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Chapter 6

TABLE OF CONTENTS Chlorine Residual Determination


Page Section 1: General.............................................................................................................................. Section 2: Introduction to Chlorine...................................................................................................... Section 3: Glossary............................................................................................................................. Section 4: Approved Methods............................................................................................................. Section 5: Sa ety and !y"iene............................................................................................................ Section #: Sa$plin"............................................................................................................................ Section %: Sensitivity.......................................................................................................................... Section &: Interpretation...................................................................................................................... 'ui( #.1................................................................................................................................................ Section ): Iodo$etric *itration............................................................................................................ Section 1+: ,-uip$ent and .ea"ents................................................................................................. Section 11: /a0oratory 1rocedures..................................................................................................... 'ui( #.2................................................................................................................................................ 3 3 3-4 4 4-5 5 5-# # % % %-& &-) 1+

Section 12: 2Iodate *itrant3 - 4escription o *est................................................................................ 1+-12 Section 13: Iodo$etric 5ac6 *itration Method.................................................................................... 'ui( #.3................................................................................................................................................ 12 12

Section 14: A$pero$etric 5ac6 *itration........................................................................................... 12-14 'ui( #.4................................................................................................................................................ 14

Section 15: A$pero$etric 4irect *itration.......................................................................................... 15-1# 'ui( #.5................................................................................................................................................ 1#

Section 1#: 414 *itration Analysis..................................................................................................... 1#-1% 'ui( #.#................................................................................................................................................ 1&

Section 1%: 414 Colori$etric............................................................................................................. 1&-2+ 'ui( #.%................................................................................................................................................ 2+

Section 1&: 7rion Speci ic Ion ,lectrode............................................................................................ 2+-22 Section 1): Inter erences.................................................................................................................... 22

Chapter # - 1

'ui( #.&................................................................................................................................................

22

Section 2+: !ach Model C8-##........................................................................................................... 22-23 Section 21: Inter erences 9ith !ach................................................................................................... 'ui( #.)................................................................................................................................................ Section 22: 'A:'C.............................................................................................................................. 23 23 24

Ans9ers to 'ui((es.............................................................................................................................. 25-2) Appendi; A: .e erences Appendi; 5: 1reparation o Che$icals Appendi; C: 'uality Assurance chec6 on +.+2&2 8 Iodine Solution Appendi; 4: Methods Chec6list

Chapter # - 2

Chapter 6
CHLOR NE!Cl"# RES D$AL DETER% NAT ON
Se&tion '( )ENERAL *he $ain purpose or the chlorination o 9ater supplies and 9aste9ater treat$ent plant e luents is the destruction o disease-producin" $icroor"anis$s. Chlorine has a variety o other uses in the 9aste9ater treat$ent plant operation includin" odor control and ly and pondin" control 2in tric6lin" ilters3. Chlorine can also provide additional 9aste9ater treat$ent 0y reactin" 9ith a$$onia< iron< $an"anese< sul ide and so$e or"anic su0stances. =n ortunately< chlorine can cause pro0le$s i its use is not controlled very care ully. >hen used as a control on the disease-producin" 0acteria< the idea is to disin ect and not sterili(e the e luent. 4isin ection is the process o 6illin" disease-producin" 0acteria. Sterili(ation is the process o 6illin" all livin" or"anis$s. I an atte$pt 9ere $ade to sterili(e the e luent< the 0iolo"ical li e in the receivin" 9aters 9ould li6ely 0e destroyed. *he 0est $ethod or controllin" the disin ection process and preventin" har$ to a-uatic li e 0y over-chlorination is to $aintain a speci ic chlorine residual level in the e luent. Se&tion "( NTROD$CT ON TO CHLOR NE RES D$AL %EAS$RE%ENT Chlorine is used to protect the pu0lic health 0y 6illin" the $icroor"anis$s ound in 9ater 9hich cause diseases. *he chlorine residual test is used to deter$ine the total a$ount o chlorine present as a residual 2the a$ount o chlorine present a ter the de$and has 0een satis ied3. 5ecause the residual deter$ines ho9 e ective the disin ection process is< it is i$portant to $a6e sure that the residual re$ains 9ithin a speci ied ran"e. *oo little chlorine 9ill not "ive ade-uate disin ection and too $uch can 6ill the a-uatic li e in the receivin" 9aters.

Se&tion *( )LOSSAR+ Chlorination( Addin" chlorine or chlorine co$pounds to 9ater or disin ection. Chlorine( An ele$ent used to 6ill $icroor"anis$s in 9ater. At roo$ te$perature and at$ospheric pressure< it is a "reenish yello9 "as. Chlorine Demand( *he a$ount o chlorine used 0y reactions 9ith su0stances that o;idi(e in the 9ater 0e ore chlorine residual can 0e $easured. It is the di erence 0et9een the a$ount o chlorine added to 9aste9ater and the a$ount o chlorine residual re$ainin" a ter a "iven contact ti$e. Chlorine de$and $ay chan"e 9ith dosa"e< ti$e< te$perature< p!< and the type and a$ount o pollutants in the 9ater. Chlorine Dosage( *he a$ount o chlorine 9hich $ust 0e added to produce a desired result 2disin ection o the e luent< control o ilter lies< pondin" and odor3.

Chapter # - 3

Chlorine Residual( *he a$ount o availa0le chlorine present in 9aste9ater a ter a "iven contact ti$e 22+ $inutes at pea6 lo9? 3+ $inutes at avera"e lo93< and under speci ic conditions includin" p! and te$perature. Com,ined A-aila,le Chlorine Residual( *he residual consistin" o chlorine that is co$0ined 9ith a$$onia< nitro"en< or nitro"enous co$pounds 2chlora$ines3. Free A-aila,le Chlorine Residual( *he residual consistin" o hypochlorite ions 27Cl 3< hypochlorous acid 2!7Cl3 or a co$0ination o the t9o. *hese are the $ost e ective in 6illin" 0acteria. Total Chlorine Residual( *he total a$ount o chlorine present in a sa$ple. *his is the su$ o the ree chlorine residual and the co$0ined availa0le chlorine residual.

Se&tion .( APPRO/ED %ETHODS *he $ethods approved or the deter$ination o chlorine residual are outlined in the @ederal .e"ister 4+ C@. 1art 13# AGuidelines ,sta0lishin" *est 1rocedures or the Analysis o 1ollutantsB 2as a$ended Cune 1)&53. *he approved $ethods are the iodo$etric 0ac6 titrations< the a$pero$etric direct and 0ac6 titrations< the 414 titration< the 414 colori$etric $ethod 2 NOTE( *his is not the 414 test 6it $ethod3 and the 7rion )%-%+ chlorine speci ic ion electrode $ethod. >aste9ater treat$ent plants 9hich treat only do$estic 2household3 9astes and have a desi"n lo9 capacity o 4+<+++ "pd or less $ay use the !ach Co$panyDs Model C8-## *otal Chlorine .esidual *est Eit.

Se&tion 0( SAFET+ AND H+) ENE It is i$portant to e;ercise special caution 9hen handlin" the che$icals used in the various $ethods or chlorine residual deter$ination 0ecause several o the$ are hi"hly to;ic. *he phenylarsine o;ide 21A73 and standard arsenite solution used in the iodo$etric and a$pero$etric $ethods are poisonous. Clean up spills -uic6ly and care ully 9ith disposa0le ra"s or to9els and 0e sure to 9ash hands thorou"hly 0e ore eatin" or s$o6in". *he 414 o;ide indicator used in the 414 titri$etric and colori$etric $ethods is also very poisonous and the sa$e precautions $ust 0e e;ercised in its use. As 9ith all la0oratory testin"< handle "lass9are care ully. /a0 "lass9are can 0rea6 easily and leave very sharp pieces o "lass. I 0rea6a"e does occur< use a "ood 0roo$ and dust pan. 4o not pic6 up 0y hand or use a to9el or spon"e that 9ill 0e used a"ain. Eeep ru00er "loves and sa ety "lasses on hand and use the$. Al9ays use a pipettin" 0ul0. 8ever pipette anythin" 0y $outh.

Chapter # - 4

Se&tion 6( SA%PL N) Chlorine in 9ater solutions is not sta0le. As a result< its concentration in sa$ples decreases rapidly. ,;posure to sunli"ht or other stron" li"ht< air< or a"itation 9ill urther reduce the -uantity o chlorine present in solutions. Sa$ples to 0e analy(ed or chlorine cannot 0e stored or preserved. *ests $ust 0e started i$$ediately a ter sa$plin". *here ore< sa$ples ta6en or the chlorine residual test $ust 0e "ra0 sa$ples only and e;cessive a"itation $ust 0e avoided. SA%PLE CONTA NERS It is not necessary to use special sa$plin" devices or containers or the chlorine residual test. !o9ever< the sa$plin" container should 0e capa0le o collectin" sa$ples ro$ a representative sa$plin" point ollo9in" chlorine contact< and should 0e $ade o resistant $aterials that 9ill not rust or corrode< and 9hich can 0e easily cleaned. NOTE( A lon" handled alu$inu$ dipper attached to a 9ooden handle< or an e-uivalent device< is accepta0le or collectin" sa$ples. 4o not use co ee cans< 0leach 0ottles< etc. SA%PLE CONTA NER PREPARAT ON All sa$ple collection containers should 0e cleaned thorou"hly on a re"ular 0asis 2pre era0ly at the end o each day3 9ith soap and 9ater and rinsed 9ell. It is advisa0le to acid clean containers on a periodic 0asis 2usually once a 9ee63. *his 9ill prevent a 0uildup o "rease and scu$ 9hich could conta$inate the sa$ples. *his is especially i$portant or sa$plin" devices used or sa$ples 9hich are hi"h in solid and:or "rease content. It is reco$$ended that each sa$ple point have its o9n sa$plin" device. I this is not possi0le< 0e sure to clean sa$plin" devices thorou"hly 0et9een collections. Se&tion 1( SENS T / T+ 4ue to the $anner in 9hich calculations are set up or the iodo$etric 0ac6-titration $ethods usin" iodine titrant< the test procedures used or these $ethods can $easure the Cl 2 residual only 0et9een +.5 and 4.+ $":/< in +.5 $":/ incre$ents< unless speciali(ed volu$etric "lass9are is used. *he iodo$etric 0ac6-titration procedure usin" a standard iodate titrant can $easure residual chlorine levels as lo9 as +.+1< 9ith a 0urette "raduated to +.+1 $/. *he a$pero$etric direct titration can also detect lo9 levels o chlorine residual< 0ut the actual $ini$u$ detecta0le concentration is dependent on the "raduations o the 1A7 dispensin" 0urette and the sensitivity o the $icroa$p$eter on the titrator. Althou"h the approved $ethods or 414 titration and colori$eter deter$inations list $ini$u$ detecta0le concentrations o +.+1& $":/ and +.+1+ $":/ respectively< the 414 $ethods should only 0e used to $easure the Cl2 residual 0et9een +.5 and 4.+ $":/. Accuracy at lo9er concentrations can 0e very di icult to o0tain unless testin" techni-ues are very "ood. *here is no speci ied $ini$u$ detecta0le li$it or chlorine residual usin" the !ach 4.1++ 414 chlorine procedure< ho9ever< the $ost reasona0le practical li$it 0y e;trapolation is +.+5 $":/. *he accuracy o e;trapolated values is suspect.

