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    458 Prepare fresh daily. Nove: Chloramine-‘ issn air sensitive slid Preferably discard tis chemical 6 months after opening. £. Pyrdine/barbitarie acid solution (wal and WAD cyanide) In the fume hood, place 15.0 barbiturie acid in atared LL container and ad 100 g water rinsing dovin the sides of the beaker to wet he barbturic cid, Add 73 w pyridine (C5H,N) with siring and mix unt the barbitrc acid dissolves. Add 18 g cone HCI, the add an seiional $25 mL, water and mix. Prepare fresh weekly 8. Stock cyanide standard, 100 mg CN“/L: Ina 1-L container dissolve 2.0 g potassium hydroxide, KOH, in approximately 800 mL water. Add 0.250 g potassium cyanide, KCN, CavHON: KCN is highly toxic. Avoid inhalation of dust oF contact with ‘the solid oF solutions. Make to final weight of 1000 g with water and invert thee times to mix, Propare fresh weekly or sandard- ize weekly using the procedure in Section 4500-CN~-Da, ‘h. Standard cyanide solutions: Prepare cyanide sandants inthe desired concentration range, wing the stock cyanide standard (fg above) and diluting with the NaOH standards diluent Gl ¢ above), 4. Procedure Set up manifold equivalent o that in Figure 4500-CN~:3 and follow the method supplied by the manufacturer or laboratory standard operating procedute for this method, 5. Calculations Prepare standard curves by plotting absorbance of standards processed through the manifold vs. cyanide concentration. The calibration curve is linea. INORGANIC NONMETALS (400 5. Precision and Bias 4, MDL. total eyanide: &420-pl. sample oop was wed inte tol eyanide method. Using published MDL metho, analysts ran 21 replicates of a 10.0-ug CN“/L standard, These gave & mean of 969 ug CN"/L, 2 stndard deviation of O86 yg NTL, and an MDL of 27 yg CN . MDL, WAD cyanide: 8 420-pL Sample loop was sed in the WAD eyanide method. Using a published MDL method, analysts an 21 replicates of « 100-yg CN" standard. These gave amean of 11.5 jg CN“/L, a standard deviation of 0.73 ug NIL, and an MDL of 23 wg CN. €. Precision study, total cyanide: Seven igections of a 100.0-ng CNM standard gave a relative standard deviation (RSD) of 108. Precision study, WAD cyanide: Ten injoctons of a 200.0-ug CNA standard gave an RSD of 1.36. . Recovery of total cyanide: Two injections each were made of solutions of potassium fericyanide and potassium ferocya de, both at concentation equivalent 19 100 ug CN“/L. Both save an average recovery of 98% 7. Reference 1. US, EwsoneewraL Prorscron Acsicy. 1989. Definition and procedure forthe determination of method detection limits. Ap pendix B 0 40 CFR 136 rev, 12.1] amended June 30, 1986, 49 CFR 43480. 4500-Cl_ CHLORINE (RESIDUAL)* 4500-Cl A. 1. Effects of Chlorination ‘The chlorination of water supplies and polluted waters serves primarily to destroy or deactivate dsease-prodacing microorgan- isms. A secondary benefit, prticulatly in treating drinking water, is the overall improvement in water quality resulting from the reaction of chlorine with ammonia, roa, manganese, sulfide, and some organic substances, CCrornation may produce adverse effects. Taste and odor cha scterstis of phenols and other organic compounds present in a ‘water supply may be intensified, Potentially carcinogenic chlorbor- ganic compounds such as chloroform may be formed. Combined ‘chlorine formed on chlorination of axamonia- or amine bearing waters adversely affects some aquatic life. To full the primacy ‘Purpose of chlorination and to minimize any adverse effet, it is Approved Wy Sunda Methods Comite, 2000, Ea sins, 2011 Introduction essential that proper testing procedures be used with a foreknow! eg of the imitations of the analytical determination, 2. Chlorine Farms and Reactions Chlorine applied to water in its molecular oF hypochlorite form initially undergoes hydrolysis to form free chlorine com sisting of aqueous molecular chlorine, hypochlorous acid, and hypochlorite ion. The relative proportion of these free chlorine forms is pH- and temperature-dependent. At the pH of most waters, hypochlorous acid and hypochlorite ion will predomi: Free chlorine reacts readily with ammonia and certain nitrog ‘enous compounds to form combined chlorine. With ammonis, chlorine reacts to form the chloramines: monchloramine, di chloramine, and niteogen trichloride, The presence and concen trations ofthese combined forms depend chiefly on pH, temper ‘ature, initial chlorine-to-nitrogen ratio, absolute chlorine de ‘mand, nd reaction time, Both fre and combined chlorine may (CHLORINE (RESIDUAL) (4500-Civitroduction ‘be preset simultaneously. Combined chlorine in water supplies ‘may be formed in the treatment of raw waters containing am- ‘monia o by the addition of emmonia or ammonium salts. Cho Fated wastewater effluents, as well as certain chlorinated in- tussial effluents, normally contain only combined chlorine. His- taccally, the principal analytical problem has been to distinguish ‘erween free and combined forms of chlorine, 3, Selection of Method In two separate bot related studies, samples were prepared and stibuted 10 participating laboratories to evaluate chlorine rmathods. Because of poor accuracy and precision and a high ‘overall (average) total error in these studies, all orhotoidine procedures except ane were dropped in the 14th edition ofthis wrork, The useful stabilized neutral orhotelidine method was deleted from the 1th edition because of the toxic nature of fonhotolidne. The leuco crystal violet (LCV) procedure was ‘dropped from the 1th edition because ofits relative difficulty and the lack of comparative advantages. ‘4 Natural and treated waters: The iodometsie methods (B and CC) are suitable for measuring total chlorine concentrations seater than 1 m/l, but the amperometric endpoint of Methods Cand D gives greater sensitivity. All acidic iodometri methods suffer from interferences, generally in proportion to the quantity of potassium iodide (KI) and HI added The amperometric titration method (D) isa standard of eom- parison forthe determination of free or combined chlorine. I is affected litle by common oxidizing agents, temperature varia- tions, turbidity, and color. The method is not as simple as the colorimetric methods and requires greater operator skill obtain tho best reliability. Loss of chlorine can occur because of rapid ‘ering in some commercial equipment, Clean and conditioned electrodes are necessary for sharp endpoint. ‘A low-level amperometric station procedure (E) has been sxided to 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 withthe standard amperometic procedure (D). The DPD methods (Methods F nnd G) are operationally simpler for deter- ‘mining free chlorine han dhe amperometric tration. Procedures ae given for estimating the separate mono- and diehloramine and combined fractions. High cancentrations of monochloramine imetere with the free chlorine determination unless the reaction 's stopped with arsenite or thioacetamide. In addition, the DPD methods are subject to interference by oxidized forms of man ganese unless compensuied for by a blank. ‘The amperometric and DPD methods are unaffected by di- chloramine concentration inthe range of 0 0 9 mg Clas Cll in the determination of free chlorine. Nitrogen tichlorde, if present, may react perially as fre chlorine in the amperometric, DPD, and FACTS methods. The extent ofthis interference inthe DPD methods does not appear tobe significant. The free chlorine test, syringaldazine (FACTS, Method H) ‘vas developed specifically for free chlorine. Ic is unaffected by Significant concentrations of monochloramine, dicloramine, ni- ‘tute, nitrite, and oxidized forms of manganese." ‘Sample color and turbidity may interfere in all colorimetic prooedures, 459 Organic contaminants may produce a false fee chlorine read- {ng in most colorimetric methods (see fb below). Many strong oxidizing agents interfere in the measurement of free eblorine in all methods. Such interferences include bromine, chlorine diox ‘de, iodine, permanganate, hydrogen peroxide, and ozone. How. ever, the reduced forms of these compounds—bromide, chlo ‘ide, iodide, manganous ion, and oxygen, in the absence of other ‘oxidants, donot interfere. Reducing agents such as ferrous ‘compounds, hydrogen sulfide, and oxidizable organic matter ‘generally do not interfere. 