Cooling Water Treatment

COOLING WATER TREATMENT MANUAL
LEVEL 1
27-MAY 2003
WATER TECHNOLOGIES DIVISION

BULAB ASIA
INDEX
1. Physical Layout of Cooling Systems

A. Types of Cooling Systems
B. Cooling Towers
C. Heat Exchangers
2. Types of Cooling Systems

A. Introduction
B. Cooling Water
C. Chilled Water
D. Free Cooling
3. Corrosion
A. Introduction
B. Types of Corrosion
C. Factors Affecting Corrosion
D. Methods of Corrosion Control
E. Corrosion Inhibitors
4. Deposition
A. Introduction
B. Types of Deposits
C. Factors Affecting Scaling
5. Cooling Water Treatment

A. Objectives
B. Treatment of Open Recirculating Cooling Systems
C. Treatment of Chilled Water Systems
D. Calculations
6. Cooling Water Microbiology

A. Introduction
B. Types of Organisms
C. Microbiological Control
7. Glossary of Terms
8. Self-Review Guide
GPS//2003
1. PHYSICAL LAYOUT OF COOLING SYSTEMS
A. Types of Cooling Systems

Once Through Cooling
Closed Loop Cooling
Open Recirculating Cooling
B. Cooling Towers
i) Types of Towers
ii) Definitions
iii) Cooling Process
C. Heat Exchangers
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1. Physical Layout of Cooling Systems
Industrial cooling water systems have one function to remove unwanted heat, regardless of
whether the heat is generated in a process or in an office building. The objective is to design
a suitable cooling system that will be capable of absorbing unwanted heat and transporting it
to where it can be rejected.
Cooling water systems vary considerably in design, function and operation; those of interest
to us are systems that employ water as the cooling media. The purpose of this section will be
to discuss the design and operation characteristics of cooling water systems, including heat
exchangers.
A. Cooling Water Systems
Cooling water systems can be categorized into three types :
ONCE THROUGH
CLOSED (CHILLED)
OPEN RECIRCULATING
HEAT ABSORPTION
e.g. HEAT EXCHANGER, etc.
WARM WATER
TO SEWER
(or OTHER PLANT USE)
COOLING WATER SUPPLY

LAKE, RIVER, WELL
Figure 1.1 Once Through heat transfer
Figure 1.1 illustrates a once through cooling water system. As can be seen, the cooling media
(water) is pumped from its source through a point of heat exchange where it absorbs the heat
and transports the heat to a point of discharge. In this system, we have heat absorption and
rejection with the water only being used once prior to discharge.
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HOT WATER OUT

WARM CHILLER
COMPRESSOR
OPEN RECIRCULATING
HEAT LOAD CHILLED
or
WATER REFRIGERATION
MACHINE ONCE THROUGH
LOOP
CIRCUIT
EXPANSION
VALVE
COLD COLD WATER
Figure 1.2 Closed Recirculating cooling water system
The system illustrated in Figure 1.2 is that of a closed recirculating cooling water system. In
this case, water is continually recirculated through the system, picking up heat at the point of
heat transfer and rejecting the heat at a second point of heat exchange. A common example
would be an automobile engine cooling system. Closed chilled water systems for air
conditioning systems would be typical of this type of cooling system design.
Evaporation
(heat rejection)
Heat Load
Cooling Tower from Process
Make Up Bleed-Off
Figure 1.3 Open Recirculating cooling water system
Figure 1.3 illustrates an open recirculating cooling water system. In this design, cooling
water is pumped through a point of heat exchange or heat transfer, absorbing heat in the
process, and transporting this heat to a cooling tower. At the cooling tower the heat is
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rejected to the atmosphere by means of evaporation (E) of a small percentage of the
recirculated water. Water lost through evaporation (E) and bleed-off (B) is replaced by fresh
makeup water (MU). The primary benefit of the open recirculating cooling system is that it
permits the re-use of the cooling water prior to discharge.
Some open recirculating system do not use a cooling tower for heat rejection to the
atmosphere, instead a spray pond is employed.
Figure 1.4 Spray Pond
Like the other cooling systems, water is pumped through a point of heat exchange picking up
Air in Air out
Water in
heat and transporting it back to the spray pond. The return water is then sprayed through
nozzles in the distribution piping as shown. This water rejects heat by evaporation and
convection and falls back into the collection basin ready for re-use.
Although spray ponds are used for the same purpose as cooling towers (heat rejection to the
atmosphere) they are inherently less efficient. The amount of space required for a spray pond
is considerably more than that required for a cooling tower. The water losses from a spray
pond in the form of spray and mist are also greater and can pose a problem of unwanted fall
out on parked cars and buildings. For these and other reasons, spray ponds have been
replaced by cooling towers.
Figure 1.5 Once Through shell and tube
It is not uncommon for cooling water designs to incorporate two or more different types of
PUMP
SHELL
& TUBE
HEAT
SOURCE
WATER SUPPLY
FROM WELL
RIVER OR POND
PUMP
SURGE DISCHARGE
TANK TO SEWER
systems into one overall system design.
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For instance, a once through cooling system (Fig. 1.5) can be tied into a closed cooling
system via a shell and tube heat exchanger. In this example, water is continually pumped
through the closed cooling loop in order to provide cooling to the heat source. The heat
absorbed is carried to the shell and tube heat exchanger where it is picked up by a once
through cooling water and is finally rejected with the discharge.
Figure 1.6 Evaporative Condensers
Figure 1.6 is another example of the use of two different types of cooling systems used in
combination. This particular system design is called an evaporative cooler or evaporative

condenser.
A cooling tower can also be used in direct combination with a closed cooling system. In this
case, the shell and tube heat exchanger can be eliminated with the heat transfer between the
two systems occurring inside the cooling tower.
In summary, cooling system designs can be placed into one of three different categories. The
above examles do not represent all of the possible varieties of cooling systems designs that
can be encountered. However, all cooling systems can be broken down to their basic
components for ease of understanding.
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B. Cooling Towers
i) TOWER TYPES
A major component of open recirculating cooling systems is the cooling tower. A cooling
tower, in essence, is a heat rejection device used to lower the temperature of the return
cooling water by evaporation of a small percentage of the water passing over it.
Air
Outlet
Figure 1.7 Induced Draft Tower
Cooling towers can be categorized as either natural draft or mechanical draft. The natural
draft
tower is exemplified by the hyperbolic tower. Air flow through the natural draft tower is by
reliance on the density differential between the warmer air inside the tower and the cooler
outside air. This is the same principle used in the design of a smoke stack on a boiler or
furnace.
The mechanical draft towers illustrated in Figure 1.7 & 1.8 can be further subdivided into
induced draft and forced draft draft design. In the case of forced draft, air is pushed through
the tower whereas induced draft air is pulled through the tower. In both cases, the goal is to
provide sufficient air flow through the tower to cool the return water.
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Warm
air out
Air blower
Figure 1.8 Forced Draft Tower
In addition to the way air is drawn through the tower, reference is made to cross-flow and
counter-flow designs. As the names denote, in counter-flow refers towers, the air flow is
opposite to water flow (Fig. 1.9). Cross-flow refers to air flow which is perpendicular to
water flow (Fig. 1.10).
Figure 1.9 Counter-flow Figure 1.10 Cross-flow

In order to understand the different cooling tower designs, it is important to have an
understanding of the various terms used to describe cooling tower function.
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ii) DEFINITIONS RELATED TO COOLING TOWERS
COOLING RANGE The difference in temperature between the hot water entering the
tower and the cold water leaving the tower.
APPROACH The difference between the temperature of the cold water leaving the tower
and the wet-bulb temperature of the air is known as the approach; the approach determines
the operating temperature of the tower and is the simple most important parameter in
determining both tower size and cost.
DRIFT Water entrained in the air flow and lost to the atmosphere. Drift loss does not
include water lost by evaporation; proper tower design will minimize drift loss.
HEAT LOAD The amount of heat to be dissipated by the tower, usually expressed in
BTU/hr (or J/hr); heat load is equal to water circulation rate times the cooling range. Heat
load is also an important factor in determining tower size and cost.
WET BULB TEMPERATURE Wet-bulb temperature is an extremely important parameter

in tower selection and design. It is the lowest temperature water will reach during
evaporation.
MAKEUP The amount of water required to replace normal losses caused by blowdown,
drift, evaporation, and leaks.
BLEED-OFF Bleed-off is the circulating water in the tower which is discharged to waste;
due to evaporation, the concentration of dissolved solids in the circulating water continually
increases; bleed-off helps keep the dissolved solids concentration of the circulating water
below a maximum limit.
iii) COOLING PROCESSES

Cooling towers cool water through two processes :
1) evaporative cooling
2) convective cooling
The return cooling water (containing heat absorded at the point of heat exchange) is returned
to the tower and distributed over the tower packing or fill. The tower fill breaks the water
into small droplets which cascade through the tower chamber. At the same time, air passes
through the tower and mixes with the falling water. As the air and water contact each other,
evaporation takes place.
During the evaporation process, heat is removed from the cooling tower water equivalent to
the latent heat of vaporization. This latent heat of vaporization is equivalent to 1,000 BTU
per pound of water evaporated. In general terms, this is equivalent to a 1oF drop in cooling
water temperature for each 0.1% of water evaporated.
For example, 1,000,000 lbs of water flows over a cooling tower and in the process, 0.5% of
the total water flow is lost due to evaporation. The heat removed due to this evaporation is
equivalent to:
(1,000,000 lbs water) x (0.005 evaporated) x (1,000 BTU/lb.evap.)= 5,000,000 BTUs

rejected.
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Since 1 BTU lost per pound of water is equal to a 1oF temperature drop, the 5,000,000 BTU
lost from 1,000,000 lbs of water would be equivalent to a 5oF drop in temperature.
Cooling towers cool water by evaporation of a given percentage of total recirculating water
flow, rejecting heat to the atmosphere, equivalent to the latent heat of vaporization. There is
a limit to the efficiency of heat rejection obtainable with a cooling tower.
Cooling towers are designed to expose a maximum amount of water droplet surfaces to the
flowing stream of air. Towers are designed to achieve the maximum amount of water
evaporation or heat rejection with a minimum amount of water flow.
The limits of cooling tower efficiency are related to the dry bulb and wet bulb temperature of
the outside air. The temperature of air on an ordinary thermometer is the dry bulb
temperature. The wet bulb temperature is the reading of a thermometer when the bulb is
covered with a wet cloth and the thermometer is whirled around in a sling (sling
The relative humidity of the air is the ratio of the quantity of water vapor actually present in a
given volume of air to the greatest amount of vapor which that air could hold at a given
temperature.
psychrometer).
When the relative humidity is 100%, water will not evaporate, thus:
dry bulb T = wet bulb T
When the relative humidity is less than 100%, however, water will evaporate and:
wet bulb T > dry bulb T
This sets the limit for the ability of a cooling tower to cool water. A cooling tower cannot
cool water below the wet bulb temperature of the outside air. The difference between the
cooling tower water effluent temperature and the wet bulb temperature is referred to as the
approach temperature.
It is important to note that not all of the cooling taking place in a cooling tower is due to
evaporative cooling. A second cooling process also takes place, which is referred to
convective cooling. Convective cooling takes place, when colder outside air flows through
the cooling tower, picking up heat from the water. Thus, when the outside humidity is 100%
@ 50oF, and the tower return water is 80oF, the cooling tower can still accomplish some
cooling of the water due to convection cooling.
In addition to evaporative water losses, water can also be lost from an open system as small
droplets entrained in the airflow exiting the tower. These water droplets, typically referred to
as windage or drift losses, are identical in composition to the recirculating water, i.e., these
droplets contain the same dissolved minerals, suspended particles and water treatment
chemicals found in the recirculating cooling water.
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Open Cooling System Windage Losses
System Type % of Recirculation Rate
Spray Pond 0.3 - 1.0
Atmospheric Tower 0.6 - 1.5
Mechanical Draft Tower 0.01 - 0.05
Evaporative Condenser 0.05 - 0.1
Table 1.1
The extent of windage or drift loss, depends on the type of heat rejecting system employed
and on the local operating / weather conditions. Table 1.1 lists typical figures for this water
loss as a percentage of the recirculating rate for a given type of heat rejecting system.
Through improved design and construction of mechanical draft towers, the windage losses in
these systems can be as low as 0.01 percent.
C. Heat Exchangers
A fundamental law of thermodynamics states that heat is transferred from a warmer body to a
cooler body. This is the basic principal upon which heat exchangers function. Two fluids or
gases pass through a heat exchanger with the warmer fluid or gas transferring heat to the
cooler fluid or gas. Our interest is with cooling systems that rely upon water as the cooling
medium. At the heat exchanger, heat is transferred by two primary mechanisms:
1) conduction
2) convection
Conduction relies upon contact of two fluids of different temperature separated by a metal
wall, transferring heat from the warmer fluid to the cooler fluid. Convection cooling plays a
role in distributing heat throughout the coolant by means of coolant flow and turbulence.
Conduction cooling plays the biggest role in overall heat transfer.
Heat transfer in a heat exchanger can be quantified, using the standard equation for heat
exchange:
Q = U x A x T
Where:
Q = total heat flow, BTU/hr
U = heat-transfer coefficient, BTU/hr/ft2/oF
A = area of the heat transfer surface, ft2
T = temperature difference between two surfaces
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GPS//2003
Figure 1.11 Shell & Tube Exchanger
The use and application for heat exchangers are incredibly numerous; in general heat
exchangers can be broken down into three classes:
1) coolers (non-condensing)
2) condensers (condensing)
3) heaters
depending upon process side activity. Regardless of design or application, the principles of
heat transfer and heat transfer efficiency are identical.
The basic principle is that the water and the fluid (gas) to be cooled is seperated by the metal
barrier. In the case where the water is on the inside of the tube, the type is referred to, as
tubeside exchanger. Figure 1.11 is an example of a shell tube exchanger.
This same style of exchanger can also be used where the water is on the exterior of the tubes
and the process stream is on the inside. This type is referred to, as shellside exchanger and is
normally used where the process stream is under high pressure (for instances, gases). In this
case, the flow would be as shown in Figure 1.12.
Cooling Water
Baffles
Figure 1.12 Shell-side Cooler
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2. TYPES OF COOLING SYSTEMS
A. Introduction
B. Cooling Water
i) Corrosion
ii) Scaling
iii) Suspended Solids
iv) Biological
C. Chilled Water
D. Free Cooling
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2. Types of Cooling Systems
A. Introduction
All cooling water programs address four issues; the importance of each will vary depending
on the plant. The four, potential water related concerns for cooling water systems are shown
below, along with the major factors that influence them:
i) CORROSION
Saturation and/or Stability Index and pH

Oxygen
Chlorides/Sulphates
Suspended Solids
Microbiological Activity
ii) SCALING AND DEPOSITION
High Heat Exchanger Skin Temperatures

Alkaline Cooling Water pH
Calcium Level
iii) SUSPENDED SOLIDS
Makeup Water
Airborne Solids
Corrosion Products
Hardness Precipitates
iv) BIOLOGICAL
Interference with the Normal Function of the Corrosion Inhibitor(s)

Growth of Anaerobic Bacteria
Flow and Heat Transfer Restriction
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B. Cooling Water
i) CORROSION
The corrosion potential of a cooling water system is influenced by several operating
conditions:
Saturation (Stability) Index and pH

The application of the Saturation Index in determining if a cooling water has scale forming or
corrosion tendencies is determined by the Langelier Index (LSI). This index takes into
account:
pH
calcium level
total alkalinity (M alk.)
total dissolved solids
temperature
As the Langelier Index of a specific cooling water rises above 0, the greater is the tendency
for CaCO3 scaling to occur, while the probability of corrosion decreases accordingly.
However, as the stability index of cooling water falls below 0, the potential for corrosion
increases and the probability of scaling diminishes.
By maintaining cooling water on the slightly alkaline side (pH of 8.2 to 8.6), its corrosivity is
substantially reduced while the scaling tendency is increased. Typically, a water with a pH in
the range of 8.2 to 8.8 would have a LSI above 2.0 and commonly around 2.5.
Cooling water can be maintained in this alkaline pH range by:
Allowing makeup water to concentrate

