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

Total Chlorine Residual

Total residual chlorine, primarily

monochloramine
Cl2:N
< 5:1,
typical

Free residual
chlorine

Cl2:N
> 5:1,
typical

Cl2:N
> 9:1,
typical

Breakpoint

BREAKPOINT CURVE

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

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

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)

CHLORAMINE FORMATION
Monochloramine - NH2Cl
NH3 + HOCl

NH2Cl + H2O

NH2Cl + HOCl

NHCl2 + H2O

Dichloramine - NHCl2
Tricholoramine (Nitrogen Trichloride) - NCl3
NHCl2 + HOCl

NCl3 + H2O

Chloramines are not as effective disinfectants as free chlorine

DEFINITION OF UNREACTED AMMONIA

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

What are chloramines?

Where are chloramines used?
H
Chlorine and Ammonia
Chloramination Objectives
The Dance of Chlorine and Ammonia
Building the Chloramination Curve
Preventing Nitrification
H
Cl

Cl

Cl

N
H

N
H
H

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

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
+ (H O)
(Cl2 )
2

Cl

Cl

HYPOCHLOROUS ACID
(HOCl)

HYPOCHLORITE
(OCl-)

CHLORINE AND AMMONIA

Ammonia

N
H
H

When hypochlorous acid is mixed with ammonia,

chloramines are formed
- MONOCHLORAMINE (NH2Cl)
HYPOCHLOROUS ACID + AMMONIA

(HOCl)

(NH3)

- DICHLORAMINE (NHCl2)
- 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 10 min

Total CL 1 min

Total CL 60 min

Total CL 360 min

14
13
12
11

Total Chlorine (mg/L)

10

> 6:1

9
8
7

> 14:1

6
5
4
3
2
1
0
0

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
Free Ammonia (mg/L)

1.1
1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0

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- +

Disinf
f-NH3

pH
DO
NO2Alk

Distribution System
Sloughing of biofilm causes Turbidity

NO3

pH
DO
NO3Alk

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

19

INDICATION OF NITRIFICATION
Chloramine residual
Free Ammonia
Temperature
Dissolved Oxygen
pH and/or alkalinity
HPC
NO2/NO3
20

CONTROL STRATEGIES FOR DISCUSSION

pH
Free ammonia
Water age
Chloramine residual
Light
TOC
Tank Mixing
21

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
HOCl
HOCl + OCl- + DPD

HCl + HOCl
H+ + OClRed complex (530 nm)

Read as soon as possible after 20 sec mix.

Reaction - Total Chlorine:

HOCl + OCl- + Chloramines + KI + DPD
HOCl + OCl- + I2 + DPD
Read at 530 nm.

Read after 3 to 6 minutes.

Red complex

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

Ideal zone for DW disinfection

II

III

CHLORAMINATION MONITORING & CONTROL

Parameters

Monochloramine
Ammonia
Total Chlorine
Free Chlorine

O
H

Data from each of the parameters above

can help determine where water is on
the breakpoint curve

Cl

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
Monochloramine = Total Cl2
Free ammonia > 0

Zone II
Monochloramine < Total Cl2
Free Ammonia = 0

Zone III
Total Cl2 > 0
Free Ammonia = 0
Monochloramine = 0

CHLORAMINATION MONITORING & CONTROL

Total Chlorine
Free Chlorine
Monochloramine
pH
Alkalinity
Nitrate/Nitrite
DO

HPC
ATP
DBP
Nitrifying Bacteria
Temperature

CHLORAMINATION
AND
CHLORAMINE ANALYSIS
HACH TRAINING ACADEMY
DRINKING WATER COURSE