'b Wastewaters: The determination of total chlorine in samples ‘containing organic mater presents special problems. Because of the ‘presence of ammonia, amines, and organic compounds, particularly ‘organic nitrogen, residual chlorine exists in a combined state. A ‘considerable residual may exis in this form, but at the same time there may be appreciable unsatisfied chlorine demand. Addition of -eagens inthe determination may change these relationships so that residual chlorine is lost during the analysis. Only the DPD method for total chlorine is performed under neweal pH conditions. In| wastewater, the differentiation between fre chlorine and combined chlorine ordiaaily is not made because wastewater chlorination seldom is carried far enough to produce free chlorine ‘The determination of residual chlorine in industrial wastes is similar to that in domestic wastewater when the waste contains organic matter, but may be similar to the determination in water ‘when the waste is low in organic mater None of these methods is applicable to estuarine or marine waters because the bromide is converted to bromine and brom- amines, which are detected as free or total chlorine. A procedure for estimating this interference is available for the DPD method ‘Although the metheds given below are useful for the determina tion of residual chlorine in wastewaters and treated effluents, select the method in accordance with sample composition. Some indus teal wastes, or mixtures of wastes with domestic wastewater, may require special precautions and modifications to obtain satisfactory result, Determine free chlorine in wastewater by any of the methods provided that known interfering substances are absent or appro- priate correction teclnigues are used, The amperometric method is the method of choice because itis not subject to interference from color, turbidity, iron, manganese, or nitite nitrogen. The DPD method is subject to interference from high concentrations of monochloramine, which is avoided by adding thioacetamie immediately after reagent addition. Oxidized forms of manga- nese at all levels encountered in. water will interfere in ‘methods except in the fre chlorine measurement of amperomet- ric trations and FACTS, but a blank correction for manganese can be made in Methods F and G. ‘The FACTS method is unaffected by concentrations of mono- chloramine, dichloramine, nitrite, iro, manganese, and other interfering Compounds normally found in domestic Wastewater, For total chlorine in samples containing significant amounts of| organic matter, use ether the DPD methods (F and G), ampero- retrc, or iodometrc back titration method (C) to prevent con- tact between the full concentration of liberated iodine and the sample. With Method C, do not use the stach-iodide end point if the concentration is less than 1 mg/L. In the absence of interference, the amperometric and sturch-iodide end point give concordant results. The amperometric endpoint is inherently ‘mote sensitive and is free of interference fom color and turbid 460 ity, which can cause diflculty withthe starch-iodide end point, (On the other hand, certain metals, surface-active agent, and ‘complex anions in Some industrial wastes interfere in the am pperometric titration and indicate the need for another method for such wastewaters. Silver in the form of soluble silver eyanide ‘complex, in concentrations of 1.0 mg Ag/L, poisons the cell st pH 40 but not at 7.0. The silver ion, in the absence of the {eyanide complex, gives extensive response in the current at pil 44.0 and gradually poisons the cell at all pH levels. Cuprous copper in te soluble copper cyanide ion, in concentrations of 5 img CufL. or less, poisons the cell at pH 4.0 and 70, Although iron and nitrite may interfere with this method, minimize the Interference by buffering to pH 4.0 before adding KL. Oxidized forms of manganese interfere in all methods for total chlorine including amperometric tation. An unusually high content of ‘organic matter may cause uncertainty in the end point ‘Regardless of endpoint detection, either phenylarsine oxide or thiosulfate may be used as the standard redcing reagent at pH 4. ‘The former is more stable and is preferred. ‘The DPD titrimetic and colorimetric methods (F and G, respectively) are applicable to determining total chlorine in Polluted waters. In addition, both DPD procedures and the am- pperometrc tration method allow for estimating monochlora- mine and dichloramine fractions. Because all methods for total chlorine depend on the stoichiometric production of iodine, Waters containing iodine-reducing substances may not be ana lyzed accurately by these methods, especially where iodine re- mains in te solution for a significant time. This problem occurs in Methods B and D. The back titration procedure (C) and “Methods F and G cause immediate reaction of the iodine gen- erated so that it has litle chance to react with other iodine- reducing substances. In all colorimetric procedures, compensate for color and tur bidity by using color and turbidity Blanks. 4500-Cl B. General Discussion 44 Principle: Chiorine will liberate free iodine from potassium fodide (KI) solutions at pH 8 of less. The liberted iodine is ‘irate with a standard solution of sodium thiosulfate (Na,8,03) with starch as the indicator. Titrate at pH 3 t0 4 because the reaction is not stoichiometric at neutral pH due to pari oxida- tion of thiosulfate to sulfate. >. Interference: Oxidized forms of manganese and other oxidizing agents interfere. Reducing agents such as organic sulfides also interfere. Although the neutral titration mii ‘mizes the interfering effect of ferric and nitrite ions, the acid titration is preferred because some forms of combined ehlo- rine do not react at pH 7. Use only acetic acid forthe acid Litration; sulfuric acid (H,SO,) will increase interferences; never use hydrochlorie acid (HCI). See 4500-Ci.A.3 for discussion of other interferences. INORGANIC NONMETALS (4000 A method (1) for total residual chlorine using & potentiometric iodide electrode is proposed. This method is suitable for analysis of chlorine residuals in natural and treated waters and wastewa. terelluents. No differentiation of free and combined chlorine is Possible. This procedure is an adaptation of other iodometic techniques and is subject to the same inferences. 