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Chlorine Demand WQT 134 Environmental Chemistry II.

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Presentation on theme: "Chlorine Demand WQT 134 Environmental Chemistry II."— Presentation transcript:

1 Chlorine Demand WQT 134 Environmental Chemistry II

2 Lab 9 Objectives Understand/Review Chlorination in the disinfection Process Reading assignment: AWWA Water Treatment, Principles and Practices of Water Supply Operation, Third Edition, American Waterworks Association, ISBN Chapter 7 Disinfection Reading assignment: AWWA Water Treatment, Principles and Practices of Water Supply Operation, Third Edition, American Waterworks Association, ISBN Chapter 7 Disinfection

3 pH Impact on Free Chlorine

4 Chlorine Chemistry in Water 1.Start with chlorine gas Cl 2 + H 2 O HOCl + HCl 2. If the pH of the water is greater than 8, the hypochlorus acid (HOCl - ) will dissociate (break) to yield hypochlorite ion. HOCl H + + OCl 3. pH is less than 7, HOCl will not dissociate. 1.Start with chlorine gas Cl 2 + H 2 O HOCl + HCl 2. If the pH of the water is greater than 8, the hypochlorus acid (HOCl - ) will dissociate (break) to yield hypochlorite ion. HOCl H + + OCl 3. pH is less than 7, HOCl will not dissociate. Free residual hypochlorous acid (HOCl) is more 1000 times more effective than combined residual monchloramine

5 Which of the following is true about chlorine chemistry? 1.pH < 7 favors hypochlorous acid 2.pH >8 hypochlorite ions form which can still disinfectant 3.HOCL is 100 times more powerful then OCL - 4.All of the above 1.pH < 7 favors hypochlorous acid 2.pH >8 hypochlorite ions form which can still disinfectant 3.HOCL is 100 times more powerful then OCL - 4.All of the above

6 HOCL is 1,000 times more powerful then monochloramine? 1.True 2.False 1.True 2.False

7 Basic Chlorine Compounds Chlorine Demand: chlorine reacted with –Clay, silt, iron, manganese, bacteria Combined Chlorine Residuals Chloramines: chlorine reacted with –Inorganic ammonia compounds (NH 3 ) –Organic nitrogen proteins (amino acids) –Less DBP –Weak against virus and protozoa Chlorine Demand: chlorine reacted with –Clay, silt, iron, manganese, bacteria Combined Chlorine Residuals Chloramines: chlorine reacted with –Inorganic ammonia compounds (NH 3 ) –Organic nitrogen proteins (amino acids) –Less DBP –Weak against virus and protozoa

8 Cl:NH 3 and pH Impact in Water 1.If ammonia (NH 3 ) is present in water, the hypochlorus acid (HOCL) will react to form one kind of chloramine depending on the pH, temperature, and reaction time. 2. Monochloramine and dichloramine are formed at pH Monochloramine is most Cl 2 :NH 3 <5:1 4. pH , Cl:NH 3 > 5:1 -Monochloramine converts to dichloramines 5. pH < 4.5, Cl 2 :NH 3 ~15:1 -Trichloramine which produces a very foul odor. 2. Monochloramine and dichloramine are formed at pH Monochloramine is most Cl 2 :NH 3 <5:1 4. pH , Cl:NH 3 > 5:1 -Monochloramine converts to dichloramines 5. pH < 4.5, Cl 2 :NH 3 ~15:1 -Trichloramine which produces a very foul odor.

