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Free and Combined Chlorine

Free and Combined Chlorine

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Published by Prafulla Pokhara

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Published by: Prafulla Pokhara on Jan 18, 2014
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 LIFETECH s.r.o. • Sumavska 15 • 602 00 Brno • Czech Republic
In addition to the compounds necessary for disinfection and oxidation of impurities, substances with adverse effect to human health are present in pool water treated by gaseous chlorine or by chlorine reagents (hypochlorite, chloroisocyanuric acid). Properly designed and operated pool technology suppresses the formation of undesirable disinfection by-products and enables permanent fulfilling of the requirements on pool water quality.
Compounds present in chlorine treated pool water
FREE CHLORINE (disinfection)
Disinfection by-products (DBP)
Other DBP
FREE CHLORINE – monitored parameter FREE CHLORINE content is a sum of concentrations of hypochlorous acid and its anion, hypochlorite. Relative distribution of these two species depends on pool water pH. FREE CHLORINE value is, however, pH-independent. Disinfection by-products (DBP) DBP are undesirable compounds with an adverse effect to human health. Some of them are classified as suspected human carcinogens. COMBINED CHLORINE – monitored parameter COMBINED CHLORINE content corresponds to the concentration of chloramines in pool water. Chloramines are major disinfection by-products in chlorinated pools with monochloramine as the predominant species at the pool water pH. Their disinfection effect is substantially lower than it is at FREE CHLORINE compounds. Because chloramines are toxic and irritating substances, their presence in pool water is undesirable. Chloramines belong among the main contributors to “chlorine smell” of the pool water. Other DBP In addition to the COMBINED CHLORINE compounds, other substances fall into the class of DBP. These substances are present at low concentrations at usual conditions. They are toxic, contribute to the “chlorine smell”, and some of them are classified as suspected human carcinogens. TOTAL CHLORINE This parameter is the sum of the free and combined chlorine contents: TOTAL CHLORINE = FREE CHLORINE + COMBINED CHLORINE
FREE CHLORINE – monitored parameter FREE CHLORINE content can be monitored by suitable sensor (measuring probe, electrode), or it can be determined in a water sample by DPD method. At the DPD method, the sample becomes red-purple and the color intensity is compared with color scale or measured by a photometer. The results are given in mg/l Cl
 or in ppm (1 mg/l=1 ppm). TOTAL CHLORINE TOTAL CHLORINE content is determined by the means introduced above, i.e. continuously by special sensor or by DPD method in a taken sample. The results are given in mg/l Cl
 or in ppm (1 mg/l=1 ppm). COMBINED CHLORINE – monitored parameter It is determined as the difference between the TOTAL CHLORINE and FREE CHLORINE values: COMBINED CHLORINE = TOTAL CHLORINE - FREE CHLORINE  Avoid mistakes in determination by DPD method!
Reagents for determination of free chlorine and combined chlorine are different.
It is necessary to keep the recommended time periods for color development (reaction) and reading of the value.
The sample cells used for free and total chlorine determinations cannot be interchanged.
The DPD method can be used only in concentration range given for the test-kit.
 At free chlorine concentrations higher than the maximum value given for the test-kit, very rapid partial or total discoloration of the sample proceeds after addition of the reagent for free or total chlorine determination and, therefore, the determined value is false. In such cases the sample has to be diluted in a suitable proportion by distilled water or, at least, by water without any oxidants, free and combined chlorine compounds inclusive.
The results can be reliable only in the case the sampling was done properly.
The samples have to be analyzed immediately after sampling. Determination of free and combined chlorine is described in ISO 7393-2 Standard.
World Health Organization in “Guidelines for safe recreational water environments, Vol. 2: Swimming pools and similar environments”, WHO 2006 Free chlorine: the limit values 1.0 or 0.5 and 3.0 mg/l, hot tubs up to 5.0 mg/l Combined chlorine:
less than 0.2 mg/l
Germany - DIN 19643-1: 1997-04 Standard Free chlorine: the limit values 0.3 and 0.6 mg/l, (hot tubs 0.7 and 1.0 mg/l) Combined chlorine:
limit value of 0.2 mg/l
USA - National Spa and Pool Institute, recommendation Free chlorine: 1.0 to 4.0 mg/l Combined chlorine:

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