4, Sampling and Storage Chlorine in aqueous solution is not stable, and the chlorine content of samples or solutions, particularly weak solutions, will, {decrease rapidly. Exposure to sunlight or other strong light or ‘agitation will accelerate the reduction of chlorine, Therefore, star chlorine determinations immesiately aftr sampling, avoid. ing excessive light and agitation. Do nat store samples to be analyzed for chlorine. 5, Reference 1. Cooren, W3., NM. Roscs & R.A. Sues 1982 Determining ise taille chlorine by DPD-, Potassium iodide, K, crystals. Standard sodium thiosulfate, ON: Dissolve 25 g 1NayS,0,* 5H,O in 1 freshly boiled distilled water and stan ardize against potassium bi-iodate or potassium dichromate after at least 2 weeks storage. This inital storage is necessary '0 (CHLORINE RESIDUAL} (4500-Cvlodometic Method | allow oxidation of any bisulfite ion present, Use boiled distilled ‘water and adda few milliliters chloroform (CHCI,) to minimize ‘bacterial decomposition. ‘Standardize 0.1NV Na,S,0, by one of the following: 1) Todate method—Dissolve 3.249 g anhydrous potassium biiodate, KH(O,)p, primary standard quality, or 3.567 g KIO, dried at 103 + 2°C Tor 1, in distilled water and dilute 10 1000 ‘mt yield 20.1000 solution. tore ina glass-toppered bottle. ‘To 80 ml distilled water, add, with constant sting, I mL. cone 1,$0, 10.00 mL. 0.1000N KH(IOs);, and 1g KI, Tita immed ately with 0.11 Na,S,0, titan uni the yellow color ofthe liber ‘ued iodine almost is discharged. Add I ml. starch indicator solution and continue tating uni the blue color disappears 2} Dichromate method—Dissolve 4904 g anhydrous potas- sium dichromate, K,Cr.0y, of primary standard quality, in dis- tilled water and dilute © 1000 mL wo yield 0.1000N solution ‘Store in a glass-toppered bole. Proceed as in the iodate method, with the following excep- tions: Substitute 10.00 mL. 0.1000N K,Cr,0; for iodate and lt reaction mixture stand 6 min in the dark before tiating with O.LN Na,8,0, titrant Normality NaiSi0s ~ Si Na,3,0, consumed 4. Standard sodium thiosulfate titrant, OLN o 0.025N: Improve the stability of OOLN or 0.025N Na,S,O, by diluting an aged O.1N solution, made as directed above, wih freshly boiled distilled water. Add 4 g sodium borate and 10 mg mercuric iodide. solution. For sccurate work, standardize this slution daily in accordance with the drecons given above, using OLN or 0.025N iodate or K,Cr,0,- Use sufficient volumes of these standard solutions so that ther final iluion isnot greater than 1 + 4. To speed up operations where ‘many samples must be trated use an automatic hare of a type in hich rubber does not come in contact with the soluon, Standard trans, 0.01000 and 0.0250, are equivalent, respectively 0 3545 tug and 88633 yg Cl as C/.00 mb. «Starch indicator solution: To 5 g starch (potato, asrowr09t, ‘or soluble), add a litle cold water and grind in @ mortar toa thin ‘paste Pour into 1 L of boiling distilled water, stir, and let sete ‘overnight. Use clear supernate. Preserve with 1.25 g salielic acid, 4g zine chloride, or a combination of 4 g sodium propi- ‘nate and 2g sodium azide/L. starch solution. Some commercial sare substitutes ae satisfactory {Standard iodine, 0.1N: See 4500-CLC.3, 1 Dilute standard iodine, 0.0282N: See 4500-CLC.3A 8. Procedure 4. Volume of sample: Selecta sample volume that will require no more than 20 mL. 0.01N Na,8,0, and no less than 0.2 mL. for ‘he starch-jodide end point. Fora chlorine range of Ito 10 mg/L, use 2 500-mL. sample; above 10 mg/L, use proportionately less sample. Use smaller samples and volumes of titant with the ‘amperometric end point. 1, Preparation for teration: Place $ ri acetic ac, or enough Wo reduce the pHl to between 3.0 and 4.0, in a flask or white Porcelain casserole. Add about | g KI estimated on a spatula Pur sample in and mix with a string rod 461 6 Titration: Trae away from direct sunlight. Ad 0.025N or QOL Na,8,0, from a buret until the yellow color of the Iiberated iodine almost is discharged. Add T ml. starch solution ‘and titrate until blue color is discharged. 1f the tization is made with 0,025W Na,S,0, instead of 0.01 then, with a 1-L sample, 1 drop is equivalent to about 50 pg/L tis not possible to dscerm the end point with greater accuracy. 4. Blank titration: Correct result of sample titration by deter mining blank contributed by oxidizing or reducing reagent im purities. The blank also compensates forthe concentration of Jndine bound to starch at the end point ‘Take a volume of distilled water corresponding tothe sample ‘used for titration in 4500-CLB.3a-c, add $ mL acetic acid, 1 g XI, and I mL starch solution, Perform blank tation as ins 1) (or 2) below, whichever applies. 1) Ia blue color develops, titrate with O.OLN or 0.025N 1Na,S,0, to disappearance of blue color and record result. B (see 4500-C1B 4) is negative. 2) If no blue color occurs, irate with 0.0282N iodine solution until a blue color appears. Back-ttrate with 0.01N or 0.025N 1Na,S,0 and record the difference. B is positive. Before calculating the chlorine concentration, subtract the blank tivation of 11) above from the sample titration; or, if necessary, add the net equivalent value of the blank titration of 12) above. 4, Calculation For standardizing chlorine solution for temporary standard: sm xnxasas ing Clas Chiat = 822% For determining total available residual chlorine in a water sample: AB) KN x 35450 me Chas Cat = where A= ma tration for sample ‘B= ml-iration for blank (positive or nopaive), and N= normality of Ni,S,0, 5, Precision and Bias Published studies" give the results of nine methods used to analyze synthetic water samples without interferences; variations of some of the methods appear inthis edition. More curent data are not now available, 6. References 1, Water Chlorine (Residual) No.1 1969, Analyte! Reference Service Rep. No. 35, US. Environmental Protection Agency, Cincinnati, On, 2, Water Chlorine (Residual) No, 2.1971. Analytical Reference Service Rep. No. 40, US. Envisonmental Protection Agency, Cincinnati Oh, 402 7. Bibliography Les, C. 1933, Chemical contr! of sewage chlorination. The use and ‘value of onttoidine test. J Se. Chem Ind (Loon) 522887. Auarucan Warex Wonks Associ, 143, Commite report. Cont ff ehernation. J. Amer. Water Works Assoc 5:1313, Mazes, HC, R Jona & FB, Srtasoonoy. 1948, Ampere tits tion offesdualehorine in sewage, Water Sewage Works 9517S 4500-Cl C. General Discussion 4, Prineiple: In this method, used for wastewater analysis, the ‘end-point signal is reversed ‘because the unreacted standard ‘reducing agent (phenylarsine oxide or thiosulfate) remaining in the sample is titrated with standard iodine or standard iodate, rather than th iodine released being titrated directly. This ind rect procedure is necessary regardless of the method of end-point detection, to avoid contact between the full concentration of Tiberated iodine and the wastewater. ‘When iodate is used as a back titrant, use only phosphoric acid. Do not use acetate buffer. >. Interference: Oxidized forms of manganese and other oxida ing agents give postive imerferences. Reducing agents, such a organi sulfides, do not interfere as much asin Method B. Minimize iton and nite interference by bufering to pH 4.0 before adding potassium iodide (KD. An unasually high conten of organic mater may cause some uncertainty in the end peint. Whenever manga: nese ron, and other interferences defintely a absent, reduce this uncertainty and improve precision by acidifying to pH 1.0. Control Imerfereace from more than 0.2 mg nite. with phosphoric cid: sulfamic acid reagent. larger faction of organic chloraines will react at lower pH along with interfering substances, See 4500 CLAS for a discussion of ater interferences. Quality control (OC): The QC practices considered tobe an integral part of each method are surumarized in Tuble 40205. 