Hypochlorite, determination

Cooling water pH affects oxidizing antimicrobial efficacy. The pH determines the relative proportions of hypochlorous acid and hypochlorite ion or, in systems treated with bromine donors, hypobromous acid and hypobromite ion. The acid forms of the halogens are usually more effective antimicrobials than the dissociated forms. Under some conditions, hypochlorous acid is 80 times more effective in controlling bacteria than the hypochlorite ion. Hypochlorous acid predominates below a pH of 7.6. Hypobromous acid predominates below pH 8.7, making bromine donors more effective than chlorine donors in alkaline cooling waters, especially where contact time is limited. 

Sta.bilizers. Cyanuric acid is used to stabilize available chlorine derived from chlorine gas, hypochlorites or chloroisocyanurates against decomposition by sunlight. Cyanuric acid and its chlorinated derivatives form a complex ionic and hydrolytic equilibrium system consisting of ten isocyanurate species. The 12 isocyanurate equilibrium constants have been determined by potentiometric and spectrophotometric techniques (30). Other measurements of two of the equilibrium constants important in swimming-pool water report significantly different and/or less precise results than the above study (41—43). A critical review of these measurements is given in Reference 44. 

The ideal recommended cyanuric acid concentration is 30—50 ppm (Table 2). Although this range can be readily maintained when using hypochlorite sanitizers, it cannot be maintained when using chloroisocyanurates since they increase the cyanuric acid concentration. The NSPI recommends a maximum of 150 ppm cyanuric acid. Many health departments limit cyanuric acid to 100 ppm. No significant increase in stabilization occurs beyond 50—100 ppm, and since high levels of cyanuric acid slow down the rate of disinfection, the pool water should be partially drained and replaced with fresh water to reduce the cyanuric acid to below recommended maximum levels. Cyanuric acid is determined turbidimetricaHy after precipitation as melamine cyanurate. 

The solubilities of Li, Na, and Ca hypochlorites in H2O at 25°C ate 40, 45, and 21%, respectively. Solubility isotherms in water at 10°C have been determined for the following systems Ca(OCl)2—CaCl2, NaOCl—NaCl, and Ca(OCl)2—NaOCl (141). The densities of approximately equimolar solutions of NaOCl and NaCl ate given in several product bulletins (142). The uv absorption spectmm of C10 shows a maximum at 292 nm with a molar absorptivity of 350 cm ( 5)- Heats of formation of alkali and alkaline earth hypochlorites ate given (143). Thermodynamic properties of the hypochlorite ion ate ... 

Laundry bleach is a solution of sodium hypochlorite (NaCIO). To determine the hypochlorite (CIO-) content of bleach (which is responsible for its bleaching action), sulfide ion is added in basic solution. The balanced equation for the reaction is... 

The amount of sodium hypochlorite in a bleach solution can be determined by using a given volume of bleach to oxidize excess iodide ion to iodine CIO- is reduced to Cl-. The amount of iodine produced by the redox reaction is determined by titration with sodium thiosulfate, Na2S203 I2 is reduced to I-. The sodium thiosulfate is oxidized to sodium tetrathionate, Na2S406. In this analysis, potassium iodide was added in excess to 5.00 ml of bleach d = 1.00 g/cm3). If 25.00 mL of 0.0700 MNa2S203 was required to reduce all the iodine produced by the bleach back to iodide, what is the mass percent of NaCIO in the bleach ... 

Note. Hypochlorites and chlorites may be reduced to chlorides with sulphur dioxide, and determined in the same way. 

Determination of sulphite by oxidation to sulphate and precipitation as barium sulphate Discussion. Sulphites may be readily converted into sulphates by boiling with excess of bromine water, sodium hypochlorite, sodium hypobromite, or ammoniacal hydrogen peroxide (equal volumes of 20-volume hydrogen peroxide and 1 1 ammonia solution). The excess of the reagent is decomposed by boiling, the solution acidified with hydrochloric acid, precipitated with barium chloride solution, and the barium sulphate collected and weighed in the usual manner (Section 11.72). 

Sodium hypochlorite (NaOCl) is the active ingredient in laundry bleach. Typically, bleach contains 5.0% of this salt by mass, which is a 0.67 M solution. Determine the concentrations of all species and compute the pH of laundiy bleach. 

After completing our analysis of the effects of the dominant equilibrium, we may need to consider the effects of other equilibria. The calculation of [H3 O ] in a solution of weak base illustrates circumstances where this secondary consideration is necessary. Here, the dominant equilibrium does not include the species, H3 O, whose concentration we wish to know. In such cases, we must turn to an equilibrium expression that has the species of interest as a product. The reactants should be species that are involved in the dominant equilibrium, because the concentrations of these species are determined by the dominant equilibrium. We can use these concentrations as the initial concentrations for our calculations based on secondary equilibria. Look again at Example for another application of this idea. In that example, the dominant equilibrium is the reaction between hypochlorite anions and water molecules H2 0 l) + OCr(c2 q) HOCl((2 q) + OH ((2 q) Working with this equilibrium, we can determine the concentrations of OCl, HOCl, and OH. To find the concentration of hydronium ions, however, we must invoke a second equilibrium, the water equilibrium 2 H2 0(/) H3 O (a q) + OH (a q)... 

