Water Distribution System Analysis 2010 – WDSA2010, Tucson, AZ, USA, Sept.

12-15, 2010

WATER DISTRIBUTION NETWORK RESIDUAL CHLORINE

MODELING BASED ON THE SYNERGY OF CHLORINE AND
CHLORINE DIOXIDE
Kui Chang, Jinliang Gao and Yixing Yuan
Harbin Institute of Technology
Harbin, Hei Longjiang, PRChina
kuichang@[Link], gjl@[Link], yyx1957@[Link]
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Wenyan Wu
Staffordshire University
Stafford, UK
[Link]@[Link]

Abstract

The kinetics and mechanisms of chlorine dioxide and chlorine in water distribution network is described,
and a multi-species network water quality model is built in this paper. Experiment was composed of two
parts, static test and dynamic test. The cast iron pipe, steel pipe, and PVC pipe were selected to carry out
static experiments. In order to study the kinetic and mechanism of the combination disinfection of
chlorine dioxide and chlorine, the reaction was under the condition of different chlorine dioxide and
chlorine dosing ratio and different chlorination method. Dynamic experiments carried out in the cast iron
pipe in different chlorine dioxide and chlorine dosing ratio and different flow conditions to study the
kinetic and mechanism of the combination disinfection of chlorine dioxide and chlorine .A multi-species
network water quality model using EPANET-MSX toolkit is built based on kinetic and mechanism of the
combination disinfection of chlorine dioxide and chlorine. The concentration of residual chlorine (Cl2),
chlorine dioxide (ClO2), chlorite in the bulk water and biofilm was taken as the main parameters. And the
model was calibrated by the experiment data. The water quality model application in a large water
distribution network, of which the total demand is 800,000 m3/d in China. The results show that the
combination of chlorine dioxide and chlorine disinfection can reduce the chlorine and chlorine dioxide
disinfection by-product and residual chlorine concentration distribution was more reasonable.

Keywords
water distribution network; residual chlorine; chlorine dioxide; water quality; EPANET-MSX

1. INTRODUCTION

In order to ensure the water quality in drinking water distribution systems, chlorination has been widely
used in the world. However, the disinfection by-products (DBPs) introduced by chlorination has a
significant hazard to human health. Compared with chlorine, chlorine dioxide disinfection can effectively
reduce the chloroform and chlorine dioxide has been seen as a new agent to replace the chlorine
disinfectant. But chlorine dioxide is unstable and its decay rate is fast, so it is difficult to apply in a large
water plant. Moreover, it has been discovered that the DBPs of chlorine dioxide is also harmful to human
body. Literatures shows that using a combination of chlorine dioxide and chlorine, instead of using each
of them as a single disinfectant for the disinfection of effluents from municipal sewage treatment plants,
produced a relatively stable high residual of both disinfectants, reduced the concentration of the
undesirable chlorite ion, while increasing the concentration of chlorine dioxide. So the kinetics and
mechanisms of chlorine dioxide and chlorine in water distribution network is described, and a muti-
species network water quality model is built in this paper.

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2. MATERIALS AND METHODS

Experiments of chlorine and chlorine dioxide mixed disinfection were finished at pipeline hygienic
laboratory of research center of water supply and drainage system of Harbin Institute of Technology.
Experiment was composed of two parts, static test and dynamic test. The cast iron pipe, steel pipe, and
polyvinyl chloride (PVC) pipe were selected to carry out static experiments. In order to study the kinetic
and mechanism of the combination disinfection of chlorine dioxide and chlorine, the reaction was under
the condition of different chlorine dioxide and chlorine dosing ratio and different chlorination method.
Dynamic experiments carried out in the cast iron pipe in different chlorine dioxide and chlorine dosing
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ratio and different flow conditions to study the kinetic and mechanism of the combination disinfection of
chlorine dioxide and chlorine. Cl2 and ClO2 were tested by Standard Method 4500-ClO2 E (American
Public Health Association, 2005). The reaction between Cl2 and ClO2 were obtained by using stopped-
flow apparatus, MOS-450/AF-CD, from Bio-Logic. The test equipments are shown in Figure 1.