2. Apparatus For a description of the amperometric endpoint detection apparatus anda discussion of is use, see 4500-CLD 2a. 8, Reagents 4. Standard phenylarsine oxide solution, 0.008 64N: Dissolve approximately 08 g phenylarsine oxide powder in 150 ml. 0.39 NaOH solution. After setting, decant 110 mL. into 800 mL Aislled water and mix thoroughly. Bring to pH 6 t0 7 with 61 HCL and dilute wo 950 ml. with distiled water. CAUTION: Severe poison, cancer suspect agent. Standardization—Accurately measure 5 to 10 ml freshly tan- ardized 0.0282N iodine solution into a Nask and add 1 ml. KI solution, Titate with phenylassine oxide solution, using the amperometric endpoint (Method D) or starch solution (see 4500- CLB.2e) as an indicator. Adjust to 0.005 64 and recheck INORGANIC NONMETALS (400 Sresnoskov, FB. H.C. Mass & DH. Hosea 1949. Application of ‘raw resid chlorine method to effluent chlorination. Sewage Works J 21:23 Nusnausy La LA. Mevenson. 1951, Detention of chlorine de. ‘mands and chlovine residsls in sewage. Sewage Ind Waster 23 68 Masss, HC. & NS. Chaussn, 1953, Determination of resis Chocine in met) finishing wastes. Anal Chem. 241885, lodometric Method II against the standard iodine solution; 1.00 ml. = 200 jg available chlotine. (Cavtion: Toxie—take care to avold Ingestion.) ©, Standard sodivon thiosulfate solution, O.1N: See 500-C1.B.2. €. Standard sodium thiosulfate solution, 0.005 64N: Prepare by diluing OLN Na,S0,. For maximum stability of the dite solution, prepare by diluting an aged 0.LN solution with freshly boiled disiled water (to minimize bacterial action) and add 4 g NajB,O,/L. To inhibit mold formation optionally add either 10 img Hil, oF 2 drops toluene per liter of solution. Standardize daily a8 directed in 4500-CL.B.2c using 0.005 64N KCr.0, or iodite soluion Use sufficient volume of sample so thatthe fina dilution does not exceed 1 + 2, Use an automatic burt of a type in which rubber does not come in contact withthe solution. 1.00 mL. = 200 yg available chiorine 4. Potassium iodide, KI, crystals. 2, Acetate buffer soluion, pH 40: Dissolve 146 g anhydrous NaCHO,, oF 243 g NaCyH,O, «34,0, in 400 mL distilled water, add 480 g cone acetic acid, and dilute to 1 L with chlorine-demand-frce water 4 Standard arsenite solution, OLN: Accurately weigh a sop ‘ered weighing bottle containing approximately 4.95 g arsenic IWioxide, AS,0,, Transfer without loss to a I-L volumetric flask and again weigh bole, Do not atempt to beush out adhering ‘oxide. Moisten As,O, with water and add 15 g NaOH and 100 rm disilled water. Swirl ask contents gently to dissolve, Diu to 250 mL with distilled water and saturate with CO;, ths converting all NaOH to NaHCO), Dilute to mark, stopper, and mix thoroughly. This solution will reserve its titer almost in- definitely. (CAUTION: Severe poison. Cancer suspect agent.) ASO; Normality = 550" {Standard iodine solution, 0.1N: Dissolve 40 g KX in 25 mL. ‘hlorine-demand-free water, add 13 g resublimed iodine, and sit ‘unl dissolved, Transfer to a I-L volumetric ask and dilue to mark, ‘Standardization—Aceurately measure 40 t0 50 mL. IN ar senite solution into a flask and titrate with 0.19 iodine solution, using starch solution as indicator. To obtain accurate results, insure tht the solution is saturated with CO: at end of ttaton by passing current of CO; through solution for a few minutes just before end points reached, or add afew drops of HCl to liberate sufficient CO to saturate solution. Alternatively standardize against No,S,0,; see 4500-CLB 2c) ‘CHLORINE (RESIDUAL) (4500-Civiodomattic Method I ‘optionally, prepare 0.1000N iodine solution directly as a standard solution by weighing 12.69 g primary standard resub- fimed iodine. Because I; may be voatilized and lose from both folid and solution, transfer the solid immediately to KI as spec- fed above. Never let solution stand in open containers for extended periods. Standard iodine titrant, .0282N. Dissolve 25 g KU ina litle aisilled water in a LLL volumetric ask, add correct amount of DIN iodine solution exactly standardized to yield @ 00282N solution, and dilate to 1 L with chlorine-demand-feee water, For courte work, standardize daily according to directions in Fg above, using 5 to 10 mL of arsenite or NayS;0, solution. Store in amber bottles or in the dark; protect solution from direct, Sunlight at all times and keep from all contact with ruber. 1 Siarch indicator: See 4500-C1.B.2. ji Standard iodate titrant, 0005 64N: Dissolve 201.2 mg pri- mary standard grade KIO, dried for Ih at 103°C, or 183.3 mg primary standard anhydrous potassium b-iodate in distilled war ter and dilute 1 L, 1k Phosphoric acd solution, HsPO,, 1 + 9. L Phosphoric acid-sulfamie acid ‘solution: Dissolve 20g NH,SO,H in LL'1 +9 phosphor acid, im Chlovine-demand:free water: Prepare chlorine-demand fee water from good-quality distiled or deionized water by adding sufficient chlorine to give S mg/l. free chlorine. After standing 2 d this solution should contain at least 2 mg/L free Chlorine: if not, discard and obtain etter-quality water. Remove remaining free chlorine by placing container in sunlight or ‘madiating with an ultraviolet lamp. After several hours take sample, add KI, and measure tora chlorine with a colorimetric method using a nessler tube to increase sensitivity. Do not use before last trace of free and combined chlorine has been re ‘moved. Distilled water commonly coatsins ammonia and also may contain reducing agents. Collet good-quality distilled or deion ied water in a sealed container from which water ean be drawn by gravity, To the air inlet ofthe container add an H,SO, rap consisting of a large test tube half filed with 1 + 1 H,SO, connected in series with a similar but empty test tube. Fit both test tubes with stoppers and inlet tubes terminating near the bottom of the tubes and outlet tubes terminating near the top of the tubes. Connect outlet tube of trap containing H,SO, to the Aisiled water container, connect inlet tube to outlet of empty test tube. Tho empty 18st tube will prevent discharge to the mosphere of H,S0, due w temperatureinduced_ pressure changes. Stored in such a container, chlorine-demand-ece water is stable for several weeks unless bacterial growth occurs, 4, Procedure «Preparation jor station 1) Volume of sample—For chlorine concentration of 10 m/L or les, titrate 200 mL. For greater chlorine concentrations, use Proportionately less sample and dilute to 200 ml. with chlotine- ‘emand-free water, Use a sample of such size that not more than 10 ml. phenylarsine oxide solution is required. 2) Preparation for tiation—Measvre 5 mL 0.005 64N phe- nylarsine oxide or thiosulfate for ehlorine concentrations from 2 10.5 mgiL, and 10 ml. for concentrations of 5 10 10 mg/L, into 4 flask of casserole for titration with standard iodine or iodte 463 Start stirring, For titration by amperometry or standart iodine, also add excess KI (approximately 1 g) and 4 ml. acetate buffer Solution or enough fo reduce the pH to between 3.5 and 4.2 ', Titrarion: Use one of the following: 1) Amperometric titration—Add 0.0282NV iodine titrant in small increments ftom a L-mL buret or pipet. Observe meter needle response as iodine is added: the pointer remains pract- cally stationary until the end point is approached, whereupon cach iodine increment causes a temporary deflection of the ‘icroammeter, with the pointer dropping back to its original position. Stop titration at end point When a small increment of Todi titrant gives a definite pointer deflection upscale and the pointer does not return promptly 10 its original postion, Record volume of iodine tirant used to reach end point. 