Chlorination, chloramines
and breakpoint
Collected and written by
Abu Alhassan Abd Elshafi
2012
Chlorination, chloramines and breakpoint
Introduction
When chlorine is added to water, a variety of chemical processes take
place. The chlorine reacts with compounds in the water and with the
water itself. Some of the results of these reactions (known as the
chlorine residual) are able to kill microorganisms in the water. In the
following sections, we will show the chemical reactions which occur
when chlorine is added to water.
Chlorine Demand
When chlorine enters water, it immediately begins to react with
compounds found in the water. The chlorine will react with organic
compounds and form trihalomethanes. It will also react with reducing
agents such as hydrogen sulfide, ferrous ions, manganous ions, and nitrite
ions.
Let's consider one example, in which chlorine reacts with hydrogen
sulfide in water. Two different reactions can occur:
Hydrogen Sulfide + Chlorine + Oxygen Ion Elemental Sulfur
+ Water + Chloride Ions
H2S + Cl2 + O2- S + H2O + 2Cl-
Hydrogen Sulfide + Chlorine + Water Sulfuric Acid +
Hydrochloric Acid
H2S + 4Cl2 + 4 H2O H2SO4 + 8 HCl
I have written each reaction using both the chemical formula and the
English name of each compound. In the first reaction, hydrogen sulfide
reacts with chlorine and oxygen to create elemental sulfur, water, and
chloride ions. The elemental sulfur precipitates out of the water and can
cause odor problems. In the second reaction, hydrogen sulfide reactions
with chlorine and water to create sulfuric acid and hydrochloric acid.
Each of these reactions uses up the chlorine in the water, producing
chloride ions or hydrochloric acid which have no disinfecting
properties. The total amount of chlorine which is used up in reactions
with compounds in the water is known as the chlorine demand. A
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Chlorination, chloramines and breakpoint
sufficient quantity of chlorine must be added to the water so that, after the
chlorine demand is met, there is still some chlorine left to kill
microorganisms in the water.
Reactions of Chlorine Gas with Water
At the same time that chlorine is being used up by compounds in the
water, some of the chlorine reacts with the water itself. The reaction
depends on what type of chlorine is added to the water as well as on the
the pH of the water itself.
Chlorine may be added as to water in the form of chlorine gas,
hypochlorite, or chlorine dioxide. All types of chlorine will kill bacteria
and some viruses, but only chlorine dioxide will effectively kill
Cryptosporidium, Giardia, protozoans, and some viruses. We will first
consider chlorine gas, which is the most pure form of chlorine, consisting
of two chlorine atoms bound together.
Chlorine gas is compressed into a liquid and stored in metal
cylinders. The gas is difficult to handle since it is toxic, heavy, corrosive,
and an irritant. At high concentrations, chlorine gas can even be fatal.
When chlorine gas enters the water, the following reaction occurs:
Chlorine + Water Hypochlorous Acid + Hydrochloric Acid
Cl2 + H2O HOCl + HCl
The chlorine reacts with water and breaks down into hypochlorous acid
and hydrochloric acid. Hypochlorous acid may further break down,
depending on pH:
Hypochlorous Acid ↔ Hydrogen Ion + Hypochlorite Ion
HOCl ↔ H+ + OCl-
Note the double-sided arrows which mean that the reaction is
reversible. Hypochlorous acid may break down into a hydrogen ion and a
hypochlorite ion, or a hydrogen ion and a hypochlorite ion may join
together to form hypochlorous acid.
The concentration of hypochlorous acid and hypochlorite ions in
chlorinated water will depend on the water's pH. A higher pH facilitates
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Chlorination, chloramines and breakpoint
the formation of more hypochlorite ions and results in less hypochlorous
acid in the water. This is an important reaction to understand because
hypochlorous acid is the most effective form of free chlorine residual,
meaning that it is chlorine available to kill microorganisms in the
water. Hypochlorite ions are much less efficient disinfectants. So
disinfection is more efficient at a low pH (with large quantities of
hypochlorous acid in the water) than at a high pH (with large quantities of
hypochlorite ions in the water.)
Hypochlorites
Instead of using chlorine gas, some plants apply chlorine to water as a
hypochlorite, also known as a bleach. Hypochlorites are less pure than
chlorine gas, which means that they are also less dangerous. However,
they have the major disadvantage that they decompose in strength over
time while in storage. Temperature, light, and physical energy can all
break down hypochlorites before they are able to react with pathogens in
water.
There are three types of hypochlorites - sodium hypochlorite, calcium
hypochlorite, and commercial bleach:
• Sodium hypochlorite (NaOCl) comes in a liquid form which
contains up to 12% chlorine.
