9: Chlorine

Chlorine Terminology

Chlorine is available in three forms: gaseous, solid, and liquid.

• Gaseous(chlorine)⁠—\(\ce{Cl2}\)
• Solid (Calcium hypochlorite)⁠—\(\ce{Ca(OCl)2}\)
• Liquid (Sodium Hypochlorite)⁠—\(\ce{NaOCl}\)

It is not explicitly known how chlorine disinfection works. One explanation is that chlorine attacks a bacterial cell and destroys it. The other theory suggests that chlorine deactivates enzymes within the cell enabling the microorganisms to use their food supply. Adding chlorine to a water supply causes chemical reactions to take place between the water and the organic and inorganic molecules within the water. After chlorine is done combing with organic and inorganic material in the water, the demand has been satisfied.

The dose of chlorine minus the demand is the residual. The reason chlorine is used in the United States over other disinfecting chemicals is Chlorine’s ability to leave a lasting residual within the framework of the water distribution system. This residual continues to fight potential disease-causing microorganisms after treatment has concluded.

Assume that you are working as an operator at a water treatment plant. Your chief operator would like to maintain a residual of 2.0 mg/L of chlorine residual in the distribution system. The demand is 1.5 mg/L. What is the dose you must add to achieve a residual of 2.0 mg/L?

\[\begin{align*} \text{Dose} &= \text{Demand} + \text{Residual} \\[4pt] &= 2.0\,\text{mg/L} + 1.5 \, \text{mg/L} \\[4pt] &= 3.5\,\text{mg/L}\end{align*}\]

Therefore, you would need to maintain an average of a 3.5 mg/L dose of Chlorine to achieve the residual requested by your chief operator.

Other Chlorine terminology includes Free Chlorine, Combined Chlorine, and Total Chlorine. It is important to understand these terms before taking a deeper dive into the chemistry of chloramination. The term Free or Available Chlorine refers to the amount of Chlorine that is “free” or “available” in the system to kill or deactivate pathogenic organisms. Combined Chlorine is chlorine that has combined with other molecules and Total Chlorine is the combination of Free or Available Chlorine and Combined Chlorine. Although Combined Chlorine lasts longer in the distribution system, it is a far less effective disinfectant. It is also important to note, not all Chlorine has the same strength. This will be covered more thoroughly later in the chemistry and math portion of the chapter.

Chlorine Content

As mentioned earlier in the chapter, Chlorine is available in different states of matter. The amount of chlorine used to dose water in a treatment plant is determined by the compound used. Below is a chart illustrating the different compounds of chlorine. The percent column indicates the percentage of Chlorine in the compound. For example, Chlorine Gas is pure Chlorine and yields the highest available percentage at 100%.

In the math section of this chapter, the impact of the Chlorine percentage will become evident. It is important to read the question and understand what concentration of chlorine is being added to the treatment plant. The third column in the table provides the lb or gallon needed of the specific compound to provide 1 lb of chlorine. For example, if your plant requires a weight or quantity of 100 lbs of chlorine and you use gas chlorine, then you will be adding 100 lbs. of Chlorine Gas. If you are using calcium hypochlorite, you will need to calculate the number of pounds required. From the table, Calcium Hypochlorite is 65% Chlorine. To determine the total number of pounds of Calcium Hypochlorite needed to provide 1 lb of Chlorine, divide the dose required by the percent chlorine.

\[100 ÷ 0.65 = 153.8\, lbs\]

Therefore, you will need to use 153.8 lbs of Calcium Hypochlorite to obtain a 100 lbs dose of chlorine.

