4-56

(4000)

INORGANIC NONMETALS

4500-Cl CHLORINE (RESIDUAL)*

4500-Cl A. Introduction
1. Effects of Chlorination
The chlorination of water supplies and polluted waters serves
primarilytodestroyordeactivatediseaseproducingmicroorganisms.
A secondary benefit, particularly in treating drinking water, is the
overall improvement in water quality resulting from the reaction of
chlorine with ammonia, iron, manganese, sulfide, and some organic
substances.
Chlorination may produce adverse effects. Taste and odor char
acteristicsofphenolsandotherorganiccompoundspresentinawater
supply may be intensified. Potentially carcinogenic chloroorganic
compounds such as chloroform may be formed. Combined chlorine
formedonchlorinationofammoniaoraminebearingwatersadversely
affectssomeaquaticlife.Tofulfilltheprimarypurposeofchlorination
andtominimizeanyadverseeffects,itis
*ApprovedbyStandardMethodsCommittee,2000.

essentialthatpropertestingproceduresbeusedwithaforeknowledgeofthe
limitationsoftheanalyticaldetermination.

2. Chlorine Forms and Reactions

Chlorineappliedtowaterinitsmolecularorhypochloriteform
initiallyundergoeshydrolysistoformfreechlorineconsistingof
aqueousmolecularchlorine, hypochlorous acid, andhypochlorite
ion.TherelativeproportionofthesefreechlorineformsispHand
temperaturedependent. At the pH of most waters, hypochlorous
acidandhypochloriteionwillpredominate.
Freechlorinereactsreadilywithammoniaandcertainnitrogenous
compoundstoformcombinedchlorine.Withammonia,chlorinereacts
toformthechloramines:monochloramine,dichloramine,andnitrogen
trichloride.Thepresenceandconcentrationsofthesecombinedforms
dependchieflyonpH,temperature,initialchlorinetonitrogenratio,
absolutechlorinede

CHLORINE (RESIDUAL) (4500-Cl)/Introduction

mand, and reaction time. Both free and combined chlorine may be
presentsimultaneously.Combinedchlorineinwatersuppliesmaybe
formedinthetreatmentofrawwaterscontainingammoniaorbythe
addition of ammonia or ammonium salts. Chlorinated wastewater
effluents,aswellascertainchlorinatedindustrialeffluents,normally
containonlycombinedchlorine.Historically,theprincipalanalytical
problemhasbeentodistinguishbetweenfreeandcombinedformsof
chlorine.

3. Selection of Method
In two separate but related studies, samples were prepared and
distributedtoparticipatinglaboratories toevaluate chlorine methods.
Becauseofpooraccuracyandprecisionandahighoverall(average)
totalerrorinthesestudies,allorthotolidineproceduresexceptonewere
droppedinthe14theditionofthiswork.Theusefulstabilizedneutral
orthotolidinemethodwasdeletedfromthe15theditionbecauseofthe
toxicnatureoforthotolidine.Theleucocrystalviolet(LCV)procedure
wasdroppedfromthe17theditionbecauseofitsrelativedifficultyand
thelackofcomparativeadvantages.
a. Naturalandtreatedwaters:Theiodometricmethods(Band
C) aresuitableformeasuringtotalchlorineconcentrationsgreaterthan
1 mg/L,buttheamperometricendpointof MethodsCandDgives
greater sensitivity. All acidic iodometric methods suffer from
interferences, generally in proportion to the quantity of potassium
iodide(KI)andHadded.
Theamperometrictitrationmethod(D)isastandardofcomparisonfor
the determination of free or combined chlorine. It is affected little by
commonoxidizingagents,temperaturevariations,turbidity,andcolor.The
methodisnotassimpleasthecolorimetricmethodsandrequiresgreater
operator skill to obtain the best reliability. Loss of chlorine can occur
because of rapid stirring in some commercial equipment. Clean and
conditionedelectrodesarenecessaryforsharpendpoints.

Alowlevelamperometrictitrationprocedure(E)hasbeenaddedto
determine total chlorine at levels below 0.2 mg/L. This method is
recommended only when quantification of such low residuals is
necessary. The interferences are similar to those found with the
standardamperometricprocedure(D).TheDPDmethods(MethodsF
andG)areoperationallysimplerfordeterminingfreechlorinethanthe
amperometrictitration.Proceduresaregivenforestimatingtheseparate
monoanddichloramineandcombinedfractions.Highconcentrations
ofmonochloramineinterferewiththefreechlorinedeterminationunless
thereactionisstoppedwitharseniteorthioacetamide.Inaddition,the
DPD methodsaresubjecttointerferencebyoxidizedformsofman
ganeseunlesscompensatedforbyablank.

The amperometric andDPD methods areunaffectedbydichloramine

concentrationsintherangeof0to9mgClasCl 2/Linthedeterminationof
free chlorine. Nitrogen trichloride, if present,may react partially as free
chlorineintheamperometric,DPD,andFACTSmethods.Theextentofthis
interferenceintheDPDmethodsdoesnotappeartobesignificant.
The free chlorine test, syringaldazine (FACTS, Method H) was
developed specifically for free chlorine. It is unaffected by significant
concentrations of monochloramine,
dichloramine, nitrate, nitrite, and
oxidizedformsofmanganese.1
Samplecolorandturbiditymayinterfereinallcolorimetricprocedures.

457

Organiccontaminantsmayproduceafalsefreechlorinereadingin
mostcolorimetric methods (see 3b below). Many strong oxidizing
agents interfere in the measurement of free chlorine in all methods.
Such interferences include bromine, chlorine dioxide, iodine,
permanganate,hydrogenperoxide,andozone.However,thereduced
forms of these compounds bromide, chloride, iodide, manganous
ion, and oxygen, in the absence of other oxidants, do not interfere.
Reducing agents such as ferrous compounds, hydrogen sulfide, and
oxidizableorganicmattergenerallydonotinterfere.
b. Wastewaters: The determination of total chlorine in samples
containing organic matter presents special problems. Because of the
presence of ammonia, amines, and organic compounds, particularly
organic nitrogen, residual chlorine exists in a combined state. A
considerableresidualmayexistinthisform,butatthesametimethere
maybeappreciableunsatisfiedchlorinedemand.Additionofreagents
in the determination may change these relationships so that residual
chlorine is lost during the analysis. Only the DPD method for total
chlorineisperformedunderneutralpHconditions.Inwastewater,the
differentiationbetweenfreechlorineandcombinedchlorineordinarily
is not made because wastewater chlorination seldom is carried far
enoughtoproducefreechlorine.
Thedeterminationofresidualchlorineinindustrialwastesissimilar
tothatindomesticwastewaterwhenthewastecontainsorganicmatter,
butmaybesimilartothedeterminationinwaterwhenthewasteislow
inorganicmatter.
Noneofthesemethodsisapplicabletoestuarineormarinewaters
becausethebromideisconvertedtobromineandbromamines,which
aredetectedasfreeortotalchlorine.Aprocedureforestimatingthis
interferenceisavailablefortheDPDmethod.
Althoughthemethodsgivenbelowareusefulforthedetermination
of residual chlorine in wastewaters and treated effluents, select the
method in accordance with sample composition. Some industrial
wastes,ormixturesofwasteswithdomesticwastewater,mayrequire
specialprecautionsandmodificationstoobtainsatisfactoryresults.
Determine free chlorine in wastewater by any of the methods
providedthatknowninterferingsubstancesareabsentorappropriate
correctiontechniquesareused.Theamperometricmethodisthemethod
ofchoicebecauseitisnotsubjecttointerferencefromcolor,turbidity,
iron, manganese, or nitrite nitrogen. The DPD method is subject to
interference from high concentrations of monochloramine, which is
avoided by adding thioacetamide immediately after reagent addition.
Oxidizedformsofmanganeseatalllevelsencounteredinwaterwill
interfere in all methods except in the free chlorine measurement of
amperometric titrations and FACTS, but a blank correction for
manganesecanbemadeinMethodsFandG.

TheFACTSmethodisunaffectedbyconcentrationsofmonochloramine,
dichloramine, nitrite, iron, manganese, and other interfering compounds
normallyfoundindomesticwastewaters.

For total chlorine in samples containing significant amounts of

organicmatter,useeithertheDPDmethods(FandG),amperometric,
oriodometricbacktitrationmethod(C)topreventcontactbetweenthe
fullconcentrationofliberatediodineandthesample.WithMethodC,
donotusethestarchiodideendpointiftheconcentrationislessthan1
mg/L. In the absence of interference, the amperometric and starch
iodideendpointsgiveconcordantresults.Theamperometricendpoint
isinherentlymoresensitiveandisfreeofinterferencefromcolorand
turbid

4-58

INORGANIC NONMETALS
(4000)

ity,whichcancausedifficultywiththestarchiodideendpoint.Onthe
otherhand,certainmetals,surfaceactiveagents,andcomplexanionsin
some industrial wastes interfere in the amperometric titration and
indicatetheneedforanothermethodforsuchwastewaters.Silverinthe
formofsolublesilvercyanidecomplex,inconcentrationsof1.0mg
Ag/L,poisonsthecellatpH4.0butnotat7.0.Thesilverion,inthe
absenceofthecyanidecomplex,givesextensiveresponseinthecurrent
at pH 4.0 and gradually poisons the cell at all pH levels. Cuprous
copperinthesolublecoppercyanideion,inconcentrationsof5mg
Cu/Lorless,poisonsthecellatpH4.0and7.0.Althoughironand
nitrite may interfere with this method, minimize the interference by
bufferingtopH4.0beforeaddingKI.Oxidizedformsofmanganese
interfere in all methods for total chlorine including amperometric
titration. An unusually high content of organic matter may cause
uncertaintyintheendpoint.
Regardless of endpoint detection, either phenylarsine oxide or
thiosulfatemaybeusedasthestandardreducingreagentatpH4.The
formerismorestableandispreferred.

