ ConstantremovalofNH3byliquefyingammoniaproductasitforms(equilibriumshiftstosidewithless
concentration–right)
• GatherandprocessinformationfromsecondarysourcestodescribetheconditionsunderwhichHaberdevelopedtheindustrialsynthesisofammoniaandevaluateitssignificanceatthattimeinworldhistory
Ø HaberwasaGermanscientistwhoinventedtheprocessin1908Ø Thisprocessallowedforthesynthesisofammoniafromitsgaseouscomponentsofhydrogenand
nitrogengas(450–500degrees,250atmospheres,magnetitecatalyst)Ø WiththehelpofCarlBosch(chemicalengineer),Haberwasabletoimplementtheprocessonan
industrialscaleby1913Ø Thiswasaturbulenttimeinworldhistory(1914wasWWI).ThealliesblockedGermanports,thus
preventingaccesstonitratesfromChile(theyreliedonimportstomakeexplosivesandfertilisers).Ø ThecommercialapplicationoftheHaberprocesswasabletoproduce200tonnesofammoniaby1914
eachday,whichwasusedtohelpGermany’swareffortsandfortheproductionoffertiliserØ Advantages
§ Germanycouldnowproducefertiliserstoincreasecropoutputandincreaseitscapacitytofeeditspopulation.Itcouldalsoproducesignificantamountsofexplosivesforthewar.
§ Itwasalsoaverysignificantscientificdevelopmentwhichshowedtheimpactofscienceongreatersociety
Ø Disadvantages
§ Itraisedsevereethicalandmoralissuesrelatingtotheuseofscience,asitresultedintheproductionofexplosiveswhichkilledpeopleanddestroyedthenaturalenvironment
§ Fertilisersfromammoniahavealsobeenoverused.Asaresult,theywashoutofsoilsandgointowaterways,endangeringmarinelife.
Ø Assessment:Overallverysignificantatthetimeitwasdeveloped,andstillissignificanttoday.Hasimpactedtheglobalnitrogencycle,pollutesgroundwaterandincreasesthelevelofatmosphericnitrogendioxide.Immensevalueinfosteringincreaseinglobalfoodandchemicalproduction,despiteitsnegativeimpactsonincreasingthefeasibilityofproducingexplosiveweaponry.
Section3Manufacturedproducts,includingfood,drugsandhouseholdchemicals,areanalysedtodetermineorensuretheirchemicalcomposition
• Deducetheionspresentinasamplefromtheresultsoftestsand
• Performfirst-handinvestigationstocarryoutarangeoftests,includingflametests,toidentifythefollowingions:phosphate,sulfate,carbonate,chloride,barium,calcium,lead,copper,ironØ Mostindustrialprocesshaveimpuritiesinionicform.
§ Qualitativetestsarecarriedouttoidentifytheionspresent(Flametests,precipitation,colourchangeofsolution)
§ Quantitativetestsdeterminehowmuchofeachionispresent(Atomicabsorptionspectroscopy)Ø FlameTest
1. CleanthenichromewirebyholdingittotheblueBunsenflameuntilthereisnoothercolour.2. Dipthewireinthesampleinconcentratedhydrochloricacid.(Chloridesaltsarethemostvolatile,
andwillproducethemostvisibleresults)3. HoldthenichromewiretotheblueBunsenflame1/3fromthebase,whichisthehottestpartofthe
flame4. Observeandrecordthecolourofthemetalioninanappropriatelytitledenclosedtable§ Theelectronswillabsorbtheheathenergyfromtheflame,andjumptoahigherenergylevel.The
electron,however,cannotremaininthisstateindefinitely.Whentheelectronfallsbackdownto
Solubilityrulesareessentialforthissection!!!
CHEMICALMONITORINGANDMANAGEMENTNOTES–ROHANBARAR2016
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groundstate(moststablestate),theextraenergyisre-releasedaslight.Ifthewavelengthoflightiswithinthevisiblespectrum,itcanbeobservedintheformofacolouredflame.
§ Onlycationscanbeidentifiedbytheflametest
Ø Reactions§ Pb2+(aq)+2Cl-(aq) PbCl2(s)ßPrimarytestwithHCl§ Pb2+(aq)+2I-(aq) PbI2(s)ßConfirmationtestwithNaI§ Ca2+(aq)+SO4
2-(aq) CaSO4(s)ßPrimarytestwithH2SO4
§ Ba2+(aq)+SO42-(aq) BaSO4(s)ßPrimarytestwithH2SO4
§ Fe2+(aq)+2OH-(aq) Fe(OH)2(s)ßPrimarytestwithNaOH
§ Fe3+(aq)+3OH-(aq) Fe(OH)3(s)ßPrimarytestwithNaOH
§ Cu2+(aq)+2OH-(aq) Cu(OH)2(s)ßPrimarytestwithNaOH
NaI
AddH2SO4
WhitepptNoppt.AddNaOH
AddingNaFwillproducewhitepptwithCabutnopptwithBa
AddingCutoNH3solutionàprecipitatedissolvestogiveadeepbluesolution
Allprecipitationreactionsareequilibrium
ß
SCN-
CHEMICALMONITORINGANDMANAGEMENTNOTES–ROHANBARAR2016
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Ø TestsforAnions
• Describetheuseofatomicabsorptionspectroscopy(AAS)indetectingconcentrationsofmetalionsinsolutionsandassessitsimpactonscientificunderstandingoftheeffectsoftraceelements
CHEMICALMONITORINGANDMANAGEMENTNOTES–ROHANBARAR2016
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Ø AASwasinventedinthe1950sbySirAlanWalsh(anAustralianscientist)atCSIROØ ThismethodisusedtodetermineconcentrationsofCATIONS(NOANIONS)atconcentrationslowerthan
1ppmØ Principle
o Thelightabsorbedbyatomsorionsinsolutionisdirectlyproportionaltotheconcentrationoftheions(asabsorptionincreases,concentrationincreases)
o Whenheatisabsorbed,electronsareexcitedandmoveuptoahigherenergystate.Whentheelectronmovesbackintoitsoriginalgroundstate,itreleasestheenergyaslight.Thisemittedlightisdifferentforeachcation,duetothecation’suniqueelectronconfiguration.