Chapter # - 5

Althou"h the concentration ran"e speci ied or the 7rion Model )%-%+ chlorine residual speci ic ion electrode is +.+1 to 2+ $":/ as Cl2< the cali0ration curve 0elo9 +.2 $":/ is not linear. Measure$ents 0elo9 +.2 $":/ can 0e $ade usin" a 0lan6 correction. *he accuracy o such readin" $ay 0e suspect. *here is no speci ied $ini$u$ detecta0le li$it or chlorine residual usin" the !ach C8-## and the $ost practical li$it 0y visual co$parison is +.2 $":/. Se&tion 2( NTERPRETAT ON *he i$portance o $aintainin" the proper chlorine residual in 9aste9ater e luents cannot 0e overly stressed. *he addition o chlorine is necessary to prevent the spread o 9ater0orne disease-producin" $icroor"anis$s< ho9ever< too $uch chlorine can har$ 0ene icial or"anis$s ound in receivin" 9aters. Chlorine residual li$its have 0een esta0lished to prevent the spread o disease and har$in" receivin" 9aters. *he >ater Control 5oard has speci ied in-strea$ chlorine li$its o +.+11 $":/ or resh9ater and +.++%5 $":/ or saline 9aters. *he actual per$it li$itation or acilities dischar"in" to sur ace 9aters is 0ased on a calculation speci ic or each plant and receivin" strea$. 5ecause o 9ater -uality considerations< so$e plants practicin" chlorination or disin ection are re-uired to dechlorinate. In such cases the li$its $ay vary ro$ non-detecta0le concentrations to +.+5 $":/. >here 9ater -uality consideration have not 0een deter$ined to 0e a actor< the esta0lished li$its o 1.5 to 2.+ $":/ chlorine residual or critical 9ater 2de ined as those 9aters 9hich co$e into close hu$an contact< such as la6es and rivers used or drin6in" 9ater< shell ishin"< and or contact 9ater sports3 and 1.+ to 2.+ $":/ or non-critical 9ater are appropriate. A ran"e o chlorine residual values should 0e esta0lished or each plant< 9ithin allo9a0le li$its< and chlorine residuals $aintained 9ithin this ran"e. Si"ni icant chan"es ro$ esta0lished values usually indicate either inade-uate treat$ent or overtreat$ent 2such as overloadin" or underloadin"3< or that so$e adFust$ent is necessary in the Cl2 dosa"e. ,;tre$e variations su""est the need or closer control o chlorine dosa"es to yield the desired -uality o treat$ent.

3ui4 65' 1. >hat is the $ain purpose or chlorination o 9ater supplies and 9aste9ater e luentsG 2. >hat are the de initions o the ollo9in" ter$s: chlorine residual? co$0ined chlorine residual? ree availa0le chlorine residual? and< total chlorine residualG 3. >hat are the usual $ini$u$ and $a;i$u$ li$itations or chlorinated e luents dischar"in" to non-critical 9atersG *o critical 9aterG 4. >hat are the approved $ethods or $easurin" chlorine residual concentrations or co$pliance 9ith 814,S per$it re-uire$entsG

Chapter # - #

Se&tion 6( ODO%ETR C T TRAT ON ! OD NE T TRAT ON#( DESCR PT ON OF TEST In the presence o an e;cess o 1henylarsine o;ide solution 21A73 and usin" a starch indicator solution< 9hen iodine is titrated into the sa$ple< the end-point is sho9n 0y the appearance o a 0lue color. *his 0lue color $eans that all o the 1A7 has co$pletely reacted. 5y su0tractin" the a$ount o iodine titrated ro$ the a$ount o 1A7 ori"inally added< the chlorine residual can 0e deter$ined. 2A conversion actor $ust 0e used in the calculation 0ecause the iodine solution is stron"er than the 1A7 solution.3 Se&tion '7( E3$ P%ENT AND REA)ENTS FOR OD NE T TRAT ON %ETHOD REA)ENTS See Appendi; 5 at the end o this chapter or the procedure or the preparation o the rea"ents used in this $ethod. 1. 2. 3. 4. 5. #. %. &. 1henylarsine o;ide solution 21A73< +.++5#4 8H Standard iodine titrant 2I 23< +.+2&2 8 1otassiu$ dichro$ate solution 2E 2Cr27%3< +.++5#4 8 1otassiu$ iodide 2EI3< crystals 1otassiu$ iodide solution 2EI3< 5I >:J Acetate 0u er solution< p! 4.+ Standard arsenite solution 2As2733< +.1 8H Starch indicator H THESE CHE% CALS ARE PO SONO$S8 SO HANDLE 9 TH E:TRE%E CA$T ON5 E3$ P%ENT 1. 2. 3. 4. 5. #. %. 25+ $/ "raduated cylinder 5 $/ $easurin" pipettes 5++ $/ ,rlen$eyer las6s 5 $/ volu$etric pipette 1+ $/ 0urette 2pre era0ly "raduated to +.+1 $/3 or 25 $/ 0urette 2"raduated to +.1 $/3 Ma"netic stirrer and stirrin" 0arsH H7ptional ,-uip$ent

Chapter # - %

Se&tion ''( LABORATOR+ PROCED$RE FOR OD NE T TRAT ON %ETHOD 1. 2. 3. 4. 5. #. %. 1our 2++ $/ o sa$ple or dilution into a 5++ $/ ,rlen$eyer las6. Jolu$etrically add 5.+ $/ +.++5#4 8 phenylarsine o;ide 21A73 solution or sodiu$ thiosul ate solution to the las6. Stir contents o las6 durin" all che$ical additions. Add appro;i$ately 1 " potassiu$ iodide 2EI3 crystals or 1 $/ o 5I EI solution to the las6. Add 4 $/ p!4-acetate 0u er solution 2or enou"h to lo9er the p! to 0et9een 3.5 and 4.23. Add 1 $/ o starch indicator. Continue stirrin" and titrate 9ith +.+2&2 8 iodine solution until the irst appearance o 0lue color that re$ains a ter co$plete $i;in".

NOTE( 5e care ul not to titrate too ast as this can $ean $issin" the end-point and inaccurate results. &. ). .ecord the value o iodine titrant used. Chec6 the nor$ality o the iodine solution at least daily 0y co$pletin" steps 1-& usin" 2++ $/ o distilled 9ater. CALC$LAT ONS FOR OD NE T TRAT ON %ETHOD $":/ Cl2 K L$/ 1A7 added - 25 ; $/ iodine titrated3M ; 2++:$/ sa$ple E:A%PLE( $/ 1A7 added K 5 $/ $/ iodine titrated K +.% $/ $/ sa$ple K 2++ $":/ Cl2 K L5 - 25 ; +.%3M ; 2++:2++ K L25 - 3.53 ; 2++M:2++ $":/ Cl2 K 21.5 ; 2++3:2++ K 1.5 $":/ *he a$ount o iodine used or the titration can 0e corrected or a non-standard iodine solution nor$ality 0y applyin" a correction actor 0ased on the actual iodine nor$ality. $":/ Cl2 K L$/ 1A7 added - 25 ; $/ iodine titrated ; C@3M ; "77;mL sample C@ K Correction @actor K Actual nor$ality o iodine:+.+2&2 8 E:A%PLE( $/ 1A7 added K 5 $/ Iodine *itrated K +.% $/ sa$ple K 2++ Actual nor$ality o Iodine K +.+25#

Chapter # - &

C@ K +.+25#:+.+2&2 K +.)1 $":/ Cl2 K L5 - 25 ; +.% ; +.)13M ; 2++:2++ $":/ Cl2 K L25 - 3.1&3 ; 2++M:2++ K 21.&2 ; 2++3:2++ K 1.&2 OD NE T TRAT ON %ETHOD Man"anese< iron< and nitrite can cause an inter erence in this $ethod. !o9ever< these can 0e $ini$i(ed 0y 0u erin" the solution to p! 4.+ 0e ore addin" potassiu$ iodide. An unusually hi"h concentration o or"anic $atter $ay cause uncertainty in the end-point. I the or"anic concentration is hi"h and $an"anese< iron< and nitrite are de initely a0sent< the end-point uncertainty can 0e reduced and precision increased 0y lo9erin" to p! 1.+ prior to addition o potassiu$ iodide. Sa$ple color and tur0idity can inter ere 0y $a6in" the starch color chan"e di icult to accurately deter$ine. Inter erence ro$ $ore than +.2 $":/ nitrite can 0e controlled 0y the addition o phosphoric acid-sul a$ic acid rea"ent.

3ui4 65" 1. >hat rea"ents are re-uired to per or$ chlorine residual $easure$ents usin" the iodo$etric 0ac6 titration 2iodine titrant3 $ethodG 2. >hat e-uip$ent< apparatus< or instru$entation is re-uired to per or$ chlorine residual $easure$ents usin" the iodo$etric 0ac6 titration 2iodine titrant3 $ethodG 3. >hat inter erences< i any< are there in the iodo$etric 0ac6 titration 2iodine titrant3 chlorine residual procedureG 4. >hat is the chlorine residual o a 2++ $/ sa$ple 9hich re-uires +.& $/ os +.+2&2 8 iodine to titrate an e;cess o +.++5#4 8 sodiu$ thiosul ate solutionG

Se&tion '"( ! ODATE T TRANT# < DESCR PT ON OF TEST In the presence o an e;cess o 1A7 and usin" a starch indicator solution< 9hen iodate solution is titrated into the sa$ple< the end-point is sho9n 0y the appearance o a 0lue color. *his 0lue color $eans that all o the 1A7 has co$pletely reacted. 5y su0tractin" the a$ount o iodate titrated or the sa$ple ro$ the a$ount o iodate titrated or a 0lan6< the chlorine residual can 0e deter$ined. E3$ P%ENT AND REA)ENTS FOR ODO%ETR C BAC= T TRAT ON %ETHOD REA)ENTS See Appendi; 5 at the end o this chapter or the procedure or the preparation o the rea"ents used in this $ethod. 1. 2. 3. 1henylarsine o;ide solution 21A73< +.++5#4 8H Sodiu$ thiosul ate solution 28a2S2733< +.++5#4 8H Standard potassiu$ iodate titrant 2EI7 33< +.++5#4 8H

Chapter # - )

4. 5. #. %. &. ).