The DPD titrimetric and colorimetric methods (F and G,

respectively)areapplicabletodeterminingtotalchlorineinpolluted
waters.Inaddition,bothDPDproceduresandtheamperometric
titration method allow for estimating monochloramine and
dichloramine fractions. Because all methods for total chlorine
depend on the stoichiometric production of iodine, waters
containing iodinereducing substances may not be analyzed
accuratelybythesemethods,especiallywhereiodineremainsin
thesolutionforasignificanttime.ThisproblemoccursinMethods
BandD.Thebacktitrationprocedure(C)andMethodsFandG
causeimmediatereactionoftheiodinegeneratedsothatithaslittle
chancetoreactwithotheriodinereducingsubstances.

Inall colorimetric procedures, compensate for color and turbidity by

usingcolorandturbidityblanks.

Amethod(I)fortotalresidualchlorineusingapotentiometriciodide
electrodeisproposed.Thismethodissuitableforanalysisofchlorine
residualsinnaturalandtreatedwatersandwastewatereffluents.No
differentiation of free and combined chlorine is possible. This
procedureisanadaptationofotheriodometrictechniquesandissubject
tothesameinferences.

4. Sampling and Storage

Chlorineinaqueoussolutionisnotstable,andthechlorinecontentof
samplesorsolutions,particularlyweaksolutions,willdecreaserapidly.
Exposuretosunlightorotherstronglightoragitationwillacceleratethe
reduction of chlorine. Therefore, start chlorine determinations
immediatelyaftersampling,avoidingexcessivelightandagitation.Do
notstoresamplestobeanalyzedforchlorine.

5. Reference
1. COOPER, W.J., N.M. ROSCHER & R.A. SLIFER. 1982. Determining free
available chlorine by DPDcolorimetric, DPDsteadifac (colorimetric) and
FACTSprocedures.J.Amer.WaterWorksAssoc.74:362.

6. Bibliography
MARKS,H.C.,D.B.WILLIAMS&G.U.GLASGOW.1951.Determinationofresidual
chlorinecompounds.J.Amer.WaterWorksAssoc.43:201.
NICOLSON, N.J. 1965. An evaluation of the methods for determining residual
chlorineinwater,Part1.Freechlorine.Analyst90:187.
WHITTLE,G.P.&A.LAPTEFF,JR.1973.Newanalyticaltechniquesforthestudy
of water disinfection. In Chemistry of Water Supply, Treatment, and
Distribution,p.63.AnnArborSciencePublishers,AnnArbor,Mich.
GUTER,W.J.,W.J.COOPER&C.A.SORBER.1974.Evaluationofexistingfieldtest
kitsfordeterminingfreechlorineresidualsinaqueoussolutions. J.Amer.
WaterWorksAssoc.66:38.

4500-Cl B. Iodometric
Method I
1.

General Discussion

a. Principle:Chlorinewillliberatefreeiodinefrompotassiumiodide
(KI)solutionsatpH8orless.Theliberatediodineistitratedwitha
standardsolutionof sodium thiosulfate (Na 2S2O3)withstarchas the
indicator.TitrateatpH3to4becausethereactionisnotstoichiometric
atneutralpHduetopartialoxidationofthiosulfatetosulfate.
b. Interference: Oxidized forms of manganese and other

oxidizingagentsinterfere.Reducingagentssuchasorganicsulfides
also interfere. Although the neutral titration minimizes the
interfering effect of ferric and nitrite ions, the acid titration is
preferredbecausesomeformsofcombinedchlorinedonotreactat
pH 7. Use only acetic acid for the acid titration; sulfuric acid
(H2SO4)willincreaseinterferences; neverusehydrochloricacid
(HCl).SeeSectionA.3fordiscussionofotherinterferences.

c. Minimum detectable concentration: The minimum detectable

concentrationapproximates40gClasCl2/Lif0.01NNa2S2O3isusedwith
a1000mLsample.Concentrationsbelow
1 mg/Lcannotbedeterminedaccuratelybythestarchiodideendpointused
in this method. Lower concentrations can be measured with the
amperometricendpointinMethodsCandD.

2. Reagents

a. Aceticacid,conc(glacial).
b. Potassiumiodide,KI,crystals.
c. Standardsodiumthiosulfate,0.1N:Dissolve25gNa2S2O35H2Oin

1 L freshly boileddistilled water and standardize against potassium bi

iodateorpotassiumdichromateafteratleast2weeksstorage.Thisinitial
storage is necessaryto allow oxidation of anybisulfite ionpresent.Use
boileddistilled

CHLORINE (RESIDUAL) (4500-Cl)/Iodometric Method I

waterandaddafewmilliliterschloroform(CHCl3)tominimizebacterial
decomposition.
Standardize0.1NNa2S2O3byoneofthefollowing:
1) Iodate methodDissolve 3.249 g anhydrous potassium biiodate,
KH(IO3)2,primarystandardquality,or3.567gKIO 3driedat1032Cfor1h,in
distilledwateranddiluteto1000mLtoyielda0.1000N solution.Storeina
glassstopperedbottle.
To80mLdistilledwater,add,withconstantstirring,1mLconcH 2SO4,10.00
mL0.1000N KH(IO3)2,and1gKI.Titrate immediatelywith0.1N Na2S2O3
titrantuntiltheyellowcoloroftheliberatediodinealmostisdischarged.Add1
mLstarchindicatorsolutionandcontinuetitratinguntilthebluecolordisappears.
2) Dichromate methodDissolve 4.904 g anhydrous potassium

dichromate,K2Cr2O7,ofprimarystandardquality,indistilledwaterand
diluteto1000mLtoyielda0.1000N solution.Storeinaglassstoppered
bottle.
Proceed as in the iodate method, with the following exceptions:
Substitute10.00mL0.1000N K2Cr2O7 foriodateandletreactionmixture
stand6mininthedarkbeforetitratingwith0.1NNa2S2O3titrant.
NormalityNa2S2O3

459
liberatediodinealmostisdischarged.Add1mLstarchsolutionandtitrate
untilbluecolorisdischarged.
Ifthetitrationismadewith0.025NNa2S2O3insteadof0.01N,then,witha
1Lsample,1dropisequivalenttoabout50g/L.Itisnotpossibleto
discerntheendpointwithgreateraccuracy.d.Blanktitration:Correctresult
ofsampletitrationbydeterminingblankcontributedbyoxidizingor
reducingreagentimpurities.Theblankalsocompensatesforthe
concentrationof

iodineboundtostarchattheendpoint.
Takeavolumeofdistilledwatercorrespondingtothesampleused
fortitrationins3ac,add5mLaceticacid,1gKI,and1mLstarch
solution. Perform blank titration as in 1) or 2) below, whichever
applies.

1) If a blue color develops, titrate with 0.01N or 0.025N Na2S2O3 to

disappearanceofbluecolorandrecordresult.B(see
4,below)isnegative.

2) Ifnobluecoloroccurs,titratewith0.0282N iodinesolutionuntila
bluecolorappears.Backtitratewith0.01Nor0.025NNa2S2O3andrecord
thedifference.Bispositive.
Beforecalculatingthechlorineconcentration,subtracttheblanktitration
of1)fromthesampletitration;or,ifnecessary,addthenetequivalent
valueoftheblanktitrationof2).

mLNa2S2O3consumed

d. Standard sodium thiosulfate titrant, 0.01N or 0.025N: Improve the

stabilityof0.01N or0.025N Na2S2O3 bydilutinganaged0.1N solution,
madeasdirectedabove,withfreshlyboileddistilledwater.Add4gsodium
borateand10mgmercuriciodide/Lsolution.Foraccuratework,standardize
this solution daily in accordance with the directions given above, using
0.01N or 0.025N iodate or K2Cr2O7. Use sufficient volumes of these
standardsolutionssothattheirfinaldilutionisnotgreaterthan14.Tospeed
upoperationswheremanysamplesmustbetitrateduseanautomaticburet
of a type in which rubber does not come in contact with the solution.
Standard titrants, 0.0100N and 0.0250N, are equivalent, respectively, to
354.5gand886.3gClasCl2/1.00mL.
e. Starch indicator solution: To 5 g starch (potato, arrowroot, or

soluble),addalittlecoldwaterandgrindinamortartoathinpaste.
Pourinto1Lofboilingdistilledwater,stir,andletsettleovernight.Use
clearsupernate.Preservewith1.25gsalicylicacid,4gzincchloride,or
acombinationof4gsodiumpropionateand2gsodiumazide/Lstarch
solution.Somecommercialstarchsubstitutesaresatisfactory.
f. Standardiodine,0.1N:SeeC.3g.
g. Dilutestandardiodine,0.0282N:SeeC.3h.

3. Procedure
a. Volumeofsample:Selectasamplevolumethatwillrequirenomore
than20mL0.01N Na2S2O3 andnolessthan0.2mLforthestarchiodide
endpoint.Forachlorinerangeof1to10mg/L,usea500mL sample;
above10mg/L,useproportionatelylesssample.Usesmallersamplesand
volumesoftitrantwiththeamperometricendpoint.
b. Preparationfortitration: Place5mLaceticacid,orenough to

reducethepHtobetween3.0and4.0,inaflaskorwhiteporcelain
casserole.Addabout1gKIestimatedonaspatula.Poursampleinand
mixwithastirringrod.

c. Titration:Titrateawayfromdirectsunlight.Add0.025Nor0.01NNa2S2O3
fromaburetuntiltheyellowcolorofthe

4. Calculation

Forstandardizingchlorinesolutionfortemporarystandards:

mgClasCl2/mL

(AB) N 35.45

mLsample

Fordeterminingtotalavailableresidualchlorineinawatersample:

mgClasCl2/L(AB)N35450mLsample

where:
A

mLtitrationforsample,

BmLtitrationforblank(positiveornegative),andNnormalityof
Na2S2O3.

