DRINKING WATER CHLORINATION

Index

1. Introduction 3
1.1 Water for human consumption 3
2. Chlorination 7
2.1. Chlorine and its by-products 7
2.2. Chlorine chemistry 7
2.3. Chlorine demand 10
2.4. Chlorination: dose and contact 12
2.5. Analytical methodology 14
2.6. Determination of continuous chlorine 16
2.6.1 Colorimetry 16
2.6.2 Amperometry 17
2.7. Chlorination protocol 19
3. Chlorination equipment 20
3.1. Pre-chlorination 22
3.2. Storage- maintenance 23
3.3. Post-chlorination 25
1. INTRODUCTION

Drinking water is a necessary but limited resource. In spite of the fact that water
is the most abundant and common substance on earth – it covers 71% of its
surface -, 97.3% of it is contained in the oceans. Of the 2.7% remaining water,
about 2.1% is located in the polar caps and in glaciers, and only 0.61% is liquid
fresh water. Of this, about 0.60% is to be found in the underground aquifers
layers, difficult to reach, and only a 0.009% represents surface fresh water
(rivers and lakes). Furthermore, only a 0.003% of the total is fresh water
available for home use. That means that, if the total amount of water on Earth
were a 100 litre container, only half a tea-spoonful water would be available for
human consumption.

Water volume in Total water

Water source
cubic kilometres percentage
Oceans 1,321,000,000 97.24%
Ice layers, glaciers 29,200,000 2.14%
Underground water 8,340,000 0.61%
Fresh water lakes 125,000 0.009%
Inland seas 104,000 0.008%
Soil humidity 66,700 0.005%
Atmosphere 12,900 0.001%
Rivers 1,250 0.0001%
Total water volume 1,360,000,000 100%
Source: Nace, U.S. Geological Survey, 1967 and
The Hydrological Cycle (leaflet), U.S. Geological Survey, 1984

From the above it can be deducted that drinking water is a very valuable and
limited resource, and that it must be consumed and managed carefully. It is of
the utmost importance to reduce its consumption and to try as far as possible to
reuse it.

1.1 WATER FOR HUMAN CONSUMPTION

Water supply to the population can be done from two well differentiated
sources:

 Surface waters: lakes, rivers, reservoirs… They are exposed to

the environment and therefore they are liable to be polluted. For
this reason it is necessary to have an in-depth processing before
they are suitable for human consumption. This is usually carried
out by the agencies in charge of operating the water resources.

3
  Underground waters: wells, springs… These are more difficult
sources to exploit, as they are not as accessible as surface
waters. Their origin is surface water which reaches the aquifer by
natural filtration through the several earth layers. This system of
natural filtration allows the purification of water to take place.
However, in order to be considered drinking water, it must meet
certain physical, chemical and microbiological conditions. Besides,
on the long term the aquifer layers may also become polluted and
because of this often it is necessary to process these waters
(even if not so intensively as in the case of surface waters).

The pollution sources of water may be natural (rain, rotten vegetable material,
soil erosion…) or man-made (cattle farming, sub-products of industrial activity,
home waste…), but both give as a result water which does not comply with the
necessary requirements to be considered drinking water.

The basic processes in the treatment of water involve several stages:

coagulation, flocculation, particle separation (sedimentation/floatation), filtration
and disinfection (chlorination/ozonisation). In several of these stages chemical
products are added to the water flow to be treated, and it is at this point that
ITC, S.L. can help you to do the correct dosage and control with its wide range
of pumps and components.

In the case of waters whose quality has been checked and found to be apt for
human consumption, such as many underground waters, and some surface
waters which comply with Annex II of Ministerial Order of 11 May 1998 of the
Spanish Government, on basic quality features which must be present in the
running surface waters meant for the production of drinking water, in order to be
classified as Type A1, their processing before human consumption consists of a
simple physical treatment (such as filtration) followed by a disinfection process.
In the case of Type A2, it is necessary to carry out a normal physical treatment,
a chemical treatment and disinfection. For Type A3 it is necessary to make
intensive physical and chemical treatments, followed by refining and
disinfection.