• Calcium hypochlorite (Ca(OCl)2), also known as HTH, is a solid
which is mixed with water to form a hypochlorite
solution. Calcium hypochlorite is 65-70% concentrated.
• Commercial bleach is the bleach which you buy in a grocery
store. The concentration of commercial bleach varies depending on
the brand - Chlorox bleach is 5% chlorine while some other brands
are 3.5% concentrated.
Hypochlorites and bleaches work in the same general manner as chlorine
gas. They react with water and form the disinfectant hypochlorous
acid. The reactions of sodium hypochlorite and calcium hypochlorite
with water are shown below:
Calcium hypochlorite + Water Hypochlorous Acid + Calcium
Hydroxide
Ca(OCl)2 + 2 H2O 2 HOCl + Ca(OH)2
Sodium hypochlorite + Water Hypochlorous Acid + Sodium Hydroxide
NaOCl + H2O HOCl + NaOH
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Chlorination, chloramines and breakpoint
In general, disinfection using chlorine gas and hypochlorites occurs in the
same manner. The differences lie in how the chlorine is fed into the
water and on handling and storage of the chlorine compounds. In
addition, the amount of each type of chlorine added to water will vary
since each compound has a different concentration of chlorine.
Effect of pH on Chlorine
The pH of water has a definite effect on the efficiency of chlorine as well
as on the corrosive properties of water (covered later in this chapter.) For
now, we will consider only the effect of pH on sanitation.
It can be seen in Table 2.a that free chlorine is most efficient in pH ranges
below the ideal range of 7.2-7.6. Some pool operators do, however,
maintain pH levels higher than the ideal range. They should also maintain
appropriately higher FAC levels to provide the same concentration of the
active HOCL for.
For example, at a pH of 8.0, 21% (about 1/5 of the FAC is in the active
form. At that pH level, it would take 2.5 ppm of FAC to provide about
0.5 ppm of HOCI. At a pH of 7.5, about 1/2 (50%) of the FAC is in the
active HOCI form. At that pH level, it would take only 1.0 ppm of FAC
to provide the same 0.5 ppm of HOCI. For this reason, many authorities
recommend that the pH of pools be maintained in the range between 7.2
and 7.6 and as close to 7.5 as practical. These conditions are also
considered to be most comfortable for the swimmers' eyes and skin.
HOCI H* OCI-
Hypochlorous Acid
Hypochlorite Ion
Killing Agent
Hydrogen Ion
Inactive, but stable form
Active, but unstable form
% Chlorine as HOCI pH % Chlorine as OCI-
90 6.5 10
73 7.0 27
66 7.2 34
45 7.6 55
21 8.0 79
10 8.5 90
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Chlorination, chloramines and breakpoint
Chloramines
Some plants use chloramines rather than hypochlorous acid to disinfect
the water. To produce chloramines, first chlorine gas or hypochlorite is
added to the water to produce hypochlorous acid. Then ammonia is
added to the water to react with the hypochlorous acid and produce a
chloramine.
Three types of chloramines can be formed in water - monochloramine,
dichloramine, and trichloramine. Monochloramine is formed from the
reaction of hypochlorous acid with ammonia:
Ammonia + Hypochlorous Acid Monochloramine + Water
NH3 + HOCl NH2Cl + H2O
Monochloramine may then react with more hypochlorous acid to form a
dichloramine:
Monochloramine + Hypochlorous Acid Dichloramine + Water
NH2Cl + HOCl NHCl2 + H2O
Finally, the dichloramine may react with hypochlorous acid to form a
trichloramine:
Dichloramine + Hypochlorous Acid Trichloramine + Water
NHCl2 + HOCl NCl3 + H2O
The number of these reactions which will take place in any given
situation depends on the pH of the water. In most cases, both
monochloramines and dichloramines are formed. Monochloramines and
dichloramines can both be used as a disinfecting agent, called a
combined chlorine residual because the chlorine is combined with
nitrogen. This is in contrast to the free chlorine residual of hypochlorous
acid which is used in other types of chlorination.
Chloramines are weaker than chlorine, but are more stable, so they are
often used as the disinfectant in the distribution lines of water treatment
systems. Despite their stability, chloramines can be broken down by
bacteria, heat, and light. Chloramines are effective at killing bacteria and
will also kill some protozoans, but they are very ineffective at killing
viruses.
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Chlorination, chloramines and breakpoint
Breakpoint Chlorination
The graph below shows what happens when chlorine (either chlorine gas
or a hypochlorite) is added to water. First (between points 1 and 2), the
water reacts with reducing compounds in the water, such as hydrogen
sulfide. These compounds use up the chlorine, producing no chlorine
residual.