5. Precision and Bias

Publishedstudies1,2givetheresultsofninemethodsusedtoanalyze
syntheticwatersampleswithoutinterferences;variationsofsomeofthe
methodsappearinthisedition.Morecurrentdataarenotnowavailable.

6. References
1. Water Chlorine (Residual) No. 1. 1969. Analytical Reference Service
Rep.No.35,U.S.EnvironmentalProtectionAgency,Cincinnati,Ohio.
2. Water Chlorine (Residual) No. 2. 1971. Analytical Reference Service
Rep.No.40,U.S.EnvironmentalProtectionAgency,Cincinnati,Ohio.

4-60

INORGANIC NONMETALS
(4000)

7. Bibliography
LEA,C.1933.Chemicalcontrolofsewagechlorination.Theuseandvalueof
orthotolidinetest.J.Soc.Chem.Ind.(London)52:245T.
AMERICANWATERWORKSASSOCIATION.1943.Committeereport.Controlof
chlorination.J.Amer.WaterWorksAssoc.35:1315.
MARKS,H.C.,R.JOINER&F.B.STRANDSKOV.1948.Amperometrictitrationof
residualchlorineinsewage.WaterSewageWorks95:175.

STRANDSKOV,F.B.,H.C.MARKS&D.H.HORCHIER.1949.Applicationofanew
residualchlorinemethodtoeffluentchlorination.SewageWorksJ.21:23.

NUSBAUM,I.&L.A.MEYERSON.1951.Determinationofchlorinedemands
andchlorineresidualsinsewage.SewageInd.Wastes23:968.
MARKS,H.C.&N.S.CHAMBERLIN.1953.Determinationofresidualchlorinein
metalfinishingwastes.Anal.Chem.24:1885.

4500-Cl C. Iodometric Method

II
1.

General Discussion

a. Principle: Inthismethod,usedforwastewateranalysis,the end

pointsignalisreversedbecausetheunreactedstandardreducingagent
(phenylarsineoxideorthiosulfate)remaininginthesampleistitrated
withstandardiodineorstandardiodate,ratherthantheiodinereleased
beingtitrateddirectly.Thisindirectprocedureisnecessaryregardless
ofthemethodofendpointdetection,toavoidcontactbetweenthefull
concentrationofliberatediodineandthewastewater.
Wheniodateisusedasabacktitrant,useonlyphosphoricacid.Donot
useacetatebuffer.

b. Interference: Oxidizedformsofmanganeseandotheroxidizing
agents give positive interferences. Reducing agents such as organic
sulfidesdonotinterfereasmuchasinMethodB.Minimizeironand
nitrite interference by buffering to pH 4.0 before adding potassium
iodide(KI). Anunusuallyhighcontentoforganicmattermaycause
some uncertainty in the end point. Whenever manganese, iron, and
other interferences definitely are absent, reduce this uncertainty and
improveprecisionbyacidifyingtopH1.0.Controlinterferencefrom
morethan0.2mgnitrite/Lwithphosphoricacidsulfamicacidreagent.
AlargerfractionoforganicchloramineswillreactatlowerpHalong
withinterferingsubstances.SeeSectionA.3foradiscussionofother
interferences.

2. Apparatus
Foradescriptionoftheamperometricendpointdetectionapparatusanda
discussionofitsuse,seeD.2a.

3. Reagents
a. Standard phenylarsine oxide solution, 0.005 64N: Dissolve
approximately0.8gphenylarsineoxidepowderin150mL0.3NNaOH
solution.Aftersettling,decant110mLinto800mLdistilledwaterand
mixthoroughly.BringtopH6to7with6NHClanddiluteto950mL
withdistilledwater.CAUTION:Severepoison,cancersuspectagent.
StandardizationAccurately measure 5 to 10 mL freshly stan
dardized0.0282Niodinesolutionintoaflaskandadd1mLKIsolution.
Titratewithphenylarsineoxidesolution,usingtheamperometricend
point(MethodD)orstarchsolution(seeB.2e)asanindicator.Adjustto
0.00564N andrecheckagainstthestandardiodinesolution;1.00mL
200 g available chlorine. (C AUTION: Toxictake care to avoid
ingestion.)
b. Standardsodiumthiosulfatesolution,0.1N:SeeB.2c.

c. Standard sodium thiosulfate solution, 0.005 64N: Prepare by

diluting0.1N Na2S2O3.Formaximumstabilityofthedilutesolution,
preparebydilutinganaged0.1N solutionwithfreshlyboileddistilled
water(tominimizebacterialaction)andadd4gNa 4B4O7/L.Toinhibit
moldformationoptionallyaddeither10mgHgI 2or2dropstolueneper
literofsolution.StandardizedailyasdirectedinB.2cusing0.00564N
K2Cr2O7oriodatesolution.Usesufficientvolumeofsamplesothatthe
finaldilutiondoesnotexceed12.Useanautomaticburetofatypein
whichrubberdoesnotcomeincontactwiththesolution.1.00mL200g
availablechlorine.
d. Potassiumiodide,KI,crystals.
e. Acetatebuffersolution,pH4.0:Dissolve146ganhydrousNaC2H3O2,
or243gNaC2H3O23H2O,in400mLdistilledwater,add480gconcacetic
acid,anddiluteto1Lwithchlorinedemandfreewater.

f. Standardarsenitesolution, 0.1N:Accuratelyweighastoppered
weighing bottle containing approximately 4.95 g arsenic trioxide,
As2O3.Transferwithoutlosstoa1Lvolumetricflaskandagainweigh
bottle.Donotattempttobrushoutadheringoxide.MoistenAs 2O3with
water and add 15 g NaOH and 100 mL distilled water. Swirl flask
contentsgentlytodissolve.Diluteto250mLwithdistilledwaterand
saturate with CO2, thus converting all NaOH to NaHCO3. Dilute to
mark,stopper,andmixthoroughly.Thissolutionwillpreserveitstiter
almostindefinitely.(CAUTION:Severepoison.Cancersuspectagent.)
Normality

gAs2O3
49.455

g. Standard iodine solution, 0.1N: Dissolve 40 g KI in 25 mL

chlorinedemandfreewater,add13gresublimediodine,andstiruntil
dissolved.Transfertoa1Lvolumetricflaskanddilutetomark.
StandardizationAccurately measure 40 to 50 mL 0.1N arsenite
solutionintoaflaskandtitratewith0.1Niodinesolution,usingstarch
solutionasindicator.Toobtainaccurateresults,insurethatthesolution
is saturated with CO2 at end of titration by passing current of CO 2
throughsolutionforafewminutesjustbeforeendpointisreached,or
addafewdropsofHCltoliberatesufficientCO 2tosaturatesolution.
AlternativelystandardizeagainstNa2S2O3;seeB.2c1).
Optionally, prepare 0.1000N iodine solution directly as a standard
solutionbyweighing12.69gprimarystandardresublimediodine.Because
I2maybevolatilizedandlosefrombothsolidandsolution,transferthesolid
immediatelytoKIasspec

CHLORINE (RESIDUAL) (4500-Cl)/Iodometric Method II

ifiedabove.Neverletsolutionstandinopencontainersforextended
periods.
h. Standardiodinetitrant,0.0282N:Dissolve25gKIinalittledistilled
waterina1Lvolumetricflask,addcorrectamountof0.1Niodinesolution
exactlystandardizedtoyielda0.0282N solution,anddilute to1Lwith
chlorinedemandfreewater.Foraccuratework,standardizedailyaccording
to directions in 3g above, using 5 to 10 mL of arsenite or Na 2S2O3
solution.Storeinamberbottlesorinthedark;protectsolutionfromdirect
sunlightatalltimesandkeepfromallcontactwithrubber.
i. Starchindicator:SeeB.2e.
j. Standard iodate titrant, 0.005 64N: Dissolve 201.2 mg primary
standardgradeKIO3,driedfor1hat103C,or183.3mgprimarystandard
anhydrouspotassiumbiiodateindistilledwateranddiluteto1L.
k. Phosphoricacidsolution,H3PO4,19.
l. Phosphoricacidsulfamicacidsolution:Dissolve20gNH2SO3Hin1L1
9phosphoricacid.

m. Chlorinedemandfree water: Prepare chlorinedemandfree

water from goodquality distilled or deionized water by adding

sufficientchlorinetogive5mg/Lfreechlorine.Afterstanding2d
thissolutionshouldcontainatleast2mg/Lfreechlorine;ifnot,
discard and obtain betterquality water. Remove remaining free
chlorine by placing container in sunlight or irradiating with an
ultraviolet lamp. After several hours take sample, add KI, and
measuretotalchlorinewithacolorimetricmethodusinganessler
tubetoincreasesensitivity.Donotusebeforelasttraceoffreeand
combinedchlorinehasbeenremoved.

Distilledwatercommonlycontainsammoniaandalsomaycontain
reducingagents.Collectgoodqualitydistilledordeionizedwaterina
sealedcontainerfromwhichwatercanbedrawnbygravity.Totheair
inletofthecontaineraddanH 2SO4trapconsistingofalargetesttube
halffilledwith11H2SO4connectedinserieswithasimilarbutempty
testtube.Fitbothtesttubeswithstoppersandinlettubesterminating
nearthebottomofthetubesandoutlettubesterminatingnearthetopof
thetubes.ConnectoutlettubeoftrapcontainingH 2SO4tothedistilled
watercontainer, connectinlettubeto outlet of emptytesttube. The
emptytesttubewillpreventdischargetotheatmosphereofH 2SO4due
totemperatureinducedpressurechanges.Storedinsuchacontainer,
chlorinedemandfreewaterisstableforseveralweeksunlessbacterial
growthoccurs.