4
 ANNEX II
Parameter Unit Type A1 Type A2 Type A3
pH - (6.5-8.5) (5.5-9.0) (5.5-9.0)
Colour Pt scale 20 100 200
Suspended solids mg/l (25) - -
Temperature ºC 25 25 25
Conductivity (20ºC) S/cm (1000) (1000) (1000)
Nitrates (*) mg/l NO3- 50 50 50
Fluoride mg/l F 1.5 (1.7) (1.7)
Dissolved iron mg/l Fe 0.3 2 (1)
Manganese mg/l Mn (0.05) (0.1) (1)
Copper mg/l Cu 0.05 (0.05) (1)
Zinc mg/l Zn 3 5 5
Boron mg/l B (1) (1) (1)
Arsenic mg/l As 0.05 0.05 0.1
Cadmium mg/l Cd 0.005 0.005 0.005
Total chromium mg/l Cr 0.05 0.05 0.05
Lead mg/l Pb 0.05 0.05 0.05
Selenium mg/l Se 0.01 0.01 0.01
Mercury mg/l Hg 0.001 0.001 0.001
Barium mg/l Ba 0.1 1 1
Cyanides mg/l CN- 0.05 0.05 0.05
Sulphate (**) mg/l SO42- 250 250 250
Chloride (**) mg/l Cl (200) (200) (200)
Surfactants mg/l (0.2) (0.2) (0.5)
laurylsulfate
Phosphate (*) mg/l P2O5 (0.4) (0.7) (0.7)
Phenols mg/l phenol 0.001 0.005 0.1
Dissolved or emulsified mg/l 0.05 0.2 1
hydrocarbons
(after extraction in petroleum ether) 0.001
PAH mg/l 0.0002 0.0002 0.005
Total pesticides mg/l 0.001 0.0025 (30)
COD mg/l O2 - - (30)
Dissolved oxygen % saturation (70) (50) (7)
BOD5 mg/l O2 (3) (5) (3)
Kjeldahl nitrogen mg/l N (1) (2) 4
Ammonia mg/l NH4+ (0.05) 1.5 (0.5)
Chloroform extractable mg/l dry (0.1) (0.2)
substances (50000)
Total Coliforms (37ºC) u/100ml (50) (5000) (20000)
Faecal Coliforms u/100ml (20) (2000) (10000)
Faecal Streptococci u/100ml (20) (1000) -
Salmonellae - None in None in
5l 1l
(*) In shallow lakes which renovate slowly
(**)Unless more appropriate waters are available for consumption.
Figures in parentheses are to be considered indicative desirable provisional values.

5
Of all the treatments we have mentioned above, in this document we shall
consider disinfection only. In this process the aim is to destroy or make inactive
the pathogens which are to be found in water, mainly bacteria, viruses and
protozoa. In the case of water of Type A2 or Type A3, these pathogens are
eliminated mainly in the process of the physicochemical treatments, but still
they are not sufficient to ensure the total harmlessness of water.

The disinfection treatments may be physical (gamma rays, X-rays, UV rays,

heat sterilization, etc.) or chemical (heavy metals, acids or alkalis, halogens,
ozone, permanganate, etc.); the chemical means being the most used ones.
Among the chemical reagents, chlorine and its by-products are the most used
disinfection agents the world over, and therefore we shall study them more in-
depth.

The values of residual chlorine are controlled by several bodies, and depend on
the final destination of water. Therefore, the recommendation for drinking water
is that the free residual chlorine be between 0.5 and 1 ppm, while in the case of
swimming pools and spas it should be kept between 1.5 – 3.0 ppm. However,
these values are in general, and each competent body determines its own. In
the case of the Generalitat de Catalunya it is specified that the value of residual
chlorine must be between 0.2 and 0.6 ppm in all the stages of the distribution
network.

6
2. CHLORINATION

2.1 CHLORINE AND ITS BY-PRODUCTS

The use of chlorine as a disinfection agent started at the beginning of the 20th
century and became the finishing process of filtration, which was already being
widely used. The chlorine by-products most regularly used for the disinfection of
water are: gaseous chlorine, sodium hypochlorite, calcium hypochlorite.

Chlorine (Cl2) is a poisonous gas, heavier than air, yellowish green in colour. It
is a very oxidizing product which reacts with quite a number of compounds. In
the presence of humidity it is extremely corrosive, and for this reason the pipes
and the materials in contact with it must be made up of special alloys. The
chlorine vapours are irritating when inhaled and may cause serious injury to
those exposed to high concentrations of the vapours. Therefore chlorine must
be handled by specialized personnel and it is necessary to have very effective
control and alarm systems. For this reason it is advisable to use hypochlorites in
solution or in solid form.

Sodium hypochlorite (NaClO) in solution is a disinfectant used since the 18th

century, and is popularly known as bleach. Industrially, it is obtained through the
reaction of gaseous chlorine with a solution of sodium hydroxide. After the
reaction, aqueous solutions of a greenish yellow colour are obtained, which
have a given concentration of active chlorine per litre. It is sold in dissolutions
with a 3 to 15% concentration in weight. Sodium hypochlorite is a very powerful
and unstable oxidizing agent. So much so, that a solution of 100 grams of active
chlorine per litre, after having been stored for three months, may contain 90
grams or even less.

Calcium hypochlorite (Ca(ClO)2) is a white solid with contents of 20 to 70%

active chlorine. It is highly corrosive and may catch fire when in contact with
some acid materials. However, it shows two advantages with respect to sodium
hypochlorite: a higher chlorine contents and a greater stability. To use it, it is
diluted in water to obtain a solution with an easier to handle concentration, for
example 2%.

2.2 CHLORINE CHEMISTRY

When Cl2 is dissolved in water, it rapidly hydrolyses and produces hypochlorous

acid and hydrochloric acid.