o Eachelementhasitsown‘spectrum’,whichcanbeusedtoidentifyit(similartoafingerprint)Ø EmissionLineSpectrumàColouredlinesonablackplateØ AbsorptionLineSpectrumàBlacklinesonacolouredplateØ Components
o LightSource:HollowCathodelampoftheelementthatisbeingtestede.g.Iftestingforcopper,acopperhollowcathodelampisused
o Flame/Nebuliser:Vaporisesthecationsinthesampleo Monochromator/Prism:Onewavelength/colourisselectedtopreventinterferencebyotheratomso PhotomultiplierTube:Detectstransmittedlightintermsofintensityo DigitalReading:Convertsthetransmittedlightintotheabsorbanceasadecimalo InitialLight–TransmittedLight=Absorption
Ø Method1. Preparea200ppmstandardsolutioncontainingthecationtobetestedfor.(similartohowstandard
solutionsfortitrationsareprepared)o Dissolvemassintosmallquantityofdistilledwater,usevolumetricflask,topwithdistilled
water2. Prepareaseriesofdilutedsamplesoftheiontobetested(e.g.100ppm,50ppm,25ppm)3. MeasuretheabsorbanceofeachofthestandardsolitonsusingAASinordertodrawacalibration
curve(alwayslinear,passesthroughorigin)4. Measuretheabsorbanceoftheunknownsolution5. Determinetheconcentrationoftheioninthesolutionusingthecalibrationcurve(ALWAYSLINEAR,
ALWAYSPASSESTHROUGH/MEETSTHEORIGIN(0,0))
Advantages Disadvantages§ Extremelysensitive(measuresconcentrationsas
lowas1ppb)§ Specificduetothehollowcathodelampwhich
emitslightofaspecificwavelength§ Nopriorpreparationofthesamplerequired
§ Onlycationscanbetested§ Veryexpensive(e.g.adifferentcathodelampis
neededforeachcation)§ Onlyoneioncanbetestedforatatime(time
consuming,impracticalinsomesituations)§ TrainedtechnicianrequiredtooperateAAS
Ø TraceElementAnalysis
o Traceelementsarethosethatarerequiredbylivingorganismsinverylowconcentrations(1-100ppm)fortheproperfunctioningofenzymesincells(Highconcentrationsareharmful)
o E.g.Zn(essentialforaminoacidmetabolismandenergyproduction),Co,Ni,Cu,Mo,Seo BeforeAAS,thepresenceandamountofthesetraceelementscouldnotbedetermined.Now,blood,
urineandtissuesamplesaretestedfortheamountoftraceelementspresent.Iftherearedeficiencies,thesecanbeidentifiedandtreated.
Ø Summaryo Introducechemicalprincipleso Discussmethod,includingcomponentso DiscussAdvantagesanddisadvantageso Discusstraceelementso Provideassessmentofthetechnology
CHEMICALMONITORINGANDMANAGEMENTNOTES–ROHANBARAR2016
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• Gather,processandpresentinformationtodescribeandexplainevidencefortheneedtomonitorlevelsofoneoftheaboveionsinsubstancesusedinsocietyØ Pb2+(Lead)Ø Toxic,heavymetal–releasedasinorganicionsororganicleadØ Enterorganismsviaingestion,inhalation,absorptionthroughskinentersfoodchainandaccumulatesinbody
(difficulttoexcrete)Ø Effects
§ Organdamagebydisruptingenzymesystems§ Intellectualretardation,neurologicaldamage–inchildren–learningdisabilities,impairedhearing–
hyperactivity,ADD§ Inhibitsformationofhaemoglobin(oxygencarryingmoleculeinblood)
Ø PastUses§ White,yellow,redpaint,leadedfuels,manufacturedtoys
Ø Monitoring§ Monitoringinhighwayareas,soil,atmosphere,urbanareas,water§ Stringentstandards(concentrationsinpaints(0.25%)andunleadedpetrol)§ Problemse.g.whenusedinmining,therefiningoflead(slagwastes,fumes,dust)andlead,acid
batteries
• Identifydata,plan,selectequipmentandperformfirsthandinvestigationstomeasurethesulfatecontentoflawnfertiliserandexplainthechemistryinvolved
and• Analyseinformationtoevaluatethereliabilityoftheresultsoftheaboveinvestigationandtoproposesolutionsto
problemsencounteredintheprocedureØ GravimetricAnalysisofSO4
2-byprecipitatingasBaSO4Ø Method:
1. Weigh0.2goffertiliseranddissolveindistilledwater.Filtertoremoveanyinsolublesubstancessuchassand.
2. Acidifythesolutionwith0.5mLofconcentratedHClandgentlyboil.(Willremovecarbonate,whichwouldotherwiseprecipitateasBaCO3)
3. 5%w/vBaCl2isaddeddropwisewithaburetteuntilnomoreprecipitateforms.Avoidexcess,asextrabariumionswillsticktotheprecipitate,increasingweight.
4. CheckthesupernatantforfurtherprecipitationbyallowingthesolidtosettleandaddingadropofBaCl2totheclearsolution.Ifthereisnocloudinessasaresult,precipitationiscomplete.
5. Thebeakerwiththeprecipitateisleftonahotplateforanhourtosettle.ThepowderyBaSO4willclumptogethermakingiteasytofilter.Heatencouragesrecombinationofions.(oppositeofdissociation)
6. FiltertheBaSO4solidusingaweighedsinteredglassfunnel(superiortofilterpaper).Thisisaveryslowprocess,soavacuumpumpcanbeusedtospeedupthisprocess.
7. Washtheprecipitatewithsmallamountsofwater3times(toremoveanybariumionsstickingtotheprecipitate).Thenrisewithsmallamountsofalcohol3times(toremovewater).
8. Drytheprecipitateinanovenat105degreesCelsiusuntilcompletelydry.Coolinadesiccatorandweigh.Continuethisprocessuntiltheweightisconstant.
Ø Safety1. Bariumchlorideistoxicifingested,henceitisimportanttowashhandsthoroughlyafterthe
experiment2. ConcentratedHydrochloricacidisverycorrosiveandcausesseveredamagetotheeyes,skinand
clothes.Wearsafetygogglesandgloves(ifpossible)3. Experimentinvolvestheuseofahotplate,whichcanburnskin.Becarefulwhenhandlingequipment
Ø Results§ DeterminemassofBaSO4§ DividethismassbythemolarmassofBaSO4todeterminethenumberofmoles§ In233.37gramsofBaSO4(1mole),thereare96gofSO4
-§ Multiply(96/233.37)withthemassofBaSO4todeterminethemassofSO4
-§ TofindthepercentageSO4,dividethemassofSO4bythemassoftheoriginalsampleoffertiliser
CHEMICALMONITORINGANDMANAGEMENTNOTES–ROHANBARAR2016
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Ø Reliability§ Thereliabilityofresultsintheaboveproceduredependupon:
• Onlysulfateionsinthefertiliserbeingprecipitatedbybariumions.• Allofthebariumsulfateprecipitatebeingcollectedbythefilterpaper.
§ Thereliabilityofresultsintheprocedurecanbeimprovedby:• Usingafineanalyticalgradequantitativefilterpaperratherthanaqualitativefilterpaper.• Repeatingtheexperimentseveraltimesandcomparingtheresultsobtainedeachtime.
§ Problems,otherthanreliabilityproblems,thatcouldpossiblybeencounteredduringtheprocedure,andpossiblesolutions,includethefollowing:
Problem Solution
Weighing:Somemassmaybeunaccountedforduetoerrorsincollectionandweighing
WashdownthebeakerwhentransferringtothefiltertoensureallBaSO4istransferred.Filterpapershouldbedriedinanoveninsteadofair,asmoisturecouldstillbepresentandcontaminantsadded.Useaverypreciseelectronicscale.
IncompletePrecipitation:BaSO4formsinanequilibrium,andthusproductionofprecipitatemaynotreachequilibrium
AddexcessBaCl2toshifttheequilibriumtotherightuntilnomoreadditionalwhiteprecipitateforms.CoolthemixtureafteraddingBaCl2inice-watertogreatlyreducethesolubilityofBaSO4.Donotusegreatvolumesofwaterandsolutions,asBaSO4ismoresolubleindilutesolutions.