1otassiu$ dichro$ate solution 2E 2Cr27%3< +.++5#4 8 1otassiu$ iodide 2EI3< crystals 1otassiu$ iodide solution 2EI3< 5I >:J Standard arsenite solution 2As2733< +.1 8H Starch indicator 1hosphoric acid solution< 2!31743< 1N)

1+. 1hosphoric acid-sul a$ic acid solutionH > THESE CHE% CALS ARE PO SONO$S8 SO HANDLE 9 TH E:TRE%E CA$T ON E3$ P%ENT 1. 2. 3. 4. 5. #. %. 25+ $/ "raduated cylinder 5 $/ $easurin" pipettes 5++ $/ ,rlen$eyer las6s 5 $/ volu$etric pipette 1+ $/ 0urette 2pre era0ly "raduated to +.+1 $/3 or 25 $/ 0urette 2"raduated to +.1 $/3 Ma"netic stirrer and stirrin" 0arsH

H7ptional ,-uip$ent LABORATOR+ PROCED$RE FOR ODO%ETR C BAC= T TRAT ON %ETHOD 1. 2. 3. 4. 5. #. %. 1our 2++ $/ o distilled 9ater into a 5++ $/ ,rlen$eyer las6 and 2++ $/ o sa$ple or dilution into a second 5++ $/ ,rlen$eyer las6. Jolu$etrically add 5.+ $/ +.++5#4 8 phenylarsine o;ide 21A73 solution or sodiu$ thiosul ate solution to each las6. Stir contents o las6 durin" all che$ical additions. Add appro;i$ately +.5 " potassiu$ iodide 2EI3 crystals or 1 $/ o 5I EI solution to each las6. Add 2 $/ o 1+I phosphoric acid solution to each las6. Add 1 $/ o starch indicator solution to each las6. *itrate the las6 containin" the distilled 9ater< 9hile stirrin"< 9ith +.++5#4 8 potassiu$ iodate solution until the irst appearance o 0lue color that re$ains a ter co$plete $i;in".

Chapter # - 1+

NOTE( 5e care ul not to titrate too ast as this can $ean $issin" the end-point and inaccurate results. &. ). .ecord the value o iodate titrant used. .epeat steps %-& 9ith the las6 containin" the sa$ple or sa$ple dilution.

1+. *he distilled 9ater titration $ust 0e per or$ed at least once daily. @or additional sa$ples< tested on the sa$e day< only the sa$ple titration needs to 0e per or$ed. ODO%ETR C BAC= T TRAT ON %ETHOD CALC$LAT ONS $":/ Cl2 K L2$/ Iodate or 0lan6 - $/ Iodate or sa$ple3 ; 2++:$/ Sa$ple E:A%PLE( $/ Iodate *itrated or 0lan6 K 5.3 $/ Iodate *itrated or Sa$ple K 3.1 $/ Sa$ple K 2++ $":/ Cl2 K L25.3 - 3.13 ; 2++M:2++ K 22.2 ; 2++3:2++ K 2.2 $":/ NTERFERENCES Se&tion '*( ODO%ETR C BAC= T TRAT ON %ETHOD Man"anese< iron< and nitrite can cause an inter erence in this $ethod. !o9ever< these can 0e $ini$i(ed 0y 0u erin" the solution to p! 4.+ 0e ore addin" potassiu$ iodide. An unusually hi"h concentration o or"anic $atter $ay cause uncertainty in the end-point. I the or"anic concentration is hi"h< and $an"anese< iron< and nitrite are de initely a0sent< the end-point uncertainty can 0e reduced and precision increased 0y lo9erin" to p! 1.+ prior to addition o potassiu$ iodide. Sa$ple color and tur0idity can inter ere 0y $a6in" the starch color chan"e di icult to accurately deter$ine. Inter erence ro$ $ore than +.2 $":/ nitrite can 0e controlled 0y the addition o phosphoric acid-sul a$ic acid rea"ent. 3ui4 65* 1. >hat rea"ents are re-uired to per or$ chlorine residual $easure$ents usin" the iodo$etric 0ac6 titration 2iodate titrant3 $ethodG 2. >hat e-uip$ent< apparatus< or instru$entation is re-uired to per or$ chlorine residual $easure$ents usin" the iodo$etric 0ac6 titration 2iodate titrant3 $ethodG 3. >hat inter erences< i any< are there in the iodo$etric 0ac6 titration 2iodate titrant3 chlorine residual procedureG 4. >hat is the chlorine residual o a 2++ $/ sa$ple 9hich re-uires 3.& $/ o +.++5#4 8 potassiu$ iodate to titrate an e;cess o +.++5#4 8 sodiu$ thiosul ate solution 2an initial 0lan6 titration re-uired 5.1 $/ o potassiu$ iodate3G

Se&tion '.( A%PERO%ETR C BAC= T TRAT ON

Chapter # - 11

DESCR PT ON OF TEST *he only di erence 0et9een the a$pero$etric $ethod and the iodo$etric $ethod is the use o a $eter to indicate the end-point. >hen the end-point has 0een reached< a chan"e 9ill occur in the electric current lo9in" throu"h the $eter< 9hich is sho9n 0y a cloc69ise $ove$ent o the needle on the $eter. In the presence o e;cess 1A7< iodine solution is added until the end-point is indicated. 5y su0tractin" the a$ount o iodine titrated ro$ the a$ount o 1A7 ori"inally added to the sa$ple< the chlorine residual can 0e deter$ined. 2A conversion actor $ust 0e used in the calculation 0ecause the iodine solution is stron"er than the 1A7 solution3. E3$ P%ENT AND REA)ENTS FOR A%PERO%ETR C BAC= T TRAT ON %ETHOD REA)ENTS See Appendi; 5 at the end o this chapter or the procedure or the preparation o the rea"ents used in this $ethod. 1. 2. 3. 4. 5. #. 1henylarsine o;ide solution 21A73< +.++5#4 8H Standard iodine titrant 2I 23< +.+2&2 8 1otassiu$ dichro$ate solution 2E 2Cr27%3< +.++5#4 8 1otassiu$ iodide solution 2EI3< 5I >:J Acetate 0u er solution< p! 4.+ Standard arsenite solution 2As2733< +.1 8H

> THESE CHE% CALS ARE PO SONO$S8 SO HANDLE 9 TH E:TRE%E CA$T ON5 E3$ P%ENT 1. 2. 3. 4. 25+ $/ "raduated cylinder 5 $/ $easurin" pipettes 5 $/ volu$etric pipette 1 $/ 0urette 2pre era0ly "raduated to +.+1 $/3 LABORATOR+ PROCED$RE FOR A%PERO%ETR C BAC= T TRAT ON %ETHOD 1. 2. 3. 4. 5. #. 1repare a$pero$etric titration apparatus or use accordin" to $anu acturerDs instructions. 1our 2++ $/ o sa$ple or sa$ple dilution into the container or use 9ith the apparatus. Add volu$etrically 5.+ $/ o +.++5#48 phenylarsine o;ide 21A73 solution to the container. Add appro;i$ately 1 " potassiu$ iodide 2EI3 crystals or 1 $/ o 5I EI solution to the container. Add 4 $/ p! 4.+ acetate 0u er solution 2or enou"h to lo9er the p! to 0et9een 3.5 and 4.23. *itrate< 9hile stirrin"< 9ith +.+2&2 8 iodine solution. *he needle on the $eter 9ill re$ain al$ost stationary until the end-point is approached. As the end-point is approached< each addition o iodine causes a te$porary $ove$ent o the needle 2in a cloc69ise or up scale direction3 9ith a

Chapter # - 12

return to its ori"inal position. *he end-point is reached 9hen a s$all addition o iodine titrant "ives a de inite $ove$ent o the needle< and the needle does not return -uic6ly to its ori"inal position. %. &. .ecord the volu$e o iodine titrant used. Chec6 the nor$ality o the iodine solution at least daily 0y co$pletin" steps 1-% usin" 2++ $/ o distilled 9ater. CALC$LAT ONS A%PERO%ETR C BAC= T TRAT ON %ETHOD $":/ Cl2 K L$/ 1A7 added - 25 ; $/ iodine titrated3M ; 2++:$/ sa$ple E:A%PLE( $/ 1A7 added K 5 $/ $/ iodine titrated K +.5 $/ $/ sa$ple K 2++ $":/ Cl2 K L5 - 25 ; +.53M ; 2++:2++ K L25 - 2.53 ; 2++M:2++ $":/ Cl2 K 22.5 ; 2++3:2++ K 2.5 *he a$ount o iodine used or the titration can 0e corrected or a non-standard iodine solution nor$ality 0y applyin" a correction actor 0ased on the actual iodine nor$ality. $":/ Cl2 K L$/ 1A7 added - 25 ; $/ iodine titrated ; C@3M ; 2++:$/ sa$ple C@ K Correction @actor K Actual nor$ality o iodine:+.+2&2 8 E:A%PLE( $/ 1A7 added K 5.+ $/ Iodine *itrated K +.5 $/ sa$ple K 2++ Actual nor$ality o Iodine K +.+2)# C@ K +.+2)#:+.+2&2 K 1.+5 $":/ Cl2 K L5 - 25 ; +.5 ; 1.+53M ; 2++:2++ $":/ Cl2 K L25 - 2.#33 ; 2++M:2++ K 22.3% ; 2++3:2++ K 2.3% NTERFERENCES A%PERO%ETR C BAC= T TRAT ON %ETHOD *he presence o nitro"en trichloride or chlorine dio;ide 9ill inter ere 0ecause they titrate partially as ree chlorine. 7r"anic chlora$ines have the sa$e e ect. @ree halo"ens other than chlorine 20ro$ine< iodine and luorine3 inter ere 0y titratin" as ree chlorine. Copper and silver cause inter erence 0y poisonin" the electrode. Jery lo9 te$peratures can slo9 the reaction ti$e< 0ut do not a ect the precision o the test. *he violent stirrin" o so$e co$$ercial titrators can cause loss o chlorine throu"h volatili(ation.