Next, between points 2 and 3, the chlorine reacts with organics and
ammonia naturally found in the water. Some combined chlorine residual
is formed - chloramines. Note that if chloramines were to be used as the
disinfecting agent, more ammonia would be added to the water to react
with the chlorine. The process would be stopped at point 3. Using
chloramine as the disinfecting agent results in little trihalomethane
production but causes taste and odor problems since chloramines
typically give a "swimming pool" odor to water.
In contrast, if hypochlorous acid is to be used as the chlorine residual,
then chlorine will be added past point 3. Between points 3 and 4, the
chlorine will break down most of the chloramines in the water, actually
lowering the chlorine residual.
Finally, the water reaches the breakpoint, shown at point 4. The
breakpoint is the point at which the chlorine demand has been totally
satisfied - the chlorine has reacted with all reducing agents, organics, and
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Chlorination, chloramines and breakpoint
ammonia in the water. When more chlorine is added past the breakpoint,
the chlorine reacts with water and forms hypochlorous acid in direct
proportion to the amount of chlorine added. This process, known as
breakpoint chlorination, is the most common form of chlorination, in
which enough chlorine is added to the water to bring it past the
breakpoint and to create some free chlorine residual.
Chlorine Dioxide
There is one other form of chlorine which can be used for disinfection -
chlorine dioxide. We have not discussed chlorine dioxide previously
because it disinfects using neither hypochlorous acid nor chloramines and
is not part of the breakpoint chlorination process.
Chlorine dioxide, ClO2, is a very effective form of chlorination since it
will kill protozoans, Cryptosporidium, Giardia, and viruses that other
systems may not kill. In addition, chlorine dioxide oxidizes all metals
and organic matter, converting the organic matter to carbon dioxide and
water. Chlorine dioxide can be used to remove sulfide compounds and
phenolic tastes and odors. When chlorine dioxide is used,
trihalomethanes are not formed and the chlorination process is unaffected
by ammonia. Finally, chlorine dioxide is effective at a higher pH than
other forms of chlorination.
So why isn't chlorine dioxide used in all systems? Chlorine dioxide must
be generated on site, which is a very costly process requiring a great deal
of technical expertise. Unlike chlorine gas, chlorine dioxide is highly
combustible and care must be taken when handling the chlorine dioxide.
Efficiency
Residual and Dosage
A variety of factors can influence disinfection efficiency when using breakpoint chlorination
or chloramines. One of the most important of these is the concentration of chlorine residual
in the water.
The chlorine residual in the clearwell should be at least 0.5 mg/L. This
residual, consisting of hypochlorous acid and/or chloramines, must kill
microorganisms already present in the water and must also kill any
pathogens which may enter the distribution system through cross-
connections or leakage. In order to ensure that the water is free of
microorganisms when it reaches the customer, the chlorine residual
should be about 0.2 mg/L at the extreme ends of the distribution
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Chlorination, chloramines and breakpoint
system. This residual in the distribution system will also act to control
microorganisms in the distribution system which produce slimes, tastes,
or odors.
Determining the correct dosage of chlorine to add to water will depend on
the quantity and type of substances in the water creating a chlorine
demand. The chlorine dose is calculated as follows:
Chlorine Dose = Chlorine Demand + Chlorine Residual
So, if the required chlorine residual is 0.5 mg/L and the chlorine demand is known to be 2
mg/L, then 2.5 mg/L of chlorine will have to be added to treat the water.
The chlorine demand will typically vary over time as the characteristics of the water
change. By testing the chlorine residual, the operator can determine whether a sufficient dose
of chlorine is being added to treat the water. In a large system, chlorine must be sampled
every two hours at the plant and at various points in the distribution system.
It is also important to understand the breakpoint curve when changing chlorine dosages. If
the water smells strongly of chlorine, it may not mean that too much chlorine is being
added. More likely, chloramines are being produced, and more chlorine needs to be added to
pass the breakpoint.
Contact Time
Contact time is just as important as the chlorine residual in determining
the efficiency of chlorination. Contact time is the amount of time which
the chlorine has to react with the microorganisms in the water, which will
equal the time between the moment when chlorine is added to the water
and the moment when that water is used by the customer. The longer the
contact time, the more efficient the disinfection process is. When using
chlorine for disinfection a minimum contact time of 30 minutes is
required for adequate disinfection.
The CT value is used as a measurement of the degree of pathogen
inactivation due to chlorination. The CT value is calculated as follows:
CT = (Chlorine residual, mg/L) (Contact time, minutes)
The CT is the Concentration multiplied by the Time. As the formula
suggests, a reduced chlorine residual can still provide adequate kill of
microorganisms if a long contact time is provided. Conversely, a smaller
chlorine residual can be used as long as the chlorine has a longer contact
time to kill the pathogens.
