Section 3.

4
CLOSED RECIRCULATING SYSTEMS

In closed recirculating systems, heat is transferred to the cooling water from the hot process,
and then it is transferred out of the cooling water by conduction in another piece of heat transfer
equipment. No water is evaporated or concentrated. A system is considered “closed” when it is
designed to be filled with water once and then run continuously for long periods of time without
any significant amount of makeup water added. In closed cooling systems, the heat is usually
dissipated by an auxiliary open cooling loop or forced air that passes over tubes containing the
closed system water (as in a fin-fan cooler).

CLOSED SYSTEMS extrusion or molding systems, continuous

casting systems in steel mills, and induction
Figure 3.4.1 illustrates a typical closed recircu-
furnaces.
lating system. The methods employed in a closed
recirculating system for transferring heat to the
Discharge restrictions —A system may be
atmosphere are not as efficient as a cooling
closed to reduce or eliminate discharge due
tower. In some applications, a closed recirculat-
to governmental regulations against chemical
ing system is preferred. The following are some
or thermal pollution, lack of adequate waste
important reasons why a closed system would
treatment facilities, or a variety of other reasons.
be used:
In these cases, air-cooled heat exchangers
(fin-fan coolers) may be used.

Limited water sources—There are limited water

sources or it is more convenient to use forced
air-cooling, as in moving vehicles.

Extended equipment life—Large amounts of

cooling are not required and the easiest method
of extending equipment life is through closing
the system, thereby reducing corrosion. Chiller
systems usually fall into this category.

Restrictions on chemical usage—Because of

Figure 3.4.1 - Schematic of a typical closed
recirculating system
Critical processes—The system requires very
clean heat transfer surfaces and it is believed that
the variability of operating conditions normally
encountered in an open recirculating system
cannot be tolerated or skin temperatures are too
high for effective scale control with an open
system. Examples are primary cooling loops in
nuclear plants, compressor cooling, plastic
the nature of the process, there may be restric-
tions against the use of some chemicals. For
example, the water used in induction furnaces
must have very low conductivity (dissolved
solids) due to the electrical current in the
induction heater. Therefore, many cooling
system products cannot be used.
Other types of equipment that do not require
cooling are also treated as closed systems. In
general, a system may be treated as closed if
there is no significant concentration of the solids
in the water and it is not directly open to the
atmosphere (not highly oxygenated).

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Section 3.4
CLOSED RECIRCULATING SYSTEMS
The following are examples of non-cooling
closed systems:
• Hot water boilers that are closed to conserve
heat but often may be treated economically
with closed system products.
• Storage tanks or other equipment that are
filled with water and closed off from the
atmosphere. Emergency stand-by tanks and
thermal storage tanks are included in this
category.
• Equipment that is tested with water (hydro-
tested) and closed from the atmosphere
during testing. Engine test stands are an
example of this type of process.
All closed systems consist of at least an appara-
tus for heating or cooling a recirculating fluid, a
recirculating pump, and a heat exchanger
designed to heat or cool another medium. This
second medium can be air, water, or an industrial
process stream. Recirculating velocities gener-
ally range from 3-5 ft/s (0.9-1.5 m/s), but can be
as high as 30-40 ft/s (9-12 m/s) for extremely
high heat flux applications, such as billet con-
tinuous casters for steel.
Table 3.4.1 - Metals used in closed recirculating cooling water systems
Group A Group B
Iron Copper
Steel Admiralty Brass
Cast Iron Admiralty Brass (Inhibited)
Monel
Red Brass
Muntz Metal
Naval Brass
Cupronickel
Aluminum Brass
Aluminum Bronze
68 CONFIDENTIAL, For Nalco Employee Use Only 2005 Nalco Company
The temperature change in the recirculating
fluid generally averages 10-15ºF (5-8ºC) for the
typical system. Occasionally, much greater
temperature changes are encountered. Maximum
temperatures can be as high as 350ºF (175ºC)
(e.g., in hot water systems), and minimum
temperatures can be as low as 30ºF (-1ºC)
(e.g., in chilled water systems). These systems
theoretically use very little makeup water,
generally averaging 0.1-0.5% of system capacity
per day. No water bleed-off from closed systems
is generally planned, but water losses usually
occur in the average system from leaks around
expansion tanks, pumps, seals, and valves.
Conditions during operation are generally
steady; however, some systems are subject to
frequent on-off conditions.
Table 3.4.1 indicates the variety of metals
typically found in a single closed recirculating
system. In general, if the system is constructed
of metals within the same group, the chance for
galvanic corrosion is reduced. The more widely
separated the coupled metals are (in terms of
groups), the greater the galvanic corrosion
potential. Galvanic corrosion is discussed in
more detail in the Corrosion section as follows.
Group C Group D
Aluminum Stainless Steel
Alclad Aluminum Nickel
PAC-3 Cooling Water Technical Manual (01-05)
 Section 3.4
CLOSED RECIRCULATING SYSTEMS