Chapter # - 13

3ui4 65. 1. >hat rea"ents are re-uired to per or$ chlorine residual $easure$ents usin" the a$pero$etric 0ac6 titration $ethodG 2. >hat e-uip$ent< apparatus or instru$entation is re-uired to per or$ chlorine residual $easure$ents usin" the a$pero$etric 0ac6 titration $ethodG 3. >hat inter erence< i any< are there in the a$pero$etric 0ac6 titration chlorine residual procedureG 4. >hat is the chlorine residual o a 2++ $/ sa$ple 9hich re-uires +.%5 $/ or +.+2&2 8 iodine to titrate an e;cess o +.++5#4 8 phenylarsine o;ide 21A73 solutionG

Se&tion '0( A%PERO%ETR C D RECT T TRAT ON DESCR PT ON OF TEST >hen 1A7 is added to a sa$ple 0u ered to p! 4.+< the e;cess iodine in the sa$ple is dischar"ed. >hen the end-point is reached< a chan"e 9ill occur in the electric current lo9in" throu"h the $eter. *his end-point is indicated 0y a cessation o counter-cloc69ise $ove$ent o the needle on the $eter. 5y readin" the volu$e o 1A7 used in the titration the chlorine residual is deter$ined. E3$ P%ENT AND REA)ENTS A%PERO%ETR C T TRAT ON %ETHOD REA)ENTS See Appendi; 5 at the end o this chapter or the procedure or the preparation o the rea"ents used in this $ethod. 1. 2. 3. 4. 5. 1henylarsine o;ide solution 21A73< +.++5#4 8H 1otassiu$ dichro$ate solution 2E 2Cr27%3< +.++5#4 8 1otassiu$ iodide solution 2EI3< 5I >:J Acetate 0u er solution< p! 4.+ Standard arsenite solution 2As2733< +.1 8H

> THESE CHE% CALS ARE PO SONO$S8 SO HANDLE 9 TH E:TRE%E CA$T ON5 E3$ P%ENT 1. 2. 3. A$pero$etric titration apparatus 25+ $/ "raduated cylinder 5 $/ $easurin" pipettes

Chapter # - 14

LABORATOR+ PROCED$RE A%PERO%ETR C T TRAT ON %ETHOD 1. 2. 3. 4. 5. 1repare a$pero$etric titration apparatus or use accordin" to $anu acturerDs instructions. 1our 2++ $/ o sa$ple or sa$ple dilution into the container to 0e used 9ith the apparatus. Add 1 $/ o 5I potassiu$ iodide 2EI3 solution to the container and $i; thorou"hly. Add 1 $/ p! 4.+ acetate 0u er solution to the container and $i; thorou"hly. *itrate< 9hile stirrin"< 9ith a +.++5#4 8 phenylarsine o;ide 21A73 solution. *he instru$entDs $eter indicator 9ill de lect counter cloc69ise or do9nscale 9ith each incre$ent o titrant added to the container. As the end-point is approached< the indicator $ove$ent 9ill slo9. *itrant incre$ents should also 0e decreased. Successive 0urette readin"s should 0e $ade 0e ore each incre$ent addition 9hen the $eter indicates the end-point is approachin". Su0tract the last s$all incre$ent that produces no response in the $eter indicator and record the volu$e o 1A7 titrant used. CALC$LAT ONS FOR A%PERO%ETR C T TRAT ON %ETHOD *here are no calculations or this test. *he volu$e o 1A7 used or the titration is e-ual to the $":/ chlorine residual. NTERFERENCES 9 TH A%PERO%ETR C T TRAT ON %ETHOD *he presence o nitro"en trichloride or chlorine dio;ide 9ill inter ere 0ecause they titrate partially as ree chlorine. 7r"anic chlora$ines have the sa$e e ect. @ree halo"ens other than chlorine 20ro$ine< iodine and luorine3 inter ere 0y titratin" as ree chlorine. Copper and silver cause inter erence 0y poisonin" the electrode. Jery lo9 te$peratures can slo9 the reaction ti$e< 0ut do not a ect the precision o the test. *he violent stirrin" o so$e co$$ercial titrators can cause loss o chlorine throu"h volatili(ation. 3ui4 650 1. >hat rea"ents are re-uired to per or$ chlorine residual $easure$ent usin" the a$pero$etric direct titration $ethodG 2. >hat e-uip$ent< apparatus or instru$entation is re-uired to per or$ chlorine residual $easure$ents usin" the a$pero$etric direct titration $ethodG 3. >hat inter erences< i any< are there in the a$pero$etric direct titration chlorine residual procedureG 4. >hat is the chlorine residual o a 2++ $/ sa$ple 9hich re-uires 2.25 $/ or +.++5#4 8 phenylarsine o;ide 21A73 solution to reach the titration end-pointG

#.

Se&tion '6( DPD T TRAT ON ANAL+S S DESCR PT ON OF TEST *he 414 titration $ethod also uses a color chan"e to deter$ine the chlorine residual. In the presence o chlorine< the 414 indicator solution has a red color. *he $ore chlorine that is present< the dar6er the

Chapter # - 15

red color 9ill 0e. @errous a$$oniu$ sul ate 2@AS3 is used as the titrant in this $ethod. >hen the end-point has 0een reached< the red color 9ill disappear. *he a$ount o chlorine present is e-ual to the a$ount o @AS titrated. E3$ P%ENT AND REA)ENTS FOR DPD T TRAT ON %ETHOD REA)ENTS See Appendi; 5 at the end o this chapter or the procedure or the preparation o the rea"ents used in each o the $ethods. 1. 2. 1hosphate 0u er solution 414 indicator solutionH

NOTE( *he 0u er and indicator are co$$ercially availa0le as a co$0ined rea"ent in sta0le po9der or$. Standard errous a$$oniu$ sul ate 2@AS3 titrant 2@e28! 4322S74323< +.++2&2 8 Standard potassiu$ dichro$ate solution 2E 2Cr27%3< +.1++ 8 1otassiu$ iodide 2EI3< crystals Concentrated 1hosphoric Acid 2!31743 Sul uric Acid solution 2!2S743< 1N5 5ariu$ diphenyla$ine sul onate< 22C #!58!C#!4-4-S73325a3< +.1I > TH S CHE% CAL S PO SONO$S8 SO HANDLE 9 TH E:TRE%E CA$T ON5 E3$ P%ENT 25+ $/ "raduated cylinder 5 $/ $easurin" pipettes 5+ $/ 0urette 5++ $/ ,rlen$eyer las6 Ma"netic stirrer and stirrin" 0arsH H7ptional e-uip$ent LABORATOR+ PROCED$RE FOR DPD T TRAT ON %ETHOD 1. 2. 3. 4. 5. #. %. *o a 5++ $/ ,rlen$eyer las6< pipette 5.+ $/ phosphate 0u er solution. Add 5.+ $/ 414 indicator solution. Add appro;i$ately 1 " potassiu$ iodide 2EI3 crystals. Add 1++ $/ o sa$ple< $i; 9ell< and let stand or 2 $inutes to allo9 color to ully develop. *itrate 9ith standard errous a$$oniu$ sul ate titrant 2@AS3 until the red color irst co$pletely disappears. .ecord volu$e o @AS titrant used. Chec6 the nor$ality o the @AS titrant at least 9ee6ly a"ainst standard potassiu$ dichro$ate.

Chapter # - 1#

DPD T TRAT ON %ETHOD CALC$LAT ONS *here should 0e no calculations necessary or this $ethod. $":/ Cl2 K $":/ @AS titrant used 9hen the @AS nor$ality is +.++2&2 8 NTERFERENCES DPD T TRAT ON %ETHOD *he inter erences 9hich are li6ely to 0e encountered in 9ater are o;idi(ed $an"anese and hi"h levels o $ono-chlora$ine. *o correct or this< place 5 $/ o phosphate 0u er solution and +.5 $/ sodiu$ arsenite solution in the titration las6. Add 1++ $/ o sa$ple and $i;. Add a0out 1 " EI crystals and 5 $/ 414 indicator< $i; and titrate 9ith @AS solution until red color is dischar"ed. =se this 0lan6 readin" in su0se-uent calculations. Copper up to 1+ $":/ is controlled 0y ,4*A in rea"ents. @ree halo"ens $ay react 9ith the 414 indicator and appear as ree availa0le chlorine. As in $ost tests 9hich depend on color chan"es< sa$ple color< tur0idity< and hi"h concentrations o or"anic $atter $ay cause so$e inter erence. 3ui4 656 1. >hat rea"ents are re-uired to per or$ chlorine residual $easure$ents usin" the 414 titration $ethodG 2. >hat e-uip$ent< apparatus or instru$entation is re-uired to per or$ chlorine residual $easure$ent usin" the 414 titration $ethodG 3. >hat inter erences< i any< are there in the 414 titration chlorine residual procedureG 4. >hat is the chlorine residual o a 1++ $/ sa$ple 9hich re-uired 1.&5 $/ o @AS 2 errous a$$oniu$ sul ate3 solution to reach the titration end pointG

Se&tion '1( DPD COLOR %ETR C DESCR PT ON OF TEST In this $ethod< the chlorine residual is deter$ined usin" a spectrophoto$eter or ilter photo$eter. 414 is used as the indicator. In the presence o chlorine< the 414 indicator solution has a red color. *he $ore chlorine that is present< the dar6er the red color 9ill 0e. *he intensity o the color is $easured a"ainst 6no9n values ro$ a standard curve. 1otassiu$ per$an"anate is used as the standard or esta0lishin" the standard curve 0ecause o the di iculty in "ettin" accurate chlorine standards and the ease o handlin" potassiu$ per$an"anate. A $odi ication o this procedure usin" pre-$easured rea"ents and a hand-held direct readin" colori$eter is also accepta0le or chlorine deter$inations. E3$ P%ENT AND REA)ENTS FOR DPD COLOR %ETR C %ETHOD REA)ENTS See Appendi; 5 at the end o this chapter or the procedure or the preparation o the rea"ents used in each o the $ethods. 1hosphate 0u er solution 414 indicator solutionH

Chapter # - 1%

1otassiu$ iodide 2EI3< crystals Standard potassiu$ per$an"anate solutions Appropriate 414 indicator or direct readin" colori$eter > THESE CHE% CALS ARE PO SONO$S8 SO HANDLE 9 TH E:TRE%E CA$T ON5 E3$ P%ENT FOR DPD COLOR %ETR C %ETHOD Spectrophoto$eter 29ith 9avelen"th o 515 n$ and a li"ht path o 1 c$ or lon"er3< ilter photo$eter 29ith a ilter havin" $a;i$u$ trans$ission in the 9avelen"th ran"e o 4)+ to 53+ n$ and a li"ht path o 1 c$ or lon"er3< or direct concentration readout colori$eter 9hich $eets the $ethod instru$ent speci ications. 15 $/ test tu0es 1 c$ sa$ple cuvettes 1+ $/ $easurin" pipette 1 $/ pipettes< "raduated to +.1 $/ 25+ $/ ,rlen$eyer las6 Appropriate sa$ple $easure$ent container or direct readin" colori$eter LABORATOR+ PROCED$RE FOR DPD COLOR %ETR C %ETHOD SPECTROPHOTO%ETER OR F LTER PHOTO%ETER 1. Set 1++I* on spectrophoto$eter or ilter photo$eter usin" a distilled 9ater 0lan6< in accordance 9ith $anu acturerDs instructions. 21repare distilled 9ater 0lan6 in the sa$e $anner as sa$ple or testin"3. 1repare a series o potassiu$ per$an"anate standards coverin" the e-uivalent chlorine ran"e o +.+5 to 4 $":/. 1lace 5 $/ o phosphate 0u er and 5 $/ o 414 indicator rea"ent in each standard las6. Add 1++ $/ o prepared standards and $i; thorou"hly. @ill photo$eter or colori$eter cell ro$ las6 and read each standard at 515 n$ 9avelen"th. 1lot standard curve o $":/ e-uivalent chlorine versus I*. 1ipette +.5 $/ phosphate 0u er solution into a test tu0e o appropriate volu$e.

2. 3. 4. 5. #. %.

NOTE( *est tu0es should have a capacity o at least 15 $/ and either have a scre9-on cap or 0e capa0le o acceptin" a ru00er stopper 9hich does not cause sa$ple to over lo9 9hen put in place. &. ). Add +.5 $/ 414 indicator solution 0y pipette. Add a e9 crystals 2appro;i$ately +.1 "3 o potassiu$ iodide 2EI3.

