PRETREATMENT
BREAKPOINT CHLORINATION PLAYS IMPORTANT ROLE IN RO
PRETREATMENT
W
hen chlorina-
tion is used
in reverse
osmosis (RO) pretreatment, breakpoint
chlorination can make or break the sys-
tem. This can be especially critical
when treating surface waters, wastewa-
ters, or recycle streams. Too low a
chlorination level can lead to microbio-
logical fouling of the RO membranes,
resulting in reduced RO performance
and increased operational costs.
Typically, the N, N-diethyl-p-phe-
nylenediamine (DPD)-free chlorine test
method is used to monitor free available
chlorine levels. Free available chlorine
is defined as the amount of chlorine that
exists in the treated system as hypo-
chlorous acid and hypochlorite ions af-
ter the chlorine demand has been satis-
fied. The DPD-free chlorine test method
has several interfering compounds that
can affect the test results. One impor-
tant interference to consider is mono-
chloramine, which is why breakpoint
chlorination can be such an important
issue.
When chlorine gas (Cl2) or bleach
(NaOCl) are added to water, they rapid-
ly hydrolyze and dissociate to form hy-
pochlorous acid (HOCl) and hypochlo-
rite ions (OCl-). Hypochlorous acid is
the much stronger of the two biocides
and can react very quickly with inorgan-
ics such as ammonia. Some dissolved
organic materials also react rapidly, but
the completion of many organo-chlo-
rine reactions can take hours (1).
By James McDonald
CROWN Solutions Inc.
ISSN:0747-8291. COPYRIGHT (C) Tall Oaks Pub-
lishing, Inc. Reproduction in whole, or in part,
including by electronic means, without permission
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36
Chloramines
If ammonia exists in the water being
pretreated for RO use, the reaction be-
tween hypochlorous acid and ammonia
is a very important reaction that must be
taken into account. Hypchlorous acid
and ammonia combine to form inorgan-
ic chloramines: monochloramine
(NH2Cl), dichloramine (NHCl2), and tri-
chloramines or nitrogen trichloride
(NCl3). The relative amounts of the chlo-
ramines formed are a function of chlo-
rine fed, the chlorine/ammonia ratio, tem-
perature, and pH. In general, mono-
chloramine is formed above pH 7 and
dominates at pH 8.3.
Monochloramine is a much weaker
biocide than hypochlorous acid. The
killing power of free residual chlorine
(i.e., hypochlorous acid and hypochlo-
rite ion) is as much as 25 times higher
than the killing power of combined avail-
able chlorines (i.e., monochloramines)
(2).
Why is all this important? As men-
tioned, monochloramine is interference
to the DPD-free chlorine test. As Table
A (3) shows, the interference in the DPD-
free chlorine test can be rather high,
considering many control ranges are in
the 0.25 to 0.5 parts per million (ppm)
free chlorine range. Your free chlorine
Figure 1. Theoretical breakpoint chlorination curve.
ULTRAPURE WATER JANUARY 2003--UP200136
tests may be showing a free chlorine
residual of 0.4 ppm, but if you have
ammonia in the source water, this read-
ing may be affected by monochlora-
mine interference. You think you have
free chlorine residual as a biocide, but
you really only have monochloramine.
How do you ensure that monochlora-
mine is not interfering with your free
chlorine test? You achieve and exceed
breakpoint chlorination.
Breakpoint Chlorination
Breakpoint chlorination is the applica-
tion of sufficient chlorine to maintain a
free available chlorine residual. The
principle purpose of breakpoint chlori-
nation is to ensure effective disinfection
by satisfying the chlorine demand of the
water. In waters that contain ammonia
such as wastewater, breakpoint chlori-
nation is a means of eliminating ammo-
nia to achieve a true free chlorine resid-
ual.
Figure 1 shows the theoretical break-
point chlorination curve. Adding chlo-
rine to water that contains ammonia or
nitrogen-containing organic matter pro-
duces an increased combined chlorine
residual. Between points A and B on the
curve, mono- and dichloramines are
formed. Point B represents the point
 where all ammonia has been oxidized to
monochloramine and dichloramine.
Complete monochloramine oxidation to
dichloramine, occurring between points
B and C, results in a decline in the
combined available residuals initially
formed. Point C is the breakpoint: the
point at which chlorine demand has
been satisfied and additional chlorine
appears as free residuals. The free
available residual chlorine increases in
direct proportion to the amount of chlo-
rine applied between Points C and D.
Many factors affect breakpoint chlori-
nation including the initial ammonia ni-
trogen concentration, pH, temperature,
and demand exerted by other inorganic
and organic species. A weight ratio of
8:1 or greater of chlorine applied to
initial ammonia nitrogen is required for
breakpoint chlorination to be reached.
If the weight ratio is less, there is insuf-
ficient chlorine present to oxidize the
chlorinated nitrogen compounds initial-
