DREW INDUSTRIAL DIVISION COOLING WATER TREATMENT

Bromination: Advances in Oxidizing Microbiocides

Bromine microbiocides are increasingly becoming Figure 1

mainstays in todays advanced cooling water treatment
programs. Bromine demonstrates several distinct HYPOHALOUS ACID (UNDISSOCIATED)
advantages over chlorine and even many non-oxidizing IN AQUEOUS SOLUTIONS
biocides. This bulletin reviews the technology and
application benefits of bromine-based microbiocides.
Percent HOCl or HOBr
100
pH Considerations
80
Bromine, like chlorine, has long been known to act as an HOBr
oxidizing microbiocide. The active toxicant is hypobromous 60
acid (HOBr) which can be formed from several different
40 HOCl
bromine donors. Hypobromous and hypochlorous acid will
both dissociate according to the following equations:
20
- +
HOBr <------> OBr + H
0
(Hypobromous Acid) (Hypobromite Ion) (Hydrogen ion) 4 5 6 7 8 9 10
pH
HOCl <------> OCl- + H+
(Hypochlorous Acid) (Hypochlorite Ion) (Hydrogen Ion)
Hydrochloric acid reacts with system alkalinity and drives
The degree of dissociation is significant due to the fact that pH downward, increasing the corrosion potential of mild
the hypohalous acid form (HOCl, HOBr) is approximately steel, copper and copper alloys while chloride ions also
80 times more toxic than the corresponding hypohalite ion. accelerate corrosion mechanisms. There are even some
The dissociation is pH dependent and greatly favors laboratory results showing that chlorine exerts 2 to 3 times
bromine over chlorine above pH 7.5. Figure 1 shows the the corrosive influence of bromine on 90/10 copper/nickel
percent available HOBr vs. HOCl over the range of at equivalent oxidant levels and pH of 8.1-8.3. Additionally,
commonly encountered cooling water pH. Thus, for the generally lower use rates of bromine mean less corrosion
systems operating at above pH 7.5, bromine is increasingly from excessive oxidant levels.
more efficient than chlorine. This benefit is particularly
important in highly alkaline cooling waters (pH 8.0-9.3)
where only a very small percent of chlorine is available as Environmental Aspects
HOCl. Discharge limitations for chlorine are becoming increasingly
strict, primarily due to the formation of undesirable
chlorinated organics in cooling systems.
Corrosion Concerns
Application of a bromine microbiocide is generally less These chlorinated by-products can be carcinogenic,
aggressive toward system metallurgy than gaseous nondegradable and acutely toxic to aquatic life. Therefore,
chlorine. When gaseous chlorine is dissolved in water, it total residual oxidant (TRO) discharge limits have often
hydrolyzes according to the following equation: been placed on chlorine.

Cl2 + H20 ------> HCl + HOCl

(Gaseous Chlorine) (Hydrochloric Acid) (Hypochlorous Acid)

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Environmentally, bromine chemistry again differs
significantly from chlorine. Bromamines, for example, have
a half-life of minutes compared to many hours for
chloramines, thereby being less persistent in the
environment. Additionally, bromamines are toxic to
microorganisms where as chloramines are significantly less
active. This is particularly advantageous in systems
contaminated with ammonia. The rate of decay trend is also
followed for organobromides and their chlorine analogs.
Figure 2 shows the relative decay ratios of bromamine and
chloramine.
Figure 2
RELATIVE DECAY RATIOS
Application
Feeding of bromine-based biocides is simple and easy to
control. Solid products can be fed via a shot feeder and timer
mechanism or simply added to an area of the tower basin
that maintains enough flow for dissolution to occur. Liquid
sodium bromide needs to be activated with sodium
hypochlorite or gaseous chlorine. When hypochlorite is
used, two chemical metering pumps and a static mixer are
employed to insure adequate contact and mixing before
introduction into the tower water. Chlorine gas may also be
used as an activator but requires the normal feed equipment
associated with gaseous chlorination.
Activation reactions for sodium bromide are as follows:
(1) Sodium Hypochlorite

NaOCl + H2O ---------> HOCl + NaOH

6
Concentration, ppm

5 Bromamine HOCl + NaBr ---------> HOBr + NaCl

4
Chloramine
(2) Gaseous Chlorine
3
2 Cl2 + H20 ---------> HOCl + HCl
1
HOCl + NaBr ---------> HOBr + NaCl
0
0.05 0.25 0.45 0.65 0.85 1.05 1.25 1.45 As with chlorine, contaminants in the system water may
exert a demand on hypobromous acid. This demand must
Time, Hours
be satisfied before a free residual bromine can be detected.
Before determining the dosage for a particular system, it is
advisable to determine the system's "bromine demand".
Safety Concerns
Bromine is available as a safe, easy-to-apply solid product or Summary
as liquid sodium bromide which is relatively non-
hazardous. In many cases, gaseous chlorine can be Bromine is a viable option for controlling microbes in
completely eliminated from the plant site when changing to cooling systems. It demonstrates many advantages over
bromine donors. Additionally, utilizing bromine as a traditional chlorination techniques and is often the
toxicant allows plants to operate their cooling systems at microbiocide of choice with todays advanced corrosion and
alkaline pH and eliminate the hazards and risks involved deposit control programs.
with handling concentrated acid.

OX-AB-020