CHLORAMINATION

AND
CHLORAMINE ANALYSIS

SW AWWA 2014
COMBINED CHLORINE - CHLORAMINATION

• Chlorine (HOCl and OCl-) reacts with ammonia to form chloramines,

commonly referred to as ‘combined chlorine’
• The predominate species are monochloramine and dichloramine. A small
fraction is trichloramine or nitrogen trichloride

2
 Total residual chlorine, primarily Free residual
monochloramine chlorine
Total Chlorine Residual

Cl2:N Cl2:N Cl2:N

< 5:1, > 5:1, > 9:1,
typical typical typical

BREAKPOINT CURVE

Breakpoint
Chlorine Added

3
 BREAKPOINT CURVE CONSIDERATIONS
• Shape of the curve is dependent upon
– amount of ammonia and other chlorine demand substances in the water
– temperature
– pH
– contact time
• Most effective disinfection, least taste and odor occurs with free residual
chlorine
• Free chlorine may lead to formation of DBP

4
CHLORAMINATION
• Chloramination: Purposeful use of chlorine and ammonia to form
monochloramine.
– Minimizes formation of chlorinated organics

– Ammonia to chlorine Ratio is controlled to favor formation of

monochloramine, typically 5:1 Cl2:N

• Total residual chlorine test: All free and combined chlorine species

5
 CHLORAMINES
• Less effective disinfection than free chlorine. HOCl is 25X more effective
biocide
• Chloramines require longer contact time and/or greater concentration than
free chlorine.
• Possible taste and odor (dichloramine)
• More stable than free chlorine (long distribution systems)
• Generally do not produce DBP (NH2Cl may form DBP – NDMA being studied)

6
 CHLORAMINE FORMATION
• Monochloramine - NH2Cl
NH3 + HOCl NH2Cl + H2O
• Dichloramine - NHCl2
NH2Cl + HOCl NHCl2 + H2O
• Tricholoramine (Nitrogen Trichloride) - NCl3
NHCl2 + HOCl NCl3 + H2O
• Chloramines are not as effective disinfectants as free chlorine

7
DEFINITION OF UNREACTED AMMONIA

• Ammonia in solution as
– NH3 Free ammonia gas dissolved in water or;
– NH4- The ammonium ion

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• What are chloramines? Cl
N
• Where are chloramines used?
H
• Chlorine and Ammonia H
• Chloramination Objectives
• The Dance of Chlorine and Ammonia
• Building the Chloramination Curve
• Preventing Nitrification
N
H H
Cl H
Cl
WHAT ARE CHLORAMINES?
• The word “chloramines” describes the group of three
compounds formed by mixing chlorine and ammonia together
– Monochloramine – ideal form for drinking water treatment
– Dichloramine
– Trichloramine

Cl
N
H
H
WHERE ARE CHLORAMINES USED?
• Chloramines are used in drinking water as an alternative to
the more aggressive disinfection of chlorine
– Chlorine reacts quickly with organic materials present in source water,
which can cause the formation of undesirable disinfection by products
(DBPs) that are regulated by the EPA
– Monochloramine
i. Is less reactive than chlorine
ii. Is a weaker disinfectant than chlorine
iii. Requires a longer contact time than chlorine
iv. Does not form DBPs
v. Is more stable and maintains a longer residual
vi. Formation is a complex process
CHLORINE AND AMMONIA
• Chlorine
– When mixed with water, chlorine forms hypochlorous acid
and hypochlorite

CHLORINE WATER HYPOCHLOROUS ACID HYPOCHLORITE

(Cl2 ) + (H O)  (HOCl) + (OCl-)
2

Cl Cl
 N
CHLORINE AND AMMONIA H H
H
• Ammonia
– When hypochlorous acid is mixed with ammonia,
chloramines are formed

- MONOCHLORAMINE (NH2Cl)

HYPOCHLOROUS ACID + AMMONIA  - DICHLORAMINE (NHCl2)

(HOCl) (NH3)
- TRICHLORAMINE (NCl3)
CHLORAMINATION OBJECTIVES
• Blend Chlorine and Ammonia
together in a 1:1 molar ratio
– The goal is to exclusively form
monochloramine
– Inhibit and/or eliminate the
formation of dichloramine and
trichloramine
• Dichloramine and trichloramine are
unstable, and create taste and odor
problems
– Minimize the introduction of
significant amounts of free ammonia
in the distribution system
• Excess free ammonia will promote
the growth of bacteria and biofilms,
and can lead to nitrification in the
distribution system
 NOM
NATURALLY ORGANIC
MATTER

15
 Total CL 1 min Total CL 10 min Total CL 60 min Total CL 360 min

14
13
12
11
10
Total Chlorine (mg/L)

9
8
> 6:1
7
6 > 14:1
5
4
3
2
1
0
0 5 10 15 20 25 30

Chlorine Added (mg/L)

USED WITH PERMISSION, GOLDEN STATE WATER

16
 Breakpoint chlorination dose of 16.4 mg/L is needed
for complete removal of free ammonia
1 min 10 min 60 min 360 min
1.4
1.3
1.2
1.1
1
Free Ammonia (mg/L)

0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0 5 10 15 20 25 30
Chlorine Added (mg/L)