4. Procedure

a. Preparationfortitration:
1) Volume of sampleFor chlorine concentration of 10 mg/L or
less, titrate 200 mL. For greater chlorine concentrations, use
proportionately less sample and dilute to 200 mL with chlorine
demandfreewater.Useasampleofsuchsizethatnotmorethan10mL
phenylarsineoxidesolutionisrequired.
2) PreparationfortitrationMeasure5mL0.00564Nphenylarsine
oxideorthiosulfateforchlorineconcentrationsfrom2to5mg/L,and
10mLforconcentrationsof5to10mg/L,intoaflaskorcasserolefor
titrationwithstandardiodineoriodate.Startstirring.Fortitrationby
amperometryorstandardiodine,

461
alsoaddexcessKI(approximately1g)and4mLacetatebuffersolutionor
enoughtoreducethepHtobetween3.5and4.2.

b.Titration:Useoneofthefollowing:
1) Amperometric titrationAdd 0.0282N iodine titrant in small
incrementsfroma1mLburetorpipet.Observemeterneedleresponse
asiodineisadded:thepointerremainspracticallystationaryuntilthe
end point is approached, whereupon each iodine increment causes a
temporarydeflectionofthemicroammeter,withthepointerdropping
backtoitsoriginalposition.Stoptitrationatendpointwhenasmall
incrementofiodinetitrantgivesadefinitepointerdeflectionupscale
andthepointerdoesnotreturnpromptlytoitsoriginalposition.Record
volumeofiodinetitrantusedtoreachendpoint.
2) Colorimetric(iodine)titrationAdd1mLstarchsolutionandtitrate
with0.0282Niodinetothefirstappearanceofbluecolorthatpersistsafter
completemixing.

3) Colorimetric (iodate) titrationTo suitable flask or casserole

add200mLchlorinedemandfreewaterandadd,withagitation,the
requiredvolumeofreductant,anexcessofKI(approximately0.5g),2
mL10%H3PO4solution,and1mLstarchsolutionintheordergiven,
and titrate immediately* with 0.005 64N iodate solution to the first
appearance of a blue color that persists after complete mixing.
Designate volume of iodate solution used as A. Repeat procedure,
substituting 200 mL sample for the 200 mL chlorinedemandfree
water.Ifsampleiscoloredorturbid,titratetothefirstchangeincolor,
using for comparison another portion of sample with H 3PO4 added.
DesignatethisvolumeofiodatesolutionasB.

5. Calculation

a.Titrationwithstandardiodine:
(A 5B)
mgClasCl2/L

200

where:
A

mL0.00564Nreductant,

B
C

mL0.0282NI2,and
mLsample.

b.Titrationwithstandardiodate:
(A
mgClasCl2/L

B)

200

where:
A
B
C

mLNa2S2O3,

mLiodaterequiredtotitrateNa2S2O3,and

mLsample.

6. Bibliography

SeeB.7.
*Titrationmaybedelayedupto10minwithoutappreciableerrorifH3PO4isnotaddeduntilimmediately
beforetitration.

4-62
(4000)

INORGANIC NONMETALS

4500-Cl D. Amperometric Titration Method

1.

General Discussion

Amperometrictitrationrequiresahigherdegreeofskillandcare
thanthecolorimetricmethods.Chlorineresidualsover2mg/Lare
measured best by means of smaller samples or by dilution with
waterthathasneitherresidualchlorinenorachlorinedemand.The
methodcanbeusedtodeterminetotalchlorineandcandifferentiate
betweenfreeandcombinedchlorine.Afurtherdifferentiationinto
monochloramineanddichloraminefractionsispossiblebycontrol
ofKIconcentrationandpH.
a. Principle:Theamperometricmethodisaspecialadaptationof
the polarographic principle. Free chlorine is titrated at a pH
between6.5and7.5,arangeinwhichthecombinedchlorinereacts
slowly.Thecombinedchlorine,inturn,istitratedinthepresenceof
theproperamountofKIinthepHrange3.5to4.5.Whenfree
chlorineisdetermined,thepHmustnotbegreaterthan7.5because
thereactionbecomessluggishathigherpHvalues,norlessthan6.5
becauseatlowerpHvaluessomecombinedchlorinemayreacteven
intheabsenceofiodide.Whencombinedchlorineisdetermined,
thepHmustnotbelessthan3.5becauseofincreasedinterferences
atlowerpHvalues,norgreaterthan4.5becausetheiodidereaction
is not quantitative at higher pH values. The tendency of
monochloramine to react more readily with iodide than does
dichloramine provides a means for further differentiation. The
additionofasmallamountofKIintheneutralpHrangeenables
estimationofmonochloraminecontent.LoweringthepHintothe
acid range and increasing the KI concentration allows the
separationdeterminationofdichloramine.
Organic chloramines can be measured as free chlorine, mono
chloramine,ordichloramine,dependingontheactivityofchlorinein
theorganiccompound.

Phenylarsineoxideisstableevenindilutesolutionandeachmole
reactswithtwoequivalentsofhalogen. Aspecialamperometric
cell is used to detect the end point of the residual chlorine
phenylarsineoxidetitration.Thecellconsistsofanonpolarizable
referenceelectrodethatisimmersedinasaltsolutionandareadily
polarizablenoblemetalelectrodethatisincontactwithboththe
saltsolutionandthesamplebeingtitrated.Insomeapplications,
endpointselectivityisimprovedbyadding200mVtotheplatinum
electrodeversussilver,silverchloride.Anotherapproachtoend
pointdetectionusesdualplatinumelectrodes,amercurycellwith
voltagedividertoimpressapotentialacrosstheelectrodes,anda
microammeter.Ifthereisnochlorineresidualinthesample,the
microammeterreadingwillbecomparativelylowbecauseofcell
polarization.Thegreatertheresidual,thegreaterthemicroammeter
reading.Themeteractsmerelyasanullpointindicatorthatis,the
actual meter reading is not important, but rather the relative
readings as the titration proceeds. The gradual addition of
phenylarsine oxide causes the cell to become more and more
polarized because of the decrease in chlorine. The end point is
recognized when no further decrease in meter reading can be
obtainedbyaddingmorephenylarsineoxide.
b. Interference:Accuratedeterminationsoffreechlorinecannotbemadein
thepresenceofnitrogentrichloride,NCl3,or

chlorinedioxide,whichtitratepartlyasfreechlorine.Whenpresent,
NCl3 can titrate partly as free chlorine and partly as dichloramine,
contributingapositiveerrorinbothfractionsatarateofapproximately
0.1%/min.Someorganicchloraminesalsocanbetitratedineachstep.
Monochloramine can intrude into the free chlorine fraction and
dichloraminecaninterfereinthemonochloraminefraction,especiallyat
high temperaturesandprolongedtitrationtimes. Freehalogens other
thanchlorinealsowilltitrateasfreechlorine.Combinedchlorinereacts
with iodide ions to produce iodine. When titration for free chlorine
followsacombinedchlorinetitration,whichrequiresadditionofKI,
erroneous results may occur unless the measuring cell is rinsed
thoroughlywithdistilledwaterbetweentitrations.

Interferencefromcopperhasbeennotedinsamplestakenfrom
copperpipeorafterheavycoppersulfatetreatmentofreservoirs,
withmetalliccopperplatingoutontheelectrode.Silverionsalso
poison the electrode. Interference occurs in some highly colored
waters and in waters containing surfaceactive agents. Very low
temperaturesslowresponseofmeasuringcellandlongertimeis
requiredforthetitration,butprecisionisnotaffected.Areduction
inreactionrateiscausedbypHvaluesabove7.5;overcomethisby
bufferingallsamplestopH7.0orless.Ontheotherhand,some
substances,suchasmanganese,nitrite,andiron,donotinterfere.
Theviolentstirringofsomecommercialtitratorscanlowerchlorine
values by volatilization. When dilution is used for samples
containinghighchlorinecontent,takecarethatthedilutionwateris
freeofchlorineandammoniaandpossessesnochlorinedemand.
SeeA.3foradiscussionofotherinterferences.

2. Apparatus
a. Endpointdetectionapparatus,consistingofacellunitconnected
toamicroammeter,withnecessaryelectricalaccessories.Thecellunit
includesanoblemetalelectrodeofsufficientsurfacearea,asaltbridge
toprovideanelectricalconnectionwithoutdiffusionofelectrolyte,and
a reference electrode of silversilver chloride in a saturated sodium
chloridesolutionconnectedintothecircuitbymeansofthesaltbridge.
Numerouscommercialsystemsareavailable.
Keep platinum electrode free of deposits and foreign matter.
Vigorous chemical cleaning generally is unnecessary. Occasional
mechanicalcleaningwithasuitableabrasiveusuallyissufficient.Keep
salt bridge in good operating condition; do not allow it to become
plugged nor permit appreciable flow of electrolyte through it. Keep
solution surrounding reference electrode free of contamination and
maintainitatconstantcompositionbyinsuringanadequatesupplyof
undissolvedsaltatalltimes.Acellwithtwometalelectrodespolarized
byasmallDCpotentialalsomaybeused.(SeeBibliography.)
b. Agitator, designedtogiveadequateagitationatthenoblemetal
electrodesurfacetoinsurepropersensitivity.Thoroughlycleanagitator
and exposed electrode system to remove all chlorine consuming
contaminantsbyimmersingtheminwatercontaining1to2mg/Lfree
chlorineforafewminutes.AddKItothesamewaterandletagitator
andelectrodesremainimmersedfor5min.Afterthoroughrinsingwith
chlorinedemandfree

CHLORINE (RESIDUAL) (4500-Cl)/Amperometric Titration

Method

waterorthesampletobetested,sensitizedelectrodesandagitator
arereadyforuse.Removeiodidereagentcompletelyfromcell.
c. Buret:Commercialtitratorsusuallyareequippedwithsuitableburets
(1mL).Manualburetsareavailable.*
d. Glassware,exposedtowatercontainingatleast10mg/Lchlorine

for3hormorebeforeuseandrinsedwithchlorinedemandfreewater.