Presenceofcontaminantions:Phosphateandcarbonatespresentmayreactwithbariumtoformexcessprecipitate
AdditionofHCldissolvestheseprecipitates
Smallsizeofprecipitatecrystals:BaSO4formsveryfinecrystals,whicheasilygothroughnormalfilterpaper,andevensinteredglasscrucibles.
HeatingthesolutionbeforeaddingBaSO4andconstantlystirringincreasestheenergyofthesolution,whichincreasesthenumberofcollisions,thuslargerparticlesareformed.AddingBaCl2slowlyallowstheBaSO4crystalstogrow,andthusbecomelarger.Addingacoagulatingagentsuchasagarsolutioncausesthecrystalstocoagulate.
Filterpapertakesalongperiodoftimetodry DrythefilterpaperinanovenFiltrationtakesalongperiodoftime Useaweighedsinteredglasscrucible
• Gather,processandpresentinformationtointerpretsecondarydatafromAASmeasurementsandevaluatethe
effectivenessofthisinpollutioncontrolADVANTAGESØ AASisextremelyeffectiveinpollutioncontrolofmetalsàaccuratelycalculateconcentrationsofpollutants
eveninlowconcentrations.Thishasgivenusabroaderunderstandingoftheenvironmentandhelpsusimprovethehealthandsafetyofecosystemsandthepublic
§ AASwasusedinBangladeshtodeterminearsenicconcentrationsofgroundwater.ThisallowsthepublictoavoiddrinkinggroundwaterwithhighconcentrationsofArsenic,whichcancausehardpatchesontheskin,skincancer,lungcancer,kidneyandbladdercancerandgangrene.
§ Leadisanothertoxicheavymetalswhichcandamagethebrain,kidneysandreproductivesystembydisruptingenzymesystemmediatedbyothermetalssuchascalcium,ironandzinc.
2PbS+O2à2PbO+2SO22PBO+Cà2Pb+CO2
TheseequationsshowhowleadmayaccumulateinworkersØ AASisarelativelycheapmethod(followingtheinitialstart-upcosts)ofregularlyanalysingwaterwaysandair
qualitytoensurethatthelevelofpollutionisatanacceptablelevel,allowingthemaintenanceofthehealthofthepopulation
Ø AASishighlyspecificandfastforeachsampleanalysed,asthesamplecanbeanalysedwithouthavingtobephysicallyseparated
Ø Thus,AASprovidesaquickandeasywayofroutinelymonitoring/detectingsuchharmfulheavymetalsinsuchworkplaces,toensurethattheyareinconcentrationsbelowwhatisrecommendedbytheappropriatehealthauthorities
CHEMICALMONITORINGANDMANAGEMENTNOTES–ROHANBARAR2016
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DISADVANTAGESØ AASisonlyusefulfortestingtheconcentrationofmetalpollutants,asitcannotbeusedtodeterminethe
concentrationofnon-metalpollutantsØ Althoughinexpensivetooperate,theinitialcostofsettinguptheAASdeviceishigh,andthusmakesthem
unaffordableforsomepollutionmonitoringagenciesØ Itcanonlybeusedtotestforonemetalatatime.Alsoforeachnewmetaltested,anewhollowcathode
lampwiththespecificmetalhastobesetupàtimeconsumingandexpensiveØ DestructiveanalysisàSampletestedcannotbereusedorreanalysedØ Water:Heavymetalssuchaslead,magnesiumandcalciumformindustrialwasteØ Soil:Lead,Mercury,Cadmium,NickelfromleachingofbatteriesandrubbishdumpØ Air:LeadfromleadedpetrolanddemolitionofoldbuildingswithleadedpaintØ Food:Leadinfruitsgrowninorchardsnearhighways.Mercurybioaccumulationinfish.Ø Mining:Testformetalsinorestodeterminewhetheritiseconomicalornottomineacertainregion
§ Assessment:AAShashadaverypositiveimpactonourabilitytocontrolpollution.WithAAS,wehavetheabilitytoaccuratelyandreliablyanalysesubstancesfordangerouscationsthatwouldotherwisegoundetected.Thishasallowedustotakebettercareofsocietyandtheenvironment.
Section4Humanactivityhascausedchangesinthecompositionandthestructureoftheatmosphere.Chemistsmonitorthesechangessothatfurtherdamagecanbelimited.• Describethecompositionandlayeredstructureoftheatmosphere
Ø Theatmosphereisalayerofgassesabout200to300kmthicksurroundingtheEarth
Ø Troposphere(0-15km)
§ Asthealtitudeincreases,temperaturedecreases§ ThehotaironthesurfaceoftheEarthwillriseduetoconvection,andthecoldairwillcomedown§ Duetothisdisturbance,gassesarewellmixedandweathereventsarefrequent§ Pollutantsaredilutedinthislayerduetotheconstantmovementofgasses
Ø Stratosphere(15-50km)§ Asaltitudeincreases,temperatureincreases§ Hotairremainsontopandcoldairremainsatthebottom(nomixingofgasses)§ Ozonelayerispresentatanaltitudeofabout20km
Ø AtmosphericComposition§ 90%ofgassesareconcentratewithinthetroposphere
CHEMICALMONITORINGANDMANAGEMENTNOTES–ROHANBARAR2016
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(Approximatevaluesfromthistableneedtobeknown)
§ Gassesofverylowconcentrationsaregiveninppm(partspermillion)• Identifythemainpollutantsfoundintheloweratmosphereandtheirsources
Pollutant Source ImpactLead • Leadedpetrolincars
• Demolishingoldbuildingswithleadedpaint
• MiningFumes
Directpoisonthataffectsthecentralnervoussystem(causesmentalretardation)
NitrogenOxides • Internalcombustionengines• Burningfossilfuelscontaining
nitrogenimpurities• Burningvegetation
Contributestoacidrainandphotochemicalsmog
SulfurDioxide • Burningfossilfuelscontainingsulfur• Smeltingmetalsulfidesinmetal
extraction• ProductionofH2SO4
Contributestotheformationofacidrain
Methane • Bacterialdecompositionoforganicmatter
• Naturalgasseepage
Contributestophotochemicalsmogandthegreenhouseeffect(climatechange)
Hydrocarbons • Vehiclesusingpetrol Contributestophotochemicalsmogandperoxyacetylnitrates(PANs)
CarbonMonoxide • Incompletecombustionofhydrocarbons
• Forestfires• Slowcombustionstores
Combineswithhaemoglobinfasterthanoxygengas,therebyreducingtheoxygencarryingabilityofblood
CarbonDioxide • ForestFires• Vehicles
Contributestoglobalwarmingandclimatechange
Chlorofluorocarbons(CFCs)
• Refrigerators• AirConditioners• AerosolCans
Destroystheozonelayer,allowingshortwavelengthUVradiationtocomedowntotheEarth’ssurfaceandcauseskincancer,sunburnandeyecataracts
Ozone • InternalcombustionenginesN2+O2à2NO2NO+O2à2NO2NO2à(sunlight)NO+O(bothradicals)O(radical)+O2àO3
Photochemicalsmog
Particulates • Sootfromincompletecombustion• Dust• Asbestos
Causesrepositorydifficulties,carcinogenicanddirtiestheenvironment
• DescribeozoneasamoleculeabletoactbothasanupperatmosphereUVradiationshieldandaloweratmosphere
pollutantØ IntheTroposphere
§ Ozoneisaseriouspollutantinthetroposphere,existingatconcentrationsaround0.02ppmincleanair§ Asshowninthetable,ozoneisformedinthetropospherebyinternalcombustionengines
CHEMICALMONITORINGANDMANAGEMENTNOTES–ROHANBARAR2016