1+. Add 1+ $/ sa$ple< stopper or cap< $i; 9ell< and let stand or t9o $inutes to allo9 color to develop. 11. 1our into photo$eter tu0e 2also called a cuvette3 and ta6e readin" o photo$eter in I*. 12. .ecord readin". *he $":/ Cl2 is read directly ro$ the standard curve prepared 0y usin" potassiu$ per$an"anate 2EMn743 as the standard.

Chapter # - 1&

D RECT CONCENTRAT ON READO$T COLOR %ETER 1. Set the (ero and $a;i$u$ concentration values accordin" to $anu acturerDs instructions usin" an untreated portion o sa$ple.

NOTE( =se appropriate sa$ple volu$e and "lass9are to ensure that the e;pected sa$ple concentration alls 9ithin the ran"e o the direct readin" colori$eter concentration readout. 2. 3. 4. 5. #. Measure an appropriate volu$e o sa$ple or sa$ple dilution into a second sa$ple cell. Add an appropriate a$ount o the colori$eter $anu acturerDs 414 indicator to the sa$ple cell< stopper or cap< $i; 9ell< and let stand or t9o $inutes to allo9 color to develop. 1lace sa$ple cell in sa$ple co$part$ent< depress actuator 0utton and read $":/ concentration ro$ the appropriate $eter scale. I sa$ple concentration is 9ithin the $":/ ran"e o the colori$eter< record readin". I sa$ple concentration e;ceeds $":/ ran"e o the colori$eter< repeat steps 1-5< as necessary< usin" a diluted sa$ple.

*he $":/ Cl2 is read directly ro$ the $eter dial o the direct readin" colori$eter. NTERFERENCES DPD COLOR %ETR C %ETHOD *he inter erences 9hich are li6ely to 0e encountered in 9ater are o;idi(ed $an"anese and hi"h levels o $ono-chlora$ine. *o correct or this< place 5 $/ o phosphate 0u er solution and +.5 $/ sodiu$ arsenite solution in the titration las6. Add 1++ $/ o sa$ple and $i;. Add a0out 1 " EI crystals and 5 $/ 414 indicator and $i;. Measure the apparent chlorine as $an"anese and use this 0lan6 readin" in su0se-uent calculations. Copper up to 1+ $":/ is controlled 0y ,4*A in rea"ents. @ree halo"ens $ay react 9ith the 414 indicator and appear as ree availa0le chlorine. As in $ost tests 9hich depend on color chan"es< sa$ple color< tur0idity and hi"h concentrations o or"anic $atter $ay cause so$e inter erences. Co$pensate or color or tur0idity in the colori$etric procedure 0y usin" an untreated sa$ple 0lan6. 3ui4 651 1. >hat rea"ents are re-uired to per or$ chlorine residual $easure$ents usin" the 414 colori$etric $ethodG 2. >hat e-uip$ent< apparatus or instru$entation is re-uired to per or$ chlorine residual $easure$ents usin" the 414 colori$etric $ethodG 3. >hat inter erences< i any< are there in the 414 colori$etric chlorine residual procedureG

Se&tion '2( OR ON SPEC F C ON ELECTRODE DESCR PT ON OF TEST *he 7rion speci ic ion electrode $ethod uses an electrical $easure$ent si$ilar to p! $eter test procedure to deter$ine the chlorine residual. Sa$ples are prepared or $easure$ent 0y addin" an

Chapter # - 1)

iodide rea"ent and an acid rea"ent. Chlorine in the sa$ple reacts 9ith iodide under acid conditions to or$ iodine. *he iodine is< in turn< $easured 0y the electrode and indicated on a p! or speci ic $eter as $v or concentration. E3$ P%ENT AND REA)ENTS FOR SPEC F C ON ELECTRODE %ETHOD REA)ENTS 1otassiu$ iodate solution< 1++ pp$ as Cl 2 !Orion Cat5 No5 611771# 1otassiu$ iodate standard< 1 $":/ Iodide rea"ent 27rion Cat. 8o. )%%+1+3 Acid rea"ent 27rion Cat. 8o. )%%+113 Chlorine 9ater 2appro;i$ately 1++ pp$ Cl 23 E3$ P%ENT Speci ic ion or p! $eter capa0le o $easurin" $v or concentration Model )%-%+ chlorine speci ic ion electrode Jolta"e source 15+ $/ 0ea6ers Ma"netic stirrer and stirrin" 0ars 7ptional e-uip$ent LABORATOR+ PROCED$RE SPEC F C ON ELECTRODE %ETHOD 1. 2. *urn on and 9ar$ up speci ic ion $eter or p! $eter accordin" to $anu acturerDs instructions. Chec6 electrode slope at least 9ee6ly usin" the ollo9in" procedures: a. 0. c. 1lace 1++ $/ distilled 9ater< 1 $/ iodide rea"ent< and 1 $/ acid rea"ent in a 15+ $/ 0ea6er. Add 1 $/ chlorine 9ater to 0ea6er and stir "ently or 2 $inutes to allo9 co$plete reaction. 1lace electrode in solution 9ith the re erence ele$ent su0$er"ed.

NOTE( 4o not stir 0ea6er contents durin" $easure$ents. d. e. . 3. 4. Set $eter unction s9itch to $v readout and adFust cali0ration control to achieve +++.++ $v readin". Add 1+ $/ chlorine 9ater to the 0ea6er. Stir "ently or 2 $inutes to allo9 co$plete reaction< then S*71 S*I..I8G. *he $eter readin" should 0e appro;i$ately 2) $v. I the readin" is less than 2# $v< the electrode instruction $anual should 0e revie9ed.

1repare resh 1 pp$ standard potassiu$ iodate solution. =sin" 4 cycle se$ilo"arith$ic "raph paper< construct a cali0ration curve 9ith 1 pp$ at the center o the lo"arith$ic scale and +++.+ $v at the center o the linear a;is. 2*he linear ran"e should 0e ro$ -#+ to N#+ $v.3 1lot one point at +++.+ $v and 1 pp$ on the "raph and a second point at 2) $v and 1+ pp$. 4ra9 a strai"ht line throu"h these points e;tendin" to at least +.1 pp$. =se this "raph or all chlorine residual $easure$ents.

Chapter # - 2+

5. #. %. &. ).

1lace the electrode in the 1 pp$ standard so that the re erence ele$ent is su0$er"ed. 47 87* S*I.. Set $eter unction s9itch to $v settin" and adFust cali0ration to read +++.+ $v. .e$ove electrode ro$ 1 pp$ standard and 0lot dry. *rans er 1++ $/ sa$ple to a 15+ $/ 0ea6er. Add 1 $/ each o iodide and acid rea"ents.

1+. Mi; contents o 0ea6er thorou"hly< then stop stirrin" and let stand or 2 $inutes to allo9 or co$plete reaction. 11. 1lace the electrode in the prepared sa$ple so that the re erence ele$ent is su0$er"ed. 12. .ecord the $v readin" ro$ the $eter. 13. .epeat steps 5-% every 2 hours to recali0rate the $eter. *he $":/ Cl2 is read directly ro$ the standard curve. Se&tion '6( NTERFERENCES ON ELECTRODE %ETHOD Stron" o;idi(in" a"ents< includin" iodate< 0ro$ine< cupric ion and o;idi(ed $an"anese< that can convert iodide to iodine< inter ere 9ith the $ethod. Silver and $ercuric ions $ust 0e 0elo9 appro;i$ately 1+ $":/. Chro$ate ion< an inter erence in the a$pero$etric $ethods< does not inter ere 9ith this procedure. Color and tur0idity do not inter ere 9ith the $ethod. *he electrode slope is una ected 0y te$perature. !o9ever< 0ecause the cali0ration curve shi ts 0y a0out +.2 $v per OC< the standardi(in" solution should 0e close to the te$perature o the sa$ples. Maintain the standardi(in" solution at or near the e;pected te$perature o the sa$ples. 3ui4 652 1. >hat rea"ents are re-uired to per or$ chlorine residual $easure$ents usin" the 7rion chlorine selective ion electrode $ethodG 2. >hat e-uip$ent< apparatus or instru$entation is re-uired to per ro$ chlorine residual $easure$ents usin" the 7rion chlorine selective ion electrode $ethodG 3. >hat inter erences< i any< are there in the 7rion Model chlorine selective ion electrode chlorine residual procedureG

Chapter # - 21

Se&tion "7( HACH %ODEL CN<66 TOTAL CHLOR NE RES D$AL TEST = T DESCR PT ON OF TEST *he !ach Co$panyDs Model C8-## *otal Chlorine .esidual *est Eit also uses the 414 rea"ent to deter$ine total chlorine residual values. *he 414 rea"ent is pac6a"ed in pre$easured a$ounts stored in disposa0le po9der pillo9s. *he 414 rea"ent is added to a portion o sa$ple. I chlorine is present< a pin6ish-red color 9ill develop. *he color produced is visually co$pared to standard colors representin" various concentrations o total chlorine residual. *he total chlorine residual is read ro$ this co$parison. E3$ P%ENT AND REA)ENTS FOR HACH CN<66 %ETHOD !ach Model C8-## color 9heel and co$parator Sa$ple vials cali0rated at 5 $/ 2237 414 po9der pillo9s< 5 $/ sa$ple volu$e LABORATOR+ PROCED$RE FOR HACH CN<66 %ETHOD 1. 2. 3. 4. 5. #. %. &. ). @ill 0oth sa$ple vials to the 5 $/ "raduation 9ith resh sa$ple to 0e tested. Add the contents o one total chlorine residual 414 po9der pillo9 to one o the vials. Stopper and $i; the vial 0y invertin" several ti$es. Allo9 the vial to set or three $inutes to develop color. 1lace the appropriate 414 chlorine color 9heel in the color co$parator. 1lace the treated sa$ple vial in the ri"ht hand 2nearest to center3 hole o the co$parator. 1lace the untreated sa$ple vial in the le t hand 2nearest to ed"e3 hole o the co$parator. 1oint the co$parator to9ards a di used outside li"ht or a steady indoor luorescent li"ht source. .otate the color 9heel until there is a $atch o color or the t9o vials.

1+. .ead the total chlorine residual $":/ o the sa$ple ro$ the co$parator and record. 11. 4iscard sa$ples< 9ash and rinse all "lass9are. *he $":/ Cl2 is read directly ro$ the color 9heel co$parator indicator. Se&tion "'( NTERFERENCES 9 TH HACH CN<66 %ETHOD *he sa$e inter erences apply to this test 9hich are noted or other 414 procedures< ho9ever< there are no provisions or co$pensatin" or $ost o these inter erences. As in any procedure usin" visual color co$parison< the individual perceptions o the analysts as 9ell as the condition o the "lass9are< the color 9heel< and the li"ht source< can all a ect the results o the test. /i$it the a$ount o error ro$ these actors 0y thorou"hly cleanin" the vials a ter each use< $aintainin" the co$parator and color 9heel< and usin" a sta0le and constant li"ht source.

