Current Technology Of Chlorine Analysis

Current Technology ofChlorine Analysisfor Water and WastewaterTechnical Information Series — Booklet No.17By Danial L. HarpLit. no. 7019L21.5 Printed in U.S.A. Hach Company, 2002. All rights are reserved.

In memory ofClifford C. Hach(1919 – 1990)inventor, mentor, leader and, foremost,dedicated chemist

Current Technology of Chlorine Analysis for Water and WastewaterTable of ContentsPage1. Overview of Chlorine Chemistry in Water Treatment .12. Analytical Methods for Chlorine and Chloramines .2a. DPD Colorimetric Method .2b. DPD Titration Method .5c. Iodometric Titration Method.6d. Amperometric Titration Methods .6e. Other Analytical Methods: .8Orthotolidine.8Syringaldazine (FACTS) .9Electrode .93. Method Interferences and Sources of Errors .11a. Sampling Considerations .11b. Interferences Common to All Chlorine Methods .11Other Disinfectants.11Manganese Compounds.12Organic Chloramines .12Bromides in Chlorinated Waters .12c. Errors Common to Total Chlorine Determinations .12d. Interferences in the DPD Methods.13Calibration Non-Linearity .13Precautions in Using Permanganate as an Equivalent Standard .13Monochloramine Interference in the Free Chlorine Test .15Stability of the Colored Reaction Product .16Compensation for Sample Color and Turbidity .16e. Interferences in the Amperometric Titration Methods .17Deposition on Electrode Surfaces .17Manganese Interference .17Nitrite Interference .17Choice of Reductant.19Effect of Iodine Demand on End Point Determinations .19Order of Reagent Addition.204. Method Comparisons and Performance Evaluations .21a. Field Kit or Laboratory Comparisons .21b. Performance Evaluations of Residual Chlorine Process Analyzers .235. Selection of the Appropriate Testing System .24a. Field Testing .24b. Laboratory Testing .25c. On-line Automated Testing.266. Conclusions .27References .29Acknowledgements .30

1. Overview of Chlorine Chemistry inWater TreatmentNH3 HOCl NH2Cl (monochloramine) H2OChlorination of public water supplies has been practicedfor almost 100 years in the United States. Although thepros and cons of disinfection with chlorine have beenextensively debated, it remains the most widely usedchemical for disinfection of water in the U.S.NH2Cl HOCl NHCl2 (dichloramine) H2ONHCl2 HOCl NCl3 (trichloramine) H2OKnown as “break-point” reactions, they are important inwater disinfection. The chloramines are potent biocidesbut not as effective as hypochlorous acid or thehypochlorite ion.Comprehensive information explaining chlorinechemistry in water treatment is available in severalexcellent references describing chlorination anddisinfection practices. (See Ref. 1.1 - 1.4). An overviewemphasizing general chemistry of chlorine disinfectionwill be presented here.Chlorine usually is added to water as the gaseous formor as sodium or calcium hypochlorite. Chlorine gasrapidly hydrolyzes to hypochlorous acid according tothe following equation:Cl2 H2O HOCl H Cl—Similarly, aqueous solutions of sodium or calciumhypochlorite will hydrolyze according to:Ca(OCl)2 2H2O Ca2 2HOCl 2OH—Figure 1.1: Typical Break-point Chlorination CurveChlorination of water to the extent that all ammonia isconverted to either trichloramine or oxidized to nitrogenor other gases is referred to as “break-point chlorination.”Figure 1.1 shows a typical break-point chlorinationcurve. Prior to the break point,“combined” chlorine(monochloramine plus dichloramine) predominates.In disinfection systems in which chloramination ispracticed, the goal is to remain at the peak of the curveprior to the break point. If the amount of unreactedammonia is minimized, monochloramine will be thepredominant chloramine.NaOCl H2O Na HOCl OH—The two chemical species formed by chlorine in water,hypochlorous acid (HOCl) and hypochlorite ion (OCl—),are commonly referred to as “free available” chlorine.Hypochlorous acid is a weak acid and will disassociateaccording to:HOCl H OCl— In waters with pH between 6.5 and 8.5, the reaction isincomplete and both species (HOCl and OCl—) will bepresent. Hypochlorous acid is the more germicidal ofthe two.After the break point, free chlorine (hypochlorous acidplus hypochlorite) is the dominant disinfectant. Typically,the free chlorine residual is adjusted to maintain aminimum level of 0.2 mg/L Cl2 throughout thedistribution system.A relatively strong oxidizing agent, chlorine can reactwith a wide variety of compounds. Of particularimportance in disinfection is the chlorine reaction withnitrogenous compounds—such as ammonia, nitrites andamino acids.The importance of break-point chlorination lies in thecontrol of taste and odor and increased germicidalefficiency. The killing power of chlorine on the right sideof the break point is 25 times higher than that of the leftside (Ref. 1.1). Hence, the presence of a free chlorineresidual is an indicator of adequate disinfection. Theshape of the break-point curve is very dependent oncontact time, water temperature, concentrations ofammonia and chlorine, and pH.Ammonia, commonly present in natural waters, will reactwith hypochlorous acid or hypochlorite ion to formmonochloramine, dichloramine and trichloramine,depending on several factors such as pH andtemperature. Typical reactions follow:1