Supplementing with sodium carbonate (soda ash) or sodium hydroxide (caustic
soda)
Feeding sulphuric acid to reduce pH of highly alkaline water.
Scale is prevented from forming under alkaline conditions by:
1) limiting the calcium concentration

2) controlling the pH (M alk.)
3) use of scale inhibiting chemicals
If the pH value falls below 4.5, then free mineral acidity (FMA) is present and corrosion will
occur regardless of the corrosion inhibitor being used or its concentration. This condition
occurs when the acid (usually sulphuric acid) being applied to the condenser system, for
alkalinity and pH control, is overfed.
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Oxygen
Passing cooling water over a cooling tower saturates it with oxygen. Oxygen is an integral
part of the corrosion process, hence a corrosion inhibitor is required to protect both the
O
X c 10
Y c
G
E 8
P
N E
R 6
C
O L
N I 4
T T
E E
N R 2
T
0
o
30 50 70 90 110 130 150 170 190 210 F
ferrous and non-ferrous metals from corrosion attack.
Figure 2.1 Solubility of Oxygen at Different Temperatures
Chlorides/Sulphates
Concentrating the makeup water in the cooling water increases the total dissolved solids
(conductivity). In particular, as the chloride and sulphate ions present in the raw water are
concentrated, this results in an increase in the corrosivity of the cooling water. Of the two
anions, chloride has the greatest impact on mild steel corrosion rates.
Suspended solids
The deposition of suspended solids on a metal surface can result in under deposit type
corrosion. This type of corrosion will occur, regardless of the corrosion inhibitor being used
or its concentration, since the treatment is unable to penetrate the deposit in order to provide a
protective film on the metal surface.
Microbiological Activity
The primary corrosion causing organisms are anaerobic bacteria. They grow beneath
deposits and are protected from oxygen present in the cooling water. Sulphate-reducing
bacteria (SRBs) are very corrosive to metals. Since the corrosion inhibitor cannot penetrate
through the deposit to protect the metal surface, it will not provide protection against this type
of organism.
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ii) SCALING & DEPOSITION
Formation of calcium and magnesium scales is the result of several controlling factors:
High heat exchange skin temperatures

High heat exchange surface temperatures combined with low flow rates through the tubes
results in the formation of carbonate in the cooling water. This thermal decomposition
reaction will result in the formation of calcium carbonate scale. A low water velocity also
reduces the flushing effect and increases the tendency for newly formed deposits to adhere
to the tube walls and begin the scale growth process.
Alkaline pH values
As the pH increases above 7 and particularly in the 8 to 9 range, bicarbonate (HCO3) is
converted to carbonate (CO3), which in turn permits to the formation of insoluble calcium
carbonate and/or calcium and magnesium silicate.
Saturation level for calcium sulphate or calcium phosphate

If the cycles of makeup water in the cooling water are allowed to exceed the solubility limit
for calcium sulphate (about 1800 ppm), then calcium sulphate deposits will form.
Similarly, calcium phosphate scales can form. Its solubility is controlled by temperature, pH,
calcium level and the ortho-phosphate concentration. If cycles of concentration are allowed
to exceed the calcium phosphate solubility limit, deposits will form.
iii) SUSPENDED SOLIDS

Suspended solids are objectionable in a cooling water system since they:
Interfere with corrosion inhibitor film formation.

Allow the formation of under-deposit type corrosion cells.
Provide the opportunity for the growth of anaerobic bacteria such as SRBs.
Can restrict or plug condenser tubes and impede heat transfer.
May interfere with the normal operation of valves, orifices, strainer etc..
Suspended solids may originate from any of the following sources:
Makeup Water
Corrosion products; the insoluble reaction products of corrosion such as iron and
copper oxide.
Precipitated hardness; calcium carbonate or calcium phosphate found in the
suspended solids. Also treatment components, such as phosphonates or
polyphosphates can degrade to give phosphate, which can then in turn react with
calcium.
Sand, silt, etc. (usually silica and aluminium silicate)
Organic matter (leaves, weed, etc.)
Biomass; both living and dead.
Airborne Solids
Dust
Inorganic and insoluble organic matter
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iv) BIOLOGICAL
Biological growth is detrimental to a cooling water program for several reasons.
Interferes with the normal function of the corrosion inhibitor(s)

The formation of bacterial slimes and deposits on the metal surfaces inhibits the development
of a strong corrosion inhibitor film. In addition, the slimes can serve to bind inorganic debris,
which fosters the development local concentration cells.
Growth of anaerobic bacteria

Anaerobic bacteria may develop under deposits since they cannot exist in the presence of
oxygen. Sulphate-reducing anaerobic bacteria (SRBs) are very destructive to metal.
Frequently, it is difficult for biocides to penetrate deposits to reach these organisms.
Flow and Heat Transfer Restriction

Biological matter will develop and grow on metal or wooden surfaces to an extent that it can
interfere in the normal operation of a cooling water system. These deposits will restrict flow
and/or plug heat exchange equipment piping, orifices, valves, strainers, etc. Also, the
biomass acts as an insulator on the heat exchange surface and impedes heat transfer rates.
C. Chilled Water
Chilled water contains all the impurities of condenser cooling water, however, they are all
present at a much lower concentration (Table 2.1).
The rather frequent no-flow operating conditions in chilled water distribution systems,
requires a different treatment approach, one that can provide low corrosion rates under these
conditions.
Comparison of Condenser Cooling Water to Chilled Water
Constituent Condenser Cooling Water Chilled Water
Hardness T.H. in makeup water Same as makeup water

X cycles of concentration
Total Dissolved Solids (T.D.S.) T.D.S. in makeup water Same as makeup water
Suspended Solids (S.S.) Present in makeup water Present in makeup water

Scrubbed from air
Corrosion products Corrosion products
Hardness Salts
Aerobic & anaerobic matter Aerobic & anaerobic matter
(alive & dead) (alive & dead)
Breakdown of corrosion inhibitor(s)

Biomass Present in makeup water Present in makeup water
Present in air, induced at cooling
tower
Oxygen High concentration (saturated) Low concentration
pH 6.5 to 8.6 9.0 to 10.5
Table 2.1
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Chilled water systems are not designed like a condenser cooling water system with
continuous bleed-off equipment. Also, they do not have a basin or sump that can be easily
cleaned, for removing any accumulated suspended solids. Being closed loops, the
expectation is that there will be no extraneous material to remove.
In addition, the chilled water systems are generally more complex as they are typically an
integral part of a system. Therefore, there are usually no convenient points in the system, to
easily flush or drain any objectionable accumulated sludge deposits from the heat exchangers
or piping.
The effective prevention and removal of particulate matter from a chilled water system is one
of the basic keys to both cooling operation and treatment.
The suspended solids originate from:
Sloughage of old deposits from the system metal surface

Formation of new corrosion products
Microbiological growths
In-line filters are required to remove objectionable particulate matter from a chilled water
system and should be an integral part of any closed loop system.
In-line cartridge type filters that will remove suspended solids down to 10 micron size should
be installed in the system. If a system is dirty, then a 50 micron size cartridge filter would be
more suitable initially. The number of cartridge filters required, their filtering capacity and
where they should be located, depend upon the particular system.
Biological problems in chilled water are far more serious and more difficult to control than in
open recirculating cooling water systems. This is because chilled water is normally shock
treated with biocide for biological problems. However, when the biocide is applied, certain
sections of the chilled water distribution lines may be out of service. The chilled water in
these stagnant lines then re-infects the chilled water, when they are put back into service.
One option to consider for systems with chronic micro problems is to use by-pass filters with
a pore size of 1 micron. These very low pore size filters will remove bacteria from the water.
The use of a biocide to reduce the microbiological population and strip biofilms from
surfaces, coupled to a small pore size filter is an effective way to remove the conditions that
encourage biological activity.
Continually monitoring the microbiological activity in a closed system and in particular the
chilled water system is essential for a trouble free operation. The use of dipslides to evaluate
bacteria levels should be used at least once per quarter. These biological tests should be
backed up with an ATP analyses when possible, to ensure that all forms of microbes are
under control.
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D. Free Cooling
Free cooling was introduced as a unique energy savings development for comfort cooling, air
conditioning systems. The energy savings features of free cooling are:
Electrical power consumption is reduced by not having to operate the refrigeration

compressor during cooler weather.
Recirculating water head pressure is reduced, since condenser and chiller units,
with their high pressure differential are not required.
Power and maintenance costs are reduced, as fewer recirculating pumps are
required.
COOLING
TOWER
CONDENSER
STRAINER
CHILLER
COOLING LOAD
Reheat requirements are reduced, as a result of warmer condenser water being

used in the chilled water system.
Figure 2.1 Free Cooling System
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Free cooling involves the flow of condenser cooling water through the chilled water system,
bypassing the out of service condenser and chiller units. The condenser cooling water from
the chilled water system, is then discharged over the cooling tower where the absorbed heat is
removed (Figure 2.1).
Normally, whenever the outside air temperature is 60oF (15oC) or below, then the free
cooling cycle can be economically justified.
Before the condenser cooling water enters the chilled water system, it first passes through a
multi tube filter. This removes any suspended solids down to approximately 100 microns in
size. The filter is automatically backwashed upon a preset pressure differential.
Operating on the free cooling cycle allows condenser water to enter the chilled water system
and this presents new water treatment problems. Therefore, very specific water conditioning
technology is required, to provide the desired results for both systems.
The intermittent static operating conditions in chilled water system, requires a much higher
level of corrosion inhibitor than for condenser cooling water, to protect the system from
corrosion. Static conditions result in the protective corrosion inhibitor film on the metal
surface being used up over a period of time. Unless there is sufficient treatment available to
continually maintain this protective film, corrosion will occur. High concentrations of
treatment are required to continuously provide a supply of corrosion inhibitor. This reserve is
essential to maintain the protective film on the metal surface, during no-flow conditions.
Condenser cooling water however, is always being recirculated (unless the system is out of
service). Therefore, a lower level of treatment will still provide a high degree of corrosion
protection for the system.
In view of the condenser cooling water also becoming the chilled water, it is essential that a
water treatment program be designed, that is both cost effective and efficient. Open system
cooling water inhibitors will not provide protection of ferrous and non-ferrous metals, under
the static operating conditions, which can be the case for extended periods of time.
It is important to appreciate the potential operating problems that may develop in allowing
condenser cooling water to enter a chilled water system, and ensure that the appropriate steps
are taken to protect the closed loop segment.
This type of system is only infrequently seen now, due to the limitation noted above.
However it is not uncommon to see free cooling systems where a heat exchanger isolates
the chilled system from the open recirculating loop. In this case, the advantages of free
cooling are realized, without the significant liabilities.
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3. CORROSION
A. Introduction
i) General Corrosion
ii) Galvanic Corrosion
iii) Pitting Corrosion
iv) Concentration Cell Corrosion
v) Dealloying
vi) Intergranular
vii) Transgranular
viii) Stress-Corrosion Cracking
ix) Other Forms of Corrosion
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3. Corrosion
A. Introduction
What is it?
Corrosion is the electrochemical reaction (destruction) of a metal due to a reaction with its
environment. It is the reversion of the refined metal to its natural state, which is commonly
an oxide. Examples are :
Fe Fe2O3
Fe(OH)3
Fe3O4
Al Al2O3
Zn ZnO
Zn(OH)2
The word corrosion comes from the Latin corrodere to gnaw away. Of the many types
of metallic corrosion, six corrosion mechanisms typical of cooling water systems, will be
discussed.
Why is it a concern?
The primary reason for concern is economic - it is estimated that :
>100 million tons of steel are required yearly to replace corroded steel.
Cost to industry in N.A. is estimated to be $10 to $15 billion annually.
What are our objectives?

There are four primary objectives, all of which help our clients to remain competitive :
Prevent or minimize equipment failure and extend their life.

Prevent or minimize production downtime.
Eliminate plant inefficiencies caused by corrosion product fouling.
Lower capital costs.
Due to its use and tendency to corrode, steel is the primary metal of concern. Of lesser
concern are copper, copper alloys and aluminum.
How does corrosion occur?

Corrosion requires four elements to occur :
An anode (negative electrode) site of oxidation

A cathode (positive electrode) site of reduction
An electrolyte (current carrier)
Conductor (metal) to complete the circuit
The above four components make up a corrosion cell and are the basis for the various
chemical treatment programs that are meant to minimize corrosion.
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Corrosion cell
The electrochemical reaction that takes place is the oxidation of iron and the use of the
electrons that are generated to reduce oxygen in the cooling water.
Anode FeO Fe+2 + 2e-

Cathode O2 + H2O + 2e- 2OH-
This reaction occurs in cooling systems, at neutral to alkaline pH range and is illustrated in
Fig. 3.1
Figure 3.1
O2 Tubercule
Fe +2 OH - OH -
e-
Anode Cathode
In single metal corrosion, cathodic and anodic sites develop on the surface and this is due to
the following factors :
Anodic Sites typically are the result of :
Strained metal
Localized areas of oxygen depletion
Imperfect surface oxide film
Impurities in the metal
Impurities on the metal
Localized temperature differences
Imperfect grain boundaries
Poor water treatment / pH
Cathodic Sites are the result of :
Unstrained metal
Localized areas of high oxygen content
Good surface oxide film
Localized low temperatures
Grain characteristics
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Corrosion cells can exist when dissimilar metals are in contact in an electrolyte. The anode is
the less noble metal this is also referred to as galvanic corrosion. In this case, if copper is
coupled to mild steel, the steel will preferentially corrode and the copper will not be affected.
No Corrosion General Corrosion

Corrosion can be the result of chemical or mechanical effects and it is critical to be able to
identify the cause/type of corrosion in order to be able to effectively correct it.
i) GENERAL CORROSION
Any fresh metal surface exposed to an aqueous environment containing dissolved oxygen and
salts will experience corrosion. A multitude of both anodes and cathodes exist on the same
O2 Tubercule
Fe +2 OH - OH -
e-
Anode Cathode
metal surface, in close proximity.
Figure 3.2
Anodes are defined as those locations where metal oxidation (corrosion) occurs (see Fig. 3.2).
Mo Mn+ + ne-,
While at the cathodes, reduction of oxygen occurs,
n/4(O2) + n/2 (H20) + ne- n(OH-)
The cathodic reaction predominates at pHs above 5. The metal ion produced at the anode is
further oxidized by dissolved oxygen to form an insoluble metal oxide. Local anodes and
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cathodes continuously shift position, resulting in a general penetration of the metal surface
exposed to the corrosive environment.
ii) GALVANIC CORROSION

Galvanic corrosion arises from the contact of two metallurgically dissimilar metals combined
with a corrosive environment. The more noble metal of the two becomes the permanent
cathode. Severe corrosion of the less noble metal occurs at the point of contact.
Intentional galvanic couples are compensated for by substantially increasing the thickness of
the anodic (less noble) metal. Prediction of galvanic relationships can be made from the data
in Table 3.1 Examples of galvanic couples would be :
Brass valve on steel line

Copper tubes in steel tube sheets
Copper plating in steel lines or exchangers
Brass bolts on zinc anode
The intensity depends on potential differences.
Galvanic series predicts severity (see Table 3.1)
1-CWT Page 25 of 117 0902

Galvanic Series of Some Commercial Metals and Alloys
ANODIC (least noble)

Magnesium
Magnesium Alloys
Zinc
Galvanized Steel
Aluminum 1100
Aluminum 2024
Mild Steel
Wrought Iron
Cast Iron
Stainless Steel 410 (Active)
Stainless Steel 304 (Active)
Lead-Tin Solders
Lead
Tin
Muntz Metal
Manganese Bronze
Naval Brass
Nichel (Active)
Inconel Alloy (Active)
Yellow Brass
Admiralty Brass
Red Brass
Copper
Silicon Bronze
70 : 30 Cupro Nickel
G-Bronze
Silver Solder
Nickel (Passive)
Inconel Alloy (Passive)
Stainless Steel 410 (Passive)
Titanium
Stainless Steel 304 (Passive)
Silver
Graphite
Gold
Platinum
CATHODIC (most noble)
Table 3.1 Galvanic Series
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iii) PITTING CORROSION