ly formed. For instantaneous chlorine
residual, the weight ratio required may
be 20:1 or more. Reaction rates are
fastest at high temperatures and pH of 7
to 8 (1).
Determining Breakpoint
A field test can lead you in the right
direction to finding the chlorination
breakpoint. Although the test cannot
replicate the exact conditions of the
system, it is a starting point. The follow-
ing procedure has been used with suc-
cess at several locations.
Test calculation data:
Household bleach 5.25% NaOCl
NaOCl molecular weight (MW) = 74.5
Cl2 MW = 71
71 / 74.5 * 5.25% = 5% as equivalent
free Cl2 or 50,000 ppm in household
bleach
Test procedure:
1. Test the ammonia level in the non-
chlorinated water to evaluated. Record
the result.
2. Add 1 milliliter (mL) of original bleach
solution to 99 mL distilled water. This
makes approximately a 500-ppm solu-
tion.
3. Check strength of 500-ppm solution
by adding 0.2 mL with a syringe to 100
mL distilled water. This should give 1-
ULTRAPURE WATER JANUARY 2003--UP200136
Figure 2. Breakpoint chlorination example.
ppm of free chlorine. Test using the
DPD-free chlorine test. Multiply the test
result by 5. Record the result. This is the
amount of Cl2 per mL that will be add to
a 100 mL sample in Step 5.
4. In five beakers, add 100 mL each of
the water to be evaluated for breakpoint
chlorination. Do not filter.
5. Add chlorine solution to each beaker.
The amount of chlorine solution added
per beaker would be dictated by the
dosage (ppm) of Cl2 desired. The
amount of chlorine added per mL of
prepared solution is: mL added * (ppm
Cl2/mL calculated in Step 3). To achieve
breakpoint chlorination, a minimum ra-
tio of 8:1 of chlorine to ammonia must be
achieved. It is recommend that beakers
1 and 2 be at dosages less than the 8:1
ratio, beaker 3 at the 8:1 ratio, and
beakers 4 and 5 be greater than the 8:1
ratio. This should give a good break-
point chlorination curve. If you have to
add more than 10 mL of chlorine solu-
tion, make a stronger chlorine solution
and start at Step 2.
6. Wait 30 minutes.
7. Test for free chlorine residual.
8. Graph your results.
Another test that can be run on the
same five beakers in the above proce-
dure is monochloramine. Hach offers a
Monochlor-F test procedure for mono-
chloramine. Monochloramine concen-
trations will be zero when breakpoint
chlorination is achieved (test accuracy
is 0.1 ppm as Cl2).
Analytical Test Options
As mentioned before, monochloramines
interfere with the results of the DPD-free
chlorine test. This also holds true for the
Nessler and Salicylate test methods for
ammonia testing. Table B summarizes
the effects of monochloramines on the
available analytical test options.
Testing for ammonia alone using an
ion selective electrode (ISE) will not
determine when breakpoint chlorinate
has been reached since the ammonia
concentration will go to zero ppm prior
to breakpoint chlorination. Point B in
Figure 1 represents the point when am-
monia concentrations are zero ppm.
Case Study #1
A large industrial plant recovered waste-
water for cooling tower makeup by us-
ing RO units. Chlorine was added up-
stream of the RO with a dechlorination
step immediately before the RO. Mem-
brane fouling was becoming a real prob-
lem. Reverse osmosis capacity was
being reduced and membrane-clean-
ing frequency was increasing. The plant
was under pressure to recover more
wastewater via the RO system. Mem-
brane biopsies revealed microbiologi-
cal fouling.
One of the first steps to take when
approaching a problem is to first deter-
mine if the steps currently being taken
are being done properly. The plant was
feeding chlorine at the proper point.
Chlorine was being feed into the clear
well, which was the point of lowest chlo-
rine demand prior to the RO system.
The test records showed a consistent
37
 free-chlorine residual being maintained.
So far so good, but was the free-chlorine
residual they were testing using the
DPD-free chlorine test method really
showing free chlorine or was there mono-
chloramine interference?
Water tested prior to chlorine addition
showed ammonia levels that ranged
from 2.5 ppm to 19 ppm. With water
temperatures of 80 oF and a free chlo-
rine residual control range of 0.25 to 0.5
ppm, you can easily see in Table A that
free-chlorine residual results could be
entirely due to monochloramine inter-
ference! The plant thought they were
getting proper chlorination prior to the
RO, but were getting a much weaker
biocide (monochloramine) instead.
The breakpoint chlorination test pro-
cedure described earlier was conduct-
ed. Figure 2 shows the results from one
round of tests. As you can see, the free
chlorine residual curve closely resem-
bles that in Figure 1. Ammonia was also
tested using the Salicylate method. Even
though monochloramine is an interfer-
ence for this method, Figure 2 shows
that the ammonia level as zero at the
breakpoint where all monochloroamine
had been oxidized. At the breakpoint