The reaction has been studied kinetically, and it is found that when a solid catalyst (CoO and/or Co203) formed by adding Co(N03)2 to a solution of NaOCl is present, the rate of the reaction is determined by the surface area of the catalyst. Hypobromites and hypoiodites are good oxidizing agents, though less commonly used than hypochlorites. One use of NaOBr is in analysis where it is used to oxidize urea and NH4+ to produce N2. 

The sample is acidified with sulfuric acid. The bromide content is then determined by the volumetric procedure described by Kolthoff and Yutzy [21 ]. In this procedure the buffered sample is treated with excess sodium hypochlorite to oxidise bromide to bromate. Excess hypochlorite is then destroyed by addition of sodium formate. Acidification of the test solution with sulfuric acid followed by addition of excess potassium iodide liberates an amount of iodine equivalent to the bromate (i.e., the original bromide) content of the sample. The liberated iodine is titrated with standard sodium thiosulfate. 

In the amperometric titration for the determination of total residual chlorine in seawater, tri-iodide ions are generated by the reaction between hypochlorite and/or hypobromite with excess iodide pH 4 (reactions (4.3) and (4.4)). The pH is buffered by adding a pH 4 acetic acid-sodium acetate buffer to the sample. 

Berg and Addullah [47] have described a spectrophotometric autoanalyser method based on phenol, sodium hypochlorite, and sodium nitroprusside for the determination of ammonia in sea and estuarine water (i.e., the indophenol blue method). 

Le Corre and Treguer [49] developed an automated procedure based on oxidation of the ammonium ion by hypochlorite in the presence of sodium bromide followed by spectrophotometric determination of the nitrite. The standard deviation on a set of samples containing 1 p,g NH -N per litre was 0.02. This method was compared with an automated method for the determination of ammonia as indophenol blue. The results from the two methods are in good agreement. 

Emmet RT (1969) Spectrophotometric determination of urea in natural waters with hypochlorite and phenol. NAVSHIPRANDLAB Annapolis Report 2663... 

The flow-cell design was introduced by Stieg and Nieman [166] in 1978 for analytical uses of CL. Burguera and Townshend [167] used the CL emission produced by the oxidation of alkylamines by benzoyl peroxide to determine aliphatic secondary and tertiary amines in chloroform or acetone. They tested various coiled flow cells for monitoring the CL emission produced by the cobalt-catalyzed oxidation of luminol by hydrogen peroxide and the fluorescein-sensitized oxidation of sulfide by sodium hypochlorite [168], Rule and Seitz [169] reported one of the first applications of flow injection analysis (FTA) in the CL detection of peroxide with luminol in the presence of a copper ion catalyst. They... 

A. Trichloramine. A mixture of 600 ml. of water (Note 2), 900 ml. of methylene chloride (Note 3), and 270 g. (1.32 moles) of calcium hypochlorite (Note 4) is cooled to 0-10° in a 3-1., three-necked, vented flask equipped with a stirrer, a thermometer, and a dropping funnel. A solution of 66.0 g. (1.23 moles) of ammonium chloride in 150 ml. of concentrated hydrochloric acid and 450 ml. of water is added dropwise with stirring over a 1-hour period at 0-10°. After an additional 20 minutes of stirring, the organic layer is separated, washed with three 200-ml. portions of cold water, and dried over anhydrous sodium sulfate. The yellow solution is filtered, and the trichloramine concentration is determined by iodometric titration (Note 5). 

The amount of hypochlorite ion present in bleach can be determined by an oxidation-reduction titration. In this experiment, an iodine-thiosulfate titration will be utilized. The iodide ion is oxidized to form iodine, I2. This iodine is then titrated with a solution of sodium thiosulfate of known concentration. Three steps are involved ... 

In this step the reddish brown color of the triiodide begins to fade to yellow and finally to clear, indicating only iodide ions present. However, this is not the best procedure for determining when all of the I3 has disappeared since it is not a sensitive reaction and the change from pale yellow to colorless is not distinct. A better procedure is to add a soluble starch solution shortly prior to reaching the end point, since if it is added to soon, too much iodine or triiodide ion may be present forming a complex that may not be reversible in the titration. The amount of thiosulfate is proportional to the amount of hypochlorite ion present. 

I. Determining The Percent Sodium Hypochlorite in Commercial Bleaching Solutions... 

III. Purpose Determine the percent sodium hypochlorite in various commercial bleaching solutions by titration. Compare the cost effectiveness of different brands of commercial bleaching solutions. 

Chemical Education Resources, Inc, "Determining the Percent Solium Hypochlorite in Commercial Bleaching Solutions," Palmyra, PA., 1992. 

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