Cl2 + H2O HClO + HCl

In the case of hypochlorites, there is a dissociation of both salts as per the

following equations:

7
 NaClO + H2O NaOH + HClO
Ca(ClO)2 + 2H2O Ca(OH)2 + 2HClO
So, in any of the cases: chlorine, sodium hypochlorite and calcium hypochlorite,
finally hypochlorous acid is produced, which is actually the disinfecting agent.
However, this is dissociated according to the following equilibrium:

HClO H+ + ClO-

This equilibrium is ruled by the following constant:

Ka 
H ClO 
 

HClO
Whose approximate value is 3.2 ·10-8.

If we carry out the minus logarithm of the expression:

 
 log K a   log H   log
ClO 


HClO 
Taking into account that –logX is known as pX, the expression will be:

pK a  pH  log
ClO  

HClO 
In the following graph the distribution of each one of the species according to
their pH can be observed.

100
90
80
70
60
50 % HClO
%

40 %ClO-
30
20
10
0
4 5 6 7 8 9 10 11
pH

8
In the graph it can be clearly observed that between pH 6 and pH 9 both agents
co-exist, while with pH values below 6 and above 9 it is considered that only
one agent exists. With a pH value equal to the pKa of the hypochlorous acid
(pKa ≈ 7.5), we can observe that the HClO and ClO- concentrations are the
same, which can be easily deducted from the previous expression.

The hypochlorous acid is a much more effective disinfectant than the

hypochlorite ion. This might be related to the lack of charge in the hypochlorous
acid molecule. Since it is a neutral molecule, it would be easier for it to
penetrate the bacterial wall, and therefore to have a germicide activity. Under
the circumstances, and taking into account what we have seen up to now, it is
easy to understand the different activity of hypochlorite as a germicide agent in
the presence of different pH values. So with a pH below 7.5 the amount of
hypochlorite needed to disinfect water is much lower than the amount needed to
disinfect that same water with a pH above 7.5.

Besides its application as a disinfectant, chlorine and its by-products have been
found useful also for:

- Control of odours and tastes

- Prevention of algae growth
- Iron and manganese removal
- Destruction of hydrosulphuric acid
- Elimination of organic dyes
- Improvement of coagulation through silica

In the following table we show briefly some of these uses and their typical
doses.

Application Dose Optimum Reaction Effectiveness

pH time
Iron 0.62 mg/mg 7.0 < 1h Good
Fe
Manganese 0.77 mg/mg 7-8 1-3 h Slow kinetics
Mn 9.5 minutes

Biological 1-2 mg/l 6-8 Good

growth

Odour/taste Variable 6-8 Variable Variable

Colour removal Variable 4-6.8 Minutes Good

Zebra mussels 2-5 mg/l Shock level Good

0.2-0.5 mg/l Residual level

Asiatic clams 0.3-0.5 mg/l Continuous Good

9
One of the drawbacks in the use of chlorine and its by-products is that it reacts
with a lot of organic matter, thus producing trihalomethanes (THM), many of
which have been shown to be toxic or carcinogens. Another drawback is the
production of chlorophenols in waters which contain phenols, which would give
rise to bad smells.

Chlorine reacts also with ammonia dissolved in water, thus producing

chloramines. These products have also a certain disinfecting power, even if
about 25 times less effective than free chlorine. However, their permanence in
water is long and sometimes they have been used as a reserve of residual
chlorine. They have two great drawbacks: they may give rise to smells and
tastes, and they are chronically potentially toxic.

NH4+ + HClO NH2Cl + H2O + H+

monochloramine

NH2Cl+ HClO NHCl2 + H2O

dichloramine

NHCl2+ HClO NCl3 + H2O + H+

trichloramine

Another chlorine by-product, which is used for disinfection, is the chlorine

dioxide (ClO2). It is as effective as the chlorine/hypochlorite, and not so
sensitive to the changes of pH as far as its disinfecting activity is concerned.
Besides, it does not combine with ammonia or with much organic matter, which
prevents chloramines and other by-products with unpleasant tastes and smells
to appear. However, it is a gas ten times more toxic than chlorine gas, and is
explosive in the air in concentrations of 8-12%. Also, as a reagent it gives rise to
chlorite, whose threat to human health is uncertain.

2.3 CHLORINE DEMAND

From all the above it can be deducted that chlorine (and its by-products),
besides reacting with micro-organisms, it does so also with other products
dissolved in the medium: organic matter, iron, manganese,… For this reason, in
order to have a given level of residual chlorine, the amount which must be
added is quite higher than the residual value obtained.

For all these reasons, before deciding the dose of chlorine to be used for
disinfection, the chlorine demand must be determined, that is the amount of
chlorine which is consumed before the residual value appears.

In the following figure we show the variation of the residual chlorine in terms of
the added chlorine for a general hypothetical case:

10
  In the first stage, the oxidation of reducing substances, mainly inorganic
ones, takes place: Fe2+, Mn2+, H2S,… All the hypochlorite added is
consumed, whereby there is no available chlorine.
 After these substances have been destroyed, a stage would start in
which chlorinated compounds would form, mainly chloramines, which
would act as residual chlorine, thereby granting a certain disinfecting
character to the system.