In industrial cooling water system, pitting corrosion is often encountered. Pitting results
when small and specific areas become anodic with respect to the majority of the metal
surface. Examples of where this type of localized corrosion occurs includes locally stressed
and strained surfaces, discontinuities in rolling mill scale, and holidays in corrosion
inhibitive films. Because of the limited surface area of the anodic region, rapid metal loss
occurs at these locations. The result is an accumulation of corrosion products which can
become sufficiently thick, thus slowing the pitting process, but allowing it to continue. The
general symptom of this type of corrosion is the accumulation of a circular mound of
corrosion products over the pit, commonly called a tubercle pitting occurs when anodic
areas remain stationary. Pitting is promoted by :
Low water velocity

Stagnant conditions
Surface differences
No Corrosion Pitting
Under deposit corrosion
Poor inhibitor film formation
High chloride concentrations
Suspended solids build up on piping
Low levels of anodic inhibitors
Overfeed of chlorine
Figure 3.5 Pitting Attack
iv) CONCENTRATION CELL CORROSION

Intense localized corrosion frequently occurs within crevices and other covered areas of
metals exposed to recirculating cooling waters. Crevice or under-deposit corrosion occurs in
stagnant water formed by gasket surfaces, surface deposits, and in crevices under bolts, etc.
Material sitting on a metal surface can give rise to depletion of oxygen at the point of contact.
In such cases the site under the deposit becomes anodic with respect to the remainder of the
metal. Localized oxygen concentration cells such as these result in severe under-deposit
corrosion.
Another cause is exposure to varying aeration because of turbulence, agitation, etc., where
specific areas are shielded from the general environment. This type of corrosion is promoted
by:
Anion concentration
Oxygen concentration
Deposits
Poorly sealed joints
Temperature differences
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These conditions may be seen in the following circumstances :
Flanged fittings
Couplings
Fasteners
Gaskets
Tube sheets at tube protrusions
v) DEALLOYING
A common problem in certain brasses is selective leaching. This type of corrosion removes
one element from a solid alloy. In the case of brass, the more active zinc is preferentially
corroded, leaving behind a copper matrix of little or no structural strength. The usual
situation is to use an appropriate alloy. For example, Admiralty brass containing 1 percent
tin and 0.015 percent arsenic is more immune to dezincification than 70:30 brass.
Dealloying can be seen in these forms :
Plug type dezincification

Uniform dealloying
Graphitic corrosion (cast iron)
When dealloying occurs, the following changes can be expected :
Embrittlement and loss of strength

Little change in size of the affected item
Metal becomes porous
Causes of dezincification vary but the conditions to look for are:
High zinc in brass alloys

High chlorides and sulfates content in the water
Low hardness, high pH (leaches Zn)
Deposits (causing differential cells)
Acidic environments affect certain alloys (high Zn)
Graphic corrosion is unique to cast iron and is a condition where iron is preferentially lost.
This leaves behind a weak, porous matrix of graphite. Typical causes are :
Warm temperature
Sulfates
Anaerobic bacteria
H2S
Deposits
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vi) INTERGRANULAR
Intergranular is a localized attack along the grain boundaries of a metal or alloy. The
distinguishing characteristics is :
Grain boundaries containing material showing different (more anodic) potentials

from the grain center.
Causes include:
Improper heat treatment

Poor welding practice (stainless steel)
Overheating
Improper stress relief annealing
This type of corrosion occurs primarily in austenitic stainless steels and certain aluminum
alloys.
vii) TRANSGRANULAR CORROSION

Is the localized attack that travels thru grain boundaries and the cause(s) are :
Intergranular corrosion enhanced by mechanical action (tensile stress or fatigue)

and a corrosive environment.
viii) STRESS CORROSION CRACKING

It is similar to transgranular in that the cracking attack is often caused by tensile stresses in
combination with a corrosive environment. The difference is the corrosion starts at the
surface. This type of corrosion can be intergranular or transgranular in nature. (See Table
3.2)
Environments Which Have Caused Stress-Corrosion Cracking
ALLOY ENVIRONMENT CRACKING

-
Brass NH4 Intergranular
Steel NO3-, OH- Intergranular
300 Series Stainless Steel Cl-, OH- Transganular (can be

intergranular if sensitized)
MONEL alloy 400 Hg, Hg-, Chromic Acid, Intergranular and
Aerated Hydrofluoric, Acid Transgranular
Vapor
INCONEL alloy 600 Fused Caustic Intergranular
Nickel 200 & 201 Hg, Hg2- Molten Metals Intergranular
Table 3.2 Environments which have caused stress-corrosion cracking
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ix) OTHER FORMS OF CORROSION
Microbiological corrosion
This form of corrosion is caused by the products of the life cycle of various forms of
organisms. There are two general types of corrosion caused by micro-organisms :
Most common types of bacteria :
Acid attack, due to the formation of acid as part of their metabolic processes. For
instance SRBs generate H2S and nitrifying bacteria can convert ammonia into
nitric acid. In addition, various organic acid can also be formed.
Under deposit corrosion although not directly caused by organisms, the

formation of a deposit can lead to localized corrosion. The deposit may be due to
inorganic material such as iron hydroxide or slime which can trap suspended
solids in the water.
Erosion corrosion
Turbulent water flow results in significant components of force acting at right angles to the
direction of flow and thus acting directly on the metal surface. The abrasive action of the
water physically removes metal from the surface. This abrasive action is accentuated by
entrained air and suspended solids. Factors that contribute to this include :
High solids liquids

High velocities of liquids gases, vapors
Vapor collapse
Turbulence
Impingement
Names given to this type of damage vary according to the cause and location :
Erosion
Cavitation
Cavitation is caused by the formation of bubbles or vapor filled cavities in low pressure
regions of the flowing fluid. The bubble later collapses, causing a breakdown of the
protective layer, on the metal surface.
Fretting
Fretting occurs at the interface between contacting metal surfaces subject to slight motion
resulting in a rubbing action. Although most commonly seen on titanium alloys, it can also
occur on stainless steel.
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The rate of corrosion is dependent on the ability of the corrosion reactions to occur. Those
reactions are dependent upon many variables such as :
pH
Conductivity (measure of waters ability to carry current)
Water Velocity
Temperature
Dissolved oxygen concentration
Velocities for Water Entering Heat Exchanger Tubes
Materials of Construction Most Favorable Velocity (fps) General Range (fps)

Carbon Steel 4.0 2.5 6
Red Brass 2.5 2.5 4
Admiralty (Inhibited) 3.0 2.5 5
Aluminum Brass 5.0 48
90-10 Cupro-nickel 7.0 8.0 6 12
70-30 Cupro-nickel 7.5 5 10
Monel 8.0 6 12
Type 316 Alloy Steel 10.0 8 15
Table 3.3 Recommended Water Velocities
Of the various factors, the water pH and temperature are usually the two most significant
factors. Although the specific pH will vary with the type of program being used, in general
alkaline (>8.3) condition are preferred.
C
O
R
RR
OA
S T
I E
O
N
TEMPERATURE
Figure 3.6 Rate vs Temperature
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NOBLE METAL AMPHOTERIC METALS
Al, Zn
R R
A A
T T
E E
ACID SOLUBLE METALS IRON

R R
A A
T T
E E
pH pH
Figure 3.7 Rate vs pH
The effect of temperature is not as clear since increasing temperature raise corrosion rates,
yet at the same time, higher temperatures also increase the speed with which protective films
can form. In general though, the higher the temperature, the greater the corrosion rate.
Just as the causes of corrosion are various, so too are the option to control or minimize
corrosion. Examples of steps that can be taken are :
Metallurgy
Use a better grade of stainless resistant to chloride induced cracking
Change brass valves to mild steel
Change mild steel components to brass or stainless
Environmental
Change flow rates
Deaeration
pH adjustments
Side stream filtration
Improve water quality
Protective coatings
Electrochemical
Sacrificial anodes
Dielectric couplers (isolate galvanic couples)
Cathodic protection
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Design
Lower velocity by using larger piping
Change flow to tube side
Change impeller size to prevent cavitation
Increase head pressure to impeller inlet (to minimize cavitation)
Welds instead of rivets or bolts
Large anode to cathode ratio
Water treatment
Although the specific program will be unique to each plant, the goals for corrosion inhibitors
are to use those that :
React quickly to establish passivation

Forgiving to changes in the system or water chemistry
Easy to monitor
Environmentally safe
Easily controlled
Compatibility with other treatments
Although these will be discussed more fully in a later section, the main characteristics of
various corrosion are as follows :
Chromates
Anodic oxidizing inhibitor
Broad usage (hard or soft water)
Works rapidly
Environmental restrictions
Can be consumed by reducers such as oils, H2S, etc.
Polyphosphates
Generally cathodic
pH, temperature sensitive
Can function as scale inhibitor
Transports iron (potable)
Can be used in soft waters
Works best with ortho phosphate
Ortho phosphate
Primarily an anodic inhibitor forming calcium, iron phosphates
pH and temperature sensitive
Works in moderate to hard water
1-CWT Page 33 of 117 0902

Zinc
Cathodic inhibitor
Works at low concentrations
pH sensitive
Usually used with other inhibitors
Discharge limitations
Works well in soft waters
Potable treatment
Nitrite
Anodic oxidizing inhibitor
Oxygen not required
Needs fairly high level without O2
Can be a nutrient for microbes
Can be used in open systems
Phosphonates
Generally cathodic inhibitors
Requires Ca+2, Zn+2 or Fe+3
Needs alkaline pHs (> 8.3)
Azoles
Chemisorbed films (direct bonding to the Cu)
Copper/copper alloy inhibitor
Molybdate
Excellent pit inhibition properties
Broad pH range
Works best in closed systems
Can be a problem in hard water
Environmentally acceptable
Used with other inhibitors
Calcium Carbonate
Cathodic inhibitor
Scale potential
pH and temperature dependent
Environmentally acceptable
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4. DEPOSITION
A. Introduction
i) Scales
ii) Suspended Solids
iii) Corrosion Products
iv) Organics
C. Factors Affecting Deposition

i) Water Chemistry
ii) System Operation
iii) Treatment Program
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4. Deposition
A. Introduction
What is it?
Deposits are the accumulation of foreign matter on heat transfer surfaces or in cooling system
components, such as tower fill, etc.
Why is it a concern?
Deposits can impair the operation of a cooling system since they can :
Inhibit heat transfer

Increase corrosion problems
Decrease equipment efficiency
Cause equipment failure and shutdown
What are our objectives?

The cooling water program should prevent the formation of deposits to :
Increase equipment life

Increase plant and system efficiency
Minimize the need for shutdown and cleaning
Reduce or eliminate disease potential (Legionella, etc.)
Increased heat transfer
Reduced pumping costs
Increasing cycles of concentration (minimize water use)
While the deposits seen in cooling systems are quite variable, they can however, be
simplified into four general groups :
i) SCALES
Caused by the precipitation of salts when their solubilities are exceeded. Scales are
crystalline in nature and include examples such as :
CaCO3
Mg SiO4
CaSO4
Ca SiO4
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The traits that scales share include :
Hard and tenacious

Forms on the critical areas of heat transfer
Insulating
pH, temperature and concentration dependent
These differ from deposits in that they form and grow specifically on heat transfer surfaces.
ii) SUSPENDED SOLIDS (SLUDGES)

As discussed previously, suspended solids may originate from several sources :
Foreign matter, scrubbed from the air

Solids entering with make up
Inorganic process leaks
Precipitated salts
These sources are self-explanatory however, the last category does merit more explanation.
Precipitates can include :

Calcium phosphate
Zinc hydroxide
Zinc phosphate
Aluminum hydroxide
Iron phosphates
Iron hydroxide
Like scales, these are dependent on temperature, pH and concentration. They are often
caused by the treatment program itself, due to :
Naturally occurring phosphate

Products being overfed
Extremely high temperatures
Corrosion mechanisms
Alum carryover
iii) CORROSION PRODUCTS

These are the by-products of corrosion which become insoluble in water and migrate through
the system. For instance, sources include:
Bacterial under-deposit corrosion occurs in an acidic environment. The metal ions

migrate into the bulk water and precipitates.
Zinc from galvanized towers
Flakes of corrosion products from water lines
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iv) ORGANICS
This is a broad category comprising materials that can originate from the industrial or
biological processes :
Organic process leaks
Bacterial slimes
Product incompatibilities
Organic process leaks
Bacterial slimes
Product incompatibilities
C. Factors Affecting Deposition
A variety of factors will influence the scaling potential of a cooling water system. In general
these can be grouped into three categories :
1) water chemistry related

2) system operation
3) treatment program
Water chemistry is normally the defining parameter and others are simply related to it,
although they can have a significant impact.
i) WATER CHEMISTRY
Temperature
Inverse solubility with temperature of several scale types, the most important
being calcium carbonate. The higher the temperature, the lower the solubility.
pH
Most scales form readily in alkaline environment
Severity increases with increasing pH
Concentration
The higher the concentration of calcium greater the potential
ii) SYSTEM OPERATION
Mineral scales
Scales can be prevented by operating at subsaturated conditions, this can be done by :
Acid adjustment of pH
Operation at lower cycles of concentration
Partial softening
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pH adjustment is achieved by dosing acid to destroy a portion of the alkalinity. The amount
needed to change the alkalinity depends on the type of chemical used.
Operation at lower cycles
This is an option but can be expensive in terms of both chemical and water costs, for
instance :
Consider an evaporative rate (E) of 200 USgpm

At 2 cycles B = 200 USgpm
At 3 cycles B = 100 USgpm
Lowering the cycles from 3 to 2 resulted in a dramatic increase in water consumption due
solely to the change in bleed-off rates.
Mechanical
Partial Softening
RO
Cold lime softening takes a considerable capital investment in equipment but can be viable if
equipment on hand is under-used. It offers an excellent approach to improve water quality
since it removes both hardness and suspended solids. RO water added to a cooling system
can dramatically lower the hardness levels, although the cost of the water is relatively high.
Deposit control of suspended solids, regardless of their source, can be addressed

mechanically using several different methods :
Sidestream filters
Clarification
Low cycles
Proper tower location
Periodic cleaning
Exchanger design
Exchanger backwash
iii) TREATMENT PROGRAM

A number of approaches can be used to moderate or eliminate scaling.
Deposit control via chemical agents such as phosphonates and polymers

Program selection
Unlike inorganic foulants/scales, organic contaminants pose a different set of concerns but
they too can be controlled by several methods. Organics could be anything, ranging from oil
to glycol, to methanol, however the approach is the same :
1) eliminate (by bleed-off)

2) mitigate the adverse affect
3) prevent a re-ocurrence
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5. COOLING WATER TREATMENT
A. Objectives
B. Treatment of Open Recirculating Cooling Systems

i) Introduction
ii) Historical
iii) Scaling
iv) Corrosion
v) Foulants
vi) Microbioligical
C. Treatment of Chilled Water Systems
D. Calculations
i) Introduction
ii) Open Recirculating
iii) Closed Loop Systems
iv) Once-Through Systems
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GPS//2003
5. COOLING WATER TREATMENT
A. Objectives
The objective for treating cooling water is to maintain optimum heat transfer by reducing
corrosion, scaling and fouling. In order to achieve this, the first step is to understand what
can contribute to reduction in cooling efficiency.
Scale
Causes
CaCO3, CaSO4, calcium phosphate, magnesium silicate, silica, MnO2
Treatment
Bleed-off
Pretreatment
Phosphonates, polymers, polyphosphates.
Alkalinity control H2SO4, NaOH, Na2CO3.
Deposition
Causes
Oil; silt; clay; muds; microbiological growths
Degraded treatments (calcium phosphate, Zn++); incompatible treatments
Process contaminants; hydrocarbons
Iron oxides, other corrosion products
Treatment
Chemical pretreatment
Filtration
Bleed-off
Side stream filtration
Polymers
Surfactants, penetrants
Microbicides
Corrosion
Causes
O2, CO2, H2S, acids, anaerobic bacteria (SRBs), corrosive anions (chlorides).
Treatment
Mechanical/chemical pretreatment
Inorganic inhibitors
Zinc; polyphosphates
Organic inhibitors
pH control agents (buffers)
1-CWT Page 41 of 117 0902