Factors of Chlorine Success

Several factors during the water treatment process will impact the effectiveness of the Chlorine. The five factors that affect chlorine treatment are:

• The concentration of chlorine, more specifically the dose
• The amount of time chlorine is in contact with the water
• The temperature of the source water
• The pH of the source water
• The constituents in the source water

The amount of time the chlorine is in contact with the water determines the effectiveness of the chlorine disinfection. The CT (Concentration multiplied by Contact Time) formula is used to calculate the time chlorine is in contact with the water. C is the concentration of chlorine residual, therefore CT is expressed as (mg/L-min). If water is leaving a drinking water storage tank, also referred to as a clearwell, at a rapid rate, then the chlorine concentration will have to be increased. If the concentration of chlorine is decreased, then the water will have to stay in contact with the disinfectant for a longer period of time. Combined Chlorine treatment associated with monochloramine disinfection will require longer holding periods due to its decreased effectiveness.

Temperature affects chlorine treatment in a variety of ways. Chlorine is more effective at killing pathogens at higher temperatures but at lower temperatures, the chlorine residual will last longer. Practically speaking, chlorine disinfection works better in warmer temperatures as more credit is given with the CT calculation. The pH level of the water is also a significant factor when treating with chlorine. The ratio of HOCl to OCl- is affected based on the pH. HOCl will remain the dominant disinfectant in water with a lower pH while OCl- will remain in higher quantities in water with a higher pH.

In the disinfection process, chlorine not only reacts with organisms that are to be killed, but it also reacts with the turbidity in the water and other substances such as ammonia. Reducing turbidity in treated water through coagulation, sedimentation, and filtration ensures disinfection will be more effective. The maximum and minimum chlorine residual in the distribution system is 4.0 mg/L and 0.2 mg/L respectively. However, corrective measures must be taken when you see the residual in the distribution system dramatically decreasing. You would never want to see the minimum chlorine residual of 0.2 in the distribution system.

Chlorine Chemistry

Below is the reaction that occurs between water and free available chlorine:

\[\ce{Cl2 \,(Chlorine) + H2O \,(Water) → HOCl \,(hypochlorous acid) + HCl\, (hydrochloric acid)}\]

Hypochlorous acid is more effective of the two forms of available chlorine. First, it is important to understand how chlorine demand works. We can do this by examining the effects of adding free available chlorine to distilled water. If we were to dose distilled water with 1.0 mg/L of free available chlorine, the residual would be 1.0 mg/L chlorine because there is nothing in distilled water that will react with the chlorine other than the water itself. Distilled water lacks impurities.

It is clear that the raw source water is filled with impurities. Chlorine will have many constituents to react with during the treatment process. When the Chlorine reacts with the water and the impurities, five different types of chlorine residuals result. The following chart illustrates the effectiveness of each type of residual. The most effective is hypochlorous acid (HOCl) so the effectiveness of the remaining four types of residuals are in comparison to HOCl.

As the chart shows, dichloramines are a “more effective” disinfectant than monochloramines but their use may cause taste and odor problems. The effectiveness of trichloramines has not been extensively researched and as with dichloramines, a pungent taste and odor problem occurs with its use. Thus the water industry only uses monochloramines as a disinfectant. Below are the chemical formulas which illustrate when hypochlorous acid disassociates and becomes a weaker disinfectant.

\[\ce{HOCl \,(Hypochlorous acid) -> H^{+} (Hydrogen ion) + OCl^{-} (Hypochlorite ion)}\]

\[\ce{HCl\, (Hypochloric acid) -> H^{+} (Hydrogen ion) + Cl^{-} (Chlorine ion)}\]

Chlorine Handling and Safety

As a Treatment operator, you will come in contact with many dangerous chemicals used to treat water. One chemical that is widely used in the water treatment industry is chlorine. As discussed earlier in the chapter chlorine comes in three different states: gas, powder, and liquid. All three types of chlorine have risks associated with the handling and storage of the chemical. It is important that proper safety procedures are followed at all times.

Chlorine Gas

Chlorine gas is 2.5 times heavier than air. The odor is pungent and the color is greenish-yellow. Gas chlorine is only visible in very high concentrations and you don’t ever want to see it. Chlorine gas is irritating to eyes, nasal passages, and the respiratory system. It is a very dangerous substance and concentrations as low as 100 parts per million can kill a person.