2+
Reducers removal: Fe ,
2+
Mn , H2S,... Chloramines formation Chloramines destruction Free chlorine

ppm combined chlorine

Residual chlorine (mg/l)

ppm free chlorine

ppm residual chlorine

Breakpoint

Chlorine added (mg/l)

 When all the ammonia and the organic amines have reacted with the
chlorine, after the curve reaches its maximum, there starts a stage of
destruction of these chlorinated compounds produced in the previous
stage. Even if more chlorine is added, no increase in the amount of
available chlorine is observed, but a decrease instead, because both the
existing residual chlorine and the added hypochlorite are consumed. In
the following equation this effect can be observed:

2 NH2Cl + HClO N2 + H2O + 3 HCl

Therefore, in this stage the disinfecting capacity of the system is

reduced.

 After the breakpoint all the added chlorine stays as free chlorine.
Therefore, it is considered that from this point on both the disinfection
and the elimination of organic matter oxidable through the chlorine, have
taken place and the water has a certain value of free residual chlorine.

The chlorine demand is the difference existing between the amount of chlorine
applied to water and that of free available chlorine. Therefore, it can be

11
considered that the chlorine demand approximately fits the dose where the
breakpoint is reached.

Free residual chlorine may appear as Cl2, HClO and/or ClO-, depending on the
working pH, and therefore it corresponds to the sum of these three compounds.

2.4 CHLORINATION DOSE AND CONTACT

Following all the above, we have already the bases to discuss more in-depth
which parameters allow us to decide when water has been correctly treated. As
we have seen, chlorination is right whenever we find values of residual chlorine
above those of the breakpoint (they meet approximately the values of the free
residual chlorine). The quantities of free chlorine recommended by the pertinent
bodies for drinking water are between 0.5 and 1.0 ppm, and between 1.5 and
3.0 ppm for swimming pools.

However, it is free chlorine, that is to say, this quantity is not the added chlorine,
since a part of it has been consumed by substances which are present in water
(chlorine demand).

Up to now we have not taken into consideration at all the reaction speed of
chlorine (hypochlorite) with micro-organisms. In this respect it is necessary to
define the Ct concept, which is the product of the concentration of hypochlorite
available (i.e. free chlorine) by the contact time between chlorine and the micro-
organisms, in order to ensure the desired disinfection. The Ct value depends on
the relevant micro-organism and the water temperature. Besides, as we have
seen before, the activity of hypochlorite is highly influenced by pH, this means
that, in terms of disinfection, it is not the same to have 5 ppm with pH 7 than to
have them with pH 8. For this reason, Ct depends also on the water pH. In the
following table we show an example of Ct. It can be observed that these values
depend also on the concentration of available chlorine.

The Ct product is stated as mg·min/l, which means it has dimensions of

concentration per time.

12
 Giardia Cysts inactivation at 20ºC
Chlorine
concentration pH 6.5 pH 7.5 pH 8.5
(mg/l)
90% 99% 99.9% 90% 99% 99.9% 90% 99% 99.9%
0.6 15 30 45 21 43 64 31 61 92
1.0 16 31 47 22 45 67 33 65 98
1.4 16 33 49 23 47 70 34 69 103
1.8 17 34 51 25 49 74 36 72 108
2.2 18 35 53 26 51 77 38 75 113
2.6 18 37 55 27 53 80 39 78 117
3.0 19 38 57 28 55 83 41 81 122

Example 1
Water at 20ºC
pH 7.5
99% inactivation
Dose to be used 1 mg/l

Giardia Cysts inactivation at 20ºC

Chlorine pH 6.5 pH 7.5 pH 8.5
concentration
(mg/l)
90% 99% 99.9% 90% 99% 99.9% 90% 99% 99.9%
0.6 15 30 45 21 43 64 31 61 92
1.0 16 31 47 22 45 67 33 65 98
1.4 16 33 49 23 47 70 34 69 103
1.8 17 34 51 25 49 74 36 72 108
2.2 18 35 53 26 51 77 38 75 113
2.6 18 37 55 27 53 80 39 78 117
3.0 19 38 57 28 55 83 41 81 122

So, the Ct = 45 mg·min/l

13
Therefore, the contact time recommended is obtained by dividing this value by
the concentration

tcontact = 45/1 = 45 min.

Example 2

We must treat the same water as in the previous example, but we use a dose of
chlorine of 3 mg/l.

In this case Ct = 55, a higher value than the previous one, but

tcontact = 55/3 = 18.3 min.

Example 3

We must treat the same water as in Example 1, but now the water pH is 8.5.

In this case Ct = 65, a higher value than the previous one, and therefore

tcontact = 65/1 = 65 min.