Biological Growths
Causes
Algae, bacteria, fungi, protozoa.
Treatment
Filtration
Oxidizing biocides
Non-oxidizing biocides
Organic penetrants
Wood deterioration
Causes
Cellulolytic fungi and bacteria
chlorine
carbonate (CO3) alkalinities
high temperature
high TDS
Treatment
Microbicides
Alkaline/acid pH control
Pressure treatment of tower wood.
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B. Treatment of Open Recirculating Cooling Water Systems
i) INTRODUCTION
Corrosion, scale and microbiological fouling, can all impede the efficient and economical
operation of open recirculating cooling water systems. Cooling water quality, availability
and disposal limitations further impact the selection of an effective water management
program. An open recirculating cooling water system consists of a combination of the
following pieces of equipment:
Distribution system piping, heat exchangers, etc.
Recirculating cooling water pump (s) hot and cold wells
Appliances to be cooled condensers, heat exchangers,

coolers, chemical reactors,
compressors, furnaces,
etc.
Heat rejection system cooling tower, spray pond or

evaporative condenser
As discussed previously, an open recirculating cooling water system functions as follows:
Cooling water is pumped from the cooling tower basin or cold well, through the
vessel, which requires cooling.
This water absorbs heat by conduction from the unit being cooled and circulates
back into the cooling tower.
The absorbed heat is then released in the tower primarily through the evaporation
of a small amount of the recirculating cooling water.
evaporation
Figure 5.1 Open recirculating cooling water system
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The water lost by evaporation is basically pure water and free of dissolved minerals. Its
quality is similar to that produced by distillation. Dissolved minerals that are present in the
recirculating cooling water do not vaporize and remain in the recirculating water.
Because water evaporates from a cooling water system, it must be continuously replaced by
makeup water, which is usually untreated incoming plant water that contains dissolved
minerals, gases, suspended solids and other impurities. Therefore, due to the evaporation
process, suspended or dissolved impurities in the recirculating cooling water will constantly
increase in concentration. Eventually the most insoluble minerals approach their saturation
limits and precipitate as scale in the system.
Suspended solids also contribute to the formation of deposits. In addition to forming hard
scale on heat transfer surfaces, high concentrations of mineral salts and suspended solids in
the water also generally accelerate the corrosion and fouling of system components.
To minimize the risk of corrosion, deposit formation and fouling of a system, a portion of the
concentrated recirculating water is continuously removed from the system through a process
referred to as bleed-off. This water and all other system water losses are constantly replaced
with fresh makeup water. The net effect is the maintenance of a consistent recirculating
water quality at a specified level of dissolved solids. Maintaining this level avoids cooling
The extent to which an open system needs to be bled-off depends upon six primary factors:
The quality and use of the recirculating water

The availability of makeup water
The nature and degree of airborne and process contaminants in the system water
The cooling circuit operating paramaters and metallurgy
Chemical treatments used
The disposal restrictions of the tower bleed-off
system problems while minimizing the discharge of recirculating water.
To provide efficient process cooling with the least amount of water consumption, the cooling
water should be concentrated to a maximum safe operation level consistent with minimizing
bleed-off.
Open recirculating cooling water systems invariably experience a number of problems if

neglected. Three such problem areas that can be controlled by the proper selection and
application of a chemical water management program include:
Excessive corrosion of system components

Formation of scale, particularly on heat exchange surfaces
Deposition of foulants (microorganisms, airborne debris, corrosion products and
process side contaminants)
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ii) HISTORICAL
Naturally occurring waters are impure and contain both dissolved and suspended minerals.
The types and quantities of these contaminants in raw water depend on the water source.
Varying amounts of:
Calcium
Magnesium
Sodium
Bicarbonate
Silica
Chloride
Sulfate
Iron
are found in the water. Phosphate, nitrate, fluoride and other dissolved species may be found
in smaller but sometimes significant concentrations, although less frequently.
A recirculating cooling water system is an excellent air washer, effectively scrubbing

suspended particles and gases (such as CO2, SO2 and NH3 ) from the surrounding air. These
impurities, plus those naturally occurring in the makeup water, often result in a recirculating
cooling water with an unusual composition.
The primary make-up water quality parameters, which determine either the corrosive or
scaling tendencies of water, include:
M-alkalinity (as ppm CaCO3)

Calcium hardness (as ppm CaCO3)
pH
Chloride (as NaCl)
Temperature
Corrosion process involves reactions that take place at either the cathode or the anode (site of
metal loss). Inhibitors tend to interact at one location or the other; those that inhibit the
corrosion process at the cathode are called cathodic inhibitors, while those that interact at the
anode are called anodic inhibitors.
Anodic Inhibitors Cathodic Inhibitors
ortho-phosphate poly-phosphate
nitrite most phosphonates
molybdate azoles
chromate zinc
Typical programs use combinations of these actives to minimize corrosion rates. Examples
of different programs are listed on the following pages.
1-CWT Page 45 of 117 0902

Chromate-Zinc
Mixtures of chromate and zinc (Zn2+) dosed at very low levels exhibit a marked improvement
in corrosion protection over either individual component. As little as 10 percent of either
ingredient yields a significant improvement in overall corrosion protection. The addition of
zinc accelerates establishment of corrosion protection.
The degree of corrosion protection for iron and steel is reasonable uniform over the pH range
of 5 to 8 but with increasing alkalinity, bulk precipitation Zn (OH)2 becomes a problem.
Copper and its alloys also show a marked decrease in penetration rate with a chromate-zinc
inhibitor. The rate of penetration is reasonably constant in the pH range 5.5 through 8.
Although extremely effective, chromate based programs are rarely found, due to
environmental concerns over chromate.
Zinc-Phosphate
The harmful effects of chromate on the environment have prompted interest in corrosion
inhibitors free of chromium.
Alkalinity control, preferably in the pH range of 6.5 - 7.0 was essential to provide maximum
corrosion protection and to avoid the problems of phosphate sludging and Zn(OH)2
deposition at higher pH. Azole was included in the treatment to reduce the amount of Cu2+
available to plate on steel and to minimize the subsequent galvanic corrosion.
Combinations of zinc and HEDPA (or PBTC) offer steel corrosion protection, which is
enhanced by the addition of tolyltriazole (TT). Not only is the corrosion protection of copper
improved by the addition of azole but also the inhibition of mild steel. As mentioned
previously, HEDPA have an advantage over aminophosphonates with regard to chemical
stability, which is an important consideration when oxidizing microbicides are used.
Other Zinc inhibitors

Polyacrylates, lignosulfonates, MBT lignins and chelating agents have been reported as
corrosion inhibitor synergists when combined with zinc salts. These treatment approaches
can generally be applied at higher pH (7.8-8.3) and in harder waters than conventional zinc
programs. Molybdate (MoO42-) supplemented zinc treatments have proven to be an effective
corrosion inhibitor.
Zinc-based corrosion inhibitors are generally very effective cooling water treatments.
However, zinc concentrations as low as 5 ppm are known to be toxic to some forms of
aquatic life. Therefore, zinc levels, in effluent discharged to ponds, streams and other public
waters, must be maintained well below this concentration and are widely restricted.
Phosphate Programs
The next evolution was the combination of ortho and polyphosphate under neutral pH
conditions. With the advent of polymers that could inhibit calcium phosphate, it became
feasible to use higher levels of ortho phosphate. These programs became the standard against
which other programs were compared to in refineries, or other high stress conditions.
A variation on this theme are low phosphate programs that operate under alkaline conditions,
where they are just below the calcium phosphate saturation index. These low phosphate
programs provide good corrosion protection with a lower risk of calcium phosphate
deposition.
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Triazole-Phosphonate blends
During the past two decades a great amount of research has been conducted on the
development of effective, non-metal cooling water treatments. Initially, low-polluting
products of this description included multi-functional treatments containing phosphonate(s)
and a non-ferrous metal inhibitor, such as BT or tolytriazole (TT), along with a conventional
natural organicpolymeric dispersants.
Synergistic blends of triazoles and phosphonates have been improved further by

incorporating ortho phosphate and/or polyphosphates in the treatment. In programs of this
type, proper control procedures are absolutely essential. Success of this treatment concept
also depends on maintaining 4-10 ppm of ortho phosphate in the treatment water.
By using effective calcium phosphate precipitation inhibitors, ortho phosphate levels as high
as 15 to 20 ppm can be carried. In addition to functioning as a cathodic inhibitor, this high
level of phosphate promotes passification at anodic corrosion sites in neutral water through
the formation of a passive iron oxide film and by directly reacting with the iron ions
generated by the corrosion process.
Molybdate formulations
There has been a considerable amount of interest in the use of molybdate as a cooling water
corrosion inhibitor. The primary advantages offered by a molybdate-based cooling water
treatment are that molybdate is non toxic.
iii) SCALING
Although the importance of good corrosion control in industrial cooling water systems cannot
be over-emphasized, preventing deposits from adhering to heat exchange surfaces is the most
important objective of virtually all cooling water treatment program. Clean, scale-free
cooling systems:
Prolong equipment life

Reduce pumping costs, conserve energy
Improve corrosion inhibitor effectiveness
Reduce equipment corrosion
Increase plant productivity through more efficient cooling
CH 3
N
N
H
Tolyltriazole (TT)
Scaling can be defined as the deposition of slightly soluble inorganic minerals on the metal
surfaces of a cooling water system. The deposits that form are usually the least soluble
substances present in the recirculating water. These deposits, or scales, are typically dense,
non-conducting hard, tightly bound particles, that adhere to metallic surfaces. Calcium
carbonate (CaCO3) is the most frequently encountered scale because of its very limited water
solubility and the high concentration of calcium and alkalinity normally found in cooling
1-CWT Page 47 of 117 0902

waters. The solubility product constants for CaCO3 and other frequently encountered cooling
Solubility Product Constants of Cooling Water Scales at 77oF / 25 oC
Scale Least soluble pK sp
Fe(OH)3 (amorphous) 38
Fe3(PO4)2 33
Ca3(PO4)2 26
Fe(OH)2 14.5
Mg(OH)2 10.7
CaCO3(calcite) 8.34
MgCO3 5.0
CaSO4 4.59
SiO2(amorphous) 2.7
More soluble
water scales are listed in Table 5.2.
Scales, such as calcium carbonate and calcium sulfate, form on cooling water heat transfer
surfaces because these substances have an inverse solubility; that is, these substances are
more soluble in cold water than in hot. The solubility of calcium carbonate is also affected
by:
M-alkalinity
calcium hardness
pH
total dissolved solids
Table 5.1
Langelier studied the role of these factors in the precipitation of calcium carbonate and
developed a calcium carbonate saturation index (LSI). Also referred to as the Langelier
Index, this index is useful in predicting the corrosive or scaling tendencies of a water.
The Langelier Index is determines from the formula
LSI = pH - pHs
where pH is the measured pH of the water in question. A negative index indicates non-
scaling, usually corrosive water, while a positive index predicts scaling tendencies. For
example, to find the LSI of a water at 120oF (49oC) which has the following characteristics:
M-alkalinity = 160 ppm as CaCO3

Calcium hardness = 100 ppm as CaCO3
pH = 7.8
Total dissolved solids = 630 ppm
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GPS//2003
It follows that:
pHs = (9.3 + A + B) (C + D)
= (9.3 + 0.2 + 1.6) (1.6 + 2.2)
= (11.1) (3.8)
= 7.3
And:
LSI = pH - pHs
= 7.8 7.3
= 0.5
Thus this water is slightly scaling and likely corrosive. The Ryznar Index is another similar
method for determining the scaling tendencies of water.
Data for Calculation of Calcium Carbonate Saturation pH

A C D
Total solids A Calcium hardness C M Alkalinity D
(mg/L) (mg/L of CaCO3) (mg/L of CaCO3)
50-300 0.1
400-1000 0.2 10-11 0.6 10-11 1.0
12-13 0.7 12.13 1.1
B
14-17 0.8 14-17 1.2
Temperature 18-22 0.9 18-22 1.3
B 23-27 1.0 23-27 1.4
O
F (OC) 28-34 1.1 28-35 1.5
32-34 (0-1.1) 2.6- 35-43 1.2 36-44 1.6
36-42 (2.2-5.5) 2.5 44-55 1.3 45-55 1.7
44-48 (6.7-8.9) 2.4 56-69 1.4 56-69 1.8
50-56 (10.0-13.3) 2.3 70-87 1.5 70-88 1.9
58-62 (14.4-16.7) 2.2 88-110 1.6 89-110 2.0
64-70 (17.8-21.1) 2.1 111-138 1.7 111-139 2.1
72-80 (22.2-26.7) 2.0 139-174 1.8 140-176 2.2
82-88 (27.8-31.1) 1.9 175-220 1.9 177-220 2.3
90-98 (27.8-31.1) 1.8 230-270 2.0 230-270 2.4
100-110 (37.8-43.3) 1.7 280-340 2.1 280-350 2.5
112-122 (44.4-50.0) 1.6 350-430 2.2 360-440 2.6
124-132(51.1-55.6) 1.5 440-550 2.3 450-550 2.7
134-146(56.7-63.3) 1.4 560-690 2.4 560-690 2.8
148-160(64.4-71.1) 1.3 700-870 2.5 700-880 2.9
162-178(72.2-81.1) 1.2 800-1000 2.6 890-1000 3.0
pH = (9.3 + A + B) (C + D)
LSI = pH pHs
Table 5.2
Prediction of Water Tendencies by the Langelier Saturation Index
LSI Water Tendencies
-2.0 Serious Corrosion
-0.5 Slightly corrosive and non-scaling
0.0 Balanced, but potential for pitting corrosion
+0.5 Slightly corrosive and scaling
+2.0 Scaling and generally non-corrosive
Table 5.3
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Another sparingly soluble salt is calcium phosphate. Its solubility at different temperatures
can be calculated from the following equation, at any given pH :
pHc = (11.75 log CaH 2 log T log PO4)
0.65
Where :
PO4 as ppm PO4 CaH as ppm CaCO3 T = oC
The insulating properties of water-formed scales is well documented. In more practical
terms, a calcium phosphate (Ca3(PO4)2) scale as thin as 0.04 inches will reduce heat transfer
approximately 8 percent.
A uniform scale of 0.04 inches in a 1.0 inch I.D. heat exchanger tube also results in an 8
percent loss of tubing capacity. Energy losses attributed to reduced heat transfer capabalities
and increased pumping costs, associated with added frictional resistance to water flow, easily
justify the time and expense of implementing a good chemical water management program.
Scale can be effectively controlled in a recirculating, evaporative cooling system, by one or

more of the following methods:
1) Limiting cycles of makeup water concentration

2) Physical removal of the impurities that contribute to the scaling potential
3) Feed of an acid to control the pH of the recirculating water
4) Use of other chemical treatment (scale inhibitors)
Increasing the bleed-off of a cooling tower is a very effective method of preventing all types
of scale. However, to minimize chemical treatment and water consumption, an evaporative
cooling system should operate at a maximum possible number of concentration cycles,
particularly in the water-short areas.
Conditioning the incoming makeup water by external pre-treatment is a viable method of

reducing or completely minimizing the deposit-forming potential in cooling water systems.
Softening by ion exchange methods offers a potentially serious disadvantage because the
softener effluent contains a higher concentration of sodium salts which in turn increases the
corrosiveness of the cooling water. Furthermore, non-zinc corrosion inhibitor programs are
typically enhanced by the presence of at least approximately 50 ppm of calcium hardness in
the recirculating cooling water.
Sulfuric (H2SO4) acid is most often used to prevent calcium carbonate scale formation. The
acid functions by converting recirculating water alkalinity to carbonic acid. Carbonic acid
(H2CO3) dissociates into carbon dioxide (CO2) and water. Gaseous CO2 is driven from the
system as the warm cooling water cascades down over the tower fill.
H2SO4 + Ca(HCO3)2 CaSO4 + 2H2CO3
H2CO3 CO2 + H2O
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GPS//2003
The use of acids as scale control agents has limitations, including handling, storage and
disposal problems. Acid use also adds additional chemical and feed equipment costs to the
treatment program. There is always the potential for over-dosing the acid, which can cause
severe corrosion of the system metals. Finally, high concentrations of sulfate salts in the
cooling water can potentially result in the formation of calcium sulfate scale.
Several additional chemical treatment methods can be used to control the formation of scales
and deposits in cooling water systems. These methods typically rely on the use of a chemical
scale inhibitor in the recirculating water. These inhibitors are effective at holding large
quantities of scaling minerals in solution at the threshold of precipitation; hence these
inhibitors are referred to as threshold treatments. These inhibitors retard/prevent
precipitation of scale in super-saturated solutions, by interfering with crystal growth. These
inhibitors also disperse particles of scale, thus preventing the adhesion of scale to heat
transfer surfaces.
The general classifications of threshold treatments that have been used in cooling water
systems, include:
1) phosphonates
2) synthetic organic polymers
3) polyphosphates
4) natural organic polymers
The concentration at which each individual material is used in a treated water, depends upon
the severity of the scaling problem. Synthetic organic polymers and phosphonates are the
most effective treatments available. These inhibitors are typically employed at 1 to 5 ppm as
active material.
A polyphosphate, such as hexametaphosphate, is also an effective calcium carbonate scale