2) Colorimetric (iodine) titration—Add I mL. starch solution ‘and titrate with 0,0282N iodine to the first appearance of blue color that persists after complete mixing. 3) Colorimetric (iodat) titration—To suitable flask or cass role add 200 mb chlorine-demand-free water and add, with ‘agitation, the required yolume of reductant, an excess of KI (pproximately 0.5 g), 2 mL. 10% HPO, solution, and 1 mL. starch solution in the order given, and titrate immeditely® with (0,005 64N iodate solution tothe first appearance of a blue color that persists after complete mixing. Designato volume of iodate solution used as A. Repeat procedure, substituting 200 mL sam- ple for the 200 ml. chlorine-demand-free water. If sample is colored or turbid, titrate to the first change in color, using for ‘comparison another portion of sample with H,PO, added. Des- Jgnate this volume of iodate solution as B. 5, Calculation 4 Titration with standard iodine: (a = 50) x20 mg Clas Cll = where: A= ml 0.0 640 educa, B= mil 00282 N 1, and C= mk sample . Toraion with standard iodate: x20 necscist ~ 4— where: A= mL NaS,0,, B= mm iodae required to irae Na,S,0,, and (C= mb simple 6. Bibliography See 4500-CLB.7. nny tad ap 10m win spree enor fF, ot 404 INORGANIC NONMETALS 4000) 4500-Cl D. Amperometric Titration Method 1. General Discussion Amperommettic titration requires 2 higher degree of skill and cate than the colorimetric methods. Chlorine residuals over 2 mg/L are measured best by means of smaller samples or by ‘luton with water that has neither residual chlorine not @ ‘chlorine demand. The method can be used to determine total chlorine and can differentiate between free and combined chlo- Fine, A further differentiation into monochloramine and dichlo- ‘amnine fractions is possible by control of KI concentration and 4. Principle: The amperometic method isa special adaptation ‘of the polarographic principle. Free chlorine is titrated ata pl between 6.5 and 75, a range in whieh the combined chlorine reacts slowly, The combined chlorine, in turn, is ttrated in the presence of the proper amount of Kl inthe pH range 3.5 to 45. When free chlorine is determined, the pH must not be greater than 7.5 because the reaction becomes sluggish at higher pH values, nor less than 6.5 because at lower pH values some ‘combined chlorine may react even in the absence of iodide. ‘When combined chlorine is determined, the pH must not be less than 3.5 because of increased interferences at lower pH values, nor greater than 45 because the iodide reaction is not quantta- tive at higher pH values. The tendency of monochloramine to react more realy with iodide than does dichloramine provides 1 means for further differentiation. The addition of small amount of KI in the neutral pH range enables estimation of monochloramine content. Lowering the pH into the acid range and inereasing the KI concentration allows the separation deter mination of dichloramine. ‘Organic chloramines can be measured as ftee chlorine, mono- chloramine, or dichloramine, depending on the activity of chlo- sine in the organic compound Phenylarsine oxide is stable even in dilute soluon and each mole reacts with two equivalents of halogen. A special ampero- metric cells used to detect the endpoint ofthe residual ehlerine- phenylarsine oxide titration, The cell consists ofa nonpolarizable reference electrode that is immersed in a salt solution and a readily polarizable noble-metal electrode that isin contact with both the salt solution and the sample being tivated. In some applications, endpoint selectivity is improved by adding +200 mV the platinum electrode versus silver, silver chloride Another approach to endpoint detection uses il pltinam elee- trodes, a mercury cell with voltage divider to impress & potential across the electrodes, anda microammeter.I'there is no eblorine residual inthe sample, the microarmmeter reading will be com- paratively low because of cell polarization. The greater the residual, the greater the microammeter reading. The meter acts ‘merely 2 a nul-point indicator—that is, the actual meter reading isnot important, but rather the relative eadings as the tation proceeds. The gradual addition of phenylatsne oxide causes the «xl to become more and more polarized because of the decrease in chlorine. The endpoint is recognized whea no further decrease ‘in meter reading can be obtained by adding more phenylarsine oxide, 5, Interference: Accurate determinations of free chlorine can not be made in the presence of nitrogen trichloride, NCly. ot chlorine dioxide, which titrate parly as free chlorine. When present, NCI, can trate partly as free chlorine and partly ae Aichloramine, contributing a postive eror in both fractions at "ate of approximately 0. v/min. Some organic chloramines als ‘canbe titrated in each step. Monochloramine can intrude into the fee chlorine fraction and dichloramine can interfere in the monochloramine fraction, especially at high temperatures and prolonged titration times. Free halogens other than chlorine also will irate as fee chlorine. Combined chlorine reacts with iodide ions to produce iodine. When titration for free chlorine follows 8 combined chlorine tiation, which requires addition of KI, ‘erroneous results may occur unless the measuring cell is rinsod thoroughly with distilled water between trations. Interference from copper has been noted in samples taken fiom copper pipe or afler heavy copper sulfate treatment of reservoirs, with metallic copper plating out on the electrode, Silver ions also poison the electrode. Interference occurs in some highly colored waters and in waters containing surface-active agents. Very low temperatures slow response of measuring cell tnd longer time is required for the tration, but precision is nat affected. A reduction in reaction rte is caused by pH values above 7'5; overcome this by buffering all samples to pH 7.0 of less. On the other hand, some substances, such as manganese, nitrite, and iron, do not interfere. The violet string of some ‘commercial titrators can lower chlorine values by volatilization When dilution is used for samples containing high chlorine content, take care thatthe dilution water is free of chlorine and ‘ammonia and possesses no chlorine demand ‘See 4500-CLA.S fora discussion of other interferences. Quality contol (QC): The QC practices considered tobe an integral part of each method are summarized in Table 4020: 2. Apparatus 1. Endpoint detection apparatus, consisting of a cell unit connected fo a microammeter, with necessary electrical acces sores. The cell unit includes a noble-metal electrode ofsuficient surface area, a salt bridge to provide an electrical connection Without diffusion of electlyte, and a reference electrode of silversilver chloride in a saturated sodium chloride solution connected into the circuit by means ofthe salt bridge. Numerous commercial systems are available. Keep platinum electrode free of deposits and foreign matter. Vigorous chemical cleaning generally is unnecessary. Oece sional mechanical cleaning with a suitable abrasive usually i sufficient. 