Chapter # - 22

3ui4 656 1. >hat rea"ents are re-uired to per or$ chlorine residual $easure$ents usin" the !ach C8-## *est EitG 2. >hat e-uip$ent< apparatus or instru$entation is re-uired to per or$ chlorine residual $easure$ents usin" the !ach C8-## *est EitG 3. >hat inter erences< i any< are there in the !ach C8-## *est Eit procedure or chlorine residualG

Se&tion ""( 3A;3C A 'uality Assurance:'uality Control pro"ra$ is re-uired 0y the 814,S per$it. 'uality Assurance 2'A3 is a set o operatin" principles that $ust 0e ollo9ed durin" sa$ple collection and analysis. /a0 0ench sheets $ust 0e $aintained that docu$ent 9hen the sa$ple 9as collected< ho9 it 9as preserved and 9hat results 9ere o0tained. 'uality Control 2'C3 includes any testin" 9hich is done to prove that the results are relia0le. 7ne o every ten sa$ples analy(ed should 0e a 'uality Control chec6. *his $ay include duplicate sa$ples< spi6e sa$ples< rea"ent 0lan6 analyses and 6no9n 'C sa$ples o0tained ro$ outside sources. 4uplicate sa$ple analysis involves analy(in" the sa$e sa$ple t9ice and co$parin" the results. *he closer the results< the $ore accurate the analysis. .esults should not di er 0y $ore than 1+I. Spi6e sa$ple analysis involves addin" 6no9n a$ounts o analyte to a sa$ple and calculatin" the percent recovery. *hese are discussed urther in Chapter 1+. In residual chlorine testin"< duplicate sa$ples should 0e run every tenth sa$ple to test or varia0ility. 'uality Control sa$ples 9ith 6no9n a$ounts o chlorine are availa0le ro$ che$ical $anu acturers.

Chapter # - 23

Ans?ers to 3ui44es 3ui4 65' 1. >hat is the $ain purpose or chlorination o 9ater supplies and 9aste9ater e luentsG The main purpose @or &hlorination o@ ?ater supplies and ?aste?ater e@@luents is the destru&tion o@ disease &ausing organisms5 2. >hat are the de initions o the ollo9in" ter$s: chlorine residual? co$0ined chlorine residual< ree availa0le chlorine residual? and total chlorine residualG a5 ,5 &5 d5 3. The amount o@ a-aila,le &hlorine a@ter a gi-en &onta&t time and under spe&i@i& &onditionsA &hlorine residual @rom &hlorine &om,ined ?ith ammonia or other nitrogen &ompoundsA hBpo&hlorite and;or hBpo&hlorous a&idA and8 the total amount o@ &hlorine a-aila,le in a sample5

>hat are the usual $ini$u$ and $a;i$u$ li$itations or chlorinated e luents dischar"in" to non-critical 9atersG *o critical 9atersG '57 to "57 and '50 to "50

4.

>hat are the approved $ethods or $easurin" chlorine residual concentrations or co$pliance 9ith 814,S per$it re-uire$entsG odometri& ,a&C titrations !iodine and iodate titrants#A Amperometri& dire&t and ,a&C titrationsA DPD titration and &olorimetri&A Orion %odel 61<17 spe&i@i& ion ele&trodeA and Ha&h CN<66 test Cit !@or domesti& @a&ilities ?ith design @lo?s less than or eDual to .78777 gpd#5

3ui4 65" 1. >hat rea"ents are re-uired to per or$ chlorine residual $easure$ents usin" the iodo$etric 0ac6 titration 2iodine titrant3 $ethodG a5 ,5 &5 d5 e5 @5 g5 2. PhenBlarsine oEide !PAO# or sodium thiosul@ate8 757706. NA iodine titrant8 757"2" NA potassium iodide != # &rBstals or 0F solutionA pH.<<a&etate ,u@@er solutionA star&h indi&ator solutionA potassium di&hromate8 757706. NA and8 Arsenite solution8 75' N5

>hat e-uip$ent< apparatus< or instru$entation is re-uired to per or$ chlorine residual $easure$ents usin" the iodo$etric 0ac6 titration 2iodine titrant3 $ethodG a5 ,5 "07 mL graduated &BlinderA 0 mL measuring pipettesA

Chapter # - 24

&5 d5 e5 @5 3.

077 mL ErlenmeBer @lasCsA 0 mL -olumetri& pipetteA '7 or "0 mL ,uretteA and8 magneti& stirrer !optional#

>hat inter erences< i any< are there in the iodo$etric 0ac6 titration 2iodine titrant3 chlorine residual procedureG %anganese8 iron8 and nitriteA sample &olor and tur,iditBA and8 unusuallB high &on&entrations o@ organi& matter5

4.

>hat is the chlorine residual o a 2++ $/ sa$ple 9hich re-uires +.& $/ o +.+2&2 8 iodine to titrate an e;cess o +.++5#4 8 sodiu$ thiosul ate solutionG '57 mg;L

3ui4 65* 1. >hat rea"ents are re-uired to per or$ chlorine residual $easure$ents usin" the iodo$etric 0ac6 titration 2iodate titrant3 $ethodG a5 ,5 &5 d5 e5 @5 g5 h5 2. PAO or sodium thiosul@ate8 757706. NA Potassium iodate8 757706. NA = &rBstals or 0F solutionA star&h solutionA '7F phosphori& a&id solutionA phosphori& a&id<sul@ami& a&id solutionA di&hromate solution 757706. NA and8 arsenite8 75' N

>hat e-uip$ent< apparatus< or instru$entation is re-uired to per or$ chlorine residual $easure$ents usin" the iodo$etric 0ac6 titration 2iodate titrant3 $ethodG a5 ,5 &5 d5 e5 @5 "07 mL graduated &BlinderA 0 mL measuring pipettesA 077 mL ErlenmeBer @lasCsA 0 mL -olumetri& pipetteA '7 or "0 mL ,uretteA and8 magneti& stirrer !optional#

3.

>hat inter erences i any< are there in the iodo$etric 0ac6 titration 2iodate titrant3 chlorine residual procedureG %anganese8 iron and nitriteA sample &olor and tur,iditBA and8 unusuallB high &on&entrations o@ organi& matter

4.

>hat is the chlorine residual o a 2++ $/ sa$ple 9hich re-uires 3.& $/ o +.++5#4 8 potassiu$ iodate to titrate an e;cess o +.++5#4 8 sodiu$ thiosul ate solution 2an initial 0lan6 titration re-uired 5.1 $/ o potassiu$ iodate3G '5* mg;L

Chapter # - 25

5.

>hat is the chlorine residual o a 2++ $/ sa$ple 9hich re-uires +.%5 $/ o +.+2&28 iodine to titrate an e;cess o +.++5#48 phenylarsine o;ide 21A73 solutionG '5"0 mg;L

3ui4 65. 1. >hat rea"ents are re-uired to per or$ chlorine residual $easure$ents usin" the a$pero$etric direct titration $ethodG a5 ,5 &5 d5 e5 2. PAO8 757706. NA = 8 0F solutionA pH.<<a&etate ,u@@er solutionA di&hromate solution8 757706. NA and8 arsenite8 75' N5

>hat e-uip$ent< apparatus or instru$entation is re-uired to per or$ chlorine residual $easure$ents usin" the a$pero$etric direct titration $ethodG Amperometri& titratorA "07 mL graduated &BlinderA and 0 mL measuring pipettes5

3.

>hat inter erences< i any< are there in the a$pero$etric direct titration chlorine residual procedureG a5 ,5 &5 d5 e5 Nitrogen tri&hloride or &hlorine dioEideA @ree halogens other than &hlorineA &opper and sil-erA organi& &hloraminesA and8 -erB lo? temperatures5

4.

>hat is the chlorine residual o a 2++ $/ sa$ple 9hich re-uires 2.25 $/ o +.++5#4 8 phenylarsine o;ide 21A73 solution to reach the titration end-pointG "5"0 mg;L

3ui4 650 1. >hat rea"ents are re-uired to per or$ chlorine residual $easure$ents usin" the 414 titration $ethodG a5 ,5 &5 d5 e5 @5 g5 2. N8 N<diethBl<p<phenBlenediamine !DPD# indi&ator solutionA phosphate ,u@@er solutionA = 8 &rBstals ,arium diphenBlamine sul@onateA @errous ammonium sul@ate !FAS#8 7577"2" NA &on&entrated phosphori& a&idA and8 sul@uri& a&id8 'G0

>hat e-uip$ent< apparatus or instru$entation is re-uired to per or$ chlorine residual $easure$ents usin" the 414 titration $ethodG a5 ,5 &5 d5 e5 "07 mL graduated &BlinderA 0 mL measuring pipettesA 077 mL ErlenmeBer @lasCA 07 mL ,uretteA and8 magneti& stirrer !optional#

Chapter # - 2#

3.

>hat inter erences< i any< are there in the 414 titration chlorine residual procedureG a5 ,5 d5 %anganese and high le-els o@ mono<&hloraminesA &opperA &olor8 tur,iditB8 and large &on&entrations o@ organi& material

4.

>hat is the chlorine residual o a 1++ $/ sa$ple 9hich re-uires 1.&5 $/ o @AS 2 errous a$$oniu$ sul ate3 solution to reach the titration end-pointG '520 mg;L

3ui4 656 1. >hat rea"ents are re-uired to per or$ chlorine residual $easure$ents usin" the 414 colori$etric $ethodG a5 ,5 &5 d5 2. DPD indi&ator solutionA phosphate ,u@@er solutionA = 8 &rBstalsA and8 standard potassium permanganate solutions

>hat e-uip$ent< apparatus or instru$entation is re-uired to per or$ chlorine residual $easure$ents usin" the 414 colori$etric $ethodG a5 ,5 &5 d5 e5 @5 '0 mL test tu,esA ' &m sample &u-ettesA '7 mL measuring pipettesA ' mL pipettes8 graduated to 75' mLA "07 mL ErlenmeBer @lasCsA and8 spe&trophotometer or &olorimeter

3.

>hat inter erences< i any< are there in the 414 colori$etric chlorine residual procedureG a5 ,5 &5 d5 %anganese and high le-els o@ mono<&hloraminesA &opper @ree halogensA and8 &olor8 tur,iditB8 and large &on&entrations o@ organi& material

3ui4 651 1. >hat rea"ents are re-uired to per or$ chlorine residual $easure$ents usin" the 7rion Model )%-%+ chlorine selective ion electrode $ethodG a5 ,5 &5 d5 e5 2. Potassium iodate solution8 '77 ppmA potassium iodate standard ' mg;LA = solutionA a&eti& a&id reagentA and8 &hlorine ?ater8 '77 ppm

>hat e-uip$ent< apparatus or instru$entation is re-uired to per or$ chlorine residual $easure$ents usin" the 7rion Model )%-%+ chlorine selective ion electrode $ethodG a5 ,5 &5 d5 Spe&i@i& ion or pH meterA Orion %odel 61<17 &hlorine ele&trodeA '07 mL ,eaCersA and8 magneti& stirrer !optional#

Chapter # - 2%

3.