USED WITH PERMISSION, GOLDEN STATE WATER

17
 NITRIFICATION IN THE DISTRIBUTION SYSTEM
Circular Problem

NH2Cl + NH3/NH4+ + NO2- + NO3-

Disinf ▼ pH ▼ pH ▼
f-NH3 ▲ DO ▼ DO ▼
NO2- ▲ NO3- ▲
Distribution System Alk ▼ Alk ▼

Sloughing of biofilm causes Turbidity ▲ Flow ▼ Customer

▲
HPC ▲ Complaints
NITRIFICATION

• Conversion of ammonia to nitrites and nitrates

– NH3 + O2 NO2-+ 3H+ + 2e-
– Nitrosomonas Nitrosococcus, and Nitrosospira.
• Conversion of nitrite to nitrate
– NO2- + H2O NO3- + 2H+ +2e-
– Nitrobacter Nitrospina, Nitrococcus, and
Nitrospira

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INDICATION OF NITRIFICATION

Chloramine residual
Free Ammonia
Temperature
Dissolved Oxygen
pH and/or alkalinity
HPC
NO2/NO3

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CONTROL STRATEGIES FOR DISCUSSION

pH

Free ammonia

Water age

Chloramine residual

Light

TOC

Tank Mixing

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NITRIFICATION

Nitrifying bacteria feed on ammonia…

producing Nitrites…
which exert a chlorine demand…
which decreases the residual…
which allows microbes to flourish…
to produce more nitrites…
which continues the spiral…
until your residual is gone!
aka … “feeding the beast”
THE DANCE OF CHLORINE AND AMMONIA

• Chlorine and Ammonia are not well suited to each other

for reaction.
– HOCl is favored at lower pH
– NH3 is favored at higher pH
– “Compromise” used is usually around pH 8-8.3.

• One ammonia molecule and one chlorine molecule are

required to form monochloramine:
– “Easy” in the laboratory, but what about:
• Ammonia in sourcewater
• Variable chlorine demand in sourcewater
 REACTION - FREE CHLORINE:

Cl2 + H2O HCl + HOCl

HOCl H+ + OCl-

HOCl + OCl- + DPD Red complex (530 nm)

Read as soon as possible after 20 sec mix.
 Reaction - Total Chlorine:

HOCl + OCl- + Chloramines + KI + DPD

HOCl + OCl- + I2 + DPD Red complex

Read at 530 nm.

Read after 3 to 6 minutes.

MONOCHLORAMINE AND FREE AMMONIA

• Method is designed for one sample. Note that 2 different

programs (curves) are used. Presume cells are matched.
• Plan your timing well, as there are 2 five minute reaction
periods.
– Program 66 for Monochloramine
– Program 388 for Free Ammonia
– The chemistry “makes monochloramine by chlorinating
free ammonia”
• The powder reagent only reacts with monochloramine
(M vial)
• The liquid reagent is chlorine and reacts with any free
ammonia, making additional monochloramine (FA vial)
• By zeroing out the monochloramine, the free ammonia
can be determined by difference
MONOCHLORAMINE AND FREE AMMONIA

• How it works:
– The powder chemistry reacts with
monochloramine and forms a proportional green
color (the M vial).
– The liquid reagent contains chlorine which
converts any free ammonia to additional
monochloramine (the FA vial).
– The difference between the 2 measurements is
equal to the free ammonia, if any.
– A great tool for any chloraminating system (DW
and WW).
BREAKPOINT CHLORINATION CURVE
I II III

Ideal zone for DW disinfection

CHLORAMINATION MONITORING & CONTROL
• Parameters
– Monochloramine O
– Ammonia H Cl
– Total Chlorine
– Free Chlorine
• Data from each of the parameters above
can help determine where water is on
the breakpoint curve
CHLORAMINATION MONITORING & CONTROL
• If the plant does a test for total chlorine, and obtains a result of 3
mg/L…
– Total chlorine = 3.0 mg/L
• Where on the breakpoint curve are they?
– What part of the curve makes a significant difference
Where is 3 mg/L Total Chlorine?

I II III

3 mg/L
CHLORAMINATION MONITORING & CONTROL
• Laboratory Tests
– Monochloramine and free ammonia with Monochlor-F reagent
• Colorimetric method
• One method sequentially determines monochloramine and free ammonia
• Can be run on spectrophotometers and some colorimeters
• Indophenol chemistry
– Free Chlorine/Total Chlorine
– DPD colorimetric method
– Chloramine can produce false positive results
– Autocat 9000 Autotitrator for chlorine
– Ammonia
– ISE (ion selective electrode)
– Colorimetric ammonia test
CHLORAMINATION MONITORING & CONTROL
• Based on data from other tests, the analyst/operator will be able to tell
where they are on the breakpoint curve
 Zone 1 Zone II Zone III
Monochloramine = Total Cl2 Monochloramine < Total Cl2 Total Cl2 > 0
Free ammonia > 0 Free Ammonia = 0 Free Ammonia = 0
Monochloramine = 0
CHLORAMINATION MONITORING & CONTROL
• Total Chlorine • HPC
• Free Chlorine • ATP
• Monochloramine • DBP
• pH • Nitrifying Bacteria
• Alkalinity • Temperature
• Nitrate/Nitrite
• DO
 CHLORAMINATION
AND
CHLORAMINE ANALYSIS

HACH TRAINING ACADEMY

DRINKING WATER COURSE