Chlorine gas is available in three different types of containers: 150-pound containers, 1-ton containers, and, for very large plant operations, in railroad containers. A majority of treatment operations will use chlorine tanks. The amount of chlorine used in a given day will determine which type of chlorine container your plant will use.

When delivered to a treatment plant, the “150-pound” chlorine gas cylinder container weighs roughly 250-280 pounds. A chlorine cylinder consists of the cylinder body, neck ring, valve, and protective hood.

Cylinders are transported around the facility with the use of a dolly or hand truck. The use of a safety chain or strap is mandatory at all times. Cylinders should never be rolled because it could lead to employee injury or the shearing off of the valve. The maximum daily withdrawal rate for a chlorine cylinder is 40 pounds.

Chlorine “ton” containers hold 2000 pounds of chlorine and usually weigh around 3700 pounds when filled with chlorine. The Containers are shipped and stored horizontally. The edge of the chlorine container has a ring, which enables cranes and hoists to move them from the truck to the storage or withdrawal area. Containers are stored on trunnions that allow operators to rotate containers with the use of a special tool. Each container has two valves, one at the top and one at the bottom. The top valve allows the chlorine to be withdrawn as a gas while the bottom valve allows chlorine to be withdrawn as a liquid. When putting containers in storage, they should placed such that the liquid chlorine is allowed to settle in the bottom of the container. The maximum daily withdrawal rate for a 1-ton tank is 400 pounds.

Gas chlorine cylinders and 1-ton containers use similar methods to feed chlorine into the water. Feeding systems include a scale, valves and piping, a chlorinator, and an injector or diffuser. The weighing scales are used to keep track of how much chlorine has been used or is left in the cylinder or tank. Record keeping is critical for all chemical use. Monitoring and reviewing the recorded data can help identify problems with the chlorine system and manage costs by reducing chemical waste.

Pictured above is a standard chlorine scale and trunnion system. The trunnion acts as a form of storage while also keeping an accurate measure of the amount of chemical left in the tanks. In California, the tanks must also be secured with straps due to earthquakes.

Valves and piping are just as important in the chlorine system as they are in the water system. Each chlorine tank or cylinder is equipped with valves which allow or prohibit the flow of the chlorine during the transfer and storage of the product. In an emergency, the valves can also be used to quickly shutoff the flow of chlorine. Large scale systems will include piping manifolds that allow for the transfer of chlorine from multiple tanks. The associated feed system will include valves and piping to provide chlorine to different feed points in the system.

The chlorinator is the piece of equipment that feeds the chlorine directly into the system. Chlorine is dispersed evenly into the system based on a dosage set point using vacuum and pressure regulators. For safety, a vacuum must be maintained in the line. The vacuum ensures that the chlorine is always being pulled into the chlorine feed system. Most modern systems have emergency shutoff valves which prevent the flow of chlorine if a leak is detected. Chlorine systems will also include alarms, leak detectors, and repair kits.

Other safety measures are also required when working around chlorine gas. For example, when switching tanks, the operator should be wearing a self-contained breathing apparatus (SCBA). As noted earlier, a 0.1 part per million dose of chlorine gas can be immediately fatal.

Hypochlorination

Gaseous chlorine is the strongest and least expensive form of chlorine even with the required use of bases such as caustic soda to increase the pH of the finished water. However, due to safety concerns associated with the use and transportation of gaseous chlorine, Hypochlorination is becoming more common in water treatment. When building or redesigning a treatment plant, an analysis of the costs and benefits of each type of chlorine will determine which type the facility will use.

The two types of hypochlorite used are calcium and sodium. Calcium hypochlorite is a whiteish-yellow dry chemical. It contains 65% available chlorine. Since it is highly reactive with organic compounds, special requirements must be used when storing it. Additionally, it is flammable if enough heat and oxygen are added. Calcium hypochlorite should always be added to water and not the opposite. Generally, Calcium hypochlorite is primarily used for disinfecting new and repaired water mains and storage tanks. It is not used for the day-to-day treatment of finished water.