COMMON OPERATING PROBLEMS recirculating systems require significant makeup

due to loss of water from leaks, overflows
Corrosion, scale, fouling, and microbial growth
through pressure-releasing valves, and unautho-
are considered the four major problems in all
rized use of water for wash-up purposes. Oxygen
types of recirculating water systems. All of these
can enter with this makeup and through air
problems are of importance in closed recirculat-
entrainment at pumps, valves, and air cushion
ing systems because corrosion is significantly
tanks.
affected by fouling and microbial activity.
Scaling interferes with heat transfer of the
Another type of attack is galvanic corrosion.
process and can lead to process-side problems.
This attack results from the potential difference
that exists when two different metals are physi-
Without any provision for the removal of
cally joined. The factors shown in Table 3.4.2
corrosion products in system blowdown,
that accelerate or control galvanic corrosion
the closed system is particularly subject to
serve as a basis for avoiding or minimizing
clogging of small valves and ports, erosive and
corrosion either by design change or by correc-
abrasive attack, and attack beneath deposits as a
tive treatment measures. Galvanic attack is of
result of the increased suspended solids resulting
particular concern in closed recirculating
from corrosion. For this reason, it is imperative
systems because joined dissimilar metals are
to minimize corrosive attack in these systems.
frequently found in such systems.
CORROSION
Table 3.4.2 - Factors affecting galvanic corrosion
The dissolution of a metal in water is essentially
an electrochemical process. Metal dissolves at Accelerates Decelerates
anodes, leaving electrons behind. These elec- Corrosion Corrosion
trons flow through the remaining metal to other Large electrode Small electrode poten-
points called cathodes where reactions that potential difference as tial difference as
evidenced by relative evidenced by relative
consume electrons occur. In this reaction, the position in galvanic position in galvanic
anode is the site of obvious corrosion. Refer to series series
Section 3.10 for more detail on corrosion issues Large ratio of cathodic Large ratio of anodic
and mechanisms. area to anodic area area to cathodic area
High electrolyte Polarization
The two points between which electrons flow content
form a corrosion cell. However, a corrosion cell High velocity Insulation
can be established as a result of a number of
Increased temperature Painting or coating
different mechanisms:
Increased aeration Cathodic protection
1. Oxygen reactions in water Corrosion Inhibitors
2. Dissimilar metal coupling
3. Differential concentration cells The metals that are of most concern when
considering galvanic corrosion are nonferrous-
Oxygen in water reacts with active metal ions type metals that are cathodic to steel in a
and upsets the normal equilibrium conditions at galvanic cell. One example is the use of steel
the metal surface, permitting corrosion to adjacent to copper or copper alloys. In this case,
continue. In a closed system, the oxygen in the the steel, being anodic to copper, corrodes
recirculating stream could be rapidly depleted rapidly. Other couples to avoid are copper-
due to corrosion. Unfortunately, many closed aluminum and steel-aluminum. Copper-alumi-

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Section 3.4
CLOSED RECIRCULATING SYSTEMS
num is an especially bad couple, because the
copper and aluminum are widely separated in
the galvanic series, and the corrosion rate of the
cell is high.
Physical deposition of solids is another impor-
tant factor that can establish a potential differ-
ence with resulting corrosion. A difference in
electrolyte concentration between two points on
a metal is sufficient to promote corrosion,
because this difference is all that is needed to
encourage the flow of electrons. The fact is that
such a difference can exist between metal
surfaces in crevices or beneath deposits. Good
system design should minimize crevice attack,
and proper water treatment should eliminate the
presence of deposits.
SCALE
Theoretically, under the conditions that exist
in a truly closed recirculating system, all of
the common scale-forming constituents in the
system water (such as calcium carbonate,
calcium sulfate, magnesium salts, and silica) can
deposit on metal surfaces without any noticeable
results because such small quantities are in-
volved. However, in the more typical, higher-
makeup closed system, additional scale will
precipitate with each new increment of water
added to the system. In time, this scale will
assume significant proportions, plugging water
passages, reducing heat transfer, and promoting
corrosion.
Another type of deposit, encrustation, can result
at leaky flanges or pump seals. Water evaporates
at these points and leaves behind all of the
dissolved solids it once carried. This type of
“scale” can cause premature failure due to
concentration cell attack on the metal beneath
moist deposits. See Section 3.9 for detailed
discussion on corrosion mechanisms.
70 CONFIDENTIAL, For Nalco Employee Use Only 2005 Nalco Company
High temperatures such as 200-220ºF (90-105ºC)
will accelerate corrosion reactions or can lead
to surface boiling and solids deposition with
subsequent differential cell attack.
FOULING
The terms scale and fouling are often used
interchangeably to include all those materials
that coat metal surfaces in recirculating systems.
With continual development of improved
treatments and better technology, it is more
descriptive to restrict the term scale to cover that
deposit resulting from the super-saturation of
otherwise soluble water constituents. Fouling, on
the other hand, includes a broader range of
materials that are generally softer, less adherent
and that come from a number of different
sources. Table 3.4.3 lists some typical foulants.
Table 3.4.3 - Common fouling materials
Foulant
Corrosion products
Sand
Cutting oils
Joint compounds
Construction debris
Process-side contamination
Hydrocarbons
Casting oils
Many of these fouling materials are the result of
residue from the construction of new systems,
contaminants introduced with makeup water, leaks
from process equipment, and most often from
incomplete or inadequate corrosion control.
When these foulants deposit on metal surfaces in
the system, the conditions for concentration cell
attack are established. In addition, these foulants
reduce system efficiency by clogging valves,
small orifices, and recirculating lines. Dispers-
ants are often used to help control corrosion
product fouling.
PAC-3 Cooling Water Technical Manual (01-05)
 Section 3.4
CLOSED RECIRCULATING SYSTEMS