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§ Ozone(photochemicalsmog)isaverystrongoxidantandwilloxidisesofttissueineyesandthroat,disruptsnormalbiochemicalreactions
§ Ozone,inhigherconcentrations,cancausebreathingproblems,aggravationofrespiratoryproblems,headaches,fatigueanddeath(inhighconcentrations)
§ Thus,Ozoneisaseriousandtoxicpollutantinthe‘loweratmosphere’(troposphere)Ø IntheStratosphere
§ Ozoneexistsatmuchhigherconcentrationsinthestratospherenaturally,ataround2to8ppm§ Ozonehasaveryimportantroleinthestratosphere,inwhichitisresponsibleforabsorbingdangerousUVB
radiationfromthesunthatwouldotherwisecauseseriousdamagetolifeonEarth(cancers,burnsandeyecataracts)
§ FormationofOzone• O2(g)à(UVonarrow)2O-
(g)• O2(g)+O-
(g)àO3(g)+heat§ ActionofOzone
• O3(g)à(UVonarrow)O2(g)+O-(g)
• O3(g)+O-(g)à2O2(g)+heat
§ UVradiationisconvertedtoheatenergy+harmlessO2-nootheratmosphericmoleculeshavetheabilitytoabsorbsolarradiationinUVrange
§ Stratospheregetswarmaslightenergyisconstantlyconvertedtoheatenergy§ HenceOzonehasanimportantroleintheStratosphere,inwhichitactsasa‘UVradiationshield’
• Describetheformationofacoordinatecovalentbond
Ø Whenthetwoelectronsthataresharedtoformacovalentbondcomefromasingleatom,thebondisknownasacoordinatecovalentbond
• DemonstratetheformationofcoordinatecovalentbondsusingLewiselectrondotstructures
Ø Covalentbondwherebothofthesharedelectronsforthebondcomefromthesameatom–morereactiveo Bondsareindistinguishablefromregularcovalentbondswhenformed
Ø E.g.NH4+,H3O+andCO
Ø Bondcomesfromlonepairsofoneatom
Ø Inordertodrawacompoundcontainingcoordinatecovalentbonds
§ Numberofelectronsneeded=numberofatoms*8§ Numberofelectronspresent=numberofelectronsatomspresentcurrentlyhave§ Numberofsharedelectrons=needed–present§ Numberofbonds=numberofsharedelectrons/2§ Positionbondsappropriatelytosatisfyallatoms(octet)
Ø Coordinatecovalentbondsaredenotedwitharrows• ComparethepropertiesoftheoxygenallotropesO2andO3andaccountforthemonthebasisofmolecularstructure
andbondingØ Allotrope:Differentphysicalformofthesameelement.Ø Oxygenhas2allotropes:Ozoneandoxygen
CHEMICALMONITORINGANDMANAGEMENTNOTES–ROHANBARAR2016
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Ozone OxygenGas
Ø ChemicalProperties§ Dependonthestrengthofthecovalentbonds.Thestrongdoublebondinoxygengasishardtobreak
butthesinglebondinO3(coordinatecovalent)isbrokeneasily(998kJ/Molvs107kJ/Mol)§ Ozoneismorereactivethanoxygen§ Bothareoxidisingagents(ozoneisstronger)
Ø PhysicalProperties O2 O3 REASON
GaseousColour Colourless Paleblue -LiquidColour Paleblue Deepblue -SolidColour Paleblue Black-violet -
BP/MP Lower(-183oand-219oC)
Higher(-111oand-193oC)
O3isslightlypolarduetoitsasymmetricelectrondensityanditsbentshape-greaterintermolecularforces
DensityasGas Lower Higher PresenceofadditionalOatominozoneSolubilityinwater Sparingly
soluble(9ppm)MoresolublethanO2
O2isnon-polar,butO3isbentandthuspolar
Reactivity Highlyreactivewithmanymetalsandnon-metals
Veryhighlyreactive,attacksdoublebondsonalkenes
CoordinatecovalentbondinO3isextremelyreactiveIntermediatesingleanddoublebondscreatingO-(anoxidant)
Odour Odourless Pungent Ø Ozonehasaslightpolarityduetothebentstructure.Therefore,therearedipole-dipoleforcesbetweenozone
moleculeswhicharestrongerthantheweakdispersionforcesinoxygengas.Thisresultsinhighermeltingandboilingpoints,aswellassolubilityinwaterascomparedtooxygengas.
• Comparethepropertiesofthegaseousformsofoxygenandtheoxygenfreeradical
Ø FreeRadical:Aneutralspeciesatomwithanunpairedelectron.OxygenfreeradicalsarepresentintheupperatmosphereduetotheeffectsofradiationsuchasUVlightProperty GasesForms(O2,O3) FreeRadicalReactivity Lessreactive(fulloutervalence
shell)Veryreactive(unpaired)
OxidationAbility Lower Higher(unpairedelectron,hightendencytotakeelectronstocompletevalenceshell)
• Identifytheoriginsofchlorofluorocarbons(CFCs)andhalonsintheatmosphere
Ø Chlorofluorocarbons(CFCs)arecompoundscontainingCarbon,ChlorineandFluorineONLY(NoH)Ø HalonsarecompoundscontainingCarbon,Bromine,Fluorine(mayormaynotcontainCl)(NoH)Ø Duringthe1930s,CFCs(and,toalesserextent,halons)replacedammonia(NH3)asthegasinrefrigeratorsandair
conditionersØ CFCswerecheaper,non-toxic,non-flammableeasilycompressibleØ SuchusesofCFCsreleasedmillionsoftonnesofCFCgassesintotheatmosphereoveraperiodofoverhalfa
century,introducingCFCsandHalonsintotheatmosphereØ NamingCFCs
§ ListC,HandF(inthatorder)andsubtract90§ E.g.Cl-CFCl-CF2-Cl=203-90=CFC113(asthereare2carbons,0hydrogensand3fluorines)
CHEMICALMONITORINGANDMANAGEMENTNOTES–ROHANBARAR2016
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Ø NamingHalons§ ListC,F,Cl,Bre.g.1211
Ø CFC-11wasusedinrefrigeratorsandairconditioners(CCl3F)• Identifyandnameexamplesofisomers(excludinggeometricalandoptical)ofhaloalkanesuptoeightcarbonatoms
Ø Isomer:Samemolecularformulabutdifferentstructures§ IsotopeàAtoms,AllotropeàElement,IsomeràCompounds
Ø Haloalkanes:AlkaneswithhalogensF,Cl,BrandIfunctionalgroupsØ Naming
1. Longestcarbonchainsasyouwouldforalkanes2. Positionofdoublebond(ifpresent)takesprecedenceoverhalogenbutnamedafter3. AddfunctionalgroupprefixesF:fluoro-Cl:chloro-Br:bromoI:Iodo-4. Numberaccordinglowestnumberedlocant(ifmorethan1typeisonsidetostartoncountingfromtheside
thatyoubegintocountfromfirstalphabetically)5. Usedi,trietc.forwritingnumberofhalogenatoms6. Order(ifmorethan1differenttypeofhalogenatom)alphabetically–i.e.chloro,fluoro
Ø E.g.1,1dibromo2-chlorohexane• DiscusstheproblemsassociatedwiththeuseofCFCsandassesstheeffectivenessofstepstakentoalleviatethese
problemsØ CFCsareextremelystableandinsolubleinwater.Therefore,theydonotcomedownfromtheatmospherewith
rainwaterorotherweatherevents,andremaininthetropospherefordecades.Ø Slowly,overmanyyears,CFCsmigratetowardstheStratosphereuntiltheyfinallyreachtheOzonelayerØ TheUVradiationpresentintheozonelayerbreakstheCarbon-ChlorinebondintheCFCandachlorinefree
radicalisformedCCl3F(g)à(UVonArrow)CCl2F•+Cl•
Ø Thischlorinefreeradicalthenattacksozone,formingahypochloritefreeradicalandoxygengas.Thehypochloritefreeradicalthenreactswithanoxygenfreeradical,formingoxygengasandreformingtheoriginalchlorinefreeradical.