inhibitor. However, the drawback is the reversion of condensed phosphates to ortho
phosphate with the subsequent risk of calcium phosphate sludging, which limits the use of
polyphosphate in open recirculating systems. Furthermore, polyphosphates are relatively
ineffective at a pH higher than 8.0 and the presence of heavy metals in the recirculating water
poison them.
Lignosulfonates (natural polymers) at unusually high concentration (15-20 ppm) are needed
to inhibit the precipitation of the same amount of calcium phosphate as 1 to 2 ppm of
synthetic organic polymers.
Synthetic organic polymers are structurally well-defined, stable at high temperatures,

effective at low dosages (1 to 5 ppm), and present no unusual feeding problems.
Polyacrylates, polyacrylamide-acrylate copolymers, and polymaleates are widely used. The
CaCO3 and CaSO4 scale inhibiting properties of these polymers are listed in Table 5.5.
Generally, some inhibition is provided by as little as 1 ppm of these materials.
Although co-polymers do not typically exhibit good CaCO3 scale inhibition, these agents can
be used to increase the effectiveness of triazole-phosphonate-phosphate corrosion inhibitors
by controlling phosphate sludge deposition at high cooling water phosphate residuals.
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Typical Efficiency of Polymeric Scale Control Agents at 2 ppm
% Efficiency
Polymer CaCO3 CaSO4
Polyacrylic acid, molecular weight 5000 90 40
Polyacrylic acid, molecular weight 1800 96 90
Polyacrylamide-acrylate copolymer 38 76
Polymaleate 98 34
Table 5.4
The most widely used materials for threshold scale control are the phosphonates. These
materials, are characterized by a direct carbon to phosphorus bond, which confers excellent
hydrolytic stability. Various members of this class of scale inhibitors are also used as boiler
water scale control agents.
Phosphonates are very effective scale inhibitors at substoichiometric concentrations (1-5

ppm). Of the phosphonates most commonly used, HEDPA is reported to be the best calcium
carbonate precipitation inhibitor although under high calcium levels, PBTC is a better choice.
These are some drawbacks to using phosphonates as scale and corrosion inhibitors.
Nitrogen-based phosphonates react with chlorine and bromine oxidizing agents used as
biocides, rendering these substances ineffective as scale retardants. Phosphonate also
contribute to the total phosphorus levels of cooling tower discharges. Additionally, the
presence of some heavy metals interfere with antiscalant activity.
iv) CORROSION
From an electrochemical viewpoint there are two distinct methods of providing corrosion
protection to a metal substrate :
1) prevent the oxidation of the metal at anodic sites

2) prevent the reduction of oxygen at cathodic sites
Water-borne inhibitors which retard the anodic reaction are termed anodic inhibitors or
passivators. Chemicals serving this function include high dosages of oxidizing agents such as
the chromate (CrO4-2), and nitrite (NO-2), phosphates (o-PO4-3) and molybdate (MoO4-2). A
passivator alone is an uneconomical means of controlling corrosion in open recirculating
cooling water systems.
v) FOULANTS
The deposition of insoluble matter other than mineral scales is defined as fouling. In addition
to producing the same undesirable effects as scales, fouling materials also combine with
precipitated minerals to produce more voluminous and tenacious deposits. Foulants also
contribute to under-deposit corrosion.
Foulants are classified as:
1) inorganic
2) organic
3) microbiological
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GPS//2003
Some examples of inorganic foulants include: sand; silt; clarifier carryover; corrosion
products; phosphate and alum sludges. Organic foulants include: lubricants; fats; greases;
plant extracts; petroleum products. Fouling occurs predominantly in high temperature, low
flow (less than approximately 1 ft/sec) areas and is more influenced by system design and
operation than by water chemistry.
Physical methods for preventing fouling include side-stream filtration and other particulate
removal techniques.
Chemical methods for controlling inorganic and organic foulants include the application of
anionic, (infrequently cationic and non-ionic polymers also), to suspend and disperse
troublesome particulates. Foulants thus treated are readily removed in the tower bleed-off.
Various surfactants are also used to penetrate and emulsify organic foulants. Anionic
dispersants are the most widely used approach and these can include both homo and co-
polymers.
vi) MICROBIOLOGICAL
Open recirculating cooling water systems are continuously exposed to microorganisms. If
unchecked, microbes rapidly multiply in the warm cooling water, and can lead to:
fouled heat exchangers

metal deterioration
degradation of cooling tower lumber
reduced flow rates
lost heat exchanger capacity
algae growth on tower decks
slime deposits
Proper application of microbicides to control microbial growths in cooling water systems

involves three steps:
Identify the types and level of microorganisms present in the cooling water
Determine which specific types of microbicides are appropriate
Establish an effective microbicide treatment program
Microbicides fall into two major classes: oxidizing and non-oxidizing types.
Examples of oxidizing biocides include:
Sodium hypochlorite (NaOCl)

Chlorine gas (HOCl)
Bromine (HOBr)
Chloride dioxide (ClO2)
Bromo Chloro Dimethyl Hydantoin (BCDMH)
Hypochlorous acid is the most widely used oxidizing microbicide, and is formed by feeding
either chlorine gas or one of several other compounds including sodium or calcium
hypochlorite. Organic chlorine donors such as the chlorinated cyanurates can also be used.
Bromine salts such as sodium bromide and BCDMH offer the advantages of chlorine but
perform better at high pHs, or in environments where amines (such as ammonia) are present.
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Chlorine and bromine biocides are effective, low cost microbicides. However, best results
are most frequently achieved when used in conjunction with a non-oxidizing microbicide or a
biodispersant, since this will improve their ability to penetrate slime or other deposits and
allow the oxidizing biocide to contact the problem organisms.
A second class of biocides are those that function not on the basis of their oxidizing ability
but by interfering with metabolic processes non-oxidizing biocides. There are two general
types of non-oxidizing microbicides:
surface active
metabolic poisons
Metabolic poisons are biocides that interfere or arrest metabolic processes by directly
affecting cellular activities. Examples of these chemicals include:
Dibromonitrilopropionamide (DBNPA)
Bromonitropropanediol (BNPD)
Bis (trichloromethyl) sulfone
Thiones
Thiocarbamates
Methylene bis thiocyanate (MBT/MBTC)
Isothiazolone (MCI)
Bromohydroxyacetophenone (BHAP)
Thiocyanomethylene benzothiazole (TCMTB)
Tetrakishydroxymethyl phosphonium sulphate (THPS)
These types of biocides must be absorbed into the cell before they can have an effect on them
and this generally makes them slower acting than either oxidizers or surface active biocides.
Surface active compounds used as microbicides include quaternary ammonium salts, amines
and polyquats. These materials are generally cationic and it is this property is what makes
them effective. However, as for most things there are exceptions (amines and
glutaraldehyde). Examples of this class of biocide include:
Benzyl quaternary amines (Quats)

WSCP (Polyquat)
DGH (dodecyl guanidine hydrochloride)
Glutaraldehyde
Since non-oxidizing biocides act on metabolic process, organisms can develop a tolerance to
them, much in the same way that bacteria can become immune to antibiotics. Hence,
alternating chemically different types of microbicides provides better control.
In many instances, the maximum utility of a microbicide is not achieved. Better control of
microbiological growths can be obtained by following a few simple guidelines during
microbicide application.
Most non-oxidizing biocides are fed on a slug basis. Slug feeding has proven to be an
effective, rapid method of reducing microbiological populations. The rate of application of a
54
GPS//2003
microbicide depends on the severity of the microbiological problem, retention time of the
microbicide, etc.
To obtain maximum retention time of the microbicide in a cooling system, it is desirable to

bleed-off heavily prior to the addition of the microbicide, add the microbicide with no bleed-
off, and after a 24-hour period return to normal operating control limits. Adjustment of the
corrosion inhibitor and antifoulant feed may be necessary during these periods.
An antifoulant is often beneficial in breaking up slime masses to allow the microbicide to

reach more organisms and to do a more effective job. A dispersant is also helpful in
removing both dead and living organisms in tower bleed-off.
C. TREATMENT OF CHILLED WATER SYSTEMS
There are three primary classes of corrosion inhibitors used in these applications:
Reducing agents
Oxidizing agents
Film formers
In conjunction with the above agents, secondary corrosion inhibitors supplement the protection
by:
Buffering/controlling pH
Minimizing yellow metal corrosion
Reducing Agents
Although rarely seen now, tannin type materials were used to both remove oxygen and form
an iron-tannin film on steel surfaces. While tannins have a number of advantages, they can
form organic deposits and are not always effective corrosion inhibitors.
A more common oxygen scavenger is sulphite. Unless there is sufficient sulphite present at all
times, free oxygen will exist and this can initiate corrosion of the boiler metal. A major
drawback is that as sulphite continues to be fed, to counteract the ongoing ingress of oxygen, the
concentration of sulphate builds and this increases the conductivity of the water. In turn, this
makes the water more corrosive, increasing the potential for SRB (sulphate reducing bacteria)
growth along with the attendant corrosion risks.
Organic reducers such as hydrazine (N2H4) and DEHA (diethylhydroxylamine) have been used
but, decomposition (catalysed by copper) and health concerns (hydrazine) have largely
eliminated their use.
Oxidizing Agents
In contrast to the preceeding type of chemicals, oxidizers either directly oxidize metal
surfaces (chromate and nitrite) or work in conjunction with oxygen (molybdate) to form a
passive film on the metal.
The standard inhibitor in this category, nitrite, has been used to inhibit mild steel corrosion for
many years in neutral or alkaline aqueous solutions. Nitrite is the only remaining anodic,
oxidizing inhibitor that can still be used. Unlike molybdate, another anodic inhibitor, nitrite can
function without the need for oxygen and for this reason is very effective in closed systems.
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Being an oxidizing agent, it has been proposed that ferrous metal is inhibited by the oxidation of
ferrous hydroxide and the subsequent reaction with another molecule of ferrous hydroxide to
generate a passive magnetite layer, the overall reaction being:
9Fe(OH)2 + NO2- 3Fe3O4 + NH4+ + 2OH- + 6H2O
When nitrite is used alone, or in conjunction with pH buffering agents, relatively high
concentrations (700 - 1200 mg/L as NaNO2) are needed to completely inhibit pitting corrosion.
It is generally recognized that the nitrite will be influenced by the amount of chloride and
sulphate present in the water since they can affect the stability of the magnetite layer.
Characteristic of anodic inhibitors, if the concentration is allowed to fall below approximately
500 mg/L (of sodium nitrite), severe pitting attack can occur.
Loss of nitrite can occur via electrochemical and biological processes. In the former case, if
corrosion continues, nitrite can be electrochemically reduced at the cathode to form ammonia
according to the equation:
NO2- + 5H+ + 6e- NH3 + 2OH-
In chilled water loops (or hot water systems, that are not in operation) exposure to bacterial
contamination has the potential to convert nitrite to nitrate, ammonia or nitrogen gas. The
ability to control biological activity is difficult since oxidizing biocides will oxidize the nitrite
to nitrate and the efficacy of non-oxidizing biocides tends to be less certain.
The use of molybdate for corrosion protection in cooling water, either open recirculating or
closed loop systems, is extremely common. While molybdate is not as strong an oxidizing
agent as chromate, it can function in this role in the presence of oxygen and its ability to
inhibit pitting attack has been well documented, especially at low concentrations in cooling
water applications.
It has been reported in literature that molybdate is too weak an oxidizing agent to convert ferrous
ions to the ferric state. In the presence of oxygen, molybdate will convert hematite to magnetite.
This process is quite visible as boilers (either hot water or steam) change from a reddish colour
to black when treated with molybdate. This mechanism predominates at higher concentrations
(>50 mg/L as Mo), since in previously reported work, at low levels (5 mg/L as Mo), it is found
to accumulate almost exclusively within pits.
The only concern regarding molybdate use is related to its accumulation in sludge from waste
treatment plants, when the sludge is spread on agricultural land. In rare cases, molybdate may
accumulate, to the point where there may be a sufficient concentration present, to interfere with
copper uptake by ruminants. Overall, based on its low human and aquatic toxicity, molybdate is
not restricted in most areas of North America.
The last oxidizer is hexavalent chromium, or chromate, which while a very effective
corrosion inhibitor, is seldom used due to concerns of health/environmental effects.
56
GPS//2003
Film Formers
Among primary corrosion inhibitors, four filmers are employed; the two most common being
ortho-phosphate and neutralized dibasic acids.
Ortho-phosphate is the most widely used inhibitor for glycols, acting both as corrosion inhibitor
and buffering agent. At the relatively high concentrations that phosphate is used at (1000 5000
mg/L as PO4), it provides positive protection against corrosion on mild steel and yellow metals.
The primary mode of action is via precipitation at the anode to form insoluble metal phosphates.
The ability of phosphate to form a protective film via a direct precipitation mechanism is both its
strength and weakness. While it will go onto the metal surfaces, it will just as readily precipitate
with metal ions or hardness salts in the bulk water. Since ortho-phosphate is an anodic inhibitor,
if the concentration falls below the critical level, rapid corrosion attack will happen.
Related to inorganic phosphate, are some phosphonates, of which HPA

(hydroxyphosphonoacetic acid) is the best example, which are effective cathodic inhibitors.
HPA is used in some applications where a product with a low environmental impact is preferred.
At the concentrations normally used, 50 200 mg/L (as HPA) acceptable corrosion rates can be
obtained.
Various dibasic acids can be used for both pH buffering and corrosion inhibition, much in the
same way as phosphate. Their limited solubility with transition metals and alkaline earth cations
make them effective corrosion inhibitors. The neutralized dibasic acid can react with the
ferrous/ferric ions (from the corrosion site) and precipitate, either directly or as related reaction
products. As this process continues, the anode becomes progressively more restricted until it is
no longer able to function as a corrosion site.
A difficulty with dibasic acids is that they display varying degrees of biodegradability and in
chilled water loops this can pose a serious limitation. This can be especially troublesome in
loops where there are other nutrients (e.g. nitrite) or a high bacterial population. In nitrite treated
chilled water systems, rapid biological growth can quickly consume the dibasic acids.
A final type of film former are some substituted triazines, that selectively react with iron to form
an inhibitory film on the metal. Although they are widely used in oil-field applications, they
have not seen extensive use in closed loops.
Buffers/pH Control
The function of corrosion inhibitors and buffering/pH control agents are intertwined. Inhibitors
generally function only across certain pHs, for instance nitrite is typically used under alkaline
conditions. Others, such as some of the dibasic acid mixtures, show best performance at neutral
pHs.
Given that most hot and chilled systems are composed of a variety of metals and elastomers, the
pH range chosen must, by definition, be a compromise. The primary metallurgies seen in North
America are mild steel and copper alloys. As a compromise between steel and copper, the fluid
pH is typically controlled in the range from 8.5 10.5
The most widely used pH control agents are buffers:
inorganic phosphate
organic amines
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borate salts
Ortho phosphate, typically dipotassium phosphate, can be used to control the pH between 8.5
10.5. At these high levels, typically used, ortho phosphate provides excellent buffering capacity.
In glycol containing loops, they are able to neutralize glycol breakdown products for extended
periods of time.
Another inorganic buffering system is borate. Borates allow a slightly higher pH and buffering
capacity but at a lower concentration than is needed for phosphates. Organic amines can also be
used to tailor the pH range, depending on the circumstances. A benefit of organic amines is that
the amount needed in the fluid is low (200 300 mg/L) and their contribution to conductivity is
less than for other buffering systems.
Yellow Metal Inhibitors