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Chlorination, chloramines and breakpoint
Other Influencing Factors
Within the disinfection process, efficiency is influenced by the chlorine residual, the type of
chemical used for chlorination, the contact time, the initial mixing of chlorine into the water,
and the location of chlorination within the treatment process. The most efficient process will
have a high chlorine residual, a long contact time, and thorough mixing.
Characteristics of the water will also affect efficiency of chlorination. As you will recall, at a
high pH, the hypochlorous acid becomes dissociated into the ineffective hypochlorite ion. So
lower pH values result in more efficient disinfection.
Temperature influences chlorination just as it does any other chemical reaction. Warmer
water can be treated more efficiently since the reactions occur more quickly. At a lower
water temperature, longer contact times or higher concentrations of chemicals must be used to
ensure adequate disinfection.
Turbidity of the water influences disinfection primarily through
influencing the chlorine demand. Turbid water tends to contain particles
which react with chlorine, reducing the concentration of chlorine residual
which is formed. Since the turbidity of the water depends to a large
extent on upstream processes (coagulation, flocculation, sedimentation,
and filtration), changes in these upstream processes will influence the
efficiency of chlorination. Turbidity is also influenced by the source
water - groundwater turbidity tends to change slowly or not at all while
the chlorine demand of surface water can change continuously, especially
during storms and the snow melt season.
Finally, and most intuitively, the number and type of microorganisms in
the water will influence chlorination efficiency. Since cyst-forming
microorganisms and viruses are very difficult to kill using chlorination,
the disinfection process will be less efficient if these pathogens are found
in the water.
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Chlorination, chloramines and breakpoint
The breakpoint experiment
First by iodometry (thiosulphate) method
1 chlorine solution
Prepared from a source of chlorine such as calcium hypochlorite Ca(OCl)2
Take little amount of Ca(OCl)2 and dissolve it in appropriate amount of distillated
water and let it to precipitate and take the clear solution .
2) Sodium thiosulphate Na2S2O3 0.1 N , 0.025 N .
3) Potassium dichromate K2Cr2O7 0.1 N
4)potassium iodide KI 5% or crystals .
5) Starch indicator (1 g in 100 ml distillated water ).
Procedure :
i) Standardize thiosulphate by dichromate as the following :
Add 10 ml of dichromate in conical flask , 5 ml KI 5% or about 1 gm KI crystals ,
,30 ml distillated water ,2 ml conc. sulfuric acid , wait about 1-3 minutes (optionally)
titrate with thiosulphate until yellow color begin to pale add 1 ml starch and
complete until blue color disappear .
ii) standardize chlorine solution to strength 1 g/L. by the same way above replacing
dichromate with chlorine solution
in the manner of 1ml = 1 mg Cl.
iii) take about 10 conical flasks , fill it with 500 ml raw water and the doses of
chlorine as the following :
Close the conical flasks with plaster and place it in dark place for the staying time of
water in precipitation pool as calculated from equation :
Staying time= Volume of precipitation pool / rate of pumped water
Shake the flasks each 30 minutes distribute the dose in the entire volume
After the time ends titrate each conical flask with thiosulphate as the following :
Add 2 ml conc. sulfuric acid , 5 ml 5% KI to each flask, titrate with thiosulphate
until pale yellow then add 1 ml starch complete titration until blue color disappears
Calculation :
(NV)S2O3=(N`V`)Cl
N`=0.025*VS2O3 /500 …………….(1)
Strength for Cl =N`*Eq.Wt
= 0.025* VS2O3*35.5 /500 g/L
=0.025* VS2O3*35.5*1000 /500 mg/L
Res Cl = VS2O3 *1.775 mg/L
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Chlorination, chloramines and breakpoint
Record your data in table like this :
Series The dose of VS2O3 mL Res Cl = VS2O3*1.775
Cl mg/l Taken in titration mg/L
1
2
3
4
5
6
7
8
9
10
Draw a plot between the doses of Cl against the Res.Cl such as:
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Chlorination, chloramines and breakpoint
Note :
Sometimes breakpoint curve appear as
The first part of curve Res Cl appear as chloramines so if ammonia present in a trace
amount the formation of chloramines decrease and one imagine the curve like straight
line but the fact that break point greater than the chloramine products and the point
that the curve incline not be clear .
In the same day of drawing the breakpoint curve showed above the chloramines
determined and the data was:
NH2Cl = 0.25 mg/L
NHCl2 =0.11 mg/L
NCl3 =0.6 mg/L
Whereas the Res.Cl at the breakpoint equals to 2.5 mg/L so the curve must appear in
the way that we show above.
Thanks very mach
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[email protected]
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