Cl•+O3(g)àClO•+O2(g)
ClO•+O•àO2(g)+Cl•Ø Thisprocesscanbedescribedasa‘chainreaction’aschlorineisnotdestroyedintheprocess(canbethoughtof
asahomogenouscatalyst).Theonlywaythiscanbestoppedisifchlorinereactswithmethane.Typically,asingleCFCcompoundcandestroyaround1000ozonemolecules.
Ø Themassdestructionofozoneinthestratosphereleadstothethinningoftheozonelayer.Theseareknownasozone‘holes’(notactualholes,justareasoflowerconcentrationofozone)
Ø Justa1%reductionintheozonelayerincreasesthechanceofskincancerby8%Ø IftheUVBradiationisincreasedby2%ithastheabilitytokillsurfaceplanktonanddisruptthefoodchainØ HalonsaremoredestructivethanCFCsastheC-Brbondbreaksmorereadily.Thebrominefreeradicaldestroys
ozoneinasimilarprocesstochlorine.Ø In1987,theMontrealProtocolbannedtheuseofCFCsandothercompoundsindevelopedcountries
§ StopusingHalonsby1994§ StopmanufacturingCFCsby1996§ PhaseoutHCFCsbythe21stcentury(2020)§ Allowlessdevelopedcountriessomegraceperiodandprovidefinancialsupport
Ø Replacements§ HCFCs
• HaveC-Hbondswitharedecomposablebyradicals–butsignificantamountstillreachesupperatmosphere
• LessharmfulthanCFCsdespitestillhavingClatoms• Temporarysubstitutewithplantstophaseoutby2020(notideal)
§ HFCs• ContainnoCl/BratomsandC-Fbondisstrong–noFfreeradicalsproduced• Donotcontributetoozonedepletion• Moreexpensive;R-124aisusedrefrigerantinAus.
CHEMICALMONITORINGANDMANAGEMENTNOTES–ROHANBARAR2016
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Ø Itispredictedthatby2050theozonelayerwillberepairednaturallyØ Equations
§ CCl2F2(g)à(UVBRadiationontopofarrow)CClF2(g)(radical)+Cl(g)(radical)§ Cl(g)(radical)+O3(g)àOCl(g)(radical)+O2(g)§ OCl(g)(radical)+O(g)(radical)àCl(g)(radical)+O2(g)
Ø Reactionsthatwillstopthechainreaction§ CH4(g)+Cl(g)(radical)àCH3(g)(radical)+HCl(g)§ NO2(g)+OCl(g)(radical)àClONO2§ Cl•+Cl•àCl2(g)
• Analysetheinformationavailablethatindicateschangesinatmosphericozoneconcentrations,describethechanges
observedandexplainhowthisinformationwasobtainedØ HighozonedepletionoverAntarcticacouldbedueto
§ TheicecrystalsintheaircatalysingthereactionbetweenHClandClONO2intheair§ HCl+ClONO2à(icecrystalsontopofarrow)Cl2+HNO3§ Cl2à(sunlightontopofarrow)2Cl(radical)§ ByOctober,theozonelayeroverAntarcticaisextremelythin,butispartiallyrepairedbylate
DecemberØ OzoneconcentrationismeasuredinDobsonUnitsØ InstrumentstoCollectData
§ DobsonSpectrophotometer(1960s)• Groundbasedinstrumentsforlongtermdataàspecificareaonly
o MeasurestheintensityoffourstandardwavelengthsofUVradiationreflectedbacktoground(2absorbedbyozone,2not)
o Ratiobetweentwointensitiesdeterminedtocalculatetotalozoneo Comparingthevalues.Thegreaterthedifference,thegreatertheozone(good-to
absorbUV)• LIDAR
o Relyonscatteringoflaserlightbyozoneo Fire2beams(oneabsorbedbyozone–308nmandonenot–351nm)o Comparevalues–profileofozoneconcentration(conc.vs.altitude)measuredo Differenceinlaserlightintensity/wavelengthssimilarlyshowspresenceofO3(which
isgoodifitishigher)• TOMS(TotalOzoneMappingSpectrometers)(1980s)
o Satellite,balloonorgroundbased–unitisDobsonUnitàdailyglobalcoverageo MeasuresintensityofawavelengthofUVradiationabsorbedbyozone–compares
tointensityofwavelengthnotabsorbedo Satellite(atalt.aboveozonelayer)observesincomingUVlightat6diff.wavelengths
+observesUVlightbackscatteredbyozoneandcomparesintensityofincomingradiationwithbackscatteredradiationtoformaprofile
o Comparesthedifferentvalueshavingpassedthrough• OMI(OzoneMeasuringInstrument)(current)
o ImprovementofTOMSwithsmallerpixelsizebutlargerviewingangleàallowtomaintaindailyglobalcoveragebutwithmoredetail
o Lookbetweencloudsattroposphere• PresentinformationfromsecondarysourcestowritetheequationstoshowthereactionsinvolvingCFCsandozoneto
demonstratetheremovalofozonefromtheatmosphere(CoveredEarlier)
• Gather,processandpresentinformationfromsecondarysourcesincludingsimulations,molecularmodelkitsor
pictorialrepresentationstomodelisomersofhaloalkanes(Self-Explanatory)
CHEMICALMONITORINGANDMANAGEMENTNOTES–ROHANBARAR2016
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• PresentinformationfromsecondarysourcestoidentifyalternativechemicalsusedtoreplaceCFCsandevaluatetheeffectivenessoftheiruseasareplacementforCFCs
1. Hydrochlorofluorocarbons(HCFCs)§ Thesehavecarbonhydrogenbindswhichbreakinthetropospherebeforethecompoundcandiffuseto
thestratosphere.Ozonedepletion,however,isstillpossibleasitalsocontainschlorine.2. Hydrofluorocarbons(HFCs)
§ Thesehavenochlorineatoms.Thecarbon-fluorinebondisextremelystronganddoesnotbreakinthepresenceofUVlight.Therefore,nofluorinefreeradicalsaregeneratedthatcanharmtheozonelater.