3. Reagents

a. Standardphenylarsineoxidetitrant:SeeC.3a.
b. Phosphate buffer solution, pH 7: Dissolve 25.4 g anhydrous

KH2PO4 and 34.1 ganhydrous Na2HPO4 in800 mLdistilledwater.

Add2mLsodiumhypochloritesolutioncontaining1%chlorineand
mix thoroughly. Protect from sunlight for 2 d. Determine that free
chlorinestillremainsinthesolution.Thenexposetosunlightuntilno
chlorineremains.Ifnecessary,carryoutthefinaldechlorinationwithan
ultravioletlamp.DeterminethatnototalchlorineremainsbyaddingKI
andmeasuringwithoneofthecolorimetrictests.Diluteto1Lwith
distilledwaterandfilterifanyprecipitateispresent.
c. Potassiumiodidesolution:Dissolve50gKIanddiluteto1Lwith
freshlyboiledandcooleddistilledwater.Storeinthedarkinabrown
glassstoppered bottle, preferably in the refrigerator. Discard when
solutionbecomesyellow.
d. Acetatebuffersolution,pH4:SeeC.3e.

463

titration after recording figure for free chlorine. Again subtract last
increment to give amount of titrant actually used in reaction with
chlorine.(Iftitrationwascontinuedwithoutrefillingburet,thisfigure
represents total chlorine. Subtracting free chlorine from total gives
combined chlorine.) Wash apparatus and sample cell thoroughly to
remove iodide ion to avoid inaccuracies when the titrator is used
subsequentlyforafreechlorinedetermination.
d. Separate samples: If desired, determine total chlorine and free
chlorineonseparatesamples.IfsamplepHisbetween3.5and9.5and
totalchlorinealoneisrequired,treatsampleimmediatelywith1mLKI
solution followed by 1 mL acetate buffer solution, and titrate with
phenylarsineoxidetitrantasdescribedin4cpreceding.
e. Monochloramine:Aftertitratingforfreechlorine,add0.2mLKI
solutiontosamesampleand,withoutrefillingburet,continuetitration
withphenylarsineoxidetitranttoendpoint.Subtractlastincrementto
obtainnetvolumeoftitrantconsumedbymonochloramine.
f. Dichloramine:Add1mLacetatebuffersolutionand1mLKIsolution
tosamesampleandtitratefinaldichloraminefractionasdescribedabove.

5. Calculation
Convertindividualtitrationsforfreechlorine,combinedchlorine,total
chlorine,monochloramine,anddichloraminebythefollowingequation:

4. Procedure

A 200

mgClasCl2/L

a. Samplevolume:Selectasamplevolumerequiringnomorethan2

mLsample

mLphenylarsineoxidetitrant.Thus,forchlorineconcentrationsof2
mg/Lorless,takea200mLsample;forchlorinelevelsinexcessof2
mg/L,use100mLorproportionatelyless.
b. Freechlorine:UnlesssamplepHisknowntobebetween6.5and
7.5,add1mLpH7phosphatebuffersolutiontoproduceapHof6.5to
7.5.Titratewithstandardphenylarsineoxidetitrant,observingcurrent
changes on microammeter. Add titrant in progressively smaller
increments untilallneedlemovement ceases.Makesuccessiveburet
readingswhenneedleactionbecomessluggish,signalingapproachof
end point. Subtract last very small increment that causes no needle
responsebecauseofovertitration.Alternatively,useasysteminvolving
continuous current measurements and determine end point
mathematically.

where:

c. Combined chlorine: To sample remaining from freechlorine

titrationadd1.00mLKIsolutionand1mLacetatebuffersolution,in
thatorder.Titratewithphenylarsineoxidetitranttotheendpoint,as
above.Donotrefillburetbutsimplycontinue

FOULK,C.W.&A.T.B AWDEN.1926.Anewtypeofendpointinelectrometric
titrationanditsapplicationtoiodimetry.J.Amer.Chem.Soc.48:2045.

*Kimax17110F,5mL,KimbleProducts,Box1035,Toledo,OH,orequivalent.

MAHAN, W.A. 1949. Simplified amperometric titration apparatus for

determiningresidualchlorineinwater.WaterSewageWorks96:171.

Continuetitratingforcombinedchlorineasdescribedin4cbeloworfor
theseparatemonochloramineanddichloraminefractionsasdetailedins4e
and4.

mLphenylarsineoxidetitration.

6. Precision and Bias

SeeB.5.
7. Bibliography

MARKS, H.C. & J.R. GLASS. 1942. A new method of determining residual
chlorine.J.Amer.WaterWorksAssoc.34:1227.
HALLER,J.F.&S.S.LISTEK.1948.Determinationofchloridedioxideandother
activechlorinecompoundsinwater.Anal.Chem.20:639.

KOLTHOFF, I.M. & J.J. L INGANE. 1952. Polarography, 2nd ed. Interscience
Publishers,NewYork,N.Y.
MORROW, J.J. 1966. Residual chlorine determination with dual polarizable
electrodes.J.Amer.WaterWorksAssoc.58:363.

4-64
(4000)

INORGANIC NONMETALS

4500-Cl E. Low-Level Amperometric Titration Method

1.

General Discussion

4. Procedure

Detection and quantification of chlorine residuals below 0.2

mg/L require special modifications to the amperometric titration
procedure.Withthesemodificationschlorineconcentrationsatthe
10g/Llevelcanbemeasured.Itisnotpossibletodifferentiate
betweenfreeandcombinedchlorineforms.Oxidizingagentsthat
interferewiththeamperometrictitrationmethod(D)willinterfere.

a. Principle:ThismethodmodifiesDbyusingamoredilutetitrantand
agraphicalproceduretodeterminetheendpoint.
b. Interference:SeeD.1b.

2. Apparatus

SeeD.2.
3. Reagents
a. Potassium biiodate, 0.002 256N: Dissolve 0.7332 g anhydrous
potassiumbiiodate,KH(IO3)2,in500mLchlorinefreedistilledwaterand
diluteto1000mL.Dilute10.00mLto100.0mLwithchlorinefreedistilled
water. Use only freshly prepared solution for the standardization of
phenylarsineoxide.
b. Potassiumiodide,KIcrystals.
c. Lowstrengthphenylarsineoxidetitrant, 0.000564N:Dilute10.00
mLof0.00564Nphenylarsineoxide(seeC.3a)to100.0mLwithchlorine
demandfreewater(seeC.3m).

StandardizationDilute5.00mL0.002256Npotassiumbiiodateto
200mLwithchlorinefreewater.Addapproximately1.5gKIandstir
todissolve.Add1mLacetatebufferandletstandinthedarkfor6min.
Titrateusingtheamperometrictitratoranddeterminetheequivalence
pointasindicatedbelow.
Normality

0.002256

Selectasamplevolumerequiringnomorethan2mLphenylarsineoxide
titrant.A200mLsamplewillbeadequateforsamplescontaininglessthan
0.2mgtotalchlorine/L.

Beforebeginningtitration,rinseburetwithtitrantseveraltimes.
Rinsesamplecontainerwithdistilledwaterandthenwithsample.
Add200mLsampletosamplecontainerandapproximately1.5g
KI.Dissolve,usingastirrerormixer.Add1mLacetatebufferand
placecontainerinendpointdetectionapparatus.Whenthecurrent
signalstabilizes,recordthereading.Initiallyadjustmetertoanear
fullscaledeflection.Titratebyaddingsmall,known,volumesof
titrant.Aftereachaddition,recordcumulativevolumeaddedand
currentreadingwhenthesignalstabilizes.Ifmeterreadingfallsto
near or below 10% of fullscale deflection, record low reading,
readjustmetertonearfullscaledeflection,andrecorddifference
betweenlowamountandreadjustedhighdeflection.Addthisvalue
toalldeflectionreadingsforsubsequenttitrantadditions.Continue
addingtitrantuntilnofurthermeterdeflectionoccurs.Iffewerthan
threetitrantadditionsweremadebeforemeterdeflectionceased,
discardsampleandrepeatanalysisusingsmallertitrantincrements.
Determine equivalence point by plotting total meter deflection
againsttitrantvolumeadded.Drawstraightlinethroughthefirstseveral
pointsintheplotandasecond,horizontalstraightlinecorrespondingto
thefinaltotaldeflectioninthemeter.Readequivalencepointasthe
volumeoftitrantaddedattheintersectionofthesetwolines.

5. Calculation
A 200 N

mgClasCl2/L

where:
A

B
N

B0.00564

mLtitrantatequivalencepoint,
samplevolume,mL,and
phenylarsineoxidenormality.

5/A

where:

AmLphenylarsineoxidetitrantrequiredtoreachthe
equivalencepointofstandardbiiodate.

d.Acetatebuffersolution,pH4:SeeC.3e.

6. Bibliography
BROOKS,A.S.&G.L.SEEGERT.1979.Lowlevelchlorineanalysisby
amperometrictitration.J.WaterPollut.ControlFed.51:2636.

4500-Cl F. DPD Ferrous Titrimetric

Method
1.

General Discussion

a.Principle:N,Ndiethylpphenylenediamine(DPD)isused asan
indicatorinthetitrimetricprocedurewithferrousammoniumsulfate
(FAS). Where complete differentiation of chlorine species is not
required, the procedure may be simplified to give only free and
combinedchlorineortotalchlorine.