The use of monochloramine as an alternate disinfectantfor drinking water has received attention lately due toconcern about the possible formation of chlorinatedby-products when using free chlorine disinfection.Considerable debate continues about the merits ofchloramination disinfection. The reader is referred toWhite’s handbook (Ref. 1.1) for an animated discussion ofthe pros and cons of chloramination practices in drinkingwater treatment.2. Analytical Methods for Chlorineand Chloramines2a. DPD Colorimetric MethodThe DPD (N, N-diethyl-p-phenylenediamine) method forresidual chlorine was first introduced by Palin in 1957(Ref. 2.1). Over the years it has become the most widelyused method for determining free and total chlorine inwater and wastewater. Hach Company introduced its firstchlorine test kit based on the DPD chemistry in 1973.In chloramination disinfection, monochloramine isformed from the reaction of anhydrous ammonia andhypochlorous acid. In general, ammonia is added firstto avoid formation of chlorinated organic compounds,which can exhibit objectionable taste and odors. Hachoffers a method specific for inorganic monochloraminedisinfectant in the presence of organic chloramines(Ref 1.2).The chemical basis for the DPD chlorine reaction isdepicted in Figure 2.1. The DPD amine is oxidized bychlorine to two oxidation products. At a near neutral pH,the primary oxidation product is a semi-quinoid cationiccompound known as a Würster dye. This relatively stablefree radical species accounts for the magenta color in theDPD colorimetric test. DPD can be further oxidized to arelatively unstable, colorless imine compound. WhenDPD reacts with small amounts of chlorine at a nearneutral pH, the Würster dye is the principal oxidationproduct. At higher oxidant levels, the formation of theunstable colorless imine is favored — resulting inapparent “fading” of the colored solution.Throughout the U.S. Today, wastewater effluents arechlorinated to kill pathogens and then dechlorinatedbefore discharge. This common practice resulted fromseveral comprehensive studies (Ref. 1.5) which quantifiedthe toxicity of chlorinated effluents on aquatic life. Theamount of total residual chlorine in the final effluent isregulated by a National Pollutant Discharge EliminationSystem (NPDES) permit. Typical permit limits for totalresidual chlorine (TRC) in the final effluent range from0.002 to 0.050 milligram per liter (mg/L). To thechlorination-dechlorination practitioner, this leveltranslates to zero mg/L TRC.Dechlorination by sulfur dioxide (SO2) is the mostcommon process to meet zero TRC effluent limits.Sodium bisulfite and sodium metabisulfite also have beenused for chemical dechlorination. In the dechlorinationprocess using SO2, sulfurous acid is formed first:SO2 H2O H2SO3Figure 2.1: DPD-Chlorine Reaction ProductsSulfurous acid then reacts with the various chlorineresidual species:The DPD Würster dye color has been measuredphotometrically at wavelengths ranging from 490 to 555nanometers (nm). The absorption spectrum (Figure 2.2)indicates a doublet peak with maxima at 512 and 553 nm.For maximum sensitivity, absorption measurements canbe made between 510 and 515 nm. Hach Company hasselected 530 nm as the measuring wavelength for mostof its DPD systems. This “saddle” between the peaksminimizes any variation in wavelength accuracy betweeninstruments and extends the working range of the teston some instruments.H2SO3 HOCl HCl H2SO4H2SO3 NH2Cl H2O NH4Cl H2SO42H2SO3 NHCl2 2H2O NH4Cl HCl 2H2SO43H2SO3 NCl3 3H2O NH4Cl 2HCl 3H2SO4It is common practice to overdose the sulfur dioxide tomaintain a level up to 5 mg/L SO2 in the effluent. Thisensures the reduction of all chlorine residual species.2