>hat inter erences< i any< are there in the 7rion Model )%-%+ chlorine selective ion electrode chlorine residual procedureG a5 ,5 &5 Strong oEidi4ing agents !iodate8 ,romine8 &upri& ion and oEidi4ed manganeseA and8 sil-er and mer&uri& ions

3ui4 652 1. >hat rea"ents are re-uired to per or$ chlorine residual $easure$ents usin" the !ach C8-## *est EitG DPD po?der pillo?s 2. >hat e-uip$ent< apparatus or instru$entation is re-uired to per or$ chlorine residual $easure$ents usin" the !ach C8-## *est EitG Ha&h %odel CN<66 test Cit &olor ?heel and &omparatorA 0 mL sample -ials5 3. >hat inter erences< i any< are there in the !ach C8-## *est Eit procedure or chlorine residualG a5 ,5 &5 d5 e5 @5 %anganese and high le-els o@ mono<&hloraminesA &opperA @ree halogensA &olor8 tur,iditB8 and large &on&entrations o@ organi& materialA glass?are and &olor ?heel &onditionA and light sour&e -ariations5

Chapter # - 2&

APPEND : A Re@eren&es 1. 2. 3. 4. 5. #. Standard Method or the ,;a$ination o >ater and >aste9ater< A1!A-A>>A->,@< 1&th ,dition< 1))2< Methods 45++-Cl A-I. Model 1%-8 >ide-.an"e p! *est Eit < test 6it instructions< !ach Co$pany. .esidual Chlorine ,lectrode Model )%-%+-++< instruction $anual< 7rion .esearch Incorporated. Model C8-## .esidual Chlorine *est Eit < test 6it instructions< !ach Co$pany. Methods or Che$ical Analysis o >ater and >astes< =.S. ,1A-#++:4-%)-+2+< March 1)%)< Methods 33+.1 - 33+.5. Annual 5oo6 o Standards< Section II< A>aterB< AS*M< Methods 41253-%#2A3 and 41253-%#253 part 1&.3.

NOTES(

Chapter # : Appendi; A : 1a"e 1

APPEND : B Preparation o@ Chemi&als At a $ini$u$< hand and eye protection should 0e used 9hen handlin" any o the che$icals $entioned in this section. 5e ore 9or6in" 9ith any che$ical< consult the appropriate Material Sa ety 4ata Sheet 2MS4S3 to deter$ine i other sa ety precautions are necessary. CHLOR NE RES D$AL REA)ENTS Iodo$etric and A$pero$etric Methods: 5 Standard PhenBlarsine OEide !PAO# Solution8 757706. N A. 5. 1repare +.3 8 sodiu$ hydro;ide solution 28a7!3 0y dissolvin" 12.+ " 8a7! in &++ $/ distilled 9ater and dilutin" to 1 liter. 1repare a #.+ 8 hydrochloric acid solution 2!Cl3 0y addin" 1+& $/ concentrated !Cl to &++ $/ distilled 9ater and dilutin" to 1 liter. !Caution( Con&entrated HCl @umes &an ,urn eBes and lungsHdo not ,reathe @umesI# 1repare an appro;i$ately +.++5#4 8 solution o 1A7 usin" the ollo9in" procedures: 1. 2. 3. 4. 4issolve appro;i$ately +.& " 1A7 po9der in 15+ $/ o +.3 8 8a7! solution< and allo9 to settle. 4ecant 11+ $/ into &++ $/ distilled 9ater and $i; thorou"hly. 5rin" to p! # to % 9ith #8 !Cl and dilute to )5+ $/ 9ith distilled 9ater. !Caution( PAO is poisonous5 9ash thoroughlB a@ter use and do not ingest5#

C.

Standardi(ation 1. Accurately $easure 5 to 1+ $/ reshly standardi(ed +.+2&2 8 iodine solution into a las6 and add 1 $/ potassiu$ iodide solution 25+" EI dissolved and diluted to 1 / 9ith reshly 0oiled and cooled distilled 9ater. *itrate 9ith 1A7 solution< usin" starch solution as an indicator< until 0lue disappears. 8or$ality 283 o 1A7 K 2$/ iodine solution ; +.+2&23:$/ 1A7 titrated. AdFust 1A7 to +.++5#4 8 and rechec6.

2. 3. 4. 5

Standard Sodium Thiosul@ate Solution8 757706. N A. 1repare a +.1 8 sodiu$ thiosul ate solution 0y dissolvin" 25 " 8a2S273 5!27 in 1+++ $/ o reshly 0oiled distilled 9ater. Store rea"ent or at least 2 9ee6s to allo9 o;idation o any 0isul ite ion present. Add a e9 $/ o chloro or$ 2C!Cl33 to $ini$i(e 0acterial deco$position.

Chapter # : Appendi; 5 : 1a"e 1

Standardi(e 0y one o the ollo9in" $ethods: 1. Iodate Method a. 4issolve 3.24) " anhydrous pri$ary standard -uality potassiu$ 0i-iodate 2E!2I7 3323 or 3.5#% " potassiu$ iodate 2EI7 33 dried at 1+3 N:-2OC or 1 hour in distilled 9ater and dilute to 1+++ $/ to yield a +.1+++ 8 iodate solution. Store in a "lass stoppered 0ottle. Add< 9ith constant stirrin"< 1 $/ concentrated sul uric acid 2!2S743< 1+ $/ +.1+++ 8 iodate solution< and 1 " potassiu$ iodide 2EI3 to &+ $/ distilled 9ater. *itrate i$$ediately 9ith +.1 8 sodiu$ thiosul ate 28a2S2733 until the yello9 color o the li0erated iodine is al$ost dischar"ed. Add 1 $/ starch indicator solution and continue titration until the 0lue color disappears. *he nor$ality 283 o the sodiu$ thiosul ate is calculated as ollo9s: 8 o 8a2S273 K 1:$/ 8a2S273 or titration

0.

c. 2.

4ichro$ate Method a. 4issolve 4.)+4 " anhydrous pri$ary standard "rade potassiu$ dichro$ate 2E2Cr27%3 in distilled 9ater and dilute to 1+++ $/ to yield a +.1+++ 8 dichro$ate solution. Store in a "lass stoppered 0ottle.

5.

@or $a;i$u$ sta0ility o the standard +.++5#4 8 sodiu$ thiosul ate solution< prepare 0y dilutin" an a"ed +.18 8a2S273 standard solution 9ith reshly 0oiled distilled 9ater. Add 1+ $" Mercuric iodide and 4 " o sodiu$ 0orate per liter o solution. Standardi(e daily usin" +.++5#4 8 potassiu$ dichro$ate or iodate solution.

Standard odine Solution ! "#8 75' N A. 5. C. 4. 4issolve 4+ " potassiu$ iodide 2EI3 in 25 $/ chlorine-de$and- ree 9ater. Add 13 " resu0li$ed iodine 2I23 and stir until dissolved. *rans er to a 1 liter volu$etric las6 and dilute to the $ar6. Standardi(ation 1. 2. 3. 4. 5. Jolu$etrically $easure 4+ to 5+ $/ +.1 8 arsenite solution into a las6. *itrate 9ith +.1 8 iodine solution usin" starch solution as an indicator. Cust 0e ore end-point is reached< add a e9 drops o hydrochloric acid solution to li0erate su icient car0on dio;ide 2C7 23 to saturate the solution. *itrate until 0lue color irst appears and re$ains. 8or$ality 283 o iodine K 2$/ o arsenite solution used ; +.13:$/ o iodine titrated

/5

Standard odine Titrant ! "#8 757"2" N A. 5. 4issolve 25 " EI in a 0ottle o distilled 9ater in a 1/ volu$etric las6. Add the correct a$ount o the e;actly standardi(ed +.1 8 iodine solution to yield a +.+2&2 8 solution.

Chapter # : Appendi; 5 : 1a"e 2

C. 4. ,. /5

4ilute to one liter 9ith chlorine-de$and- ree 9ater. Store iodine solutions in a$0er 0ottles or in the dar6< and protect ro$ e;posure to direct sunli"ht. 4o not use ru00er stoppers? 6eep iodine ro$ all contact 9ith ru00er. Chec6 titrant nor$ality daily a"ainst +.++5#4 8 1A7 or sodiu$ thiosul ate solution. A procedure or calculatin" a correction actor or this titrant is "iven in Appendi; C.

Standard Potassium odate Titrant != O *#8 757706. N A. 4issolve 2+1.2 $" pri$ary standard "rade potassiu$ iodate 2EI733< dried or 1 hour at 1+3OC< or 1&3.3 $" pri$ary standard "rade anhydrous potassiu$ 0i-iodate 2E!2I7332J3 in distilled 9ater. 4ilute to 1 liter volu$etrically. Store in "lass 0ottles in the dar6 and protect ro$ e;posure to direct sunli"ht.

5. C. /5

Potassium odide Solution != #8 0F 9;/ A. 5. C. 4issolve 5+ " EI in reshly 0oiled and cooled distilled 9ater and dilute to 1 liter. Store in a 0ro9n "lass-stoppered 0ottle in the dar6< pre era0ly at 4OC. 4iscard 9hen solution 0eco$es yello9.

/ 5 A&etate Bu@@er Solution8 pH .57 A. 5. C. 4issolve 14# " anhydrous sodiu$ acetate 28aC2!372 3!273 in 4++ $/ distilled 9ater. CA.,@=//P add 45& $/ concentrated 2"lacial3 acetic acid. 4ilute to 1 liter 9ith chlorine-de$and- ree 9ater.

/ 5 Standard Arsenite Solution !As"O*#8 75'N A. Accurately 9ei"h a dried< cooled stoppered 9ei"hin" 0ottle.

NOTE( =se orceps or ton"sQdo not handle 9ei"hin" 0ottle 9ith in"ers. 5. C. In 9ei"hin" 0ottle< 9ei"h out appro;i$ately 4.)5 " arsenic trio;ide 2As 2733. *rans er 9ithout loss to a 1 liter volu$etric las6

NOTE( 4o not atte$pt to 0rush out re$ainin" arsenic trio;ide3. 4. ,. @. G. .e9ei"h 0ottle and record 9ei"ht o arsenic trio;ide trans erred. Add enou"h distilled 9ater to $oisten the arsenic trio;ide. Add 15 " sodiu$ hydro;ide 28a7!3 and 1++ $/ distilled 9ater. S9irl las6 "ently until As273 is dissolved.

Chapter # : Appendi; 5 : 1a"e 3

!.

4ilute to 25+ $/ and saturate the solution 9ith car0on dio;ide 2C7 23 0y 0u00lin" C72 "as throu"h the solution or a e9 $inutes.

NOTE( *his converts the sodiu$ hydro;ide 28a7!3 to sodiu$ 0icar0onate 28a!C7 33. I. C. 4ilute to the 1 liter $ar6< stopper< and $i; thorou"hly. *his solution has an al$ost inde inite shel li e.