§ 1,1,1,2-TetrafluoethaneisthegasusedinairconditionersandrefrigeratorsCompoundType OzoneDepletionPotential(ODP)
Halon 10CFC 1HCFC 0.1HFC 0
Section5Humanactivityalsoimpactsonwaterways.Chemicalmonitoringandmanagementassistsinprovidingsafewaterforhumanuseandtoprotectthehabitatsofotherorganisms.• Identifythatwaterqualitycanbedeterminedbyconsidering:concentrationsofcommonions,totaldissolvedsolids,
hardness,turbidity,acidity,dissolvedoxygenandbiochemicaloxygendemand§ ConcentrationsofCommonIons(generallymeasuredinppm).§ Totaldissolvedsolids(TDS):Ameasurethemassofsolidsdissolvedinaunitvolumeofwater(generally
measuredinppm).§ Hardness:Ameasureoftheconcentrationofcalciumandmagnesiumions.§ Turbidity:Ameasureoftheamountofcolloidalsuspendedmatter,whichtranslatesintoadegreeof
cloudinessortransparency(measuredinrelativeunitscallednephelometricturbidityunits,orNTUs).§ Acidity:Ameasureoftheconcentrationofhydrogenions(measuredinpH).§ Dissolvedoxygen(DO):Ameasureoftheconcentrationofoxygen(generallymeasuredinppm).§ Biochemicaloxygendemand(BOD):Ameasureoftheconcentrationofdissolvedoxygenthatisneededfor
thecompletebreakdownoftheorganicmatterinasamplebyaerobicbacteria(generallymeasuredinppm).Goodqualitydrinkingwaterisknownaspotablewater.Itshouldhavethefollowingproperties.
§ Completelyclearandcolourless§ Odourless§ PleasantTaste§ Lowsaltcontent§ Nopathogens§ Notoxicmaterials/substances
Testscanbecarriedouttodeterminewaterqualitybymeasuringthe:
§ Concentrationofcommonionso QualitativeTests
§ FlameTest(C)§ PrecipitationTest(C&A)§ LineSpectrum(Emissionorabsorption)(C)
o QuantitativeTests§ Titrations(C&A)
• TheconcentrationofchlorinecanbedeterminedthroughtitrationwithHNO3,alongwithK2CrO4(yellow)indicator.Thecolourchangesfromyellowtobrickredwhentheendpointhasbeenreached.RedAg2CrO4precipitateswhenthereisnomorechlorine.(PrecipitationTitration)
• Chlorinecanalsobedeterminedbyreactionwithexcesssilvernitrate§ Gravimetry(C&A)§ AAS(AtomicAbsorptionSpectroscopy)(C)§ IonSensitiveElectrode(A)
CHEMICALMONITORINGANDMANAGEMENTNOTES–ROHANBARAR2016
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• SimilartopHmeters• Measurevoltagedifferenceandconvertresulttochlorineorfluorineconcentration
o Example:GravimetricAnalysisofChlorine§ WeightaknownamountofwateràEvaporateàConcentratedSampleàAcidifywith
HNO3andaddAgNO3àAgClPrecipitateàFilterandDryàWeigh
§ TotalDissolvedSolids(TDS)o QuantitativeTests
§ GravimetricAnalysis• Filterthewatersampletoremoveinsolublesubstances• Weigh• Evaporatetodrynessinapreviouslyweighedevaporatingbasin• Coolandweigh• Provideresultsinppm
§ MeasurementofconductivityconvertedtoTDSinppm
§ Hardnesso HardnessisduetoCa2+andMg2+ionsbeingpresentinthewatero QualitativeàCheckifsoaplathersinwater,orifitformsaninsolublescumo QuantitativeàEDTAComplexometryTitration,AAS
§ Add25.0mLofwaterintoaflask§ Add2mLofNH3/NH4ClbasicbuffersolutionàWillmaintainpHwhenEDTAmakessolution
acidic§ Add3dropsofEriochromeBlackTindicator§ Titratewith0.020mol/LEDTAuntilthereisachangeincolour(redàblue)§ Repeattitrationuntil3readingswithin0.1mLofeachother§ Ca2+IndicatorComplex(Red)+EDTAà[CaEDTA]2-+Indicator(Blue)
• HardnessisreportedasCaCO3ppmevenifitisduetoMagnesium• nCaCO3=nCa=nEDTA(as1:1ratio)=CEDTA*VEDTA=0.01*VolumeofEDTAusedin
Litres.• Dividethisresultby25,multiplyby1000(1litre),then100(mmCaCO3,then1000).
ThiswillgiveareadingofCaCO3inmgin1000mL(ppm).§ If<75ppmthenlow§ If15-150ppmthenmoderate§ If150-300pmmthenhard§ If300-500ppmthenveryhard§ If>500thensaline
o Therearetwotypesofhardness§ Temporary:IfthereisdissolvedCO2,boilingwillremoveCaasCaCO3§ Permanent:NeedtoaddwashingsodaNa2CO3whichremovesCaasCaCO3
§ Turbidity
o Cloudinessorlackoftransparencyisknownasturbidityo Suspendedsolids,suchasclay,resultinturbidityo QualitativeTests
§ SecchiDisks:Insertdiskintowateruntilthecrossatthebasecannotbeseen.Thelengthofthestringiscompared.
§ TurbidityTube:Addwaterintotubeuntilthecrossatthebaseofthetubecannotbeseen.o Quantitative
§ TurbidityismeasuredinNTU(NephelometricTurbidityUnits)§ TurbidityMeter
• Lightispassedthroughasampleofthewater,andtheresultantlighttransmittedismeasured.ThelighttransmittedisinverselyproportionaltotheturbidityinNTU.
• Nephelometer:Lightispassedthroughasampleofwater.Theresultantscatteringoflightismeasured.ThescatteringoflightisproportionaltotheturbidityinNTU.