As it has been shown in the previous examples, the time for disinfection
depends on many parameters and the fact of having a given concentration of
free chlorine does not ensure an appropriate disinfection, if there is no strict
control both of the contact time and of all the other factors: pH, temperature,…

2.5 ANALYTICAL METHODOLOGY

Usually determination of residual chlorine in water is made by reaction with o-

toluidine or N,N-diethyl-p-phenylen-diamine (DPD). The first method is simple
to carry out, but its disadvantage is that it does not allow a good differentiation
between free residual chlorine and combined chlorine. O-toluidine reacts rapidly
with free chlorine but after 5 seconds it also reacts with the combined chlorine;
therefore they cannot be determined separately as it is almost impossible to
carry out the analysis of each of them separately in such a short period of time.
As we cannot determine if there actually is free chlorine (and its amount), we
might have wrongly chlorinated water: high contents of combined chlorine but
lack of free chlorine (it is to say, we would be dosing below the breakpoint). In
addition, o-toluidine is a toxic product which is potentially carcinogenic.

Because of the above, it is more advisable to use DPD, which allows to

differentiate between free and combined chlorine. DPD, with a pH between 6.2
and 6.5 produces a reddish colour which is proportional to the amount of free
chlorine existing in the medium. Compared with a colour scale, free chlorine can
be determined. On the same sample potassium iodide is added, which releases
the combined chlorine and makes it react with the DPD, so finally we can get a
reading of the total residual chlorine. By simple subtraction between the two
figures, we may determine the combined residual chlorine.

14
 Phosphate buffer
KI
Water

DPD

Free residual chlorine Total residual chlorine

This reaction may be monitored easily in the form of reaction kits, available
through many suppliers. The use of a photometer, which is the instrument that
takes the reading of colour intensity and allows relating it directly with the
products concentration, is a more precise way to carry out this determination.
Chlorine colorimetric determination by reaction with DPD is recognised as the
standard method of EPA 4500-Cl G. There are devices in the market which
allow carrying out these reactions on line, but they are not commonly used due
to their cost and complexity.

As chlorine and its by-products are oxidizing substances, its presence in the
medium produces a variation in the value of the water redox potential, (ORP,
oxidation-reduction potential). Maintaining an ORP value within the assigned
range ensures that the quantity of oxidant is appropriate for guaranteeing the
disinfection process. However, there is not a direct relationship between the
ORP value and chlorine concentration. It means that different types of water
with different chlorine concentrations may have the same ORP value. In 1972
The World Health Organization adopted a value of 650mV as the appropriate
value for purified water. The German Standards Agency adopted a value of
750mV for the disinfection of public swimming pools whereas the National
Swimming Pool Institute proposed a value of 650mV for public spas.

The redox potential can be easily measured by means of electrodes which allow
carrying out continuous readings in the treated water flow. Besides, they are
very economical elements. All this makes the chlorination control through the
redox potential very attractive. Nevertheless, we should be aware that the
measurement of ORP can only be taken as a guidance system. Any change in
the nature of water (even though maintaining constant chlorine level) leads to a
change in the redox potential reading. Generally, the use of ORP is not
recommended as a monitoring system for free chlorine, unless the water being
treated does not change its characteristics, composition pH or temperature. Nor
would it be an appropriate system in installations in which the exact level of
chlorine contained in the water is important, such as drinking water chlorination.

The amperometric method is another system for chlorine determination. A

sensor is introduced in the solution, in one of its electrodes the reduction of the
chlorine present in the water is produced, which generates a current intensity
that is proportional to the chlorine concentration. There are versions which
allow determining free chlorine or total chlorine with differentiated
characteristics which will be discussed in section 2.6. The great advantage of
this method is that continuous readings may be carried out, which allows on-line
control of chlorination with actual readings of the chlorine values.

15
2.6 CONTINUOUS DETERMINATION OF CHLORINE

Above, the most common analytical methodologies for the determination of free
chlorine are shown. Today, the only methodologies recommended for
continuous measuring are the colorimetric method with DPD and amperometric
method. Next, these techniques are discussed.

2.6.1 Colorimetry

The base of the colorimetric method is the addition of reagents which produce a
colour development. This method applicability at the laboratory level or as a
single measurement is undeniable since the sequential addition of reagents is
carried out on a static sample which is always the same. However, in
continuous systems the aliquot to be analysed changes continuously.

Colorimetric systems for continuous readings are based on a timing sampling of

water, and in each water sample all reagents are added. Therefore, one-time
readings distributed over time are obtained, which gives us an idea of the
system development but not the reading in each of the moments. This fact
becomes even worse if we consider that addition and mixture of reagents and
colour development takes some time, in this way reducing the sampling
frequency. Another problem regarding kinetics is that the reaction speed
depends on the medium salinity. Thus, in systems with considerable salinity
variations it might happen that for the reaction period of time set, in some cases
colour is developed and not in other cases.

For all these reasons, colorimetric equipments for continuous determinations

are quite complex. Such equipments are provided with electrovalves for
carrying out the sampling and pumps for adding the reagents. Automation of
these components is also important as the reading accuracy depends on the
correct coordination among them. Furthermore, in order to ensure correct
readings, good maintenance of such components and avoiding blockage of the
hydraulic circuits is required. It is obvious, but it is necessary to emphasize that
there is a continuous consumption of reagents which need to be replaced at a
certain frequency and whose exhaustion would produce the lack of reading.