Intheabsenceofiodideion,freechlorinereactsinstantlywithDPD
indicatortoproducearedcolor.Subsequentadditionofasmallamount
ofiodideionactscatalyticallytocausemonochloraminetoproduce
color.Additionofiodideiontoexcessevokesarapidresponsefrom
dichloramine. In the presence of iodide ion, part of the nitrogen
trichloride (NCl3) is included with dichloramine and part with free
chlorine.Asupplementarypro

CHLORINE (RESIDUAL) (4500-Cl)/DPD Ferrous Titrimetric

Method
cedurebasedonaddingiodideionbeforeDPDpermitsestimatingproportionof
NCl3appearingwithfreechlorine.
Chlorinedioxide(ClO2)appears,totheextentofonefifthofitstotalchlorine
content,withfreechlorine.AfullresponsefromClO 2,correspondingtoitstotal
chlorinecontent,maybeobtainedifthesamplefirstisacidifiedinthepresence
ofiodideionandsubsequentlyisbroughtbacktoanapproximatelyneutralpHby
adding bicarbonate ion. Bromine, bromamine, and iodine react with DPD
indicatorandappearwithfreechlorine.

Additionofglycinebeforedeterminationoffreechlorineconverts
free chlorine to unreactive forms, with only bromine and iodine
residualsremaining.Subtractionsoftheseresidualsfromtheresidual
measuredwithoutglycinepermitsdifferentiationoffreechlorinefrom
bromineandiodine.
b. pHcontrol: ForaccurateresultscarefulpHcontrolis essential.
AttheproperpHof6.2to6.5,theredcolorsproducedmaybetitrated
tosharpcolorlessendpoints.Titrateassoonastheredcolorisformed
in each step. Too low a pH in the first step tends to make the
monochloramineshowinthefreechlorinestepandthedichloramine
inthemonochloraminestep.ToohighapHcausesdissolvedoxygento
giveacolor.
c. Temperature control: In all methods for differentiating free
chlorinefromchloramines,highertemperaturesincreasethetendency
forchloramines to react andleadtoincreasedapparent freechlorine
results. Higher temperatures also increase color fading. Complete
measurementsrapidly,especiallyathighertemperature.
d. Interference:Themostsignificantinterferingsubstancelikely

tobeencounteredinwaterisoxidizedmanganese.Tocorrectfor
this, place 5 mL buffer solution and 0.5 mL sodium arsenite
solutioninthetitrationflask.Add100mLsampleandmix.Add5
mL DPD indicator solution, mix, and titrate with standard FAS
titrantuntilredcolorisdischarged.SubtractreadingfromReading
Aobtainedbythenormalprocedureasdescribedin3a1)ofthis
methodorfromthetotalchlorinereadingobtainedinthesimplified
proceduregivenin3a4).Ifthecombinedreagentinpowderform
(seebelow)isused,firstaddKIandarsenitetothesampleandmix,
thenaddcombinedbufferindicatorreagent.
As an alternative to sodium arsenite use a 0.25% solution of
thioacetamide,adding0.5mLto100mLsample.

Interferencebycopperuptoapproximately10mgCu/Lisovercome
bytheEDTAincorporatedinthereagents.EDTAenhancesstabilityof
DPDindicatorsolutionbyretardingdeteriorationduetooxidation,and
inthetestitself,providessuppressionofdissolvedoxygenerrorsby
preventingtracemetalcatalysis.
Chromateinexcessof2mg/Linterfereswithendpointdetermination.
Addbariumchloridetomaskthisinterferencebyprecipitation.

Highconcentrationsofcombinedchlorinecanbreakthroughintothe
freechlorinefraction.Iffreechlorineistobemeasuredinthepresence
of more than 0.5 mg/L combined chlorine, use the thioacetamide
modification.Ifthismodificationisnotused,acolordevelopmenttime
in excess of 1 min leads to progressively greater interference from
monochloramine. Adding thioacetamide (0.5 mL 0.25% solution to
100 mL) immediately after mixing DPD reagent with sample
completelystopsfurtherreactionwithcombinedchlorineinthefree
chlorine measurement. Continue immediately with FAS titration to
obtainfreechlorine.

465
Obtaintotalchlorinefromthenormalprocedure,i.e.,withoutthioacetamide.

Becausehighconcentrationsofiodideareusedtomeasurecombined
chlorine and only traces of iodide greatly increase chloramine
interferenceinfreechlorinemeasurements,takecaretoavoidiodide
contaminationbyrinsingbetweensamplesorusingseparateglassware.
SeeA.3foradiscussionofotherinterferences.

e. Minimumdetectableconcentration:Approximately18gClasCl2/L.This
detectionlimitisachievableunderidealconditions;normalworkingdetection
limitstypicallyarehigher.

2. Reagents
a. Phosphatebuffersolution: Dissolve 24g anhydrous Na2HPO4
and46ganhydrousKH 2PO4indistilledwater.Combinewith100mL
distilledwaterinwhich800mgdisodiumethylenediaminetetraacetate
dihydrate(EDTA)havebeendissolved.Diluteto1Lwithdistilled
water and optionally add either 20 mg HgCl 2 or 2 drops toluene to
preventmoldgrowth.Interferencefromtraceamountsofiodideinthe
reagentscanbenegatedbyoptionaladditionof20mgHgCl 2 tothe
solution.(CAUTION:HgCl2istoxictakecaretoavoidingestion.)
b. N,NDiethylpphenylenediamine (DPD) indicator solution:
Dissolve1gDPDoxalate,*or1.5gDPDsulfatepentahydrate,or1.1g
anhydrousDPDsulfateinchlorinefreedistilledwatercontaining8mL13
H2SO4 and200mgdisodiumEDTA.Makeupto1L,storeinabrown
glassstopperedbottleinthedark,anddiscardwhendiscolored.Periodically
checksolutionblankforabsorbanceanddiscardwhenabsorbanceat

515 nm exceeds 0.002/cm. (The buffer and indicator sulfate are

available commercially as a combined reagent in stable powder
form.)CAUTION:Theoxalateistoxictakecaretoavoidingestion.

c. Standardferrousammoniumsulfate(FAS)titrant:Dissolve1.106
gFe(NH4)2(SO4)26H2Oindistilledwatercontaining1mL13H2SO4
andmakeupto1Lwithfreshlyboiledandcooleddistilledwater.This
standardmaybeusedfor1month,andthetitercheckedbypotassium
dichromate.Forthispurposeadd10mL15H 2SO4,5mLconcH3PO4,
and2mL0.1%bariumdiphenylaminesulfonateindicatortoa100mL
sampleofFASandtitratewithpotassiumdichromatetoavioletend
point that persists for 30 s. FAS titrant equivalent to 100 g Cl as
Cl2/1.00mLrequires20.00mLdichromatefortitration.
d. Potassiumiodide,KI,crystals.
e. Potassiumiodidesolution:Dissolve500mgKIanddiluteto100
mL,usingfreshlyboiledandcooleddistilledwater.Storeinabrown
glassstoppered bottle, preferably in a refrigerator. Discard when
solutionbecomesyellow.
f. Potassiumdichromatesolution,0.691gto1000mL.
g. Barium diphenylaminesulfonate, 0.1%: Dissolve 0.1 g (C6H5NHC6H44
SO3)2Bain100mLdistilledwater.

h. Sodium arsenite solution: Dissolve 5.0 g NaAsO2 in distilled

wateranddiluteto1L.(CAUTION:Toxictakecaretoavoidingestion.)
*EastmanchemicalNo.7102orequivalent.
AvailablefromGallardSchlesingerChemicalMfg.Corp.,584MineloaAvenue,CarlePlace,NY
11514,orequivalent.

4-66
i. Thioacetamide solution: Dissolve 250 mg CH3CSNH2 in 100 mL
distilledwater.(CAUTION: Cancersuspectagent.Take caretoavoidskin
contactoringestion.)
j. Chlorinedemandfreewater:SeeC.3m.
k. Glycine solution: Dissolve 20 g glycine (aminoacetic acid) in

sufficientchlorinedemandfreewatertobringto100mLtotalvolume.
Storeunderrefrigeratedconditionsanddiscardifcloudinessdevelops.
l. Bariumchloridecrystals,BaCl22H2O.

3. Procedure
Thequantitiesgivenbelowaresuitableforconcentrationsoftotal
chlorineupto5mg/L.Iftotalchlorineexceeds5mg/L,useasmaller
sampleanddilutetoatotalvolumeof100mL.Mixusualvolumesof
bufferreagentandDPDindicatorsolution,orusualamountofDPD
powder,withdistilledwater before addingsufficientsampletobring
totalvolumeto100mL.(Ifsampleisaddedbeforebuffer,testdoesnot
work.)

If chromate is present ( 2 mg/L) add and mix 0.2 g BaCl 2

2H2O/100mLsamplebeforeaddingotherreagents.If,inaddition,
sulfateis500mg/L,use0.4gBaCl22H2O/100mLsample.
a. Freechlorineorchloramine: Place5mLeachofbufferreagent
andDPDindicatorsolutionintitrationflaskandmix(oruseabout500
mgDPDpowder).Add100mLsample,ordilutedsample,andmix.
1)FreechlorineTitraterapidlywithstandardFAStitrantuntilredcolor
isdischarged(ReadingA).

2)MonochloramineAddoneverysmallcrystalofKI(about

0.5 mg)or0.1mL(2drops)KIsolutionandmix.Continuetitratinguntil
redcolorisdischargedagain(ReadingB).

3)DichloramineAddseveralcrystalsKI(about1g)andmixto
dissolve.Letstandfor2minandcontinuetitratinguntilredcoloris
discharged(Reading C).Fordichloramineconcentrationsgreater
than 1 mg/L, let stand 2 min more if color driftback indicates
slightly incomplete reaction. When dichloramine concentrations
arenotexpectedtobehigh,usehalfthespecifiedamountofKI.
4) Simplified procedure for free and combined chlorine or total
chlorineOmit2)abovetoobtainmonochloramineanddichloramine
togetherascombinedchlorine.Toobtaintotalchlorineinonereading,
addfullamountofKIatthestart,withthespecifiedamountsofbuffer
reagentandDPDindicator,andtitrateafter2minstanding.

b. Nitrogentrichloride:PlaceoneverysmallcrystalofKI(about
0.5mg)or0.1mLKIsolutioninatitrationflask.Add100mL
sampleandmix.Addcontentstoasecondflaskcontaining5mL
eachofbufferreagentandDPDindicatorsolution(oraddabout
500mgDPDpowderdirecttothefirstflask).Titraterapidlywith
standardFAStitrantuntilredcolorisdischarged(ReadingN).