9 Chlorine-Ammonia (chloramines) 1. Rates of formation of mono and dichloramine. 2. pH 3. Temperature 4. Time 5. Cl:NH 3 ratio Fact: High Cl:NH 3 ratio, low temp & pH favor dichloramine Combined Available Chlorine- chlorine existing in the water in chemical combination with ammonia-nitrogen or organic nitrogen 1. Rates of formation of mono and dichloramine. 2. pH 3. Temperature 4. Time 5. Cl:NH 3 ratio Fact: High Cl:NH 3 ratio, low temp & pH favor dichloramine Combined Available Chlorine- chlorine existing in the water in chemical combination with ammonia-nitrogen or organic nitrogen Chlorine- Ammonia reactions are governed by:

10 Chloramines in Water 3. pH ; pH Monochloramine: NH 3 + HOCl NH 2 Cl + H 2 O 2. pH ; pH Dichloramine: NH 2 Cl + 2HOCl NHCl 2 + 2H 2 O 4. pH <4.5 Trichloramine: NHCl 2 + 3HOCl NHCl 3 + 3H 2 O 3. pH ; pH Monochloramine: NH 3 + HOCl NH 2 Cl + H 2 O 2. pH ; pH Dichloramine: NH 2 Cl + 2HOCl NHCl 2 + 2H 2 O 4. pH <4.5 Trichloramine: NHCl 2 + 3HOCl NHCl 3 + 3H 2 O Chloramines are an effective disinfectant against bacteria but not against viruses. Add more chlorine to the wastewater to prevent the formation of chloramines and form stronger disinfectants. Chloramines are an effective disinfectant against bacteria but not against viruses. Add more chlorine to the wastewater to prevent the formation of chloramines and form stronger disinfectants. Chloramines

11 Add the Extra Free Chlorine (HOCL) 5. Additional free chlorine (HOCL or OCL-) reacts with chloramine to produce hydrogen ion, water, and nitrogen gas which will come out of solution. In the case of the monochloramine, the following reaction occurs: 2NH 2 Cl + HOCl N 2 + 6HCl + H 2 O Added free chlorine reduces the concentration of chloramines in the disinfection process. Instead the chlorine that is added is allowed to form the stronger disinfectant, hypochlorus acid. 5. Additional free chlorine (HOCL or OCL-) reacts with chloramine to produce hydrogen ion, water, and nitrogen gas which will come out of solution. In the case of the monochloramine, the following reaction occurs: 2NH 2 Cl + HOCl N 2 + 6HCl + H 2 O Added free chlorine reduces the concentration of chloramines in the disinfection process. Instead the chlorine that is added is allowed to form the stronger disinfectant, hypochlorus acid.

12 If abundant (15 times) Cl is around and the pH < 4.5 Trichloramine is the most likely chloramine to form? 1.True 2.False 1.True 2.False

13 Which of the following impact chloramine disinfection? 1.pH 2.Temperature 3.Time 4.All of the above 1.pH 2.Temperature 3.Time 4.All of the above

14 Ammonium nitrogen and chlorine

15 Taste and Odor Problems Free (HOCL)20 mg/L Monochloramine5 mg/L Dichloramine.8 mg/L Trichloramine.02 mg/L Free (HOCL)20 mg/L Monochloramine5 mg/L Dichloramine.8 mg/L Trichloramine.02 mg/L

16 Chlorine Chemistry Summary Cl 2 + H 2 O HCl + HOCl Chlorine Hydrochloric Hypochlorous Ca(OCl) 2 (aqueous) Ca OCl - Calcium Hypochlorite Hypochlorite NaOCl 2 (aqueous ) Na + + OCl - Sodium Hypochlorite Hypochlorite HOCl H + + OCl - Hypochlorous Hypochlorite HOCl + NH 3 NH 2 Cl + H 2 O Hypochlorous Ammonia Chloramine Cl 2 + H 2 O HCl + HOCl Chlorine Hydrochloric Hypochlorous Ca(OCl) 2 (aqueous) Ca OCl - Calcium Hypochlorite Hypochlorite NaOCl 2 (aqueous ) Na + + OCl - Sodium Hypochlorite Hypochlorite HOCl H + + OCl - Hypochlorous Hypochlorite HOCl + NH 3 NH 2 Cl + H 2 O Hypochlorous Ammonia Chloramine

17 Chlorine Residual Analysis Starch Iodide Titration: common in wastewater Amperometric Titration: common in wastewater with cloudy or turbidity problems DPD colorometric- common in water and wastewater. Measures free residual or combined residual. Starch Iodide Titration: common in wastewater Amperometric Titration: common in wastewater with cloudy or turbidity problems DPD colorometric- common in water and wastewater. Measures free residual or combined residual.