It is considered to be a destructive method. Water samples analysed cannot be

used again as reagents developing heat have been added. This is an important
detail for drinking water samples.

Finally, it is worth noting that this system cannot be used with systems working
under pressure as the optical part, which is the most delicate part, could be
damaged.

To summarize, we could conclude that the colorimetric system is the reference

system but its adaptation to continuous reading systems is not well solved.

16
2.6.2 Amperometry

The amperometric measuring system, despite being conceptually more

complex, is easier to be installed than the colorimetric system. It is simply a
sensor consisting of several electrodes on whose surface chlorine reacts
producing a current flow. There are several technologies applied to this type of
measurement. They are described below.

Galvanometric sensor

The electrode system consists of two electrodes Cu and Pt (Au). Between those
electrodes, a voltage appropriate for chlorine reduction appears. In fact, it would
be equivalent to a galvanic cell producing a voltage which corresponds to
chlorine reduction. Thus, it is a voltage which is spontaneously generated and it
is totally uncontrolled. Any type of change in the electrode environment such as
pH, conductivity, sample composition..., may lead to changes in the voltage
generated with the subsequent change in the electrical response obtained.
Because the surface of the copper electrode is being continuously oxidized,
changes in its composition would also lead to the modification of the voltage
generated. For this reason, it is essential to always keep the surface clean and
habitually cleaning abrasive systems (brushes or glass balls which are
accelerated by the water speed) are used, which are not always 100% effective.
Due to this operation mode, a continuous loss of the electrode mass is
produced, being necessary to be replaced when they are worn. Equipments are
often out of calibration because it cannot be guaranteed that the electrode
system is always under optimal operating conditions.

Closed-cell potentiostatic sensor

In order to control the working voltage, it means working at constant potential

(=potentiostatic), a reference electrode needs to be used to allow adjusting the
voltage applied, depending on the changes observed in the medium. In this
way, the measurement is much more stable than in the case of the
galvanometric sensor.

To prevent soiling of working electrodes, the entire electrode system is

separated from the reading media through a selective membrane which allows
discriminating between different types of analytes with the same reading media.
The cell, in which the electrodes are immersed, contains a support electrolyte
which allows chlorine to be diffused from the water to the electrodes.
Composition of such electrolyte changes continuously due to the continuous
flow of matter inwards. Then, it needs to be often replaced.

A problem associated to the use of membranes is its plugging. If the membrane

is plugged, the analyte cannot reach the electrode system and the correct
response will not be obtained. This is the reason why it is not advisable to use
this type of sensors in dirty waters.

17
On the other hand, resistance to pressure and depression of this type of
membranes is low and frequently break.

Open-cell amperometric sensor

With the objective to solve the limitations previously described, cutting-edge

sensors have been developed which allow to operate under specially complex
conditions.

This type of sensor is not protected by a membrane and therefore problems

arising from its use are avoided. In contrast, working electrodes are exposed to
the medium at all times and therefore they are susceptible to soiling. However,
the use of an electrochemical cleaning system, during which the working
potential is changed in order to produce an electrochemical reaction, allows the
electrode surface returning to its original state.

ITC has developed its own sensor, which is based on this technology, for the
determination of free chlorine in all types of water, both drinking water and
process water with a maximum concentration of 3 mg/l and a pH between 6.5
and 9.0.

18
2.7 CHLORINATION PROCEDURE

Generally speaking, a chlorination procedure can be established which follows

several stages:

1. Estimating the chlorine demand or breakpoint. This will allow us to

determine the dose of chlorine to be supplied in order to attain a full
disinfection of water.

2. Fixing the Ct value needed for work. This will allow us to work out the
contact time between hypochlorite and the micro-organisms so that we
may obtain disinfected water. Usually, the dosage of disinfectant is
carried out in a tank in the distribution network, in order to allow the
highest homogenization of water. The sizes of the treatment tanks must
take into account the Ct parameter in order to allow a residence time
suitable for the treatment. Generally speaking, it is considered that for a
pH lower than 8, a contact time of 30 minutes is sufficient. It is
recommended that the residence time of the water in the tank be less
than 48 hours.
If the tank was already in use before starting the chlorination and it was
smaller than needed, it might happen that the residence time of water
was not sufficient, which would give as a result a bad disinfection. In
such cases, in order to keep the Ct parameter it would be necessary to
increase the treatment dose.

3. After disinfecting the water, it must be checked that the amount of

residual chlorine in the farthest point of the supply network is within the
standards fixed by the qualified bodies by using a chlorine determination
kit. Should it be too low, the dose of chlorine supplied should be
increased after the disinfection. On the contrary, if the dose is too high –
as would be the case if the tank were too small- the addition of a reducer
(such as sodium bisulphite or metabisulphite) would allow the elimination
of residual chlorine to the necessary level.

The above procedure is given only for guidance and is not to be considered as
a fixed recipe to be followed. In case of doubt, we suggest to ask the advice of
the pertinent Public Health bodies.