MICROBIAL GROWTH
It may seem that because the average closed
system sees little sunlight and has low oxygen
content and few nutrients, there is no problem
with microbial growth. In reality, microbial
growth can be severe for the following reasons:

• Higher makeup rates introduce more oxy-

gen, debris, and nutrients and serve to
inoculate the system.

• Process leaks can also provide excessive

high amounts of food.
• Many closed systems use tanks that are open
to the atmosphere or have entrainment of air
at seals, so oxygen levels can be at or close
to saturation.
• Some corrosion inhibitors can become food
for bugs.
All of these factors point to microbial problems
in many systems, and experience has proved this
to be the case. Microbial problems contribute to
fouling, corrosion, and loss of heat transfer. In
fact, biofilms are among the most insulating
deposits encountered on heat transfer surfaces.
Figure 3.4.2 - Cooper sheets plated on steel as
a result of acid reuse
Another type of very distinctive metal attack,
caused by vibration, occurs more frequently than
supposed in closed systems. Vibration causes
physical breakdown or cavitation of the metal by
water. This results in a honeycombed appearance
of the metal. (See Figure 3.4.3.) The pieces of
metal torn free can, like corrosion products,
deposit elsewhere in the system to set up gal-
vanic or differential cell attack. They can also
clog small control parts, or, in being carried by
the water stream, cause abrasive attack on other
metal or seal surfaces.

OTHER PROBLEMS
Closed recirculating systems are also subject to
the deposition of metallic ions that have been
removed from parent metal elsewhere in the
system. For example, copper ions corroded from
heat exchange tubes can be reduced to pure
copper on other metals with a resulting bimetal-
lic couple. (See Figure 3.4.2.) Severe pitting
corrosion will result. Acid used initially to clean
copper alloy heat exchangers and subsequently
used to clean other metals can cause copper
plating. The dissolved copper ions in the acid
can coat the steel or other more active metals,
resulting in bimetallic couples and severe Figure 3.4.3 -Result of vibration attack on
corrosion. engine cylinder

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PAC-3 Cooling Water Technical Manual (01-05)
Section 3.4
CLOSED RECIRCULATING SYSTEMS
CORROSION CONTROL
At this point, it is desirable to decide just what
is meant by practical corrosion control in closed
recirculating systems. In some systems, this term
can be defined by corrosion rates less than a
certain value on a specific type of metal. For
example, a general etch attack on mild steel of
less than 3 mpy (<75 µm/y) is usually considered
satisfactory protection in open recirculating
systems.
On the other hand, practical corrosion control
can also be defined in terms of maintenance
costs or system operating efficiency. Most
frequently, in closed recirculating systems,
control is considered to be satisfactory as long as
the system continues to operate efficiently with
a minimal amount of necessary maintenance.
Because of the characteristics of closed systems
and the more than usual problems that corrosion
products cause, it is important to minimize
corrosion from the start of system operation.
NON-CHEMICAL TECHNIQUES
A number of non-chemical steps can be taken
to minimize corrosion in a closed recirculating
system. The basic objective is to design and
operate the system efficiently by effectively
eliminating or minimizing water losses and
eliminating bimetallic couples.
Probably the most important step involves taking
actions that eliminate or minimize loss of water.
Thus, less fresh makeup water is required and
treatment residuals are more easily maintained.
Water added to a system brings oxygen and
other dissolved gases that renew or intensify the
corrosion in the system. In addition, system
makeup water can carry suspended solids that
can also promote corrosion.
Tightening up connections within a system,
periodically checking all possible water take-off
points, and eliminating or minimizing system
72
draining and flushing can all help reduce corro-
sion or indicate those points where system
modifications may be necessary to maximize
corrosion protection.
Ion exchange softened water, demineralized
water, and even steam condensate have been
used as makeup water for closed systems.
Softened water reduces the chances of scaling,
but increases the corrosivity of water by unbal-
ancing the calcium/alkalinity relationship.
Subsequent chemical treatment of the recirculat-
ing water can compensate for this increased
corrosivity. However, it is generally not neces-
sary to use softened water for closed system
makeup, particularly if the amount of makeup
water is low, except in high heat flux applica-
tions or high temperature systems, which must at
least have softened water makeup. The type of
suspended solids-free water usually available
from a municipal or well water source is almost
always satisfactory unless considerable makeup
is required.
Finally, corrosion resistance of a system
can be maximized through the selection
of corrosion-resistant metals. Economics gener-
ally is the deciding factor in materials selection.
Ideally, a single metal should be specified
throughout a system to avoid dissimilar metal
corrosion. Minimizing the number of different
metals to reduce galvanic corrosion problems
will greatly improve corrosion control. Occa-
sionally, coatings have been applied to metal
surfaces in a closed system to reduce corrosion.
CHEMICAL TREATMENT
SYSTEM PREPARATION
When considering chemical treatment tech-
niques, it is important to provide corrosion
protection from the very start in a new system
or in a system from which deposits are to be
removed prior to startup.
CONFIDENTIAL, For Nalco Employee Use Only 2005 Nalco Company
PAC-3 Cooling Water Technical Manual (01-05)