Sodium hypochlorite is a clear to yellowish liquid available in a variety of different concentrations. Household sodium hypochlorite, known as bleach, is available in a 5% solution. Treatment plant operations will use an industrial-strength concentration of 12.5% available chlorine. Sodium hypochlorite does not have special storage requirements, but it is a strong base at 9-11 on the pH scale so it is highly corrosive. Additionally, the chemical loses its effectiveness over time in storage. Stored for a month, the chemical can lose 2% to 4% of its chlorine content. Direct exposure to sun and/or heat will further the loss of available chlorine. Therefore, it is recommended that sodium hypochlorite be stored no more than two weeks (in the event the treatment plant is offline) in a temperature-controlled room to prevent excessive strength loss.

Cylinder Tank Safety and Connecting

When attaching a chlorine regulator to a tank to go into service, safety precautions must be used. Any time you are dealing with gas chlorine the operator must wear a respirator, but a SCBA is recommended. The SCBA has a 30-60 minute supply of oxygen. SCBA’s operate under positive pressure, so in the event of a leak, no chlorine gas will be able to enter your mask, assuming a proper seal of the mask has been established. Along with a respirator or SCBA the operator should wear gloves and a long sleeve shirt when changing cylinders or tanks.

A new lead washer should be used every time a new tank is put into service. Inspect the lead washer for any deformities, cracks, or bends. Washers must be thrown out after one use. When the chlorine tank valve is first opened, rapidly open and close the valve. Use an ammonia solution near the valve and tubing to check for leaks. The ammonia solution used is commercial Be ammonia. If chlorine is present, you will see a white cloud. In the event of a white cloud, a leak is present. The operator will have to remove the regulator from the valve and use a new lead washer.

Lastly, be vigilant. Changing chlorine cylinders will become routine as it is something you will have to do often if your facility uses chlorine gas. Chlorine gas is a highly dangerous chemical that must be respected. Forgetting how dangerous it is, could lead to serious harm or death for you or your co-workers.

Chapter Review

1. The form of Chlorine which is 100% available chlorine is?
   1. Sodium hypochlorite
   2. Calcium hypochlorite
   3. Calcium hydroxide
   4. Gaseous chlorine
2. What is the minimum amount of chlorine residual required in the distribution system?
   1. There is no minimum
   2. mg/L
   3. 0.2 mg/L
   4. mg/L
3. What is the approximate pH range of sodium hypochlorite?
   1. 4-5
   2. 6-7
   3. 9-11
   4. 12-14
4. What is the typical concentration of sodium hypochlorite utilized by water treatment professionals?
   1. 5%
   2. 65%
   3. 100%
   4. 12.5%
5. Chlorine demand refers to ___________.
   1. Chlorine in the system for a given time
   2. The difference between chlorine applied and chlorine residual—usually caused by inorganics, organics, bacteria, algae, ammonia, etc.
   3. Chlorine needed to produce a higher pH
   4. None of the above
6. What is the most effective chlorine disinfectant?
   1. Dichloramine
   2. Trichloramine
   3. Hypochlorite ion
   4. Hypochlorous acid
7. What can form when chlorine reacts with natural organic matter in source water?
   1. Disinfectant by-products
   2. Sulfur
   3. Algae
   4. Coliform bacteria
8. What is the maximum withdrawal rate per day for a 150-pound chlorine cylinder?
   1. There is no maximum
   2. 20 pounds
   3. 40 pounds
   4. 50 pounds
9. What kind of solution is used to check for a gas chlorine leak?
   1. Sodium hydroxide
   2. Ozone
   3. Ammonia
   4. Calcium hypochlorite
10. Chlorine is ___________.
    1. Heavier than air
    2. Lighter than air
    3. Brown in color
    4. Not harmful to your health
11. Chlorine demand may vary due to ___________.
    1. Chlorine demand always stays the same
    2. Temperature
    3. pH
    4. Both 2 and 3
12. What effect does high turbidity have on disinfection?
    1. It can increase chlorine demand
    2. It has no effect
    3. It gives the water a milky appearance that will clear out after some time
    4. You must increase the temperature of the water