CE 121

Chlorination
Chlorine Breakpoint
Chlorination
Chlorination of wastewater is the application of chlorine to
a wastewater to accomplish some definite purpose.  The
purpose of chlorination may not always be disinfection
and may, in fact, involve odor control or some other
objective which will be noted.  Chlorine may be applied in
two general ways, gaseous and liquid.  In general, the
effective chemical form of chlorine that either destroys the
microbe or acts against odor, etc., is the same. Gaseous
forms of chlorine are generally first dissolved in water prior
to addition to the wastewater stream, while liquid forms of
chlorine (called hypochlorites) are sold in the form of
water soluble salts.
Reactions of Chlorine in Wastewaters
In order to determine at what points in the treatment process, and how
much chlorine should be applied to accomplish the purpose desired, it
is necessary to know what reactions occur when chlorine is mixed with
a wastewater.  When chlorine is mixed with pure water, it immediately
dissolves, forming first hypochlorous acid and then hypochlorites: 
The forms of chlorine (hypochlorous acid and
hypochlorite ion) are called "free" residual chlorine, as
opposed to the reaction products of chlorine with other
compounds that can also be detected using analytical
techniques that are called "combined" residual chlorine. 
 Free residual chlorine is a more effective disinfecting
agent than combined residual chlorine, and generally
hypochlorous acid is a much more effective disinfectant
than hypochlorite ion.  In wastewaters, free residual
chlorine is seldom detected and chlorine is usually found
in the "combined" residual form.
Chlorine is a extremely active chemical it will react to
many substances in waste waters even in a small amount
is added to wastewater it will react rapidly.
The quantity of reducing substances, both organic and inorganic, in
wastewaters, varies, so that the amount of chlorine that has to be added
to wastewater for different purposes will also vary.  The chlorine used by
these organic and inorganic reducing substances is defined as the
chlorine demand.  Chlorine demand is equal to the amount of chlorine
added minus that remaining as combined chlorine after a period of time,
which is generally 15 minutes.  This relationship can be written as: 

Chlorine Demand  =  (Applied Chlorine Dose)  -  (Chlorine Residual)  

It is important to note that disinfection is carried out by that amount of

chlorine remaining after the chlorine demand has been satisfied.  This
quantity of chlorine in excess of the chlorine demand is defined as residual
chlorine and expressed as milligrams per liter.
Theoretically, while microorganisms are killed as the
chlorine demand is being satisfied, disinfection is
generally the result of chlorine residual or the amount
of chlorine remaining after the chlorine demand has
been satisfied.
Chlorine is seldom applied to wastewaters to reach
"breakpoint" levels.  This is because the amount of
chlorine required prior to observing free available
chlorine would be very high (approximately 150
mg/L).  Generally chlorine is applied only to give a
combined residual. 
Purpose of Chlorination
Disinfection 

Chlorine is a very effective disinfecting agent and has been the

agent of choice in reducing bacterial numbers in wastewater
effluents.  As noted, neither primary nor secondary methods of
wastewater treatment can completely eliminate pathogenic
bacteria which are always potentially present.  When
wastewaters or treated effluents are discharged to bodies of water
which are, or may be used as a source of public water supply, or
for recreational purposes, treatment or disinfection for the
destruction of pathogenic organisms is required to minimize the
health hazards of pollution to these receiving waters. 
Chlorine Dioxide
Chlorine dioxide is a chemical compound with the formula ClO2. This
yellowish-green gas crystallizes as orange crystals at −59 °C. As one of
several oxides of chlorine, it is a potent and useful oxidizing agent used in
water treatment and in bleaching.
Dechlorination
At times it is necessary to dechlorinate, or remove
chlorine from a wastewater by the addition of
dechlorinating agents.  Generally this must be done to
counteract the reactive effects of chlorine in effluent
samples, for example, in determining coliforms or
BOD's.  At present only a small number of treatment
plants in New York State dechlorinate, however, in the
future it may become a more common practice to
dechlorinate treated wastewater. 
Chlorine Breakpoint
The point at which the chlorine dosage in a water treatment
process has satisfied the Chlorine Demand. To eliminate the
taste and odor associated with processed water, sufficient
chlorine must be added to reach the breakpoint. Increasing the
chlorine dose beyond the breakpoint produces a free chlorine
residual, which is free to kill microorganisms. When chlorine is
added to water, it first combines with constituents in the water
such as iron, manganese, and nitrites. It is important to add
enough chlorine to the water initially to ensure that these
constituents are oxidized and to ensure that a residual is formed
to react with the ammonia and organic matter in the water. Taste
and odor problems result when chlorine dosages are either below
the breakpoint, or well beyond the breakpoint.
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.  
Is Chlorine Dangerous?
Chlorine used to disinfect swimming pools is widely recognized as a
health hazard. New research suggests that children who swim frequently
in chlorinated pools may have increased risks of developing allergies or
asthma. Among adults exposure to chlorine in swimming pools has been
linked with other health problems including bladder and rectal cancer
and, possibly, an increased risk for coronary heart disease.
Next is Chemical Equations….