18 Breakpoint Chlorination Breakpoint chlorination: The point at which near complete oxidation of nitrogen compounds are reached. Any point beyond breakpoint is mostly free chlorine (HOCL and OCL - ) A. Amount of chlorine required Theory: 7.6 to 15 times the ammonia nitrogen content of the water Practice: up to 25 times the ammonia nitrogen content B. Beyond breakpoint 90% free residual chlorine (HOCL and OCL - ) 10% combined chlorine C. Why must breakpoint chlorination be reached? Necessary for the production of free residual chlorine (HOCL and OCL - ) Reduces taste and odors Reduces chloramines Breakpoint chlorination: The point at which near complete oxidation of nitrogen compounds are reached. Any point beyond breakpoint is mostly free chlorine (HOCL and OCL - ) A. Amount of chlorine required Theory: 7.6 to 15 times the ammonia nitrogen content of the water Practice: up to 25 times the ammonia nitrogen content B. Beyond breakpoint 90% free residual chlorine (HOCL and OCL - ) 10% combined chlorine C. Why must breakpoint chlorination be reached? Necessary for the production of free residual chlorine (HOCL and OCL - ) Reduces taste and odors Reduces chloramines

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20 Breakpoint Chlorination Zone I: Chlorine is destroyed by reducing agents such as iron, manganese, clay and silt. Chlorine reduced to chloride Zone II: Chlorine comes into contact with organics and ammonia. Chloroorganics and chloramines are formed. Zone III: Chloroorganics and chloramines are partially destroyed. Chloramines are broken down and converted to nitrogen gas which leaves the system Zone IV: Breakpoint. Beyond this point, free available residual is formed. Some chloroorganics still remain as combined residual. Chlorine demand is difference between applied chlorine and the free chlorine residual at any two points on the breakpoint curve. Zone I: Chlorine is destroyed by reducing agents such as iron, manganese, clay and silt. Chlorine reduced to chloride Zone II: Chlorine comes into contact with organics and ammonia. Chloroorganics and chloramines are formed. Zone III: Chloroorganics and chloramines are partially destroyed. Chloramines are broken down and converted to nitrogen gas which leaves the system Zone IV: Breakpoint. Beyond this point, free available residual is formed. Some chloroorganics still remain as combined residual. Chlorine demand is difference between applied chlorine and the free chlorine residual at any two points on the breakpoint curve.

21 In Zone 1 most of the chlorine dose gets used by chlorine demand ? 1.True 2.False 1.True 2.False

22 In Zone II chlorine reacts with ammonia to form combined chlorine ? 1.True 2.False 1.True 2.False

23 In Zone III some combined chlorine gets broken down to nitrogen gas ? 1.True 2.False 1.True 2.False

24 At Breakpoint chlorine added becomes free available chlorine? 1.True 2.False 1.True 2.False

25 Application of Chlorine in Water Treatment Distribution Free Chlorine Residual- chlorine dosed in excess of the demand and beyond the breakpoint will produce free chlorine residual HOC (hypochlorous acid) and OCL - (hypochlorite ion). Free Chlorine Residual- chlorine dosed in excess of the demand and beyond the breakpoint will produce free chlorine residual HOC (hypochlorous acid) and OCL - (hypochlorite ion). Free chlorine – 10 to 100 times more effective then combined residual Oxidizes certain taste and odor compounds like H 2 S Oxidizes Fe +2, Mn +2 Controls biofilms on filters and mains Free chlorine – 10 to 100 times more effective then combined residual Oxidizes certain taste and odor compounds like H 2 S Oxidizes Fe +2, Mn +2 Controls biofilms on filters and mains