CLOSED RECIRCULATING SYSTEMS
Previous discussion has shown that suspended
solids in a closed recirculating system are the
cause of problems such as corrosion beneath
deposits, erosion of metal surfaces, clogging of
lines and ports, and damage to mechanical seal
surfaces. Therefore, for the most effective
corrosion protection of either a new or dirty
system, the system must be cleaned. In new
systems, materials to be removed include mill
scale, pipe dope, dirt, grease, and sand. In a
system that as been in operation or has been
standing idle, the same materials may be found,
as well as corrosion products.
A three-step program is generally recommended
to put a new system into condition for effective
corrosion control.
1. The system must be cleaned with wetting
agents, an iron clean-up program, or inhibited
acids (in the case of heavy deposits).
2. The metal surface must be prepared for the
acceptance of a protective film.
3. Metal surfaces must be passivated by laying
down a corrosion-resistant film.
To a large extent, the practice today is to start
operating a new system without any prior
treatment. Occasionally, the system is flushed
with untreated water, a practice that may initiate
corrosion. By the time treatment is started, some
damage has been done. After acid cleaning and
neutralization, it is not unusual to observe the
formation of a thin film of corrosion products on
metal surfaces. This is due to the reaction of the
very active surface of the acid-cleaned metal
with the oxygen of the air. These corrosion
products will resist formation of a protective
film once inhibitor is added and will contribute
to the suspended solids concentration in the
recirculating water.
CONFIDENTIAL, For Nalco Employee Use Only 2005 Nalco Company
PAC-3 Cooling Water Technical Manual (01-05)
Section 3.4
Therefore, it is most desirable in new and acid-
cleaned equipment not only to remove deposits
of every kind before starting up the system but
also to minimize the time between system
cleaning and the addition of treatment. Chemical
formulations are available today to perform all
three functions (cleaning, passivating, and film-
forming) in one application. Figure 3.4.4 illus-
trates the type of performance that can be
expected from these materials.
A B
Figure 3.4.4 - (A) Heat exchanger channel
showing corrosion resulting from hydrotesting
(B) Heat exchanger channel after pretreatment
CHEMICAL TREATMENT TECHNIQUES
Various types of chemicals are capable of
protecting closed system metals effectively and
very economically. The most widely used types
today are various boron-nitrite formulations,
molybdate blends, all-organic programs, and
dispersible oils. (Environmental concerns have
placed restrictions on the use of chromate-based
treatments, which were commonly used in the
past. Their use is already low and expected to
decline further.) Occasionally, sodium silicate
formulations, chelating agents, special filming
agents, and oxygen scavenging materials have
been used for specific applications.
73
Section 3.4
CLOSED RECIRCULATING SYSTEMS
These chemicals protect system metals against
corrosion by forming extremely thin, highly
corrosion-resistant films on metal surfaces. In
many cases, these films are the result of an
interaction between the chemical inhibitor and
the reactive metal surface. In other cases, purely
physical films of the inhibitor are laid down. To
maintain these films, a certain minimum level of
inhibitor must be maintained. Below these
minimum levels, a previously established film
will be removed from the metal, and corrosion
will take place. Because temperature will affect
corrosion rates, higher levels of treatment will
be required at higher temperatures.
In closed recirculating systems, maximum
corrosion prevention involves the use of high
inhibitor levels that are definitely more eco-
nomical than they would be in open recirculating
systems. High inhibitor levels are required to
assure the practical elimination of corrosion
resulting from the coupling of dissimilar metals.
They also provide back-up protection should an
unexpected water loss lower treatment levels.
This insurance is particularly important in closed
recirculating systems, because the start of
corrosion will introduce insoluble corrosion
products with their attendant problems.
In the past, exceptionally high levels of
chromates had been thought to be responsible
for failure of mechanical seals in closed recircu-
lating systems. This failure was theoretically the
result of an actual chemical attack on the seal
surfaces. Data have shown that chemical corro-
sion-inhibiting treatments, including chromates,
are no more responsible for these problems than
are other dissolved and suspended solids usually
found in recirculating water. Equally important
is the proper installation of pump seals.
A question often arises when pump seal failures
occur: Should the inhibitor be eliminated to
protect the pump seals, allowing corrosion to
74 CONFIDENTIAL, For Nalco Employee Use Only 2005 Nalco Company
occur in the system with plugging and possible
failure of the metal components? The reasonable
answer is to fix or modify the weakest link in the
system (the pump seal) rather than to permit the
entire system to fail.
The goal of corrosion control in closed systems
is to establish as close to 100% protection as
possible of all metals. Effective treatments, when
properly controlled and maintained, approach
this goal.
Chromate-Based Treatment—Treatment with
buffered chromate or dichromate salts of sodium
has been used historically in closed recirculating
systems and has provided extremely low corro-
sion rates of 0.01 mpy (0.25 µm/y) or less on
steel. Chromate treatments are used at pH levels
of 7.0-9.5, depending upon the system character-
istics. The most commonly recommended chro-
mate levels are in the range of 600-1500 mg/L
CrO4. The lower end of this range is generally
recommended for low-temperature systems,
such as chilled water loops. Higher chromate
levels, in excess of 1500 mg/L, are sometimes
recommended to provide the greatest possible
protection against galvanic corrosion resulting
from dissimilar metals. These higher levels have
proved to be extremely effective in preventing
galvanic attack, although it is very difficult, if
not impossible, to eliminate this type of attack
completely when widely different metals are
joined. Finally, maintaining higher levels of
chromate in a closed system appears to offer a
degree of protection against erosive attack due to
high water velocities or high-suspended solids.
Because chromate is an anodic inhibitor, it is
essential that a continuous chromate film be
maintained at all times. At chromate levels
below 200 mg/L, an inhibiting film can develop
inconsistencies. All attack will be concentrated
at individual points, causing severe pitting.
PAC-3 Cooling Water Technical Manual (01-05)