CA$T ON( This solution is highlB poisonous and is a suspe&ted &an&er &ausing agent( handle &are@ullBI :5 Star&h ndi&ator A. 5. C. 4. >ei"h out 5 " solu0le or potato starch. Add enou"h distilled 9ater to $a6e a thin paste. 1our into 1 liter 0oilin" distilled 9ater< stir and let settle overni"ht. *rans er clear supernatant into a stora"e container and preserve 0y addin" 1.25 " salicylic acid< 4 " (inc chloride< or a co$0ination o 4 " sodiu$ propionate and 2 " sodiu$ a(ide per liter o starch solution. So$e co$$ercial starch su0stitutes or po9der indicators are accepta0le.

,. :5

Phosphori& A&id solution !H*PO.#8 ' G 6 A. 5. Care ully add 1++ $/ o phosphoric acid 2!31743< &5I< to )++ $/ o reshly 0oiled distilled 9ater. Caution should 0e used 9hen handlin" this solution< as it can 0e corrosive.

:5

Phosphori& A&idHSul@ami& A&id Solution A. 4issolve 2+ " sul a$ic acid 28!2S73!3 in 1 liter o 1 N ) phosphoric acid 2! 31743.

DPD Titrimetri& %ethod 5 Phosphate Bu@@er Solution A. 4issolve 24 " anhydrous disodiu$ hydro"en phosphate 28a2!1743 in 4++ to 5++ $/ distilled 9ater. Add 4# " anhydrous potassiu$ dihydro"en phosphate 2E! 21743. 4issolve &++ $" disodiu$ ethylenedia$inetetraacetate dihydrate 2,4*A3 in a separate container.

5. C.

NOTE( *his che$ical is also 6no9n as 2ethylenedia$ine3 tetraacetic acid sodiu$ salt. 4. ,. Co$0ine the 2 solutions and dilute to 1 liter. Add 2+ $" $ercuric chloride to prevent $old "ro9th.

Chapter # : Appendi; 5 : 1a"e 4

@. 5

Caution: Mercuric chloride is to;ic. *a6e care to avoid in"estion.

DPD ndi&ator Solution A. Add & $/ o a 1 N 3 sul uric acid solution 2! 2S743 into 5++ $/ distilled 9ater. 1repare 0y $i;in" one part concentrated !2S74 to 3 parts distilled 9ater. 2@or e;a$ple< 5 $/ ! 2S74 to 15 $/ distilled 9ater.3 Add 2++ $" ,4*A 2disodiu$ ethylenedia$inetetraacetate dihydrate3. Add 1 " 414 7;alate 28< 8-4iethyl-p-phenylenedia$ine o;alate3. 4ilute to 1 liter and store in a 0ro9n "lass-stoppered 0ottle and discard 9hen discolored.

5. C. 4.

CA$T ON( The DPD oEalate is poisonous8 handle &are@ullBI 5 Standard Ferrous Ammonium Sul@ate !FAS# Titrant8 7577"2" N A. Add 1 $/ o 1 N 3 sul uric acid solution 2! 2S743 to 5++ $/ o reshly 0oiled and cooled distilled 9ater. 1repare 0y addin" one part concentrated ! 2S74 to 3 parts distilled 9ater. 4issolve 1.1+# " errous a$$oniu$ sul ate 2@e28! 4322S7432 #!273 4ilute to 1 liter. *his standard can 0e used or 1 $onth 0e ore replace$ent. Standardi(e 9ee6ly usin" the ollo9in" procedure: 1. 2. 3. 4. Measure 1++ $/ o @AS standard solution into an ,rlen$eyer las6. Add 1+ $/ o 1 N 5 sul uric acid. 1repare 0y addin" one part concentrated ! 2S74 to 5 parts distilled 9ater. Add 5 $/ concentrated phosphoric acid. Add 2 $/ +.1I 0ariu$ diphenyla$ine sul onate indicator. 1repare 0y dissolvin" +.1 " 2C#!58!C#!4-4-S733 5a in 1++ $/ distilled 9ater. *itrate 9ith +.1++8 potassiu$ dichro$ate 2see iodo$etric and a$pero$etric section or preparation directions3 to a violet end-point that persists or 3+ seconds.

5. C. 4. ,.

5.

DPD Colorimetri& %ethod 5 Phosphate Bu@@er Solution 2see 414 *itri$etric Method che$icals3 5 DPD ndi&ator Solution 2see 414 *itri$etric Method che$icals3 5 Potassium Permanganate Sta&C Solution A. 4issolve &)1 $" potassiu$ per$an"anate 2EMn7 43 in distilled 9ater and dilute to 1+++ $/.

Chapter # : Appendi; 5 : 1a"e 5

/5

Potassium Permanganate Standard Solution A. 5. C. 4ilute 1+ $/ o stoc6 solution to 1++ $/ in a volu$etric las6. 1 $/ o the standard solution diluted to 1++ $/ 9ith distilled 9ater 9ill 0e e-uivalent to 1.+ $":/ chlorine residual in a 414 reaction. 1repare standard solutions 0y dilutin" appropriate volu$es to 1++ $/ 9ith distilled 9ater.

I a direct concentration readout colori$eter is used< the 414 and 0u er rea"ents should 0e prepared or ordered in accordance 9ith the instru$ent $anu acturerDs instructions. I the !ach 4.1++ colori$eter is used< the prepared 414 po9der pillo9s used 9ith the !ach direct readin" colori$eters $ay 0e purchased ro$ the !ach Co$pany at the ollo9in" address: !ach Co$pany 1.7. 5o; 3&) /oveland< Colorado &+53) Orion %odel 61<17 Ele&trode %ethod >ith the e;ception o the 1 pp$ potassiu$ iodate standard and the chlorine 9ater 21++ pp$3< all o the rea"ents re-uired or this $ethod can 0e purchased ro$ 7rion .esearch at the ollo9in" address: 7rion .esearch Incorporated &4+ Me$orial 4rive Ca$0rid"e< Massachusetts +213) 5 5 1repare a 1 $":/ iodate standard 0y volu$etrically dilutin" 1 $/ o the 1++ pp$ iodate standard to 1++ $/ 9ith distilled 9ater. 1repare the chlorine 9ater 2appro;i$ately 1++ pp$3 0y dilutin" 1 $/ hypochlorite solution 2household chlorine 0leach3 to 5++ $/ 9ith distilled 9ater.

Ha&h %odel CN<66 Test =it %ethod *he 414 indicator po9der pillo9s used in the !ach Model C8-## *est Eit $ay 0e purchased ro$ the !ach Co$pany at the ollo9in" address: !ach Co$pany 1.7. 5o; 3&) /oveland< Colorado &+53)

Chapter # : Appendi; 5 : 1a"e #

APPEND : C 3ualitB Assuran&e &he&C on 757"2" N odine Solution A5 ntrodu&tion +.+2&2 8 iodine *itrant deco$poses very easily and should 0e stored in a$0er 0ottles and protected ro$ stron" li"ht. It also $ust 0e 6ept ro$ co$in" into contact 9ith ru00er or plastics 2such as those used in a$pero$etric titrator pu$p asse$0lies3. ,;perience has sho9n that the iodine deco$position can 0e retarded 0y re ri"eratin" the solution durin" stora"e. ,ven 9hen ta6in" the a0ove precautionary $easures< Iodine still slo9ly deco$poses. A -uality assurance chec6 can 0e $ade and a correction actor o0tained to co$pensate or any chan"e in the nor$ality o the solution. !o9ever< i there is any dou0t a0out the -uality o the iodine solution< the solution should 0e chec6ed 0y standardi(ation or replaced 9ith resh solution. B5 3ualitB Assuran&e Test La,oratorB Pro&edure( 1. 2. 3. 1ipette 5.+ $/ +.++5#4 8 1henylarsine o;ide solution 21A73 into a 5++ $/ ,rlen$eyer las6. 1our in 2++ $/ distilled 9ater and stir 9ell. Starch-iodide ,nd-point: Add 1.+ $/ o starch indicator. *itrate< 9hile stirrin"< 9ith the supposed +.+2&2 8 iodine titrant until the irst appearance o 0lue color that re$ains a ter co$plete $i;in". Amperometri& End<point( *itrate< 9hile stirrin"< 9ith the supposed +.+2&2 8 Iodine titrant to the end-point< accordin" to the instructions o the speci ic titrator used. 4. C5 .ecord the volu$e o iodine titrant used.

Cal&ulation o@ NormalitB o@ the iodine Titrant( 8or$ality o the iodine titrant 28i3 ; Jolu$e 2$/3 o iodine titrant 2J i3 K 8or$ality o 1A7 28p3 ; Jolu$e 2$/3 o 21A73 2Jp3: 8i ; Ji K 8p ; Jp ,;a$ple: $/ o iodine 2Ji3 K 1.1 8or$ality o 1A7 K +.++5#4 $/ o 1A7 2Jp3 K 5 $/ 8i ; 1.1 $/ K +.++5#4 ; 5 $/ K +.+25#

Chapter # : Appendi; C : 1a"e 1

D5

Corre&tion Fa&tor Cal&ulation Correction @actor K 8or$ality o iodine titrant 28 i3:1roper 8or$ality o iodine titrant 283 ,;a$ple: Measured 8or$ality o iodine 28i3 K +.+25# .e-uired 8or$ality o iodine 283 K +.+2&2 Correction @actor K 8i:8 K +.+25#:+.+2&2 K +.)1

E5

Determination o@ Corre&ted /olume o@ 757"2" N iodine *o deter$ine the corrected volu$e o +.+2&2 8 iodine to use in the calculation or the iodine 0ac6-titration procedure< the $/ o iodine used in the analysis o a chlorinated sa$ple is $ultiplied 0y the correction actor. ,;a$ple: Jolu$e o iodine used in sa$ple analysis K +.% $/ Correction @actor K +.)1 Corrected volu$e o iodine K +.)1 ; +.% $/ K +.#4 $/

F5

Cal&ulation o@ Corre&ted Chlorine Residual o@ a Sample $":/ Cl2 K L2$/ 1A7 added3 - 25 ; $/ iodine used3M ; 2++:Jolu$e o Sa$ple ,;a$ple: Jolu$e 1A7 added to sa$ple K 5 $/ Jolu$e +.+2&28 iodine used in titration K +.#4 $/ Jolu$e o sa$ple K 2++ $/ $":/ Cl2 K L5 - 25 ; +.#43M ; 2++:2++ K 1.& $":/

)5

Dis&laimer It $ust 0e stressed that this procedure is only $eant to 0e a -uic6 -uality assurance chec6 and not a standardi(ation o the iodine solution. I there is any dou0t a0out the -uality o the iodine solution or i the correction actor 0eco$es e;cessive 2less the +.)+ or $ore than 1.1+3< the solution should 0e chec6ed 0y standardi(ation or replaced 9ith resh iodine solution.

Chapter # : Appendi; C : 1a"e 2