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 elec- trode free of contamination and maintain it at constant compo sition by insuring an adequate supply of undissolved sat at all times. cell with two metal electrodes polarized by a small DC potential also may be used, (See 4500-CLD7.) ». Agiaior, designed to give adequate agitation atthe noble metal electrode surface to insure proper sensitivity, Thoroughly clean agitator and exposed electrade system to remove all che sine consuming contaminants by immersing them in water con- taining 1 to 2 mg/L free chlorine fora few minutes. Add KI 1 (CHLORINE (RESIDUAL) (4500-CIvAmperometc Tiation Method the seme Water and et agitator and electrodes remain immersed for 5 min, Afler thorough rinsing with chlorine-demand-free ‘water or the sample t0 be tested, sensitized electrodes and tpilator are ready for use, Remove iodide reagent completely ‘fom cell. “e Buret: Commercial irators usually are equipped with suit: able burets (1 mL), Manval bureis are available.” id Glassware, exposed to water containing at least 10 mg/l. cllorine for 3h of more before use and rinsed with chlorine emand-fee water, 3. Reagents 4 Standard phenylarsine oxide titrant: See 4500-CLC 3a Phosphate buffer solution, pH 7: Dissolve 25.4 g anhydrous KH,PO, and 34.1 g anhydrous Na,HPO, in 800 mL. distilled ‘water, Add 2 ml. sodium hypochlorite solution containing. 1% chlorine and mix thoroughly. Protect from sunlight for 2 Determine that free chlorine still remains in the solution, Then expose f0 sunlight until no chlorine remains. IF necessary, cary ‘out the final dechlorination with an vltraviolet lamp, Determine that no total chlorine remains by adding KI and measuring with one of the colorimetric tests. Dilute 1 L with distilled water and fier if any precipitate is present ‘Potassium iodide solution: Dissolve 5D g Kl and dilute to 1 LL with freshly boiled and cooled distilled water. Store inthe dark in a brown glass-stoppered botle, preferably inthe reigerator. Discard when solution becomes yellow. 4. Acetate buffer solution, pH 4: See 4500-C.C.3. 4, Procedure 4. Sample volume: Select «sample volume requiring no more than 2 mL phenylarsine oxide tivant. Thus, for chlorine concen: tuntions of 2 mg/L or les, take a 200-miL. sample, for chlorine levels in excess of 2 mg/L, use 100 ml. or proportionately less. b. Free chlorine: Unless sample pl is knovn to be between 65 and 75, add 1 mL pHi 7 phosphate buffer solution to produce a pH of 65 t 75. Titrte with standard phenylarsine oxide titrant, observing current changes on microammeter. Add titrant in progressively smaller increments until all needle movement ceases. Make suecessive buret readings when needle action becomes sluggish, signaling approach of endpoint. Subtract last very small increment that causes no needle response because of overtiation. Alternatively, use a system involving continuous ‘current measurements and determine endpoint mathematically Continue titrating for combined chlorine as described in Je below or for the separate monochloramine and dichloramine fractions as detailed in 4s and f below. Combined chlorine: To sample remaining from fiee-chlo- ‘ine tization add 1.00 mL. KI solution and 1 mL acetate butter solution, in that order. Titrate with phenylarsine oxide titrant to Kiar I7HO.F Sm, Kimble rcs, Ho 108, Tol, OF, or quale. 465 the end point, as above. Do not refill buret but simply continue titration after recording figure for free chlorine. Again subtract last increment wo give amount of tirant actually used in reaction ‘with chlorine. (If tration was continued without refilling bure, this figure represents total chlosine. Subtracting free chlorine from tol gives combined chlorine.) Wash apparatus and sample cel thoroughly to remove iodide ion to avoid inaccuracies when the tirator is used subsequently fora free chlorine determination. 4. Separate samples: If desired, determine toil chlorine and fee ehlorine on separate samples. If sample pH is between 3.5 and 95 and total chlorine alone is required, treat sample imme- diately with 1 mL KT solution followed by T mL acetate buffer solution, and titrate with phenylarsine oxide titrant as deseribed inc above. &. Monochloramine: After uirating for free chlorine, add 0.2 ‘mL. KI solution to same sample and, without refiling buret, continue titration with phenylarsine oxide titrant to end point Subtract last increment to obtain net volume of titrant consumed bby monochoramine. {f Dickloramine: Add 1 ml. acetate buffer solution and 1 mL K{soluton to same sample and titrate final dichloramine fraction as described above. 5. Calculation Convert individual titrations for fee chlorine, combined chlo- rine, total chlorine, monochloramine, and dichloramine by the following equation: Ax 200 BEC CLL sample where: A= mi phenylrsine oxide tation, 6. Precision and Bias See 4500-CLBS. 7. Bibliography Funk, CW. & A:T. BasbEs, 1925. A new type of endpoint in els ttomeirctitaion and its application fo odimety, J. Amer. Chem, Soe. 48.2045, ‘Manis, HC & 1. Gtass 1942. A now method of determining residual ‘chloe, J Amer. Water Work Aste. 41227 Haire, JF. & SS. sree 1948, Determination of chloride dioride and ‘other ative chlorine compounds in water. Anal. Chem. 20:638 Manas, W.A. 1949. Simplified amperometric tration apparats for ‘determining residual chlorine i wate, Water Sewage Works 95: 17 Kocmingr, LM. 1. Loca 1952, Polarography, 2a Taterscience Publishers, New York. N-Y. Moniow. 1.1966. Residual chlorine determination with dual polar: able electrodes. J Amer. Water Works Astoc 58363. 468 INORGANIC NONMETALS (4000) 4500-Cl E. Low-Level Amperometric Titration Method 1. General Discussion Detection and quantification of chlorine residuals below 0.2 rmgiL require special modifications 10 the amperometric stration procedure. With these modifications chlorine concentrations at the 10-yg/L level can be measured. It is not possible to difer- entiate between fee and combined chlorine forms, Oxidizing agents that interfere wih the amperometric tiation method (D) will interfere. 4, Principle: This method modifies D by using & more dilute titrant and a graphical procedure to determine the end point, ', Interference: See 4500-CL.D. 10, €. Quality control(QC): The QC practices considered tobe an integral part of each method are surumarized in Table 4020. 2. Apparatus See D2. 3. Reagents ‘Potassium bi-lodate, 0,002 256N: Dissolve 0.7332 g aahy- ‘drous potassium bi-iodate, KH(IO,)y in 300 mL. chlorine-free distilled water and dilate to 1000 mi. Dilute 10.00 mL to 100.0 1 with chlorine-ree distilled water. Use only freshly prepared solution forthe standardization of phenylarsne oxide. 