CLOSED RECIRCULATING SYSTEMS
Three limitations apply to the use of chromates
in closed recirculating systems:
1. Chromate is a priority pollutant and faces
severe environmental restrictions. Relatively
few locations continue to use chromate today.
2. The chromate ion will react with ethylene
glycol and common antifreeze alcohols. The
reaction results in inactivation of the chro-
mate as a corrosion inhibitor and the forma-
tion of a precipitate. In those cases where it is
necessary to use antifreeze in a closed system,
other inhibitors, such as nitrite and molyb-
date, should be selected.
3. Chromate in the hexavalent form (which is the
inhibiting form) is subject to reduction to the
trivalent form (non-inhibiting and sludging
form) by a number of chemicals, such as
hydrogen sulfide, stack gases, nitrites, and
many organics. Chromate cannot be used in
systems containing such compounds.
Boron-Nitrite-Based Treatment—Blended
formulations containing sodium nitrite (NaNO2)
are perhaps the most common treatment pro-
grams used today in closed loop systems, both
hot and cold. The formulations typically contain
borate to buffer the system pH between 8 and
10.5 and azoles for copper alloy corrosion
protection. Additional components might include
nitrate or silicate for aluminum corrosion
protection, polymers for suspended solids
dispersion, and scale inhibitors. Nitrite works
well in reducing environments. Nitrite oxidizes
mild steel surfaces to form an extremely thin and
highly tenacious corrosion product layer. When
mild steel corrodes, the nitrite will oxidize the
ferrous iron (Fe+2) released by the metal to iron
oxides. The nitrite is reduced to ammonia in this
reaction. This passivation process will consume
nitrite, but the amount of nitrite lost is generally
CONFIDENTIAL, For Nalco Employee Use Only 2005 Nalco Company
PAC-3 Cooling Water Technical Manual (01-05)
Section 3.4
small, especially if sufficient nitrite is present
and passivation occurs quickly. If nitrite con-
sumption is high, it is indicative of a number of
problems, primarily microbial oxidation of
nitrite to nitrate, but it can also indicate repeated
corrosion and re-passivation of the metal.
Boron-nitrite inhibitors are compatible with
ethylene glycol and alcohol antifreeze mixtures.
The effectiveness of boron-nitrite formulations
is illustrated in Table 3.4.4.
Nitrite is an oxidizing, anodic corrosion inhibi-
tor for mild steel and requires a minimum nitrite
concentration within the water to maintain the
passive metal film and good corrosion control. If
the nitrite concentration repeatedly drops below
the minimum critical concentration, mild steel
corrosion will increase. The typical mode of
corrosion when dropping below the critical
concentration of nitrite is pitting corrosion. High
chloride and sulfate levels will increase the
demand for inhibitor because of increased
corrosiveness of the water and potential break-
down of the oxide film. The critical nitrite
concentration is system specific and depends on
water chemistry, temperature, metallurgy, and
operating conditions. Maintaining the minimum
nitrite concentration is critical to successful
application of a nitrite treatment program.
Dosages of boron-nitrite inhibitors generally
range from 500-2000 mg/L active nitrite.
Besides the initial nitrite loss due to system
passivation and on-going corrosion control,
nitrite loss can be due to several other mecha-
nisms. It is important to understand and be able
to identify these mechanisms so that corrective
action can be taken to prevent nitrite loss and
maintain the minimum nitrite concentration.
Several mechanisms that can lead to nitrite loss
in closed loop systems are discussed as follows.
75
Section 3.4
CLOSED RECIRCULATING SYSTEMS