a) Static test equipment b) Dynamic test equipment c)Stopped-flow apparatus

Figure1. Test equipment

3. THE KINETICS MODEL OF COMBINED CHLORINE AND CHLORINE DIOXIDE

DISINFECTION

3.1 The Kinetic Model of Chlorine

In order to build the kinetic model of combined Cl2 and ClO2, the kinetic model of Cl2 was researched
firstly. Three different pipe materials were used in the study: cast iron, steel, and polyvinyl chloride
(PVC).

Disinfecting drinking water is considered important for the maintenance of water quality in transmission
and distribution systems. For Cl2, the elementary reaction can be formulated as:

Cl2 + B → Pr oducts

Where B is an organic or inorganic compound.

Chlorine consumption in the distribution system is normally described in terms of an apparent first-order
equation (Wable et al, 1991; Biswas et al, 1993; Rossman et al., 1994; Kie´ne´ et al., 1998) as follows:

d [Cl2 ]
= − k1 [Cl2 ]
dt

where d [Cl2 ] / dt is the rate of chlorine decay, mg/L per day; k1 is chlorine first-order kinetic constant or
first-order decay coefficient, day ; [Cl2 ] is Cl2 concentration at time t, mg/L.
−1

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While a substance moves down a pipe or resides in storage it can undergo reaction with constituents in the
water column. For first order kinetics, the rate of a bulk flow reaction can be expressed as:

d [Cl2 ]
= − kb1 [Cl2 ] (1)
dt

Where kb1 is bulk flow reaction rate constant (1/time).

While flowing through pipes, dissolved substances can be transported to the pipe wall and react with
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material such as corrosion products or biofilm that are on or close to the wall (EPANET user manual).
Chlorine decay at the pipe wall surface is a function of both mass transport of chlorine from the bulk
liquid to the pipe wall surface, and the chemical reaction at, or with, the pipe wall surface. The value of
the wall decay constant described above represents the effective decay constant (Kw), units 1/time. Such
a constant is a function of the hydraulics, and the intrinsic wall decay constant (Kw), units of length per
time (Rossman et al.,1994). For first order kinetics, the rate of a pipe wall reaction can be expressed as:

d [Cl2 ] 2k w1 k f 1 [Cl2 ]
=−
dt R(k w1 + k f 1 )

Where kw1 is wall reaction rate constant (length/time), k f 1 is mass transfer coefficient (length/time), and
R is pipe radius.

For zero-order kinetics the reaction rate cannot be any higher than the rate of mass transfer, so

d [Cl2 ]
= − min( k w , k f [Cl2 ])(4 / D )
dt

Where D is pipe diameter.

In this work, the zero-order kinetic model was used. The kinetic rate of wall reaction for Cl2 can be
expressed as:

d [Cl2 ]
= −4 ∗ k w1 / D (2)
dt

The first-order kinetic constant for chlorine consumption by the constituents of the water alone, kb, was
determined by conducting a similar test in a clean, chlorine-consumption free bottle. This test was
repeated five times during the study period to observe any change in bulk rate constant. The chlorine wall
decay constant, kw, is determined as the difference between the overall decay constant and the bulk decay
constant. The test result is show in Figure2. As is shown in Figure 2, the disinfection effect of Cl2 in PVC
pipe is better than iron pipe, and the iron pipe is better than steel pipe.

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Figure 2. The test result of Cl2 consumption. T=19.2℃, pH=7.34.