1b. Potassium iodide, KU crystals, & Lowstength phenslarsine oxide titrant, 0,000 S64N: Dilste 10.00 mi of 0.005 64N phenyarsine oxide (te 4500-CLC:3a) to 100.0 ml. with chlrine-demand-free water (see 4500-CLC.3m), ‘Standaedization—Dilute 5.00 mL. 0.002 256 potassium bi- jedate 0 200 mL. with chlorine-ree water. Add approximately LS g Kl and stir t dissolve, Add 1 mL. acetate bulfer and let stand in the dark for 6 min, Titrate using the amperometric Uirator and determine the equivalence point as indicated below. Normality = 0.000256 x Sia where A= ml phenylasine oxide tant required to reach the euivalence point of standard bi ode, 4. Acetate bufer solution, pH 4: See 4500-C1.C.3e 4, Procedure Selecta sample volume requiring ao more than 2 ml. pheny- larsine oxide titrant. A 200-mL. sample will be adequate for samples containing less than 0.2 mg total chlorine/ Before beginning titration, riase buret with titrant several times. Rinse sample container with distilled water and thea with sample. Add 200 mL sample to sample container and approxi mately 1.5 g KL Dissolve, using a stimer or mixer. Add 1 mi. acetate buffer and place container in end-point detection apps: ratus. When the current signal stabilizes, record the reading, Initially adjust meter to a near full-scale deflection. Titrate by adding small, known, volumes of titrant After each addition, record cumulative volume added and current reading when the signal stabilizes. IF meter reading falls to near or below 10% of {ll-seale deflection, record low reading readjust meter 0 near full-scale deflection, and record difference between low amount and readjusted high deflection. Add this value to all deflection readings for subsequent titrant additions. Continue adding titrant until no further meter deflection occurs. I fewer than three titrant additions were made before meter deflection ceased, discard sample and repeat analysis using smaller titrant increments ‘Determine equivalence point by potting total meter deflection against titrant volume added, Draw straight line through the fist several points in the plot and a second, horizontal straight line comesponding to the final total deflection in Ube meter. Read ‘equivalence point asthe volume of titrant added atthe intersec- ton of these two lines 5. Calculation Ax 200 x N BX 0.00564 img Clas Chit where: ‘A= mL tan at equivalence point 12 = sample volume, mL, and 1 = phenylrsine oxide noma, 6. Bibliography BROOKS, A. 8. & G. 1. SewosKt, 1979, Low-level chlorine analysis by amperomtnc titration. J. Water Pole. Control Fed. $1:2636. 4500-Cl F. DPD Ferrous Titrimetric Method 1. General Discussion 4. Principle: N,N-dithyl-p-phenylenediamine (DPD) is used as an indiator in the titrimetric procedure with ferrous arnmno- sium sulfate (FAS). Where complete differentiation of chlorine species is not required, the procedure may be simplified to give only free and combined chlorine or total chlorine In he absence of iodide ion, free chlorine reacts instandy with DPD indicator to produce a red color. Subsequent addition of ‘small amount of foie ion act catalytically to cause monocl- amine to produce color. Addition of iodide ion to excess evokes 4 rapid response from chloramine. In the presence of iodide jon, part of the nitrogen trichloride (NCI) is included with chloramine and part with free chlorine. A supplementary pro- HLORINE (RESIDUAL) (4500-CDPD Ferrous Tikimete Method edie based on adding iodide ion before DPD permits estima ing proportion of NCly appearing wih fe ehionne Chlorine dione (C10) appears, tothe extent of one-fifth of its total chlorine content, wih fre chlorine fll response from 10, coresponding to is toil chlorine content, may be ob- tine ifthe sample fist is aciited in the presence of iodide ion aod subsequent is brought bck oan approximately neural pt by adding bicarbonate ion. Bromine. bromanine, aod iodine ‘eect with DPD indicator and appear with fee chlorine. ‘dition of glycine before deteminaton of fre cblorne converts ftee chlorine to uneacive forms, with only bromine tod iodine residuals remaining. Subractons of these residuals ffom the residual measured without glycine permits diferent don of fe chlorine from bromine and iodine. °. pH control: For accurate ests careful pl{ control is essonial. At the proper pH of 6:2 106.5, the red colors produced ‘maybe titrated to sharp colores endpoints. Titrate as soon as the red eoloris forme in each step. Too low spl inthe fist sep tends to make the monochloramine show inthe free-. NIN-Diethy-p-phenylenediamine (DPD) indicator solu- tion: Dissolve 1 g DPD oxalate,” or 1 g DPD sulfate penta- hydrate of LL g anhydrous DPD sulfate in chlorine-free dis- tilled water containing 8 ml. 1 + 3 H,SO, and 200 mg disodium EDTA. Make up t0 1, store in a brown glas-stoppered boctle in the dark, and discard when discolored. Periodically check Solution blank for absorbance and discard when absorbance at 515 nm exceeds 0.002/em. (The buffer and indicator sulfate are available commercially as @ combined reagent in stable powder form.) CavTiow: The oxalate is toxic—take care to avoid Ingestion. © Standard ferrous ammonium sulfte (FAS) trant: Dissolve 1.106 g Fe(NH,),(S0,);* 68,0 in distilled water containing 1 mL | +3 H,SO, and make up to 1 L with freshly boiled and cooled distilled water. This standard may be wsed for 1 month, and the titer checked by potassium dichromate. For tis purpose add 10 mL 1 + 5 H,SO,, 5 mL. cone H,PO,, and 2 mL. 0.1% barium diphenylamine sulfonate indicator toa 100-m. sample af FFAS and titrate with potassium dichromate toa violet end point tha persists for 30 8. FAS titrant equivalent to 100 jg Cl as C1100 mL requires 20.00 ml. dichromate for tration. 4. Potassium iodide, KI, crystal. «Potassium iodide solution: Dissolve 500 mg KI and dilute {100 ml, using freshly boiled and cooled distilled wate. Store in a brown glas-stoppered botle, preferably in a refrigerator. Discard when solution becomes yellow. 4 Potassium dichromate solution, 0.691 g.t0 1000 mt. & Barium diphenylaminesulfonate, 0.1%: Dissolve 0.1. g (CoH NHC,H,4-80,)9Ba in 100 mb. distilled water. *Fasiran cence No, 7102 oe equivalent. 1 Avail fom Galas Seeger Chercal Mg. Cor, $84 Mina Ave tee, Cae Phew, NY 11514 or ease, 488, 1h Sodium arsenite solution: Dissolve 5.0 g NaAsOs in dis tilled water and dilute fo TL. (Cattion: Toxie—take care to avoid ingestion.) 1. Thioacetamide solution: Dissolve 250 mg CH,CSNH, in 100 mL distilled water. (CavTIon: Cancer suspet agent. Take ‘are to avoid skin contact oF ingestion.) 4. Chlorine-demand:-free water: See 4500-CL.C 3m. Glycine solution: Dissolve 20 g glycine (aminoacetic acid) in sufficient ehlorine-demand-iree water to bring to 100 ml. total ‘volume. Store under refrigerated conditions and discard if cloud: ness develops. 1. Barium chloride erystals, BaCl, * 28,0. 8. Procedure ‘The quantities given below are suitable for concentrations of total chlorine up to mg/L If total chlorine exceeds 5 mg/L, use ‘smaller sample and dilute to a total volume of 100 mL. Mix ‘usual volumes of butfer agent and DPD indicator solution, ot ‘usual amount of DPD powder, with distiled water before adding sufficient sample to bring total volume to 100 ml, (I sample is added before buffer, test does not work.) If chromate is present (>2 mg/L) add and min 02 BaCl, « 2,0/100 mi. sample before adding other reagents. If {in addition, sulfate is >300 mg/L, use 0.4 g BaCl,» 2H1,0/100 mL sample. 1a Pree chlorine or chloramine: Place $ ml each of butter ‘reagent and DPD indicator solution in tiation Mask and mix (or ‘use about $00 mg DPD powder). Add 100 ml sample, or dilated sample, and mix 1) Free chlorine—Titrate rapidly with standard FAS sirant until red color is discharged (Reading 4), 2) Monochloramine—Add one very small crystal of KI (about (05 mg) or 0.1 mL. (2 drops) KI solution and mix. Continue titrating until red color is discharged again (Reading B). 