CHEMICALMONITORINGANDMANAGEMENTNOTES–ROHANBARAR2016
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§ 1-5NTUispotable§ Lessthan25NTUissuitableforwaterlife
§ Acidity
o Themaincauseofacidityisacidraino MiningcanalsocauseacidityasFeSgetsoxidisedtoSO4
2-àH2SO4.LowpHwilldissolvetoxicmetalsionssuchasaluminium,whichwillbetakenupbyplantsandaquaticlife.
o PotablewatershouldhaveapHof6.5-8.5o Itisnormalforwatertoappearacidicathighertemperatures,astheforwardreactionoftheself-
ionisationofwaterequilibriumisexothermic.Thiscausesgreaterconcentrationsofhydroniumandhydroxide.SincepHmetersonlymeasurehydronium,thewaterappearsacidicathighertemperatures.
o QualitativeàIndicatorso QuantitativeàCalibratedpHmeter+thermometertomeasuretemperature(astempaffectspH)
§ DissolvedOxygen
o OxygendiffusesfromtheairintothewaterandwaterplantsproduceO2inphotosynthesiso Movingwater(e.g.rapids)havemoreDOduetothegreatersurfaceareao DOismeasuredinppm
§ 6-8ppmUnpolluted§ 4-6ppmPolluted§ 2-4SeverelyPolluted§ <2DeadWater
• Atlowerthan5ppm,aquaticlifeisinseverestresso DOdependson
§ Temperature(O2(g) O2(aq)+heat)(LCP)(ThermalPollution)§ AtmosphericPressure:Aspressureincreases,equilibriumshiftsforward,increasingDO
(LCP)§ Presenceofsalt:Assaltconcentrationincreases,DOdecreasesassaltismoresolublein
waterthannon-polaroxygen§ BiologicalOxygenDemand(BOD):AsBODincreases,DOdecreases.
o QualitativeTests:Methyleneblueindicatorturnsblueofthereisoxygeninthewatero QuantitativeTests
§ CalibratedDOmeter§ WinklerTitration
• O2(aq)+2Mn2+(aq)+4OH-(aq)à2MnO(OH)2(s)
• MnO(OH)2(s)+8H+(aq)à2Mn4+(aq)+6H2O(l)
• 2Mn4+(aq)+4I-(aq)à2Mn2+(aq)+2I2(aq)• 2I2(aq)+4S2O3
2-(aq)à4I-(aq)+2S4O6
2-(aq)
• 1:4ratiobetweenoxygengasandthiosulfate• Method
o A250.0reagentbottleisfilledwithwaterandstopperedunderwatertopreventanyairbubblesentering
o Add5mLofMnSO4/NaOH/KIandallowtheprecipitatetosettleo Add1mLofconcentratedH2SO4andmixtodissolvetheprecipitateo Transfer100mLintoatitrationflaskandtitratewith0.025Msodium
thiosulfateNa2S2O3inaburetteusingstarchastheindicator(BlueàColourless)
o Repeat• Results
o nO2=nNa2S2O3/4(as1:4ratio)=0.025*volumeofNa2S2O3used/4o nO2*32(molarmass)*1000(mg)*1000/100(1L)=oxygeninmg/L
(ppm)
CHEMICALMONITORINGANDMANAGEMENTNOTES–ROHANBARAR2016
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§ BiochemicalOxygenDemand(BOD)o Ameasureoftheorganicmatterinasampleofwaterthatisbrokendownbybacteria(lowerthe
bottle)o ThestandardisBOD-5:Thisistheamountofoxygen(ppm)thatis1Lofwaterwillreactwithat20
degreesCelsiusinthedark(preventphotosynthesis)in5dayso MethodBOD-5
§ Filltwo250.0mLreagentbottleswithwaterandstopperunderwater§ DOofonebottleismeasuredimmediatelyusingtheWinklerTitration§ Theotherbottleisleftinadarkplaceat20degreesCelsiusfor5days,thenDOismeasured
bytheWinklerTitrationo Results
§ SubtractsecondresultfromfirstresulttoobtainBODinppm§ IfBOD>3ppm,thenthewaterispolluted
o BODinvariouslocations§ Cleanriverwater=1-3ppm§ DomesticSewage=350ppm§ Abattoirwaste=2600ppm§ Paperpulpmills=25000ppm
• Identifyfactorsthataffecttheconcentrationsofarangeofionsinsolutioninnaturalbodiesofwatersuchasrivers
andoceansØ Rain
§ CO32-fromdissolvedCO2
§ Na+,Cl-,SO42-fromseaspray
§ Whenrainwaterrunsalongtheground,itcanpickupNO3-,PO4
3-,Mg2+§ Iftherainwaterisacidic,toxicheavymetalslikealuminiumcandissolve
Ø HumanActivity§ Landclearing§ Growingcropsandpasture,fertiliserrunoff,etc.
Ø EffluentDischarge§ Rawortreatedsewage§ Stormwaterrunoff§ Industrialeffluente.g.Pb2+,Cd2+,Cr2+,Cu2+,Zn2+
Ø Leachingfromrubbishdumps§ Ni2+,Cd2+,Pb2+,Hg2+fromdiscardedbatteriescanleachintowaterwayswithrainwater
• Describeandassesstheeffectivenessofmethodsusedtopurifyandsanitisemasswatersupplies
Ø SCREENINGPriortoleavingdamsiteandagainonenteringthetreatmentplants,waterisscreenedtoremovemacro-objectsandscreenablesolids.Freshwaterpassesthroughfinescreenstoremovesolidobjectslikefish,logsandleaves.
Ø AERATIONAerationistheintimateexposureofwaterandair.Whenairismixedwithwater,someimpuritiesinthewater,suchasironandmanganese,becomeoxidized.Onceoxidized,thesechemicalsfalloutofsolutionandbecomesuspendedinthewater.Aerationwillremovetastesandodoursfromwateriftheproblemiscausedbyrelativelyvolatilegasesandorganiccompounds.
Ø COAGULATION/FLOCCULATIONDuringcoagulation,liquidaluminiumsulfate(alumAl2(SO4)3)(orsometimesFeCl3,whichformsFe(OH)3)isaddedtountreatedwater.Whenmixedwiththewater,thiscausesthetinyparticlesofdirtinthewatertosticktogetherorcoagulate.Next,groupsofdirtparticlessticktogethertoformlarger,heavierparticlescalledflocswhichareeasiertoremovebysettlingorfiltration.
Al3+(aq)+H2O(l)àAl(OH)3(s)
CHEMICALMONITORINGANDMANAGEMENTNOTES–ROHANBARAR2016
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Ø SEDIMENTATIONAsthewaterandtheflocparticlesprogressthroughthetreatmentprocess,theymoveintosedimentationbasinswherethewatermovesslowly,causingtheheavyflocparticlestosettletothebottom.Flocwhichcollectsonthebottomofthebasiniscalledsludge,andispipedtodryinglagoons.
Ø FILTRATIONTheflocculatedstreamisthensentunderpressuretoafilterwhereitpassesthroughabedcomprisedofcrushedanthracite,sandandgravel.Remainingsuspendedsolidsareremovedgivingastreamoflowturbidity.
Ø CHLORINATIONWaterisdisinfectedbeforeitentersthedistributionsystemtoensurethatanydisease-causingbacteria,viruses,andparasitesaredestroyed.Residualconcentrationscanbemaintainedtoguardagainstpossiblebiologicalcontaminationinthewaterdistributionsystem.
Ø FLUORIDATIONFluorideisaddedtothewaterunderthedirectionofNSWHealthtohelppreventtoothdecay.Drinkingwatermustcontainonemilligramoffluorideforeachlitreofwater.
Ø pHADJUSTMENTSLimeisaddedtothefilteredwatertoadjustthepHandstabilisethenaturallysoftwaterinordertominimisecorrosioninthedistributionsystem,andwithincustomers’plumbing.