Table 3.4.4 - Corrosion control in closed polymetallic cooling systems

Corrosion Rates, MPY* (Coupled)

Commercial Antifreeze No. 1 Commercial Antifreeze No. 2
Metal Uninhibited 0.75 oz/gal Uninhibited 0.75 oz/gal
Boron Nitrite Boron Nitrite
Cast Iron 6.3 0.2 3.5 0.2
Aluminum 11.4 0.7 66.7 2.4
Solder .07 1.0 0.5 0.7
Copper 1.1 0.5 0.6 0.2
Brass .07 0.2 0.5 0.1
(Insulated)
Cast Iron 4.3 0.3 9.6 0.3
Aluminum 13.8 0.5 17.6 0.6
Copper 2.1 0.5 1.9 0.5
Brass 0.8 0.3 1.5 0.2
* 7 days at 189°F (87°C)

WATER LOSS often be detected by measuring the water

Obviously, if water loss occurs in a closed loop
system, the treatment products will be lost too.
Water losses are common in many closed loop
systems, and this is a common cause of low
treatment residual. Performing a Diagnostic
TRASAR® procedure is an excellent method to
determine if water losses are occurring, as well
as to measure the system volume accurately.
Note that sealing gland losses from the recircula-
tion pumps can represent a significant water loss
from a closed loop system.
Water loss from a closed loop system can often
be confirmed with conductivity testing. If both
the treatment residual and the water conductivity
decrease, water loss is likely. If only the treat-
ment residual decreases, then another cause for
nitrite loss should be investigated.
BIOLOGICAL ACTIVITY
A common biological problem in closed loop
systems treated with nitrite is nitrifying bacteria,
which oxidize nitrite to nitrate. This problem can
conductivity and comparing the nitrite and
nitrate concentrations. If nitrifying bacteria are
an issue, the nitrite residual will decrease while
the nitrate concentration will increase. The water
conductivity will remain relatively unchanged,
but the water pH can drop due to the formation
of nitric acid. If the water conductivity decreases
along with the nitrite residual, then water loss is
likely responsible and should be investigated.
Denitrifying bacteria can also be a problem
in closed loop systems. Denitrifying bacteria
convert nitrite and nitrate to nitrogen gas or
ammonia, which can increase corrosion of
copper alloys. Denitrifying bacteria may be
simply Pseudomonas. Keep in mind that
Pseudomonas bacteria will convert nitrite in
areas of the system that are low in oxygen. They
prefer to use oxygen, but in its absence, they
will use nitrite. Another area to consider is
slime masses or biofilm. Although bulk bacteria
counts may look good, if there is any slime
build-up in the system, nitrite could be reduced
without showing any denitrifiers in a bulk water