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3. CHLORINATION EQUIPMENT

Over the disinfection process of water for human consumption, there are three
stages, in which different procedures should be applied:

A. Pre-chlorination: In this stage the amount of chlorine needed to exceed

the breakpoint is added. This ensures that the level of residual chlorine is
appropriate for farther disinfection. Usually, dosage of chlorine is carried
out proportionally to the water flow to be treated.

B. Disinfection-storage-maintenance: This stage takes place inside the

tank and it is when disinfection as such is produced. If the residence time
is high, it is necessary to maintain a residual level of chlorine to ensure
that a possible new microbiological contamination has not been
produced. To carry out the corresponding chlorine input, a monitoring
and dosing system in the tank is needed. The same working
methodology is applied to tanks acting as a buffer, which receive water
that has already been treated or in a close system such a swimming
pool.

C. Post-chlorination: When water has come out from the tank and is
distributed for being used, it may happen that an additional chlorine input
is needed to ensure that the levels of residual chlorine are as required at
the consumption points. These are re-chlorination stations in wide
distribution networks. In this case, the on-line control equipment is of
great importance as it will be the final responsible for maintaining the
chlorine level.

Next, the nature of equipments to be used in each stage is described.

20
 DISINFECTION-STORAGE-MAINTENANCE
DESINFECCIÓN-MANTENIMIENTO

21
PRE-CHLORINATION
PRE-CLORACIÓN
POST-CHLORINATION
POST-CLORACIÓN
3.1 PRE-CHLORINATION

The main objective of this stage is the addition of the amount of chlorine needed
to ensure that the breakpoint has been exceeded. Usually, this is the
chlorination process stage in which a higher amount of chlorine is needed and
therefore large pumps are used.

Chlorination is usually carried out in the line of water intake, before going into
the disinfection tank. For this reason, the way water is delivered will set two
different work methodologies with the objective to maintain the same proportion
of chlorine in the water.

1.- Water entry at constant flow: In this case, in order to maintain the
proportionality between the entry water and chlorine, it is only necessary to
maintain a constant dosing flow. When water entry is produced, the dosing
pump must be started up. Depending on the chlorine needs of the system, there
are two types of models: DOSITEC MD (for flows up to 9l/h) and DOSTEC (for
higher flows).

2.- Water entry at variable flow: If the water flow is not constant, a
monitoring system, which allows adjusting the dosed flow in accordance with
this variable, is needed. In this case, the system is more complex than the
previous system because more elements are needed. Therefore, for chlorine
flows lower than 9l/h, a water meter sending pulses to a DOSITEC Q pump,
which works proportionally to these pulses, can be used. On the contrary, for
higher flows the system consists of a flowmeter whose readings are managed
by a WTRpro Q controller, which modifies the adjustment of the DOSTEC
pump in order to maintain the previously set proportionality.

For correct chlorination at this stage, it is necessary that the chlorine demand
(breakpoint) of the water sample is correctly determined. In installations where
the water intake is carried out from a single origin, whose nature does not vary
(such as a well or a spring), this parameter is clearly defined. However, if the
composition of the intake water is variable ( for instance, mixture of different
origins), it is necessary to know the needs of each water sample and carry out
the chlorination at levels exceeding the breakpoint of each sample. If not, the
level of residual chlorine would be lower than needed if the intake water is rich
in water with a high level of chlorine demand.

Another factor to be considered in the definition of the chlorine amount to be

added is the dimensions of the disinfection/storage tank and the C.t parameter,
because it will determine the needed level of residual chlorine for correct
disinfection.

Thus, a general formula can be established to calculate the dimensions of the

dosing pump:

22
 Q H 2O  D  C 
QCl 
10  %

Where:
QCl is the flow of hypochlorite in l/h
QH2O is the flow of water to be treated in m3/h
D is the demand of chlorine of the water sample in ppm (mg/l)
C is the level of residual chlorine in accordance with the parameter C·t, in ppm
% is the percentage of purity of commercial hypochlorite

Example

It is necessary to chlorinate spring water with an entry flow into the treatment
tank between 50 and 250 m3/h. The chlorine demand of the sample is 10 mg/l.
Depending on the residence time in the tank (and according to the C.t tables),
the chlorine dose needed is 1mg/l and it will be supplied from a trade product
with 5% active chlorine content.

As the water flow is variable, it is necessary to estimate the pump flow at

extreme conditions.

Thus, when the water flow is 50 m3/h, the calculation is

50  (10  1)
QCl   11 l / h
10  5
And for 250 m3/h

250  (10  1)
QCl   55 l / h
10  5

Therefore, to ensure the correct chlorination at this stage, a DOSTEC pump

able to dose the 55l/h with a WTRpro Q is needed. This range of pumps can be
adjusted up to 10% of its nominal flow. In this way, the needs in the two
extreme cases would be met.