INORGANIC NONMETALS
(4000)

c.Freechlorineinpresenceofbromineoriodine: Determine free

chlorineasin3a1).Toasecond100mLsample,add1mLglycine
solutionbeforeaddingDPDandbuffer.Titrateaccordingto3a1).
SubtractthesecondreadingfromthefirsttoobtainReadingA.

4. Calculation
Fora100mLsample,1.00mLstandardFAStitrant1.00mgClasCl2/L.

Reading

NCl3Absent

NCl3Present

FreeCl

FreeCl

BA

NH2Cl

CB

NHCl

NH2Cl
NHCl

2NCl
3

N
2(NA)
CN

FreeCl12NCl3
NCl3

NHCl2

IntheeventthatmonochloramineispresentwithNCl 3,itwillbeincludedin
N,inwhichcaseobtainNCl3from2(NB).

Chlorinedioxide,ifpresent,isincludedinAtotheextentofonefifthof
itstotalchlorinecontent.
Inthesimplifiedprocedureforfreeandcombinedchlorine,onlyA(free
Cl)andC(totalCl)arerequired.ObtaincombinedchlorinefromCA.
Theresultobtainedinthesimplifiedtotalchlorineprocedurecorresponds
toC.

5. Precision and Bias

SeeB.5.
6. Bibliography
PALIN,A.T.1957.Thedeterminationoffreeandcombinedchlorineinwaterby
theuseofdiethylpphenylenediamine.J.Amer.Water
WorksAssoc.49:873.
PALIN,A.T.1960.Colorimetricdeterminationofchlorinedioxideinwater.Water
SewageWorks107:457.
PALIN,A.T.1961.Thedeterminationoffreeresidualbromineinwater.
WaterSewageWorks108:461.
NICOLSON,N.J.1963,1965,1966.Determinationofchlorineinwater,Parts1,2,
and3.WaterRes.Assoc.Tech.Pap.Nos.29,47,and53.
PALIN,A.T.1967.Methodsfordetermination,inwater,offreeandcombined
available chlorine, chlorine dioxide and chlorite, bromine, iodine, and
ozoneusingdiethylpphenylenediamine(DPD).
J.Inst.WaterEng.21:537.
PALIN, A.T. 1968. Determination of nitrogen trichloride in water.
J.Amer.WaterWorksAssoc.60:847.
PALIN,A.T.1975.CurrentDPDmethodsforresidualhalogencompoundsand
ozoneinwater.J.Amer.WaterWorksAssoc.67:32.
Methods for the Examination of Waters and Associated Materials. Chemical
DisinfectingAgentsinWaterandEffluents,andChlorineDemand.1980.
HerMajestys Stationery Off., London, England.

CHLORINE (RESIDUAL) (4500-Cl)/DPD Colorimetric Method

4-67

4500-Cl G. DPD Colorimetric Method

1.

General Discussion

a. Principle:ThisisacolorimetricversionoftheDPDmethodandis
basedonthesameprinciples.Insteadoftitrationwithstandardferrous
ammonium sulfate (FAS) solution as in the titrimetric method, a
colorimetricprocedureisused.
b. Interference:SeeA.3andF.1d.Compensateforcolorandturbidityby
usingsampletozerophotometer.Minimizechromateinterferencebyusing
thethioacetamideblankcorrection.

c. Minimumdetectableconcentration:Approximately10gClasCl2/L.This
detectionlimitisachievableunderidealconditions;normalworkingdetection
limitstypicallyarehigher.

2. Apparatus
a. Photometric equipment: One of the following is required: 1)
Spectrophotometer,foruseatawavelengthof515nmand

providingalightpathof1cmorlonger.

2) Filter photometer, equipped with a filter having maximum

transmissioninthewavelengthrangeof490to530nmandprovidingalight
pathof1cmorlonger.

b. Glassware: Use separate glassware, including separate

spectrophotometer cells, for free and combined (dichloramine)
measurements, to avoid iodide contamination in free chlorine
measurement.

3. Reagents

SeeF.2a,b,c,d,e,h,i,andj.
4. Procedure
a. Calibration of photometric equipment: Calibrate instrument with
chlorineorpotassiumpermanganatesolutions.

1) Chlorine solutionsPrepare chlorine standards in the range of

0.05to4mg/Lfromabout100mg/Lchlorinewaterstandardizedas
follows:Place2mLaceticacidand10to25mLchlorinedemandfree
waterinaflask.Addabout1gKI.Measureintotheflaskasuitable
volumeofchlorinesolution.Inchoosingaconvenientvolume,notethat
1mL0.025NNa2S2O3titrant(seeB.2d)isequivalenttoabout0.9mg
chlorine. Titrate with standardized 0.025N Na2S2O3 titrant until the
yellowiodinecoloralmostdisappears.Add1to2mLstarchindicator
solutionandcontinuetitratingtodisappearanceofbluecolor.
Determinetheblankbyaddingidenticalquantitiesofacid,KI,and
starch indicator to a volume of chlorinedemandfree water
correspondingtothesampleusedfortitration.PerformblanktitrationA
orB,whicheverapplies,accordingtoB.3d.
mgClasCl2/mL

(AB) N 35.45

mLsample

where:
NnormalityofNa2S2O3,AmL
titrantforsample,

BmLtitrantforblank(tobeaddedorsubtractedaccordingtorequired
blanktitration.SeeB.3d).

Usechlorinedemandfreewaterandglasswaretopreparethese
standards.Developcolorbyfirstplacing5mLphosphatebuffer
solutionand5mLDPDindicatorreagentinflaskandthenadding
100mLchlorinestandardwiththoroughmixingasdescribedinb
andcbelow.Fillphotometerorcolorimetercellfromflaskandread
color at 515 nm. Return cell contents to flask and titrate with
standardFAStitrantasacheckonchlorineconcentration.
2) Potassium permanganate solutionsPrepare a stock solution
containing891mgKMnO4/1000mL.Dilute10.00mLstocksolutionto
100mLwithdistilledwaterinavolumetricflask.When1mLofthis
solutionisdilutedto100mLwithdistilledwater,achlorineequivalent
of1.00mg/LwillbeproducedintheDPDreaction.Prepareaseriesof
KMnO4 standardscoveringthechlorineequivalentrangeof0.05to4
mg/L.Developcolorbyfirstplacing5mLphosphatebufferand5mL
DPD indicator reagent in flask and adding 100 mL standard with
thorough mixing as described in b and c below. Fill photometer or
colorimeter cell from flask and read color at 515 nm. Return cell
contents to flask and titrate with FAS titrant as a check on any
absorptionofpermanganatebydistilledwater.
Obtain all readings by comparison to color standards or the standard
curvebeforeuseincalculation.

b. Volume of sample: Use a sample volume appropriate to the

photometerorcolorimeter.Thefollowingprocedureisbasedonusing
10mL volumes; adjust reagent quantities proportionately for other
samplevolumes.Dilutesamplewithchlorinedemandfreewaterwhen
totalchlorineexceeds4mg/L.
c. Free chlorine: Place 0.5 mL each of buffer reagent and DPD
indicatorreagentinatesttubeorphotometercell.Add10mLsample
andmix.Readcolorimmediately(ReadingA).
d. Monochloramine: Continuebyaddingoneverysmallcrystalof
KI(about0.1mg)andmix.Ifdichloramineconcentrationisexpectedto
behigh,insteadofsmallcrystaladd0.1mL(2drops)freshlyprepared
KIsolution(0.1g/100mL).Readcolorimmediately(ReadingB).
e. Dichloramine: ContinuebyaddingseveralcrystalsofKI (about
0.1 g) and mix to dissolve. Let stand about 2 min and read color
(ReadingC).
f. Nitrogentrichloride:PlaceaverysmallcrystalofKI(about
0.1 mg)inacleantesttubeorphotometercell.Add10mLsampleand
mix.Toasecondtubeorcelladd0.5mLeachofbufferandindicator
reagents;mix.Addcontentstofirsttubeorcellandmix.Readcolor
immediately(ReadingN).

g. Chromate correction using thioacetamide: Add 0.5 mL

thioacetamidesolution(F.2i)to100mLsample.Aftermixing,add
buffer and DPD reagent. Read color immediately. Add several
crystalsofKI(about0.1g)andmixtodissolve.Letstandabout2
minandreadcolor.SubtractthefirstreadingfromReadingAand
thesecondreadingfromReadingCanduseincalculations.
h. Simplified procedure for total chlorine: Omit Step d above to
obtain monochloramine and dichloramine together as combined
chlorine.Toobtaintotalchlorineinonereading,addthefullamountof
KIatthestart,withthespecifiedamountsofbufferreagentandDPD
indicator.Readcolorafter2min.

4-68

INORGANIC NONMETALS
(4000)

5. Calculation
Reading

NCl3Absent

NCl3Present
FreeCl

FreeCl

BA

NH2Cl

NH2Cl

CB
N
2(NA)
CN

NHCl2

NHCl212NCl3

FreeCl12NCl3
NCl3

IntheeventthatmonochloramineispresentwithNCl 3,itwillbe
includedinReadingN,inwhichcaseobtainNCl3from2(NB).
6. Bibliography

SeeF.6.

NHCl2

4500-Cl H. Syringaldazine (FACTS)

Method
1.