and beyond, monochloramine does not
exist and is not an interference to chlo-
rine or ammonia testing.
The two solutions available to the plant
were to increase chlorine feed or sup-
plement with another biocide. Because
of variation in ammonia levels and the
large chlorine demand required to reach
breakpoint chlorination, the plant de-
cided to use dibromocyanoacetamide
(DBNPA) as a supplemental biocide.
With a comparatively minimal DBNPA
usage rate, the plant was able to signif-
icantly increase membrane life and the
time between cleanings.
Case Study #2
A large industrial plant used river water
as makeup to a 2,000-gallons per minute
(gpm) RO system for boiler feedwater
makeup. Due to fouling problems, each
bank of membranes was cleaned twice
a week. Cleaning at this frequency is
not only bad for the membranes, but
requires a lot of manpower commitment.
Reverse osmosis pressure differences,
permeate quality, and RO feed pres-
sure were significantly affected by the
fouling. The plant knew this was a
problem, but had already had many
experts review their system over the
years with no solution. Nine separate
companies had already tried. They were
38
TABLE A
DPD Free Chlorine Interference (ppm)
Monochloramine Sample Temperature F (C)
(NH2Cl) Level (ppm) 40 (5) 50 (10) 68 (20) 83 (30)
1.2 +0.15 0.19 0.30 0.29
2.5 +0.35 0.38 0.55 0.61
3.5 +0.38 0.56 0.69 0.73
5.0 +0.68 0.75 0.93 1.05
Source: Reference 3
TABLE B
Analytical Test Options with Monochloramine
Analysis Test Methods Monochloramine
Interference
Free chlorine DPD yes
Total chlorine DPD no
Monochloramine Monochlor-F no
Ammonia salicylate yes
nessler Yes
ion-selective electrode no
resistant to trying anything else and did membranes, feedwater pressure, and
not want the RO touched. permeate quality were each greatly im-
The advantages of solving this prob- proved.
lem were obvious: longer service runs, With the result of the pilot study as
less damage to membranes, minimized proof, the plant implemented breakpoint
membrane replacement costs, reduced chlorination dosages on the current RO
manpower costs, lower water produc- and experienced a similar success.
tion costs, and decreased pumping
costs. Conclusion
First, the concepts of breakpoint chlo- The application of breakpoint chlorina-
rination were applied. The ammonia tion with RO pretreatment has success-
concentration in the makeup water was fully been used to solve baffling micro-
determined. The breakpoint chlorina- biological fouling problems of RO mem-
tion test procedure previously described branes. Although the customers thought
was conducted to find the proper chlo- they were applying sufficient chlorine
rine dosage to reach breakpoint chlori- for disinfection, what they were actually
nation. The plants current chlorine dos- measuring was monochloramine inter-
age was nowhere near that required for ference to the DPD free chlorine test.
breakpoint chlorination. A higher dos- Determining the breakpoint chlorination
age was required for proper disinfec- allowed the customers to better disin-
tion of the raw water prior to being intro- fect their RO feedwater and resulted in
duced to the RO. longer service runs between membrane
Next, to prove the findings, a pilot RO cleanings.
unit was set up parallel with the current Reverse osmosis systems are compli-
RO system. Breakpoint chlorination cated with many factors to consider.
dosages of chlorine were added to the The application of breakpoint chlorina-
pilot RO pretreatment train with the wa- tion is just one of those factors that must
ter being dechlorinated prior to entering be considered. When approaching any
the RO. Once breakpoint chlorination problem, one of the first steps should be
was achieved and a true free chlorine to ensure that the current technology
residual was maintained throughout the and treatments are being properly ap-
pretreatment train, the pilot RO perfor- plied. Taking into account breakpoint
mance was greatly improved over that chlorination, as described in this article,
of the current RO system. Much longer is a good method to determine if chlo-
service runs between cleanings were rine chemistry is being properly
observed. Pressure drops across the applied.
ULTRAPURE WATER JANUARY 2003--UP200136
 References
1. Betz Handbook of Industrial Water Con-
ditioning, 9th ed., Betz Laboratories, Inc.,
Trevose, Pa., pp. 196-199, (1991).
2. White, G.C. The Handbook of Chlorina-
tion, 2nd ed., Van Nostrand Reinhold Co.,
New York, N.Y., pp. 162-167 (1986).
3. Water Analysis Handbook, 3rd ed., Hach
Co., Loveland, Colo., p. 351 (1992).

Author James McDonald, EIT, is a tech-

nical support engineer and MIS director
with CROWN Solutions Inc. in Dayton,
Ohio. He holds a masters of engineering
degree for chemical engineering from
the University of Louisville J.B. Speed
Scientific School.

Key words: CHLORAMINES, CHLO-

RINE, MEMBRANES, MICROBIALS,
PRETREATMENT, REVERSE OSMOSIS

ULTRAPURE WATER JANUARY 2003--UP200136 39