Figure 2.2: Absorption Spectrum - DPD Würster CompoundMonochloramine and dichloramine are slow to reactdirectly with DPD at a near neutral pH. To quantify thesespecies, the test is performed under slightly acidicconditions in the presence of iodide ion. The iodidereacts with the chloramines to form iodine as thetriiodide ion (I3—):Standard 38 408 G4 for free and total chlorine ismodeled after ISO 7393/2. Table 2.1 shows the maindifferences between Standard Methods 4500-Cl G andISO 7393/2.Both Standard Methods and ISO procedures call forliquid DPD reagents prepared from DPD sulfate or DPDoxalate salts. Liquid DPD reagents, inherently unstable, aresubject to oxidation from either atmospheric oxygen ordissolved oxygen present in the preparation water. It hasbeen shown that the oxidation of DPD by oxygen ispH–dependent (Ref. 2.5). The liquid DPD formulationsattempt to retard oxidation by lowering the pH of theindicator reagent.NH2Cl 3I— H2O H NH4OH Cl— I3—NHCl2 3I— H2O 2H NH4OH 2Cl— I3—The triiodide, in turn, reacts with DPD, forming theWürster oxidation product. There is very little confirmedevidence that trichloramine species can be quantifiedwhen using iodide with DPD (Ref. 2.2).The liquid formulations also incorporate disodiumethylenediamine tetraacetate (Na2EDTA) in order to“retard deterioration due to oxidation and, in the testitself, provide suppression of dissolved oxygen errors bypreventing trace metal catalysis” (Ref 2.6). The practiceof adding Na2EDTA to the DPD indicator reagent isquestionable because of the low solubility of EDTA indilute acid solutions.In practice, only a trace of iodide is required at pH 6.26. 5 to resolve monochloramine. Standard Methods forthe Examination of Water and Wastewater (Ref. 2.3)stipulates the addition of approximately 0.1 mg ofpotassium iodide to a 10-mL sample to determinemonochloramine. By adding excess potassium iodide (anadditional 0.1 gram or more per 10-mL sample),dichloramine is included. It is not entirely clear at whatlevel of iodide the dichloramine fraction begins tointrude into the monochloramine results.Standard Methods and ISO procedures both usephosphate buffers to adjust the sample pH to between6.2 and 6.5. The slightly acidic pH is preferred toquantitatively resolve the chloramine species and tominimize interferences. Phosphate buffers, however, donot work in hard or brackish waters. Calcium andmagnesium ions in the sample will precipitate thephosphate and destroy the buffering capacity (Ref. 2.7).Because aqueous phosphate solutions are excellentgrowth media for biological growth, highly toxicmercuric chloride is added to preserve the reagent.Two “standard” DPD colorimetric methods generally arerecognized in the international community. These arethe Standard Methods 4500-Cl G and InternationalOrganization for Standardization (ISO) Method 7393/2(Ref. 2.4). The ISO method has been adopted by most ofthe members of the European Union. Germany’s DIN3