According to the test result, the bulk rate constant, kb1 , is 4.64 day and wall decay constant, kw1 , of iron
−1

pipe is 1.64 m ⋅ day . The wall decay constant, kw2 , of steel pipe is 2.98 m ⋅ day . The wall decay constant,
−1 −1

kw3 , of PVC pipe is 0.52 m ⋅ day . −1

3.2 The Kinetics Model of ClO2

For ClO2, the elementary reaction can be formulated as:

ClO2 + B → Pr oducts

ClO2 consumption in the distribution system is also described by a first-order equation as follows:

d [ClO 2 ]
= − k2 [ClO2 ]
dt

where d [ClO2 ] / dt is the rate of ClO2 decay, mg/L per day; k2 is ClO2 first-order kinetic constant or first-
order decay coefficient, day ; [ClO2 ] is ClO2 concentration at time t, mg/L.
-1

Kinetic rate of bulk flow reaction for ClO2 can be expressed as:

d [Cl2 ]
= − kb 2 [Cl2 ] (3)
dt

Kinetic rate of wall flow reaction for ClO2 can be expressed as:

d [ClO 2 ]
= −4 ∗ k w1 / D (4)
dt

ClO2 consumption test result in bottle, iron pipe, steel pipe and PVC pipe is shown in Figure 3. As is
shown in Figure 2, the disinfection effect of ClO2 in PVC pipe is better than steel pipe, and the steel pipe
is better than iron pipe.

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Figure 3. The test result of ClO2 consumption. T=19.2 , pH=7.34

According to the static test result, the bulk rate constant, kb 2 , is 1.72 day and wall decay constant, kw4 ,
-1

of iron pipe is 8.93 m ⋅ day . The wall decay constant, m ⋅ day , of steel pipe is 3.14 m ⋅ day . The wall
−1 −1 −1

decay constant, kw6 , of PVC pipe is 1.72 m ⋅ day .−1

3.3 The Kinetic Model of the Reaction Between ClO2 and Cl2

Literature shows that the combination of Cl2 and ClO2 produced a relatively stable high residual of both
disinfectants, reduced the concentration of the undesirable chlorite ion, while increasing the concentration
of chlorine dioxide (Katz, A etc 1994). In this work, combination of Cl2 and ClO2 was applied in
distribution system. The experiment data shows combination of Cl2 and ClO2 has a longer residence time
and Cl2 may reacts with chlorite, the disinfection by-products of ClO2. The result of ClO2 consumption is
shown in Figure4.

Figure 4. ClO2 consumption in iron pipe

Emmenegger and Gordon supported the existence of such an intermediate in their study of the reaction
between ClO2− and HOCl/Cl2(aq) (Emmenegger and Gordon, 1969). Reactions of oxochlorine species that
involve a Cl2O2 intermediate were first discussed by Taube and Dodgen(Taube and Dodgen, 1949).
Research show that Cl2/ ClO2− interaction can be considered to proceed by adduct formation, and Cl2 reacts
much faster than HOCl with (Nicoson etc, 2001). The Cl2/ ClO2− interaction can be considered to proceed
by adduct formation:

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Cl2 ൅ ClO2ି ՜ ClClOClOି

Followed by a loss of Cl −

ClClOClO − → ClOClO + Cl −

So the reaction between Cl2 and ClO2− could be described as:

Cl2 + 2ClO2− → 2ClO2 + 2Cl −

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The rate expression is as follow:

d [Cl2 ]
= − k3 [Cl2 ][ClO2− ] (5)
dt

Where k3 is the kinetic constant.

According to the experiment data, k3 = 684.17 M −1 s −1 , which was obtained by using stopped-flow
apparatus. Absorbance was measured at 260 nm.

4. CASE STUDY

4.1 Description

As shown in Figure 5, the water distribution network is composed of 4542 nodes, 7 reservoirs, 5449
pipes, and 48 pumps. The total demand is 800,000 m3/d.