3.2 STORAGE- MAINTENANCE

When the minimum period of contact time has elapsed, it can be considered
that the water has been appropriately chlorinated and therefore it is disinfected.
The guarantee of this is the presence of a level of residual chlorine in the water
stored in the tank. However, if the residence time is too long, chlorine losses,
which endanger its disinfection, may be produced. For this reason, it is
necessary to maintain a residual chlorine level not only during the disinfection
process but also during storage. The chlorination process is carried out at this
stage in accordance with a set point of residual free chlorine. This means that
the chlorine content inside the tank is continuously monitored and chemical
product additions are carried out to maintain the levels required.

23
This approximation is similar to the management of a water tank which acts as
a buffer with the aim to supply at high demand moments, such as hotels,
factories... In this case, the water feeding the tank is consumption water which
is duly chlorinated, but during its storage, the chlorine existing may disappear
and supplementary intakes maintaining its level in accordance with the current
regulation for human consumption waters are required.

The same equipment would be used for the maintenance of the chlorine level in
swimming pools or in any other installation consisting of a tank (more or less
large), which contains previously treated water and where it is necessary to
maintain a specified level of free chlorine.

The material needed would include a monitoring and control equipment

WTRpro pH-Cl for the free chlorine with the corresponding chlorine and pH
sensors and a dosing pump DOSTEC or DOSITEC, depending on the flow to
be supplied.

The equipment WTRpro pH-Cl would carry out the measurement of the amount
of chlorine existing in the water at all times. As the reading of the chlorine
sensors depends on the pH of the sample, it is necessary to carry out
corrections of it considering the pH value. When the chlorine reading has been
carried out, if the value obtained is lower than the set point required, the
equipment WTRpro would start the dosing pump until reaching it. The
additional chlorine supply would be controlled proportionally to the difference
between the actual reading and the set point. In this way, the amount added
would be lower as we were reaching the set point with the aim to minimize the
overdosing. The control output may be a proportional relay or a 4-20mA

24
analogue signal. The first one would allow us controlling a DOSITEC MD pump,
whereas a 4-20mA signal would be needed to control a DOSTEC pump.

As the chlorine supplies are always carried out on the same water sample, it is
important to guarantee an appropriate homogenization of it in order to avoid
wrong readings and wrong actuations which may result in overdosing.

3.3 POST-CHLORINATION

In certain occasions, an additional chlorine supply in the conduction may be

necessary. It would be the case of a pumping and re-chlorination station in the
main line of water distribution.

The material needed for the control and adjustment of the amount of free
chlorine in an online system is exactly the same as in the case of dosing inside
a tank: monitoring and control equipment for the free chlorine WTRpro pH-Cl
with the corresponding chlorine and pH sensors and a dosing pump DOSTEC
or DOSITEC depending on the flow to be supplied; but its starting up must be
differently configured.

Cl

Cl

MIXING
ELEMENT

When dosing online, the amount of chlorine added is mixed with a specific
portion of water because it flows continuously. Cumulative effect of successive
additions inside a tank does not exist. Therefore, proportional approximation
cannot be used to reach the set point, as it is in the case of a tank, because
each portion of water treated goes only once through the treatment point. In
these situations, a proportional-integral mathematical algorithmic (PI) is used,
which is able to carry out on line adjustments.

The proportional-integral approximation is based on the continuous analysis of

the effect of each chemical product addition. For this reason, in this case the

25
reading of chlorine content is carried out after the injection. In this way, the
control equipment is able to analyse the effect on the level of free chlorine of the
last chlorine addition and according to it, readjust the amount to be added in the
next chlorine injection. For a PI process to be successful, it is necessary that all
the other parameters affecting the reading (pH, water flow,…) remain constant
because if not, changes in the chlorine reading due to these other parameters
would be wrongly attributed to the changes in the amount dosed.

In many cases of on line post-chlorination installations, the amount of water

going through the pipe is variable because it depends on the immediate
consumption of water. For example, water consumption at dawn is much lower
than in the early morning hours. If changes in the water flow are frequent, it
may happen that the set point could not be reached at any time. In order to
avoid this type of problems, ITC has developed special control equipments
WTRpro PIQ, that in addition to the usual entries for pH and chlorine, include a
connection port for a flowmeter. In this way, continuous reading of the
immediate flow can be carried out and the amount of chlorine dosed
immediately corrected.

Let us suppose the case of an installation with a 10m3/h flow, where the free
chlorine set point is 1mg/l obtained when the dosing pump is operating at 20%
of its capacity. At a certain point in time, the flow circulating through the
installation is instantly set at 20m3/h. If the control equipment is a WTRpro pH-
Cl, the change in flow is not detected and the dosing pump continues operating
under the same conditions. As the circulating flow has doubled, the amount of
chlorine present is set at 0.5mg/l. From this moment, the controller would start
the process of approximation to the set point until reaching it again. However, if
the equipment installed was a WTRpro PIQ, the change in flow would be
detected immediately and the controller would modify the dosing pump
adjustment according to it. Thus, in the example above, the pump would be
automatically set at 40% and the set point maintained at 1mg/l all the time.

26