Control of copper corrosion is critical in any closed loop. While copper (or its alloys) are
quite corrosion resistant, the impact of even low corrosion rates can be dramatic. When
copper corrodes, the soluble copper ions are available to plate out onto mild steel
components. When this happens, the more inert copper metal becomes a fixed cathode on
the metal surface. At this point, the entire corrosion process becomes more and more
localized. As this proceeds, instead of having a low general corrosion rate, high local
corrosion rates will be seen.
In order to prevent both the initial corrosion of copper alloys, as well as to inhibit copper
deposits on mild steel surfaces, azoles are used. TT (tolyltriazole) has become the inhibitor
of choice since it provides improved formulating ease and superior resistance to the corrosive
effect of chloride ions. In contrast to precipitating agents, azoles bond onto the metal surface
via co-ordination between the nitrogen atoms and copper oxide molecules on the surface.
D. CALCULATIONS
i) INTRODUCTION
As previously mentioned, there are three basic types of cooling water systems that may exist
alone or in combinations:
1) once-through
2) closed recirculating
3) open recirculating
As always, there are exceptions, for instance it is not uncommon to find a once-through
cooling water partially or wholly used as makeup to an open recirculating system. A closed
system that is open to the atmosphere such as a central sump, in this case the sump serves
only as a collecting point for the cooling waters; evaporative cooling does not take place.
Although one may encounter cooling systems that do not seem to fit the simple categories,
the approach to treating these systems will usually be based on the considerations of whether
the systems are once-through, closed or open recirculating.
Calculations are based on whether a system is:
1) non-evaporative
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GPS//2003
2) evaporative
Figure 5.2 Open Recirculating Cooling Water System

Non-evaporative system treatment calculations are straightforward. Since the water into a
once-through (or closed recirculating) system equals the water discharged and the discharged
water is essentially the same quality as the entering water, the only modification is the
temperature rise due to the absorption of heat.
Evaporative cooling system, which utilizes the latent heat of vaporization plus convection
cooling, cause substantial changes to the water used. Concentration of mineral impurities due
to evaporation must be considered when calculating treatment requirements.
ii) OPEN RECIRCULATING SYSTEMS

The primary function of all cooling water systems is to remove unwanted heat. Figure 5.2
illustrates the essential elements of an open recirculating water cooling system.
In this design, cooling water is pumped through a point of heat exchange or heat transfer,
increasing the temperature of the cooling water to T2. The cooling water flows through the
recirculating lines to the cooling tower deck from which the water falls by gravity through the
tower packing (or fill) to the tower basin. Heat is rejected to the atmosphere by means of
evaporation (E) as cooling water droplets are broken up in the packing and air passes upward
by means of mechanical or natural draft. The rejection of heat in the recirculating water (R)
by evaporation (E) restores the cooling water to temperature T1, at which point the cooling
cycle begins again. The cooling tower serves two purposes:
heat rejection
water conservation
In the operation of the cooling tower, water is continuously evaporated and must be replaced
Evaporation
(heat rejection)
Heat Load
Cooling Tower from Process
Make Up Bleed-Off
with fresh makeup water. This results in an increase in the concentration of dissolved solids
in the recirculating water. The ratio of the total dissolved solids in the recirculating water to
the total dissolved solids in the makeup water (TDSR/TDSM) is called C (cycles of
concentration).
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C = TDSR (1)
TDSM
As cycles of concentration (C) increase, some of the dissolved solids in the recirculating
water approach the limit of their solubility in water. This is especially significant for
dissolved minerals, which form scales, as they become less soluble as the temperature of the
recirculating water increases. Therefore, they tend to deposit in areas of elevated temperature
and lower water velocity such as in heat exchange equipment.
In order to prevent the formation of scales, a portion of the concentrated recirculating water is
bled (bleed-off) from the system and replaced by less concentrated makeup water. Bleed-off
(B) maintains the recirculating water at the desired level of cycles of concentration.
In addition to bleed-off, some water droplets containing concentrated dissolved solids are lost
through the evaporation equipment in the cooling tower. This windage (W) loss may vary
from one cooling tower to another between 0.05% and 0.1% of the recirculating rate (R). For
most cooling tower calculations, windage (W) is included in the tower bleed-off (B).
Make-up is the sum of all water losses:
M=E+B+W or M = E + B* (2)
*Includes windage (W), leaks, overflow, losses, etc.
Evaporation can be estimated for the system using the following expression:
E = .001 x R x T x f (3)
This expression indicates that the evaporation rate (E) is approximately equal to 0.1% of the
water circulated (R) over the tower for each 1oF of temperature drop times a factor (f).
The factor (f) represents the percent of cooling that is contributed by evaporation only. The
total cooling effect when warm water is in contact with cooler air is not due to evaporation
alone. Sensible heat transfer from the warm return water to the cooler air will accomplish a
certain percentage of the cooling depending on the temperature of the ambient air. The
convective cooling effect may range from 40% in winter to 10% in summer or conversely f
will vary between .6 and .9 depending upon time of year. A typical number is 0.8 for a
yearly average.
To calculate the amount of bleed-off water (B) required to maintain a given level of cycles of
concentration (C), use the equation:
B=E
C-1 (4)
60
GPS//2003
Upper Unit - Once-Through

10000
R = 10,000 GPM
T = 20OF
Make-up (GPM)
Makeup (M)
1000
Blowdown (M-E)
Evaporation (E)
200 Lower Limit - Evaporation

100
1 1.1 1.25 1.5 2 3 4 5 6 7 8
Cycles of Concentration
Figure 5-3 Water savings as a function of cycles of concentration
Figure 5-4 Makeup flow as a function of cycles of concentrations
In practice, the quantity of makeup water required for the operation of a given cooling tower
may be estimated with a fair degree of accuracy, using the previous equations.
50
40
Bleed-off (GPM)
Savings
30 3 Cycle s
4 Cycle s
5 Cycle s
20 6 Cycle s
10
0
0 20 40 60 80 100 120
Evaporation (GPM)
Cycles of concentration, (C), are frequently determined, not by total dissolved solids
measurement, but by specific conductance or by any non-reactive chemical constituent which
can be accurately tested in both the makeup and the recirculating water. Care should be taken
that the measured constituent is not one, which is added with the treatment chemicals.
Chloride ion is often used but is not well suited for this purpose when chlorination is
practiced or other treatment products containing appreciable chloride are added to the system.
1-CWT Page 61 of 117 0902

The concept of cycles of concentration is an important consideration in the operation of an
open recirculating cooling system. The greater the number of cycles of concentration a
system is capable of operating, the less water (and treatment) the system will lose via bleed-
off. In recent years, some treatment programs have been able to achieve a zero bleed-off
condition in certain cooling systems, the cycles of concentration being limited by windage
losses only. Figures 5.3 & 5.4 graphically illustrate the relationship between bleed-off
requirements and cycles of concentration.
In most open recirculating cooling water systems, the concentration of treatment in the
cooling water required to inhibit scale and corrosion is relatively constant. Therefore, as
cycles of concentration are increased to a maximum, the amount of treatment required to
maintain a given concentration in the recirculating water is diminished proportionately. In
order to determine the quantity of treatment needed to maintain a given concentration in the
recirculating water, use:
lbs treatment / unit time = B* (Gal/unit time) X ppm (treatment) (5a)

120,000
kgs treatment/ unit time = B* (kgs/unit time) X ppm (treatment) (5b)

106
*Includes windage, leaks, overflow, etc.
As cycles of concentration increase, the potential for corrosion, scale or fouling generally
increases. There is a practical limit beyond which cycles of concentration cannot be
increased for most cooling systems. Potential problems and their control are discussed in a
later section.
The quantity of treatment required to slug dose a cooling system of V (Gal) is:
lbs treatment = V(gal) X ppm (Treatment) (6a)

120,000
kgs treatment = V (L) X ppm (Treatment) (6b)

106
It is frequently useful to determine the time elapsed to deplete the cooling system of a given
species of treatment or of a contaminant. The half-life (t1/2) of a given species within a
cooling system is a special case of equation (6):
t1/2 (time) = 0.7 (7)

Losses (B)
This is the amount of the time required to reduce the concentration of treatment (or
contaminant) by 50%.
62
GPS//2003
EXAMPLE
An open recirculating cooling water system has a design recirculating rate of 12,000 USgpm
and operates consistently 24 hours per day, year round.
The cooling range measured across the cooling tower is 18oF (108oF at the top of the tower
and 90oF in the tower sump). The heat load on the system is constant. There are no water
meters on the tower makeup line, but the blowdown line has been monitored and flow
measured at 60 USgpm. The design specifications for the tower indicate windage losses at
0.05% of the recirculating rate.
Use equation (3) to determine the evaporation rate (E):
E = .001 x R x T x f
E = .001 x 12,000 USgpm x 18oF x 0.8 = 172.8 USgpm
The specific conductance of the recirculating water measure four times that of the makeup
water indicating that the system is operating at four cycles of concentration. This was
confirmed by the silica concentrations as well:
The blowdown rate, is then calculated using the equation as follows:
B = E/(C-1)
B = 172.8 gpm/(4-1)
B = 57.6 gpm
Using the design specification for windage, 0.05 of the recirculating rate, or 6 USgpm, the
calculated blowdown rate compares reasonably well with the measured rate of 60 USgpm.
Equation (1) is used to determine makeup requirements for the system and may be compared
with other plant water consumption data (when available) for accuracy.
M=E+B
M = 172.8 + 57.6
M = 230.4 USgpm
To determine water treatment quantities needed to maintain a recommended concentration

(115 ppm) in the recirculating water, use equation (5).
lbs treatment/min = B(gpm) X ppm (treatment)

120,000
lbs treatment/min = 57.6 gpm X 115 ppm

120,000
lbs treatment/min = .0552 lbs/min = 79.5 lbs/day
Biocides, are frequently slug fed to a cooling water system, at a recommended dosage (65
ppm, for example). The total system volume has been determined to be 75,000 gallons. The
quantity of biocide required to slug dose the system can be determined from equation (5).
1-CWT Page 63 of 117 0902

lbs treatment = Volume(gal) X ppm (treatment)
120,000
lbs treatment = 75,000 X 65

120,000
lbs treatment = 40.6 lbs
Occasionally, the cooling water system becomes fouled with oil contamination. To
determine how long it will take to blowdown 50% of a 300 ppm oil contamination at a
maximum bleed rate of 100 gallons/minute, use equation (7):
t1/2 = 0.7 (75,000 USg)

100 USgpm
= 525 minutes
= 8.75 hrs
Limits of Cycles of Concentration

The concentration of solids in open recirculating cooling systems must be limited in order to
prevent fouling or deposition of insoluble materials on heat exchange equipment or other
critical areas within the circuit. Typically, cooling water cycles of concentration are limited
by one of the following parameters:
Calcium carbonate (LSI)

Calcium phosphate
Silica (SiO2, calcium silicate, or magnesium silicate)
Calcium sulfate
Suspended solids (fouling)
Leaks or overflow
Each of the above factors must be taken into consideration prior to selection of a treatment
program.
To determine the maximum number of cycles of concentration in a cooling system without

risking fouling or deposition, the actual limit on cycles will be the smallest number of cycles
determined for any single parameter.
Calcium carbonate
Cycles of concentration in many systems are limited by calcium carbonate solubility. The
common measure of calcium carbonate solubility for cooling water systems is the Langelier
Saturation Index (LSI). For maximizing cycles of concentration when applying moderate
duty products, limit the LSI to +2.0. For heavy duty products limit the LSI to +2.5 to +2.75.
Calcium phosphate
In the makeup water for the cooling water system which contain phosphate (ortho or poly),
the cycles of concentration will usually be limited by calcium phosphate solubility. Using the
calcium hardness, ortho phosphate, pH and maximum heat exchanger exit temperature of the
recirculating water, determine the maximum cycles of concentration based upon calcium
phosphate solubility.
64
GPS//2003
Silica
Some cooling water systems are limited in cycles of concentration by silica (SiO2). Silica
solubility is a complex function of several variables including silica concentration, pH,
temperature, magnesium and calcium concentrations. In general, bulk silica deposition
occurs in the colder areas of the system and is relatively independent of pH. The solubility of
magnesium and calcium silicate salts is very pH dependent. They tend to deposit on hot
surfaces at elevated pH like other salts with inverse temperature solubility curves. As a
general rule, keep silica concentrations below 170 ppm (SiO2) to limit cycles of concentration
and to prevent silica-based deposits.
Calcium sulfate
In sulfuric acid-modified cooling systems, calcium sulfate may become the limiting factor for
maximizing cycles of concentration. Where sulfuric acid is fed, add the sulfate in the
makeup water to the M alkalinity removed from the makeup water before multiplying by
the anticipated cycles. Using the calcium hardness and the sulfate concentration, one can
determine if precipitation is expected (or not) under various conditions. Calcium sulfate
precipitation is independent of pH.
Suspended solids
To prevent fouling of critical heat exchange equipment by dirt, airborne debris, or other
various sources of suspended solids, limit cycles of concentration to around 7. If a system
has side-stream filtration, it is possible to operate at much higher cycles of concentration.
Leaks or overflow
Some cooling systems are limited in cycles of concentration by windage, leaks,
uncontrollable system losses, or uncontrollable sources of makeup (in-flow). In these
circumstances, these other parameters will be the controlling factor.
Alkalinity/pH Control
Although the trend in cooling water treatment appears to de-emphasize control of cooling
water alkalinity or pH due to the disadvantages and dangers of feeding acid, the concept is
widely used and should be considered where difficult water supplies exist or if water
availability is limited.
Sulfuric acid (66O Baume, 93% H2SO4 density 1.8) is is the most commonly used. The
reaction with bicarbonate alkalinity:
Since the equivalent weights of CaCO3 and H2SO4 are approximately the same, approximately
1 ppm of acid is necessary to react with 1 ppm M alkalinity. For all practical purposes and
for speed of calculation H2SO4 reacts with M alkalinity on a 1:1 basis.
Ca(HCO3)2 + H2SO4 CaSO4 + 2CO2 + 2H2O
In water chemistry, total alkalinity is expressed as calcium carbonate. Therefore, ions such as
HCO3 and CO3, which are responsible for the bulk of alkalinity in water supplies, are also
expressed as CaCO3.
The original concept of feeding acid was predicated on maintaining the solubility of the
calcium compound, calcium carbonate. Assuming that carbonate ion will only exist in a
cooling water at above pH 8.3, enough acid is fed to depress pH of the cooling water below
1-CWT Page 65 of 117 0902

the phenolphthalein P end point. It is thus logical to conclude that, in the absence of P,
most alkalinity is bicarbonate (HCO3-) alkalinity, which is highly soluble and will not
produce scale.
Acid was fed to cooling waters, then to maintain a pH range below the P alkalinity end
point (pH 8.3). This precluded the presence of CO3 ion, which would unite with Ca+2 to form
CaCO3 scale.
Originally, when acid feed was adopted, the control range was expressed as ppm M
alkalinity in the recirculating water. P alkalinity was always zero. Sufficient acid was
applied to maintain a safe M alkalinity range whereby non-scaling conditions would exist
and to provide a margin of safety in the event of a temporary acid feed insufficiency.
This method of control is still reliable and is utilized for treatment programs such as zinc-
phosphate, zinc-polyphosphate, zinc-phosphonate and high phosphate. The trend today is for
alkaline treatment programs in which acid is used to maintain pH (and M alkalinity) in the
alkaline range, generally above 8.3 where corrosion is minimized and scale is inhibited has
resulted in a different control strategy.
Acid requirements based on M alkalinity are much easier to calculate. The M alkalinity
desired in pH-controlled cooling water can vary from approximately 20 to as high as 500
ppm depending upon the treatment program. Buffering, common ion effect, varying
temperature, errors in pH measurement, etc, tend to influence pH readings which, in turn,
make pH control less dependable than alkalinity measurements.
The recommended procedure for the control of cooling water pH is to CORRELATE pH