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sample. If denitrifying bacteria are suspected,
the nitrite and ammonia concentrations should
be tracked.
Differential Microbiological Analysis (DMA)
can be used on both water samples and surface
swabs, but nitrifying and denitrifying bacteria
are difficult to culture and detect. Bulk water
DMA results only indicate a presence or absence
of denitrifying or nitrifying bacteria in the bulk
water sample taken. A swab DMA result is more
useful because these bacteria tend to be in
biofilm rather than in bulk water. For these
bacteria, other monitoring methods are often
more reliable. Typically, when nitrite loss is
believed to be due to biological activity, nitrite,
nitrate, and ammonia concentrations should be
tracked for confirmation.
OXIDATION
The standard Redox tables show the reaction of
nitrite and oxygen to form nitrate to be thermo-
dynamically unfavored at high pH but favored at
low pH. If the nitrite program is buffered to
produce a system pH greater than 8.5, the
oxidation of nitrite by air is not a real concern.
However, it is possible in a closed loop system
for oxygen to promote corrosion, and the nitrite
can then be consumed repassivating the metal as
discussed above.
Lab work and field experience with nitrite
in open recirculating systems show that nitrite is
not readily oxidized by air in alkaline water
systems. Nitrite does not oxidize appreciably to
nitrate from contact with the air in the cooling
tower. However, nitrite does react quickly to
form nitrate on contact with an oxidizing
biocide. Therefore, oxidizing biocides should not
be used with nitrite in closed loop systems.
In a Pilot Cooling Tower (PCT) study, nitrite was
maintained in an open recirculating water
system. However, it required the use of nonoxi-
dizing biocides to keep the tower water micro-
CONFIDENTIAL, For Nalco Employee Use Only 2005 Nalco Company
PAC-3 Cooling Water Technical Manual (01-05)
Section 3.4
bial counts very low. Once biological activity
was established, the nitrite was rapidly converted
to nitrate. The major problem with nitrite in open
systems is biological, not oxidation by oxygen.
Nitrite can either be oxidized to nitrate or
reduced to nitrogen by bacteria.
In the absence of the enzymes provided by the
microbial activity, nitrite does not react readily
with oxygen at typical cooling water pH. How-
ever, it is still good practice to minimize aeration
in closed loop systems. Oxygen ingress to a
closed system might increase corrosion, particu-
larly if the nitrite level is lower than the optimal
recommended (500-2000 mg/L). The increased
corrosion will increase nitrite consumption to re-
passivate the metal surface, but again, this loss
should be low, unless the nitrite level is below
500 mg/L initially, and corrosion continues to
occur. The source of the oxygen ingress should
be found and mechanical methods used to
eliminate the oxygen. Methods might include
replacing pump packing with mechanical seals,
replacing air with an inert gas in the suction
tank, and using an expansion tank with a bladder
to prevent air contact with the closed loop water.
Water returning to a tank should be directed
below the water surface to prevent unnecessary
turbulence and aeration.
Any ingress of oxidants will tend to oxidize the
nitrite to nitrate. Therefore, oxidants should not
be used for biocontrol. If the closed loop system
can be contaminated by another system, such as
a cooling tower system containing an oxidant,
additional monitoring should be implemented to
detect and correct the contamination.
HIGH TEMPERATURE
The Merck Index reports the decomposition
temperature for sodium nitrite as 320°F
(160°C). Additionally, a number of water
treatment people have reported problems main-
taining nitrite residual in high temperature
applications. Based on this information, nitrite
77
Section 3.4
CLOSED RECIRCULATING SYSTEMS

should not be used in applications over about the conductivity of the water might help. If stray
300°F (150°C). If nitrite is needed in high currents are indeed involved, there may also be
temperature applications, extra monitoring damage by stray current corrosion. The system
should be implemented to assure adequate nitrite may have strict conductivity limits set by the
residual. The extra monitoring should include manufacturer of critical equipment, such as
nitrate and ammonia, which are potential induction furnaces and welding arms.
decomposition products.
Molybdate-Based Treatment—Molybdate
ELECTROLYSIS inhibits general and localized corrosion on
ferrous and non-ferrous metals by forming a
If part of the closed loop system is under volt-
passivating film. It is generally accepted that the
age, nitrite loss may be related to stray currents
corrosion inhibition of iron is achieved by
in the system. Equation 1 is one of the possible
adsorption of molybdate onto the porous oxide
Redox reactions that may be involved. As can be
surface. The adsorption produces a layer imper-
seen, this reaction would be more favorable at
meable to other anions, particularly chlorides
elevated pH, such as generally experienced in
and sulfates. Molybdate blends are designed to
closed loop systems.
buffer the pH to the 8.5-10.5 range. One advan-
tage of molybdate over nitrite is that it is not a
NO2 − + 2OH − → NO3− + H 2O + 2e − (1)
nutrient for bacteria.
In a temperature control loop for a fluoride
The typical dosage range for molybdate, when
electrolysis cell, stray electrical current caused
used alone or in a blend, is 200-1000 mg/L as
nearly complete conversion of nitrite to nitrate in
MoO4. Initial passivation dosages should be at
both cold and hot water at 194°F (90°C) that was
the upper end of the typical operating range.
alternated through the cell. Reversion was quick
and complete. In the hot water, one would not
Nitrite-Molybdate Blends — Nitrite-molybdate
expect bacteria to be a problem. A simple
blends inhibit corrosion in the same way as
laboratory test confirmed that nitrite can be
described for the individual components. The
converted to nitrate by passing a 10 mA current
nitrite increases the effectiveness of the molybdate,
through a solution at a positive overvoltage of
producing enhanced passivation and improving an
4 Volts DC. Half of the 300 mg/L nitrite in a
otherwise unacceptable cost imbalance. One
200 mL volume was converted to nitrate.
advantage of nitrite-molybdate blends is that if
the nitrite is consumed by bacteria, the molybdate
Stray currents may not be so obvious in a closed
still offers some corrosion protection. The nitrite-
loop system as in an electrolysis cell. However,
molybdate blend is designed to buffer the pH in the
if the system contains welding equipment or
range of 8.5-10.5.
electrical furnaces or if system grounding is
defective, stray currents and associated nitrite
A variety of nitrite-molybdate blends are avail-
conversion are possible.
able, and their ratios vary. Typical dosages range
from 500-1500 mg/L nitrite and 75-200 mg/L
If stray currents are the root cause, flushing of
molybdate. Dosage depends heavily on the
the system, increasing the biocide dosage, or
temperature of the system.
iron clean-up programs will not give the desired
effect. Improved electrical insulation or reducing