26 Which of the following waters would have the highest concentration of hypochlorous acid? a. pH of 7 b. pH of 8 c. pH of 9 d. pH of 10 a. pH of 7 b. pH of 8 c. pH of 9 d. pH of 10

27 Which of the following compounds is considered to be "free" chlorine in its present state? 1.HCl 2.Ca(OCl) 2 3.NaOCl 4.HOCl 1.HCl 2.Ca(OCl) 2 3.NaOCl 4.HOCl

28 The amount of chlorine used by organic matter in water is a portion of the: 1.chlorine demand 2.chlorine dioxide 3.free available chlorine 4.chlorine residual 1.chlorine demand 2.chlorine dioxide 3.free available chlorine 4.chlorine residual

29 When feeding chlorine gas and ammonia, it is noticed that you have gone over the "hump", this means that you could be 1.feeding "free" chlorine 2.past the breakpoint toward the "free" point on the curve 3.forming chloramines 4.destroying chloramines and building DBP's 1.feeding "free" chlorine 2.past the breakpoint toward the "free" point on the curve 3.forming chloramines 4.destroying chloramines and building DBP's

30 Chlorine can react with nitrogen in several ways to form chloramine products. Which of the following is the trichloramine (nitrogen trichloride) compound mostly responsible for taste & odor development, when using ammonia and chlorine as a disinfectant? 1.NCl 3 2.NHCl 2 3.NH 2 Cl 4.N 3 HCl 2 1.NCl 3 2.NHCl 2 3.NH 2 Cl 4.N 3 HCl 2

31 Breakpoint chlorination is achieved when 1.no chlorine residual is detected 2.the strong chlorine taste at the plant is not found in the distribution system 3.the ammonia level in the water decreases 4.a chlorine dose increase results in an increase of chlorine residual 1.no chlorine residual is detected 2.the strong chlorine taste at the plant is not found in the distribution system 3.the ammonia level in the water decreases 4.a chlorine dose increase results in an increase of chlorine residual

32 The chlorine curve has three locations where a measurable residual can be detected. The strongest, most aggressive form of chlorine is found on the _______ portion of the curve. 1.disinfection-by-product (DBP) 2.chloramine destruction 3.free-chlorine 4.monochloramine buildup 1.disinfection-by-product (DBP) 2.chloramine destruction 3.free-chlorine 4.monochloramine buildup

33 In water disinfection, hypochlorination refers to the use of _________ hypochlorite 1.Sodium 2.Calcium 3.Magnesium 4.Potassium 1.Sodium 2.Calcium 3.Magnesium 4.Potassium

34 Chlorine residual may be determined using the reagent: 1.Diethyl-p-phenylene diamine 2.Ethylene diamine tetraacetic acid 3.Polychlorinated biphenyls 4.Sodium thiosulfate 1.Diethyl-p-phenylene diamine 2.Ethylene diamine tetraacetic acid 3.Polychlorinated biphenyls 4.Sodium thiosulfate

35 A chlorine demand test will show the: 1.Safe amount of chlorine that may be fed without killing people 2.Number of lbs required to kill 100% of coliforms 3.Amount of chlorine required to give a desired residual after a given time 4.Amount of chlorine required to satisfy the biochemical oxygen demand 1.Safe amount of chlorine that may be fed without killing people 2.Number of lbs required to kill 100% of coliforms 3.Amount of chlorine required to give a desired residual after a given time 4.Amount of chlorine required to satisfy the biochemical oxygen demand

36 Which of the following methods is not used to determine chlorine residual? 1.Photometric 2.Iodometric 3.Titrimetric 4.Amperometric 1.Photometric 2.Iodometric 3.Titrimetric 4.Amperometric

37 Today's Lecture Objectives: To understand basic chlorine demand chemistry has been met? 1.Strongly Agree 2.Agree 3.Neutral 4.Disagree 5.Strongly Disagree 1.Strongly Agree 2.Agree 3.Neutral 4.Disagree 5.Strongly Disagree


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