CONTROL WITH M ALKALINITY CONTROL. This simply means that pH and M
measurements should both be determined to establish and maintain a definite comparison
profile for each individual cooling water. M alkalinity readings will correlate with
whatever pH range is desired.
The pH control agent (acid) dosage will be determined by the amount of M alkalinity
desired as well as its activity. H2SO4 requirements may readily be calculated after the
desired pH range of M alkalinity range is determined.
66
GPS//2003
Example:
An open recirculating system is to be treated with acid to prevent scale and an inhibitor for
corrosion control. It is estimated that the desired M alkalinity should be in the control
range of 20-40 ppm in the recirculating water. In most instances this will produce an average
cooling water pH 7.0 7.5.
The makeup water contains 270 ppm M and the system operates at 3 cycles. What quantity
of H2SO4 must be fed to the makeup to produce an average of 30 ppm M in the
recirculation cooling water?
If 30 ppm M is desired in the cooling water, then the alkalinity of the makeup water must
be reduced to 10 ppm M. The 10 ppm M x 3 cycles will concentrate to 30 ppm M in
the cooling water.
M in makeup M desired in makeup = ppm
M to be neutralized = ppm H2SO4
or:
270 ppm M 10 ppm M = 260 ppm M or 260 ppm H2SO4
then:
Makeup USgpd X 260 ppm = lbs H2SO4 required per day
120,000
iii) CLOSED LOOP SYSTEMS

Calculation of treatment dosage for closed system is not dependent upon evaporation or flow
rate. Treatment dosage (corrosion inhibitor) is predicted upon system volume capacity. The
treatment dosage can be calculated using equations (6a) or (6b). In effect, this is a variation
on the calculation for a slug dosage and the same calculations are used.
Example:
System volume (V) = 100 M3

Treatment desired = 1,500 ppm
100,000 L X 1,500 ppm = 150 kgs treatment
106
1-CWT Page 67 of 117 0902

iv) Once-Through Systems
Calculations for once-through systems are based solely on the flow rate, as no evaporation
effect (cycles of concentration) is applicable. Because the flow rates on once-through water
are normally quite high, it becomes readily apparent that treatment levels must stay low in
order to be cost effective.
lbs treatment = Flow (USg/unit time) X ppm treatment (8a)

(unit time) 120,000
kgs treatment = Flow (L/unit time) X ppm treatment (8b)

(unit time) 106
Example:
Once-though water used to cool air compressors flows at 300 gal/min before discharge to the
river. How many lbs/day of a polyphosphate product is required if the recommended dosage
is 3 ppm?
300 (USgpm) (1,440 min/day) X 3 ppm = 10.8 lbs/day
120,000
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GPS//2003
6. COOLING WATER MICROBIOLOGY

A. Introduction
B. Types of Micro-organisms
i) Bacteria
ii) Fungi
iii) Algae
i) Oxidizing Biocides
ii) Non-oxidizing Biocides
iii) Selection Criteria
iv) Monitoring
1-CWT Page 69 of 117 0902

6. Cooling Water Microbiology
A. Introduction
Microorganisms foul and corrode cooling systems. For these reasons (and others), it is
important to maintain control of microbiological activity.
Cooling towers are designed and operated to dissipate waste heat from industrial
manufacturing processes and air conditioning systems. In typical refrigerant condensers
(chillers), water enters at 80-90oF and leaves 90-100oF. Similar heat loads are seen in many
industrial processes. This waste heat is then removed from the water across the cooling
tower.
During the cooling process, the warm water is pumped to a distribution deck from which it
cascades over the tower fill as droplets or a thin film. Having the water as small droplets
allows for creation of greater surface area, which is exposed to the air flow. This enhances
the cooling effect. The cooled water is pumped back through the heat exchangers (or
condenser system), and the cycle is repeated.
As cooling and evaporation of the water takes place, the dissolved solids in the water
concentrate. As the impurities in the cooling water concentrate up, nutrients also increase,
which enhances the potential for biological activity.
Microbiological activity in cooling water systems reveals itself in various ways. The most
obvious are the visible signs of slime, sludge, and algae deposits on the cooling tower itself.
Less obvious are the problems of reduced cooling efficiency and ineffective corrosion
protection.
Microbiological fouling in cooling water systems results from the growth and multiplication
of bacteria, fungi, and algae through the various parts of a system. A few slime-forming
organisms enter the tower water from the air or make-up water and multiply very rapidly to
form slime masses. Cooling towers and their recirculating water environment are able to
provide the invading organisms with nutrients, temperature, and pH necessary for growth. As
they grow, these bacteria secrete large amounts of a sticky, glue-like slime, also called EPS
extra-cellular polysaccharide, which coats condenser tubes, transmission piping, and cooling
tower surfaces (Figure 6.1).
The sticky nature of EPS allows it to trap other organisms, dirt and silt. These biological
slime growths may show different physical properties depending on the type of organisms
involved : stringy, gelatinous, thick and viscous, or leathery.
The resulting effects of slime formation include plugged recirculation lines and condenser
tubes, reduced filter flow, reduced heat transfer efficiency, formation of hot spots,
establishment of potential corrosion sites, and related problems.
70
GPS//2003
O2
OH- Microbial
colony
M2+
Cathodic area
Anodic area
Figure 6.1 Slime mass on a metal surface setting up a differential cell
Loss of heat transfer efficiency is probably the most common cause of excessive operating
costs in water cooled air conditioning systems.
For example, slime deposits as small as 0.012 inch (less than 1/64on a condenser tube will
cause a chiller unit to consume 10-20% more electricity than when the tubes are clean.
Corrosion, which occurs beneath slime deposits, can result in pits completely penetrating
condenser tubes.
Slime formation is only one of several problems that can be related to microbiological
contamination.
Fouling
Loss of heat transfer
Energy losses (pumping problems)
Reduced efficiency
Could cause shutdowns
Health risks (Legionella, etc.)
Corrosion
Equipment replacement
Production losses
Tower components
Deterioration of wood
Plugging
Reduced tower efficiency
Tower replacement
B. Types of Microorganisms
1-CWT Page 71 of 117 0902

i) BACTERIA
Aerobic requiring oxygen

This class of microbes can cause several types of problems related to the type of activity they
engage in. For instance :
Slime formers forms a protective sheet that entrap solids which can:
- Causes underdeposit corrosion
- Plugs heat exchanger
- Reduces flow through piping
- Interferes with treatments
- Survives best in pH range of 5-9
Bacterial slimes can :

- Lead to underdeposit corrosion
- Provide a good environment for anaerobic bacteria
- Can reduce flow
- Affect heat transfer
- Entraps solids
Iron Bacteria
- Uses ferrous iron in its metabolic process Fe+2 Fe+3
- Deposits red/brown slime mass
- May lead to plugging
- Promote underdeposit corrosion
- Thrive in the pH range of 7.5-9.5
Sulfur Bacteria
- Uses sulfides or sulfur for metabolic process
- Cause depressed pH and severe corrosion
- Thrive in acidic environments
- Can support sulfate reducers
Nitrogen Bacteria
- Can be slime formers
- Usually found in conjunction with nitrite reducers
- Acid producing NH3 NO3- + H+
- Can cause severe copper corrosion to occur
- Thrives in the pH range of 4-8
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GPS//2003
Anaerobic lives in the absence of O2

Sulfate Reducers (SRBs) are a type of organisms that is characteristic of this class, their traits
are :
- Forms H2S
- Very corrosive to steel and copper
- Typically grows under slimes
- Iron and copper sulfide deposits are formed
- Thrive in pH range of 4-8
The Characteristics of Microorganisms Commonly Occuring in Cooling Water

pH and
Technical Temp. Air & Light
Type Shape Concerns
Name (s) Range Requirements
Algae Chlorella Single Cell 5.5 to 9.5 Require air (aerobes) Green and blue-green slimy
Ulothrix or thread- 60 to 130oF and light for growth growths in lighted areas.
Oscillatoria like
Melosira
Bacteria Flavobacterium Spheres and 5 to 9 Most require air Slime masses due to capsule
Aerobacter rods 60 to 150oF (aerobes) for growth. or waste materials can plug
Pseudomonas occuring However, there are heat exchangers, reduce heat
Bacillus singly or in some that cannot transfer efficiency, accelerate
Achromobacter chains tolerate any air corrosion and cause build-up
(anaerobes). Do not of foulants. Color of slime
require light. mass is usually gray-brown.
Iron Gallionella Single Cell 5.5 to 8.2 Require air (aerobes) Require ferrous iron for
Bacteria Crenothrix or thread- 41 to 77oF and light for growth growth. Deposit insoluble
like ferric hydroxide which results
in a red-brown slime mass.
The slime mass can plug heat
exchangers, piping and can
materially reduce heat
transfer efficiency.
Sulfate Desulfovibrio Single rods 5.5 to 8.5 Generally cannot Black insoluble ferrous
Reducing straight or 77 to 140oF tolerate air. Do not sulfide deposits plus heat
Bacteria curved require light to grow exchangers and accelerate
corrosion. Capable of
generating large quantities of
hydrogen sulfide.
Table 6-1
Facultative
These types of bacterial make up part of most bacterial colonies, since they :
- Are slime formers

- Thrive with O2 but can grow in anaerobic conditions
- Grow in the pH range of 4-8
1-CWT Page 73 of 117 0902

ii) FUNGI
These are higher types of microbes compared to bacteria and are not as prevalent, except in
very specialized applications.
Molds
Filamentous
Cause surface rot of wood
Slime
Nutrients
Yeasts
Slime formers
Very thick rubbery growth
Difficult to kill
Basidiomycetes
Internal wood rot, uses cellulose
Very difficult to kill
All the above form spores which are practically impossible to kill. These organisms thrive in
a very broad pH range anywhere from 2-8.
ii) ALGAE
As can be seen in Table 6.1, algae shares many characteristics in common with bacteria,
except for one they can produce their own food. Algae :
Requires sunlight
Can form thick mats on decks and fill
Can cause rapid deposit formation
Is difficult to control
Can cause severe flow problems
Provides nutrients for bacteria
May cause severe corrosion of galvanized decks
Thrive at a pH range of 5-9
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GPS//2003
i) OXIDIZING BIOCIDES
Oxidizing biocides are widely used and offer a variety of advantages however, their
application must be matched to the particular system to see the strengths realized.
Chlorine
The most commonly used biocide is chlorine and it is the standard against which all others
are compared. Chlorine gas is typically fed continuously to maintain a free residual
chlorine level of 0.2 0.5 ppm. The feed rate is usually based on the recirculation rate of
the cooling water.
Cl2 gas reacts to give :

Cl2 + H2O HOCl + HCl
As the pH rises a second reaction takes place:
HOCl H+ + OCl-
Chlorine is an extremely effective microbicide at low concentrations; however, it reacts with

a wide variety of organic chemicals, which give many waters a chlorine demand. This
chlorine demand must be satisfied before a free chlorine residual is achieved. This requires
excessive chlorine feed in many systems. Also chlorine becomes somewhat less effective at
a pH greater than 7.5, due to the neutralization of hypochlorous acid and its conversion to the
less effective OCl anion.
Other disadvantages of chlorine are its short persistence, thus requiring frequent feed, its lack
of effectiveness on some species of fungi and algae, and its inability to penetrate slime
masses. High dosages will cause deterioration of tower lumber, and chlorine gas is
dangerous to handle. In addition, chlorine in water discharged is generally not permitted.
The more common practice is to use bleach (sodium hypochlorite) as the chlorine source.
The strength of sodium hypochlorite can vary considerably from <10% to over 12%. Also,
sodium hypochlorite solutions are inherently unstable and will auto-decompose to oxygen gas
and chloride. The rate of breakdown is governed by temperature and the quality of the bleach
solution.
Hypochlorous acid is an effective, low cost microbicide. However, best results are most
frequently achieved when used in conjunction with a non-oxidizing microbicide or a
biodispersant.
Typical feed regimes would be :
Continuous: 0.1 to 0.5 ppm Free Available Chlorine (FAC)
Intermittent: 0.3 to 0.7 ppm Free Available, held for 3 to 6 hours
1-CWT Page 75 of 117 0902

Chlorine gas
Advantages :
Economical
Effective on nearly all microorganisms
Easily applied
Easily controlled
Disadvantages :
Feed equipment can be costly

pH dependent
May form high levels of undesirable by-products chloramines
Affects pH (1 ppm Cl2 reduces M alkalinity by 1.2 ppm)
Must meet chlorine demand
Can be very corrosive
Consumed by reducing agents
Hazardous to handle
Chlorine Feed Methods Comparison

Remarks
Program
Continuous Chlorination Most effective
Free Residual Most costly
Not always technically or economically
feasible due to high chlorine demand
Continuous Chlorination Less effective

Combined residual Less costly
Inadequate for severe problems
Intermittent Chlorination Usually effective

Free residual Less costly than continuous chlorination
Intermittent Chlorination Least effective

Combined Residual Least costly
Table 6.2
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GPS//2003
Sodium Hypochlorite
Advantages :
Convenient liquid
Economical
Easy to feed
Easy to test
Disadvantages
Not stable can auto-decompose

Affects pH and alkalinity - 1 ppm M increase/ppm NaOCl
Large volume storage required
Calcium hypochlorite
A common name for this material is HTH and is routinely sold for swimming pool use.
Advantages :
Powder
Disadvantages :
Adds hardness
Adds alkalinity
Chlorine dioxide
Chlorine dioxide has been widely used as a disinfectant for many years. It is effective over a
wide pH range (6-10) and is a stronger oxidizing agent than hypochlorous acid. It does not
react with ammonia or amines, which gives it a distinct advantage over hypochlorous acid in
amine contaminated systems. However, it does react with other contaminants, which can
result in a high chlorine dioxide demand. It is frequently generated on site using chlorine and
sodium chlorite and is considerably more expensive on a weight-to-weight comparison with
chlorine gas.
Advantages :
Effective at higher pH, since it does not ionize

Lower organics demand
Destroys phenols
1-CWT Page 77 of 117 0902

Disadvantages :
Very expensive
Requires special generation on site
Cl2 + NaClO2 2 NaCl + 2 ClO2
HCl + HOCl + 2NaClO2 2 ClO2 + NaCl + H2O
Forms explosive gas

Volatile
Can be corrosive
Chlorine releasing biocides (isocyanurates)
Advantages :
Easy to handle
No special equipment
Works well at higher pH
Cuts slimes
Little effect on pH
Dissolves slowly
Disadvantages :
Expensive
Can be extremely corrosive
Feeding can be a problem
Ozone
Advantages :
Powerful oxidizer
Works well on all living organisms
No undesirable reaction products
No effect on system water chemistry
Decomposes photochemically
Harmless to aquatic life
Disadvantages :
Cost and toxicity

Ozone demand
Can delignify wood if overfed
Destroyed by reducing agents
No secondary biocides formed
Not a good penetrant
Residual is difficult to achieve
78
GPS//2003
Bromine
Bromine salts such as sodium bromide and BCDMH offer the advantages of chlorine but
perform better at high pHs. Sodium bromine on its own has no biological activity and must
be activated by an oxidizing agent. The most common one is bleach and the reaction is:
NaOCl + NaBr NaOBr + NaCl
In a water system, a significant portion of the NaOBr is actually present as HOBr, a non-
ionized species.
In contrast to the need to feed two separate liquids (sodium bromide and hypochlorite
solutions) the advantages of bromine chemistry can be achieved using BCDMH. BCDMH is
available in several forms (powder, granules, tablets), although the tablet form is the most
widely used.
Unlike sodium bromide, BCDMH generates only active material:
BCDMH + 2H2O HOBr + HOCl + DMH (inert)
Since the halogen is attached to the BCDMH, it acts like a donor and prevents the halogen
from reacting (to some degree) with trash organics in the cooling water.
Advantages :
Bromine more effective at pH values above 7.5

Environmental acceptability
- Low levels of actual oxidant
- Tri halo compounds rapidly degrade
- Bromamines degrade rapidly
Bromamines are excellent biocides but degrade rapidly

Easy to handle
- Solid hydantoins
- Generation with NaBr
Excellent slime control
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Disadvantages :
Feed equipment can be costly
Concentrations of Hypohalous Acid vs pH
pH % HOCl % HOBr
6.0 97 100
7.0 76 98
7.5 50 94
8.0 24 83
8.5 9 60
9.0 3 33
Table 6-3
In Table 6-3, one can see that at any given pH there is a significantly higher concentration of
the non-ionized HOBr than there is for HOCl. Since the hypohalous acid can more readily
penetrate the micro organisms cell wall, it is more effective as a biocide. This is the
advantage of using bromine chemistry compared to chlorine its ability to achieve more
rapid kills under alkaline conditions.
ii) NON-OXIDIZING BIOCIDES