General Discussion

a. Principle: The free (available) chlorine test, syringaldazine

(FACTS)measuresfreechlorineovertherangeof0.1to10mg/L.A
saturated solution of syringaldazine (3,5dimethoxy4
hydroxybenzaldazine)in2propanolisused.Syringaldazineisoxidized
byfreechlorineona1:1molarbasistoproduceacoloredproductwith
anabsorptionmaximumof530nm.Thecolorproductisonlyslightly
soluble in water; therefore, at chlorine concentrations greater than 1
mg/L, the final reaction mixture must contain 2propanol to prevent
productprecipitationandcolorfading.

The optimum color and solubility (minimum fading) are ob

tainedinasolutionhavingapHbetween6.5and6.8.AtapHless
than6,colordevelopmentisslowandreproducibilityispoor.Ata
pHgreaterthan7,thecolordevelopsrapidlybutfadesquickly.A
buffer is required to maintain the reaction mixture pH at
approximately 6.7. Take care with waters of high acidity or
alkalinitytoassurethattheaddedbuffermaintainstheproperpH.

Temperature has a minimal effect on the color reaction. The

maximum error observed at temperature extremes of 5 and 35C is
10%.
b. Interferences: Interferences common to other methods for
determining free chlorine do not affect the FACTS procedure.
Monochloramine concentrations up to 18 mg/L, dichloramine
concentrationsupto10mg/L,andmanganeseconcentrations(oxidized
forms)upto1mg/Ldonotinterfere.Trichloramineatlevelsabove0.6
mg/L produces an apparent free chlorine reaction. Very high
concentrationsofmonochloramine(35mg/L)andoxidizedmanganese
(2.6mg/L)produceacolorwithsyringaldazineslowly.Ferricironcan
reactwithsyringaldazine;however,concentrationsupto10mg/Ldo
notinterfere.Nitrite(250mg/L),nitrate(100mg/L),sulfate(1000
mg/L),andchloride(1000mg/L)donotinterfere.Waterswithhigh
hardness ( 500 mg/L) will produce a cloudy solution that can be
compensatedforbyusingablank.Oxygendoesnotinterfere.
Otherstrongoxidizingagents,suchasiodine,bromine,andozone,
willproduceacolor.
c. Minimum detectable concentration: The FACTS procedure is
sensitivetofreechlorineconcentrationsof0.1mg/Lorless.

2. Apparatus

Colorimetricequipment:Oneofthefollowingisrequired:
a. Filter photometer, providing a lightpath of 1cm for chlorine
concentrations1mg/Loralightpathfrom1to10mmforchlorine
concentrationsabove1mg/L;alsoequippedwithafilterhavingaband
passof500to560nm.
b. Spectrophotometer,foruseat530nm,providingthelightpathsnoted
above.

3. Reagents
a. Chlorinedemandfree water: See C.3m. Use to prepare reagent
solutionsandsampledilutions.
b. Syringaldazine indicator: Dissolve 115 mg 3,5dimethoxy4
hydroxybenzaldazine*in1L2propanol.
c. 2Propanol:Toaidindissolutionuseultrasonicagitationorgentle

heating and stirring. Redistill reagentgrade 2propanol to remove

chlorinedemand.Usea30.5cmVigreuxcolumnandtakethemiddle
75% fraction. Alternatively, chlorinate goodquality 2propanol to
maintainafreeresidualovernight;thenexposetoUVlightorsunlight
todechlorinate.CAUTION:2Propanolisextremelyflammable.
d. Buffer:Dissolve17.01gKH2PO4in250mLwater;pHshouldbe
4.4.Dissolve17.75gNa2HPO4in250mLwater;thepHshouldbe9.9.
MixequalvolumesofthesesolutionstoobtainFACTSbuffer,pH6.6.
VerifypHwithpHmeter.Forwaterscontainingconsiderablehardness
orhighalkalinityotherpH6.6bufferscanbeused,forexample,23.21
gmaleicacidand16.5mL50%NaOHperliterofwater.
e. Hypochlorite solution: Dilute household hypochlorite solution,
which contains about 30 000 to 50 000 mg Cl equivalent/L, to a
strength between 100 and 1000 mg/L. Standardize as directed in
G.4a1).

4. Procedure
a. Calibration of photometer: Prepare a calibration curve by making
dilutionsofastandardizedhypochloritesolution(3e).

*AldrichNo.17,7539,AldrichChemicalCompany,Inc.,1001WestSt.PaulAve.,Milwaukee,WI
53233,orequivalent.

CHLORINE (RESIDUAL) (4500-Cl)/Iodometric Electrode

Technique

Develop and measure colors as described in 4b, below. Check

calibrationregularly,especiallyasreagentages.

b.Freechlorineanalysis:Add3mLsampleand0.1mLbufferto
a5mLcapacitytesttube.Add1mLsyringaldazineindicator,cap
tube, and invert twice to mix. Transfer to a photometer tube or
spectrophotometer cell and measure absorbance. Compare
absorbance value obtained with calibration curve and report
correspondingvalueasmilligramsfreechlorineperliter.

469

5. Bibliography
BAUER,R.&C.R UPE.1971.Useofsyringaldazineinaphotometricmethodfor
estimatingfreechlorineinwater.Anal.Chem.43:421.
COOPER,W.J.,C.A.SORBER&E.P.MEIER.1975.Arapid,free,availablechlorine
testwithsyringaldazine(FACTS).J.Amer.WaterWorksAssoc.67:34.

COOPER,W.J.,P.H.GIBBS,E.M.OTT&P.PATEL.1983.Equivalencytesting
of procedures for measuring free available chlorine: amperometric
titration,DPD,andFACTS.J.Amer.WaterWorksAssoc.75:625.

4500-Cl I. Iodometric Electrode

Technique
1. General Discussion
a. Principle: This method involves the direct potentiometric
measurementofiodinereleasedontheadditionofpotassiumiodideto
an acidified sample. A platinumiodide electrode pair is used in
combinationwithanexpandedscalepHmeter.
b. Interference: All oxidizing agents that interfere with other
iodometric procedures interfere. These include oxidized manganese
andiodate,bromine,andcupricions.Silverandmercuricionsabove10
and20mg/Linterfere.

2. Apparatus
a. Electrodes:Useeitheracombinationelectrodeconsistingofa
platinum electrode and an iodide ionselective electrode or two
individualelectrodes.Bothsystemsareavailablecommercially.
b. pH/millivoltmeter:UseanexpandedscalepH/millivoltmeter
with0.1mVreadabilityoradirectreadingselectiveionmeter.

3. Reagents
a. pH4buffersolution:SeeC.3e.
b. Chlorinedemandfreewater:SeeC.3m.
c. Potassiumiodidesolution:Dissolve42gKIand0.2gNa2CO3in
500mLchlorinedemandfree,distilledwater.Storeinadarkbottle.
d. Standardpotassium iodate 0.00281N: Dissolve 0.1002g KIO3 in
chlorinedemandfree,distilledwateranddiluteto1000mL.Each1.0mL,
whendilutedto100mL,producesasolutionequivalentto1mg/LasCl2.

4. Procedure
a. Standardization: Pipetintothree100mLstopperedvolumetric
flasks0.20,1.00,and5.00mLstandardiodatesolution.Addtoeach
flask,andafourthflasktobeusedasareagentblank,1mLeachof
acetatebuffersolutionandKIsolution.Stopper,swirltomix,andlet
stand 2 min before dilution. Dilute each standard to 100 mL with
chlorinedemandfreedistilledwater.Stopper,invertflaskseveraltimes
to mix, and pour into separate 150mL beakers. Stir gently without
turbulence,usinga magneticstirrer,andimmerse electrode(s) in the
0.2mg/L(0.2

mL)standard.Waitforthepotentialtostabilizeandrecordpotential
in mV. Rinse electrodes with chlorinedemandfree water and
repeat for each standard and for the reagent blank. Prepare a
calibrationcurvebyplotting,onsemilogarithmicpaper,potential
(linear axis) against concentration. Determine apparent chlorine
concentrationinthereagentblankfromthisgraph(ReadingB).
b.Analysis:Selectavolumeofsamplecontainingnomorethan
0.5mgchlorine.Pipet1mLacetatebuffersolutionand1mLKI
intoa100mLglassstopperedvolumetricflask.Stopper,swirland
letstandforatleast2min.AdjustsamplepHto4to5,ifnecessary
(midrangepHpaperisadequateforpHmeasurement),byadding
aceticacid.AddpHadjustedsampletovolumetricflaskanddilute
tomark.Stopperandmixbyinversionseveraltimes.Letstandfor
2min.Pourintoa150mLbeaker,immersetheelectrode(s),wait
for the potential to stabilize, and record. If the mV reading is
greaterthanthatrecordedforthe5mg/Lstandard,repeatanalysis
withasmallervolumeofsample.
5. Calculation
Determinechlorineconcentration(mg/L)correspondingtotherecorded
mVreadingfromthestandardcurve.ThisisReading A. Determinetotal
residualchlorinefromthefollowing:

Totalresidualchlorine

100/V

where V samplevolume,mL.Iftotalresidualchlorineisbelow0.2mg/L,
subtractapparentchlorineinreagentblank(Reading B)toobtainthetrue
totalresidualchlorinevalue.

6. Bibliography
DIMMOCK,N.A.&D.MIDGLEY.1981.DeterminationofTotalResidualChlorine
inCooling Water with the Orion 9770Ion Selective Electrode.Central
ElectricityGeneratingBoard(U.K.)ReportRD/L/2159N81.
JENKINS,R.L.&R.B.BAIRD.1979.Determinationoftotalchlorineresidualin
treatedwastewatersbyelectrode.Anal.Letters12:125.
SYNNOTT,J.C.&A.M.S MITH.1985.TotalResidualChlorinebyIonSelective
ElectrodefromBenchToptoContinuousMonitor.Paperpresentedat5th
International Conf. on Chemistry for Protection of the Environment,
Leuven,Belgium.