§ EffectivenessofWaterTreatment
o Advantages§ Flocculation
• Remove99.9%ofbacteria+99%ofviruses• Someorganicmatterfromsoil/vegetationremoved
§ SandFiltration• Removesahighproportionofparticulatematterinlargevolumes(notefficientforsmall
particulates)§ Chlorination
• Removesmostmicro-organismsfromwaterandrelativelylowcosto Disadvantages
§ Cleconomicallyeffective(limitedagainstsomeprotozoansthatformcystsinwater)(somesuchasGiardiaorCryptosporidiumcanstillsurvive)
§ Membranefiltrationanddisinfectionwithozonearemoreeffectivealternatives(butmoreexpensive)
§ HardwatercannotbesoftenedbythewaterpurificationmethodinNSW.Todothis,ionexchangetubesmustbeused(ormicroscopicmembranefilters).
o Effectiveifaccompaniedbypropercatchmentmanagement(combinationofflocculation,sandfiltration,chlorination)
• Describethedesignandcompositionofmicroscopicmembranefiltersandexplainhowtheypurifycontaminated
waterØ Composition
§ Thinsheetsofpolypropylene,polysulfoneorpolytetrafluoroethylenewithtinyholes
Ø Design
§ Rolledintothintubes.Largenumberoftubesarebundledintoafilter.§ Waterrunacrossthesurface(notat)topreventclogging
• Usegravity,vacuum,pressurepumpstoforceliquidthroughmembranewhereparticulatesarecollected
§ Sheet• Foldedbypleating/windinginspiralaroundacore• Housedinanouterplasticcontainertoformacartridge–inserted/removedeasilyinto
filtrationline
ßPolypropyleneStructure
CHEMICALMONITORINGANDMANAGEMENTNOTES–ROHANBARAR2016
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• Canbebackflushedandreused§ Capillary
• Composedofhollowfibres• Waterrunsalongoutsideofcapillariesandcleanwaterpenetratesporestoinsideofeach
capillary• Manycapillariesbundledtogethertoformamicro-filtrationunitwithlargesurfacearea
§ Filterspurifywaterbyremoveparticulates/microorganismsetc.toimprovewaterqualityØ Watergoesthroughtheholesbutparticlessuchasbacteriacannotpassthroughthesheets.Thefiltercanbe
clearedbypassingcompressedairintheoppositedirectiontowhichthewaterwouldnormallyflowin.Thebacteriacanthenbedislodged.
Ø Ifthesheetsarecoatedwithdeoxycholicacid,heavymetalionscanalsoberemoved(calciumandmagnesium).Usedinindustrywheresoftdrinksandbottledwaterareproduced.
Ø Microfiltration§ 100–1000nmporesize§ Bundlesofhollowpolymerthreads§ Removefinesilt,colloids,rangeofmicrobes(but
fewviruses)Ø Ultrafiltration
§ 5–50nmporesize§ Polymers(e.g.Polysulfoneandcelluloseacetate)
–ionsremovedonlyifmembraneshavespecialsurfactantcoating
§ Removesallmicrobesincl.viruses+largerorganicmolecules
Ø Nanofiltration§ 0.5–5nmporesize§ Polymers(e.g.polyamideorcelluloseacetate)§ Removesallorganicmolecules>300FW+some
saltscontainingdivalentandtrivalentionsØ Advantages
§ Filterverysmallparticles§ Thin,soliquidsflowrapidly§ Reasonablestrong;canbecleanedandreused
Ø Disadvantages§ Expensive;sometimescloggedwithsewerage
• Performfirst-handinvestigationstousequalitativeandquantitativeteststoanalyseandcomparethequalityofwater
samples(Coveredin3.5.1)
• Gather,processandpresentinformationontherangeandchemistryofthetestsusedto:identifyheavymetalpollutionofwaterandmonitorpossibleeutrophicationofwaterways
Ø Phosphates(PO43-)§ Phosphatesareusedindetergentsandfabricsoftenersastheyarecapableoftyingupcalcium,
magnesium,ironandmanganeseions,therebyimprovingoverallwashingperformance.Phosphatesalsoaidinkillinggerms.
§ Phosphatescancontributetoanoversupplyofphosphate(eutrophication)inwaterwaysandcauseanimbalanceoftheaquaticecosystem.Excessivealgalgrowth(sometimesintheformofalgalblooms)canoccurwiththeadditionofavailablephosphatestothefreshwatersystem.Bloomsofcyanobacteria(blue-greenalgae)mayalsobetoxic.Thistoxicitymaybeacute(shorttermsevere)orchronic(longer-termlow-level),andcanbecarcinogenic.Decomposerorganismsthatrequireoxygenmayincrease,whichcandepletetheamountofoxygendissolvedinthewater.Thiscancauseotheraquaticlife,suchasfishandcrustaceans,todie.Thealgaealsocoverthesurfaceofthewaterway,preventinglightfrompenetratingintothewater.Thispreventsaquaticplantsfromphotosynthesising.
CHEMICALMONITORINGANDMANAGEMENTNOTES–ROHANBARAR2016
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§ Totalphosphorusisdeterminedusingcolourimetry.BoilthewatersamplewithconcentratedsulfuricacidandconcentratednitricacidtoconvertallphosphatestoPO4
3-.Addammoniummolybdateandascorbicacidtogiveabluesolution.MakeaseriesofPO4
3-standards,measuretheabsorbance,andplotthecalibrationgraph.Determinethe[PO4
3-]inthewatersamplefromthegraph.Ø Nitrates(NO3
-)§ Nitratesalsocontributetotheeutrophicationofwaterwaysandencourageexcessivealgalgrowth§ EnterthewaterwayduetoSewerageandFertiliser§ CanbemeasuredquantitativelythroughKjeldahlmethod
• Thewatersampleisboiledwithconcentratedsulfuricacidtoconvertallnitrogento(NH4)2SO4
• ExcessNaOHisaddedandboiledtoremoveallammoniumasammoniagas• NH4
+(aq)+OH-
(aq)àNH3(g)+H2O(l)• TheunreactedNaOHisbacktitratedwithHCl• HCl(aq)+NaOH(aq)àNaCl(aq)+H2O(l)• ThereactedNaOHiscalculatednNaOH=nNH3=nN
Ø HeavyMetals§ Lead,Mercury,Cadmium,Chromium,Copper,Zinc§ Pollutionofwaterbytransitionmetals(Hg,Cd,As)–enterwaterwaysfromindustrialdischarges,
roadrunoff,landfill,agriculturalrunoff§ HeavymetalsInterferewithenzymesystemsandmetabolisminthebody,Bioaccumulate(buildup
intissue),Biomagnify(concentrationincreasesasheavymetalmovesupfoodchain)andpersistinenvironmentforlongperiodsoftime
§ Canbetestedforusingprecipitationreactions(if>1ppm)andAAS(Atomicabsorptionspectroscopy)§ Othertests:IonSelectiveElectrodes(ISE),FlameAtomicAbsorptionSpectroscopy(FAAS),Graphite
Furnace(GFAAS),X-RayFluorescenceSpectroscopy(XRFS)• Gather,processandpresentinformationonthefeaturesofthelocaltownwatersupplyintermsof:catchmentarea,
possiblesourcesofcontaminationinthiscatchment,chemicaltestsavailabletodeterminelevelsandtypesofcontaminants,physicalandchemicalprocessesusedtopurifywater,chemicaladditivesinthewaterandthereasonsforthepresenceoftheseadditives
(RefertoResearchDocumentforthissection)