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PAC-3 Cooling Water Technical Manual (01-05)
 Section 3.4
CLOSED RECIRCULATING SYSTEMS

Dispersible Oil Treatment —A third class of Avoid treating high heat flux systems with hard
closed system inhibitors is the dispersible oils, water with silicate-based programs. This combi-
so called because they are blends of organics nation could cause magnesium silicate scale to
that are dispersible in water. These materials also form. If aluminum is present in a high-heat flux
form a corrosion-resistant film on metal surfaces system and silicate is desired, soft water makeup
and are usually as effective as the boron-nitrite should be used.
inhibitors on all metals. The very high level of
dispersibility of these materials assures thorough SPECIAL CLOSED SYSTEMS
film formation in all parts of a system. However,
High-Temperature Systems—Pressurized hot
as the dispersible oils free deposits, they have a
water heating systems with temperatures in
tendency to open leaks in a system that may
excess of 300°F (150°C), can sometimes be
have experienced extensive corrosion in the past.
treated with oxygen scavengers and organic
Generally, dispersible oils require higher dosage
dispersants, much the same as low-pressure
levels than boron-nitrite inhibitors to assure
boilers. Standard treatments, such as boron-
protection. In addition, because the dispersible
nitrite and molybdate inhibitors, can also be
oils lay down a purely physical film, it is neces-
effective in high-temperature systems. Nitrite-
sary to maintain inhibitor levels and circulation
based treatments have an upper temperature
to assure film maintenance. Off-On operation
limit of about 300°F (150°C) before nitrite
can degrade the performance of dispersible oils.
decomposition significantly affects performance.
When switching from a nitrite or molybdate
program to an oil program or vice versa, specific
Continuous Casting Mold Water Systems—
system cleaning is required.
In the primary metals industry, straight nitrite
programs controlled at 300-500 mg/L nitrite
Dosage typically ranges from 5000-10000 mg/L
work well in continuous casting mold water
of product in the treated water. The pH should be
systems. These closed systems have heat transfer
kept between 8.4 and 8.8. Also, these products
surfaces exceeding 500000 Btu/ft2•h (1.4 million
usually do not contain any scale inhibitors and
kcal/m2•h). Total hardness must be maintained
should be used primarily in soft water applica-
below 1 mg/L as CaCO3 to avoid scaling.
tions. Before using an oil-based treatment
This type of treatment program is necessary
program, it is important that local regulations
because water losses can be as much as 1-5 gpm
regarding oil and grease discharge be checked.
(0.2-1 m3/h), and a conventional blended closed
system treatment program would be cost pro-
Silicate Blends—Silicate serves as an anodic
hibitive. For further information on these critical
inhibitor and is often blended with nitrite formula-
and specialized systems, contact a member of
tions to provide corrosion inhibition for systems
the Primary Metals business unit.
containing aluminum. The inhibiting properties of
silicates increase with temperature and pH and are
Low Conductivity Systems—These are specialized
most successfully applied to soft, alkaline waters.
applications where the cooling water in the closed
Silicates do not perform as well in systems where
system must maintain the water conductivity
the pH is below 7.0. Film formation for silicates is
below a specified set point, such as 500 or 1000
slow and takes several days or weeks to form.
micromhos (microsiemens). The conductivity limit
Dosage ranges from 20-50 mg/L above the
is imposed due to the nature of the equipment
inorganic silica content in the water.
being cooled. Typically, these systems cool

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PAC-3 Cooling Water Technical Manual (01-05)
Section 3.4
CLOSED RECIRCULATING SYSTEMS
equipment using high voltage or current applica-
tions where elevated water conductivity can lead to
stray currents and short-circuiting of the electrical
equipment. Using a conventional nitrite or molyb-
date treatment program with the standard plant
water supply as makeup will usually exceed the
conductivity limit. Therefore, these systems
generally must be treated using demineralized
water as makeup and a modified treatment pro-
gram to accommodate the low conductivity limit.
Some success has been achieved using low-level
80 CONFIDENTIAL, For Nalco Employee Use Only 2005 Nalco Company
molybdate programs, modified all-organic pro-
grams, and even oxygen scavenger and passivation
programs that are more commonly used in boiler
feedwater applications. The keys to successful
treatment in these systems are extensive monitor-
ing to detect problems early and rapid response to
all problems. Pre-cleaning, passivation, and
sidestream filtration are musts in these systems to
maintain clean metal surfaces and minimize
fouling issues.
PAC-3 Cooling Water Technical Manual (01-05)
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