3) Dichloramine—Add several erystals KT (about Ig) and mix to dissolve. Let stand for 2 min and continue tating uatl red ‘olor is discharged (Reading C), For dichloramine concentra- tions greater than 1 mg/L, let stand 2 min more if colerdefiback indicates slightly incomplete reaction. When dichloramine con centrations are not expected 10 be high, use half the specified amount of Kl 44) Simplified procedure for free and combined chlorine oF {otal chlorine—Omit 2) hove to obtain monochloranine and dichloramine together as combined chlotine. To obuin total chlorine in one reading, add full amount of KI at the start, with the specified amounts of buffer reagent and DPD indicator, and titrate ater 2 min standing ». Nitrogen trichloride: Place one very small crystal of KI (about 05 mg) or 0.1 mL KI solution in a tization flask. Add 100 ‘mL. sample and mix. Add contents to a second flask containing ‘Sm exch of buffer reagent and DPD indicator solution ( add bout 500 mg DPD powder direct to the first ask). Titrate rapidly with standard FAS titrant until red color is discharged (Reading W), INORGANIC NONMETALS (4005) «Free chlorine in presence of bromine or iodine: Determine free chlorine asin fal) above. Toa second 100-ml. sample, add 1 mb. glycine solution before adding DPD and ble. Titate sccording to al) above. Subtract the second reading from the first to obtain Reading A. 4. Calculation For ¢ 100-mL sample, 1.00 mL. standard FAS titrant = 1.00 img Clas ClyL, INCI, Absent Cl Present Free Cl Free Cl NECI NaCl NHC, NHC, + YN, “ Fee + “NCH, = Nc S NHC, In the event that monochloramine is present with NCI, it will be included in N, in which caso obtain NCI, from 2(N~B) CCilorine dioxide, if present, is included in A to the extent of| ‘one-fifth ofits total chlorine contest In the simplified procedure for free and combined chlorine, only A (ee Cl) and C (otal Cl) ate required. Obtain combined chlorine from CA. ‘The result obtained in the simplified total chlorine procedure corresponds to C, 65, Precision and Bias ‘See 4500-C1.B 5. 6. Bibliography Pum, AT. 1987. The determination of fee an combined chlorine in Tater by the use of ety p-phenlene diamise. J. Amer: Water Works Asoc. 493873, ALR, AT. 1960. Colorimetric determination of chlorine dioxide in wales Water Sewage Works 10757. Pu, AT. 1961. The determination of ee rsa! bromine in water Water Sewage Works 108-46 Necusen, NI 1963, 1965, 1966. Deeinaton of chlorine in water Pas 1,2. and 3. Water Res, Asso, Tec, Pap. Nos, 29,47, and 53 Pau, AT. 1967. Methods for determination, in wate, of fee and ‘combined available chlorine, chlorine doxide and chlorite, yo nine, odin, aod ozone wing diethyl p-phenyenediamine (DPD) I nse Water Eng. 21337 Pas, AT. 196%, Determination of aitogen chloride ia water “Amer. Water Works Aeoe. 0847 Paws, AT. 1975. Curent DPD methods for resial halogen com pounds and ozone in water. J. Amer. Water Works Asoc. 67:32 [Mettods for the Examination of Waters and Associated Mater (Chemical Disnfcting Agent in Water and Events, and Chioene Demand, 1980, Her Msjcstys Stationery Off, London, England. SHLORINE (RESIDUAL) (£800-CYOPD Colorimetric Method 469 4500-Cl G. DPD Colorimetric Method 4. General Discussion «Principle: This isa colorimetric version ofthe DPD method sad is based on the same principles, Instead of titration with standard ferrous ammonium sulfate (FAS) solution as in the jtrimetic method, a colorimetic procedure is used by Interference: See 4500-CLLA.3 and Fld. Compensate for color ind turbidity by using sample to zero photometer. Minimize chro- rae imerference by using the thioacetamide blank correction, Minimum detectable concentration: Approximately 10 ug ‘]as ChyL. This detection limit is achievable under ideal con- Sisons; normal working detection limits typically are higher 4. Quality control (QC):"The QC practices considered tobe an ‘tegral part of each method are summarized in Table 4020: 2. Anparatus 1, Photometric equipment: One ofthe following is required: 1) Spectrophotometer for use at a wavelength of 515 nm and providing a light path of 1 em or longer 2) Filter photometer, equipped with afer having maximam transmission in the wavelength range of 490 to $30 nm and providing a light path of 1 em or longer b, Glassware: Use. separate glassware, including separate spectrophotometer cells, for free and combined (dichloramine) mmessurements, to avoid iodide contamination in free chlorine 3. Reagents, See 4500-CLF.2a, b, 6d. ei andj 4. Procodure 4 Calibration of photometric equipment: Calibrate instrument with chlorine or potassium permanganate solutions 1) Chlorine solutions —Prepare chlorine standards inthe range (0.05 to 4 mg/L. from about 100 mil chlorine water standard- iued as follows: Place 2 mL acetic acid and 10 to 25 mL. ctlorne-demand-Aree water ins flask. Add about 1 g KI. Mes sure into the flask a suitable volume of chlorine solution. In choosing a convenient volume, note that | ml. 0.025N Na,S,0; titrant (See 4500-Cl.B.2d) is equivalent to about 0.9 mg chlorine. ‘Titrae with standardized 0.025N Na,S,0, titrant uni the yellow iodine color almost disappears. Add 1 10 2 mi starch indicator Solation and continue titrating to disappearance of blue color. Determine the blank by adding identical quantities of acid, KI, {nd starch indicator to a volume of ehlorine-demand-free water ‘omesponding to the sample used for titration, Perform blank tiation A or B, whichever applies, according to 4500-CL.B.3¢. A+ By xN 3545 mg Clas Cibo mple normality of Na8,0,, rita for sample, ri tixant for blank (o be added or subracted according to ‘required blink ization, See 4500 C13 Use chlorine-demand-fee water and glassware to prepare these standards, Develop color by first placing $ ml. phosphate buffer solution and $ mL DPD indicator reagent in flask and then ‘adding 100 mL. chlorine standard with thorough mixing as de- seribed in fsb and c below. Fill photometer or colorimeter cell from flask and read color at $15 nm. Return cel contents to flask tnd itate with standard FAS titrant as a check on chlorine concentration, 2) Potassium permanganate solutions-—Prepare a stock solu- tion containing 891 mg KMnO,1000 mL. Dilute 10.00 mL stock solution to 100 mL with distilled water in a volumetric flask. When I mL. of this solution is diluted to 100 ml. with distilled water, » chlorine equivalent of 1.00 mg/l. will be produced in the DPD reaction, Prepare series of KMnO, Standards covering the chlorine equivalent range of 0.05 to 4 mg/L. Develop color by frst placing 5 mi phosphate buffer and 5 ml. DPD indicator reagent in flask and adding 100 ml stan dard with thorough mixing as described in Ys b and c below. Fill photometer or colorimeter cell fom flask and read color at $15 ‘im, Return cell coatents to lask and titrate with PAS titrant as 8 check on any absorption of permanganate by distilled water. (Obtain all readings by comparison to color standards or the standard curve before use in calculation. °, Volume of sample: Use a sample volume appropriate to the photometer or colorimeter. The following procedure is based on using 10-mL volumes; adjust reagent quantities proportionately for other sample volumes. Dilute sample wit chlorine-demand- free water when total chlorine exceeds 4 mil. ‘c Pree chlorine: Place 0.5 mL. each of buffer reagent and DPD indicator reagent in atest tube or photometer cell. Add 10 mL. sample and mix. Read color immediately (Reading A). 4, Monochloramine: Continue by adding ene very small rys- tal of KI (about 0.1 mg) and mix. If dichloramine concentration is expected tobe high, instead of small crystal add 0.1 ml. (2

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