Figure 5. Water distribution network topology

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4.2 Multi-specie Model for the Synergy of Cl2 and ClO2

A three species consisting of Cl2, ClO2, and chlorite was invested for modeling residual chlorine in water
distribution system when Cl2 and ClO2 were combined. The reaction is described by chemical reaction
models (1) - (4). The differential equations which describe the time-varying rates of change of the three
species are as follow:

d [ClO2− ]
= kb 2 [ClO2 ] − k3 [Cl2 ][ClO2− ]
dt
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d [Cl2 ]
= − kb1 [Cl2 ] − 4 * a * k w1 / D − k3 [Cl2 ][ClO2− ]
dt

d [ClO 2 ]
= − kb 2 [ClO2 ] − 4a * kw 4 / D + k3 [Cl2 ][ClO2− ]
dt

Where a is constant.

A multi-species network water quality model using EPANET-MSX toolkit was built based on kinetic and
mechanism of the combination disinfection of ClO2 and Cl2. The concentration of Cl2, ClO2, chlorite in
the bulk water and biofilm was taken as the main parameters. The rate constants, k1 , k2 , and k3 , are 6.28
−1 −1
day ,10.65 day , and 684.17 M s , respectively.
-1 -1

The result is shown in Figure 6.

a) Cl2 consumption b) ClO2 consumption

Figure 6. Residual disinfectant distribution for the combination of Cl2 and ClO2

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a) Cl2 consumption b) ClO2 consumption

Figure 7. Residual disinfectant distribution for Cl2 and ClO2 used separately

The results show that the combination of chlorine dioxide and chlorine disinfection can reduce the
chlorine and chlorine dioxide disinfection by-product and residual chlorine concentration distribution was
more reasonable.

5. CONCLUSION

The consumption of Cl2 and ClO2 in bottle, PVC pipe, steel pipe and iron pipe were researched by
disinfecting drinking water together and separately in this paper. A water quality model based on the
synergy of Cl2 and ClO2 was built using EPANET-MSX and EPANET toolkit. The kinetic rate constants
for Cl2 consumption and ClO2 were obtained according to the experiment data, and kinetic rate constant
between Cl2 and chlorite was also researched by stepped-flow test. The results showed that the
disinfection effect of Cl2 in PVC pipe is better than iron pipe, and the iron pipe is better than steel pipe,
that the disinfection effect of ClO2 in PVC pipe is better than steel pipe, and the steel pipe is better than
iron pipe, and that the disinfection time of ClO2 combined with Cl2 at the ratio of 4:1 was longer than it
was used separately.

References

APHA (American Public Health Association), American Water Works Association and Water
Environment Federation. 2005. Standard methods for the examination of water and wastewater. 21st
edition. American Public Health Association, Washington, DC
Biswas, P., Lu, C., Clark, R., 1993. A Model for chlorine concentration decay in pipes. Water Res. 27
(12), 1715–1724.

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 Water Distribution System Analysis 2010 – WDSA2010, Tucson, AZ, USA, Sept. 12-15, 2010

Emmenegger F. and Gordon G., 1969. The rapid interaction between sodium chlorite and dissolved
chlorine, Inorg. Chem., 6(3):663-635.
Katz, A, Narkis, N, Orshansky, F, Friedland, E, Kott, Y, 1994. Disinfection of effluent by combinations of
equal doses of chlorine dioxide and chlorine added simultaneously over varying contact times. Water
Research. 28(10), 2133-2138.
Kie´ne´ , L., Lu, W., Le´vi, Y., 1998. Relative importance of the phenomena responsible for chlorine
decay in drinking water distribution systems. Water [Link]. 38 (6),219–227.
Rossman, L.A., Clark, R.M., and Grayman, W.M. (1994). “Modeling chlorine residuals in drinking-water
distribution systems”, Jour. Env. Eng., 120(4), 803-820.
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Taube, H.; Dodgen, H., 1949. Applications of radioactive chlorine to the study of the mechanisms of
reactions involving changes in the oxidation state of chlorine. J. Am. Chem. Soc.. 71 (10): 3330–3336

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