This is a broad category of biocides, since it is comprised of various different chemistries,
each with their specific advantages.
It is common to combine an antifoulant (biopenetrant) with non-oxidizing biocides to

enhance their efficacy. An organic penetrant is often beneficial in breaking up slime masses
to allow the microbicide to reach more organisms and to do a more effective job. A
dispersant is also helpful in removing both dead and living organisms in tower bleed-off.
Characteristics
Can be more effective than the oxidizers in many situations

Limited numbers are available because of environmental impact
All have limitations and should be used in conjunction with other biocides
All are biodegradable
They are slower acting than oxidizers
Are more expensive than oxidizers
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Surface Active Agents

Quaternary ammonium chlorides (quats)
The quaternary ammonium salts have one or more long hydrocarbon chains of eight to 25
carbon atoms bound to a nitrogen atom. These compounds are effective over a wide pH
range against bacteria and algae. Being surface active, these compounds also have dispersant
activity and tend to foam excessively when overfed. In heavily fouled systems, these
compounds may lose some of their activity because of competing adsorption reactions.
Mode of Action :
Attacks components of the cell wall

Reduces flow across the cell wall
Reacts with protein causing cell breakdown
Advantages :
Broad spectrum
Good for molds
Good dispersant qualities
Excellent algaecide
Disadvantages :
Many incompatibilities, due to be cationically charged

Precipitates in high hardness > 400
Most cause foam at higher dosages
Not sporicidal
Not cost effective on slime or fouled systems
Amine types (DGH, dodecyl guanadine hydrochloride)

Amines and diamines have broad spectrum activity over a wide pH range. These compounds
also have detergent action and foam excessively if overfed.
Mode of Action :
Broad spectrum
Broad pH range
Exibits some surfactant/detergent action
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Disadvantages :
Less effective in fouled systems

Incompatibilities with anionics
Resistance easily developed
Not sporicidal
Can foam
Not as effective on molds, fungi and filamentous bacteria
Moderate cationic charge
Glutaraldehyde
Mode of Action :
Crosslinks with primary amines

Effects cell wall permeability
Causes starvation and poisoning
Advantages :
Effective against a broad spectrum of microorganisms

Compatible with corrosion inhibitors and surfactants
Ability to clean biologically fouled systems
Non-corrosive
Effective at a broad pH range
Not effected by the presence of organics
No foaming or odor
Disadvantages :
Deactivated by primary and secondary amines
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Metabolic Poisons
MCI (Isothiazolones)
This is perhaps one of the most widely used biocides due to it wide range of application.
Mode of Action :
Metabolic Inhibitor
Advantages :
Broad spectrum
No odor
Wide pH activity
Not affected by foulants
Nonionic
Biodegrades chlorine resistant
Photo-degrades
Very good for nitrite reducers
Disadvantages :
Inactivated by
Amines
Sulfides
Long retention times required (4 6 hours)
Is skin sensitizer and irritant
Weak algicide
Methylene bis (thiocyanate)

Methylene bis thiocyanate (MBT or MBTC) is an effective, broad spectrum microbicide.
However, the activity of this compound decreases at higher pH levels due to hydrolysis. The
hydrolysis products are significantly less toxic than MBT, thus making it an environmentally
attractive microbicide. MBT is extremely effective against slime forming bacteria.
Mode of Action :
Enzyme poison
Chelates iron in energy producing step
Advantages :
Non-ionic
Broad spection
Excellent for sulfate reducers
Rapid decomposition
Good fungicide
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Disadvantages :
pH sensitive (max. effectiveness between 6.5 7.5)

May be consumed by iron
Slow acting (6 10 hours)
Thiones
Thione (tetrahydro-3, 5-dimethyl-2H-1, 3, 5 triadiazine-2-thione) is a reducing biocide. It
will react with iron (corrosion products) and forms a dark precipitate. Thione hydrolyzes in
water to form formaldehyde a known carcinogen. It also reduces the efficacy of DBNPA and
oxidizers. It can also produce MITC (methyl iso thiocyanate).
Mode of Action :
Reproductive Inhibitor
It is recommended fro aerobic and filamentous bacteri but, not for fungi, anaerobic bacteria
and SRBs.
Sulfones
Sulfone (bis (trichloromethyl) sulfone) is not commonly used in microbicide formations. The
activity of this compound is pH sensitive being effective in a pH range of 6.5 to 8.5.
Characteristics and modes of action are similar to Methylene bis (thiocyanate)

Similar advantages and disadvantages
It has a strong odor
Breakdown products are stable and biocidal in their own right
It is a very persistent active
Carbamates
Thiocarbamates are excellent microbicides against slime forming bacteria, cellulolytic fungi
and sulfate reducers. At low dosages these compounds are not effective.
Similar characteristics and modes of action to other sulfur containing biocides
Advantages :
Similar to others
Broad pH range
Not affected by foulants
Good for sulfate reducers
Disadvantages :
Precipitated by metals
Not effective on algae
Slow acting (at least 6 hours contact)
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DBNPA
Dibromonitrilopropionamide (DBNPA) is gaining increasing acceptance due to its ability to
hydrolyze to essential harmless degradation products. It is effective at low dosages and has
broad spectrum activity. However, it does decompose rapidly at high pH and is, therefore,
limited to use in systems operating at a pH of 7.5 or less.
Mode of Action :
Not clearly defined

Interferes with energy cycle
Advantages :
Broad spectrum
Fast acting (80% kill in 30 minutes)
Effective at low concentrations
Nonfoaming
Non-ionic not affected by foulants
Degrades rapidly
Decomposes to nontoxic products
Disadvantages :
pH sensitive hydrolyzes above pH 8.0

Deactivated by reducing agents such as sulfides or sulfite
Reduced efficacy in presence of ammonia (75 ppm)
Hydrolyses at high temperatures and with sunlight
BNPD
Bromonitropropane diol (BNPD) is gaining market share due to its safety profile. It is widely
used as a preservative for cosmetics, shampoos and pharmaceuticals.
Mode of Action :
Inhibits membrane bound enzymes
Advantages :
Broad spectrum
Safe to use / enviromentally acceptable
Nonfoaming
Non-ionic not affected by foulants
Disadvantages :
Slow acting (recommended 6 hours contact time)

pH limitation (less stable above pH 9.5)
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TCMTB
2-(thocyano-methythio) benzothiazide (TCMTB) is widely used by Buckman in a number of
market segments.
Mode of Action :
Enzyme inhibitor
Advantages :
Broad pH range
Excellent on mold, fungi and algae
Good as a preservative
Disadvantages :
Not as effective on bacteria

Not recommended for SRBs
THPS
THPS (tetrakis hydroxymethyl phosphonium sulphate) is only now beginning to be seen in
cooling water applications, although it is not a new biocide.
Mode of Action :
Not clearly defined
Advantages :
Broad spectrum
Particularly effective against SRBs
Good environmental profile
Formulated with a low form anionic surfactant to enhance biofilm removal
Disadvantages :
Not effective on fungi
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BHAP
BHAP (2-bromo-4-hydroxyacetophenone) is used by Buckman on a limited basis.
Mode of Action :
Not clearly defined
Advantages :
Broad spectrum
Good under alkaline conditions
Effective on slime and deposits containing filamentous iron bacteria
Disadvantages :
Loss of efficacy when used in the presence of metals and ammonia

Not recommended for air washers and once through cooling
iii) SELECTION CONSIDERATIONS
An effective biocide program is :
Chosen properly
Applied properly
Alternated using different classes of biocides
Monitored properly
Targeted to control the actual problem
In addition, it is important to determine :
If there are there any restrictions on disposal?

What are the economics?
- Frequency of addition
- Choice of proprietary or open market
What is the system water pH?
What are the system foulants?
Is there an incompatibility consideration?
Is handling a problem?
Is odor a problem?
Is foaming a problem?
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Effect of contaminants
Cooling water systems are not static environments and a variety of contaminants can enter
these systems. The impact on the biocide program can range from negligible to significant.
Examples of comtaminants include :
Organics
Oils and greases

Slimes
Treatment chemicals
- Oils and grease reduce the effectiveness of quats and amine based biocides
- They add to halogen demand
- Slimes cause the adsorbtion of cationic biocides rendering them ineffective
- Treatment chemicals such as anionic polymers can precipitate quats
Reducing agents
Sulfite
Bisulfite
Sulfides
- All reduce the effectiveness of oxidizers
- Sulfides consume MCI and DBNPA
Amines including ammonia
These add to halogen demand

Reduce the efficacy of some biocides
Iron
Ferric iron reacts with MBT reducing efficiency

Precipitates with carbamates
Anionic organics
Anionic antifoulants
Tannins
Lignins
Humic acid
All the above, anionic organics, reduce the effectiveness of Quats and amine biocides by
precipitation due to charge neutralization.
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System pH
pH range 7.0-8.0 no problem

pH range 8.0-9.0
- MBT hydrolyzes rapidly
- DBNPA and BNPD begins to hydrolyze increasing at pH > 8.0
- Chlorine has reduced efficacy
Water hardness
Hardness greater than 400 ppm reduces efficiency of Quats
Retention time
Long retention time any biocide can be used, for instance

- Isothiazolone, Carbamate, MBT
Short retention time use fast acting agents such as

- Quats
- DBNPA
- Oxidizers
Environmental restrictions
Local ordinances regulating sewer discharge

- Problem biocides are oxidizers, algistats
Discharge to waste treatment governed by the plant and local agencies
Practical restrictions
Aside from theoretical/chemical aspects, there are several additional factors that can
influence the biocide selection. These include :
Foam
- Safety hazard
- Can limit equipment efficiency
- Can cause physical damage
- Unsightly
Odor
- Usually only a minor complaint
Handling and control

- Consider labor involved
- Equipment limitations
- Difficulty of addition
- Health and safety
- Single or dual liquid feeding
Dosage-consider problem you are treating
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iii) MONITORING
Monitoring is the cornerstone of the biocide program regardless of whether it consits of

simply inspecting or testing. This activity can be broken down into 5 types of monitoring :
Water sampling
ATP (Adenosine Triphosphate)

Dipslides
Sulfate reducers
Lab analysis
Biocide sensitivity
Deposit samples
To detect sulfate reducers

To determine contamination
Visual inspections
Sump-for deposit and slime build-up

Decks-slime formation, algae, contamination, wood integrity
Bulk water check for foam, murkiness, color, contamination
Physical inspections
Tower support structure-check for delignification, slime growth

Wood slats-strength, biological growth, integrity, and function
Other methods
Biological fouling tube for slime growth

Field sensitivity studies using dipslides/ATP
Field culturing and bacteria counts
Tower wood evaluation by the lab
Biocide Enhancement
All biocides are the primary tool to maintain biological control; other steps can be taken to
enhance their performance both physical and chemical.
Physical cleaning
Reduces biocide demand

Limits re-infection
Surfactants/Biopenetrants
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Improves penetration of the biocide

Removes dead growth
Wetting agent make the cell wall more susceptible to biocide
Solubilizes nutrients such as oil and greases
Chlorine enhancer (WSCP)
Removes silts and dirt
Figure 6.10 Microbiological Program showing good control
The above diagram shows what one would expect given a good control program. Namely
B iological A ctivity
B iocide
F eed
L evel
T im e
that the level of micro activity (regardless of whether ATP or CFUs are used as the
controlling parameter) is kept below a pre-selected value. Once the micro level reaches the
action-point, the biocide is dosed to the system and kills the organisms to a lower value,
where it remains for a period of time before rising back to the action-point.
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7. Glossary
Some definitions in this glossary are specific to cooling water applications and as such their
usage in other areas may vary.
A
Acid: A compound that dissociates in water to give an increase in hydrogen
ion concentration.
Acid Cleaning: The act of removing adhering deposits by dissolving with an acid
solution in which the deposited material is converted into a soluble
state or where the binding material is made soluble. In the latter
action, the insoluble part is disintegrated or dislodged.
Admiralty Brass: An alloy of 70 percent copper, 29 percent zinc and 1 percent tin.
Arsenic or antimony may be included to minimize dezincification.
Aerated: A condition where a solution contains dissolved oxygen.
Aeration: The act of dissolving or bringing into solution atmospheric gases,

specifically, oxygen.
Algae: Simple forms of aquatic plant life which use sunlight for
photosynthesis and as part of their life cycle.
Alkalinity: Acid neutralizing power of a solution, it is generally expressed as ppm

CaCO3.
Amides: A generic name for compounds of the general structure R-CONH2.

These are typically surface active compounds and DMAD is an
example of a compound in this class.
Amperometric: An analytical method based on the determination of a flow of current

where the current flow is related to the concentration of the material
being determined, typically chlorine or bromine.
Anodic: Related to that area or portion of an electrolytic cell where chemical

oxidation takes place and loss of metal occurs.
Anodic Inhibitor: A chemical that prevents or reduces corrosion by a chemical action at

the anodic surface of a metal.
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B
Bacteria: A lower form of life. These organisms are usually in the form of rods,
or spheres. Bacteria are responsible for slime in cooling water
systems.
Base: A compound that dissociates in water to give an increase in hydroxyl

ion (-OH) concentration.
Basin: That part of a cooling tower that receives the water that has passed
through the tower. This may sometimes be referred to as the sump or
it may also be used to designate the pond area of a constructed spray
cooling system.
Bicarbonate: A form of alkalinity found in varying amounts in all natural waters and
in cooling water systems. It represents carbonic acid with half of the
acidity neutralized or it can be considered carbonate with half of the
alkalinity neutralized.
Bimetallic Couple: Two metals in electrical contact that have different electromotive
activity in a solution to produce an electrochemical cell with corrosion
occurring on the more soluble or active metal.
Biocide: Any toxic agent effective in destroying microorganisms in cooling

water systems.
Biological Fouling: In cooling systems this represents obstructive growth or accumulation

of various organisms surch as algae, bacteria and molds/fungi.
Bleed-off: That part of a recirculating water that is deliberately withdrawn in

regulated amount to reduce the mineral salt concentration. This action
may also be termed bleed.
Blowdown: Refer to bleed-off
Bleed-off Rate: This generally refers to continuous bleed-off where the regulated
amount of water withdrawn.
Brass: Alloys of copper and zinc in various ratios.
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C
Calcium Hardness: Water hardness due to the soluble calcium in a water.
Calcium Sulfate: In precipitated or insoluble form, it can produce a very inert, adherent
deposit or scale.
Carbon Dioxide: A gas that has an acidic reaction when dissolved in water, it forms
carbonic acid.
Cathodic: A condition related to that area or portion of an electrolytic cell on

which a chemical reduction takes place.
Cathodic Inhibitor: A chemical that prevents or reduces chemical reactions at the cathodic
surface of a metal.
Cellulose: The fibrous material that is a component of wood.
Chelation: The act of complexing ions into soluble species.
Chemical Balances: Refers to the concentration of soluble compounds in a solution, and

generally to those constituents that are important in the cooling system.
Chloride: Soluble ionic form of element chlorine. Sometime useful as a measure

of bleed-off control.
Chlorination: The treatment of water by gaseous chlorine or by a chlorine releasing

agent. In cooling water systems, chlorine is used to control biological
fouling.
Chromate: Refers particularly to a chemical type inhibitor containing hexavalent

chromium in the compound. Generally considered to be sodium
chromate. However, when referring to a chromate treatment, it can
include any compound containing the chromate or dichromate.
Clarification: The act of removing suspended matter by physical means employing

flocculating agents, settling, and filtration.
Chilled Water: Closed recirculating cooling water systems usually operated in

conjunction with some form of refrigeration or secondary cooling.
Color Comparator: Test equipment for determining concentration of chemical constituents

in solution. Test procedure depends on use of reagents that develop
characteristic colors with degree of color directly related to
concentration of constituent being measured.
Concentration: The amount of material dissolved in a unit volume of solution.
Conductance: Measure of electrical current carrying capacity of a water. It is

determined by applying a fixed voltage between two electrodes of
fixed area and set at a fixed distance apart.
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Continuous Feed: The act of continuously adding chemicals to a water in appropriate
amounts. Generally requires some means of control or regulation to
proportion chemicals into the water being treated.
Cooling Tower: A structure, generally of wood parts in the larger units, that provides
for cooling of water by its evaporation. Water is dispersed and flows
downward through a flow of air.
Cooling Water: Any water that removes heat from a point or area of higher
temperature and delivers to a point or area of lower
temperature.
Corrosion: Destruction of a metal by chemical or electrochemical reaction with its

environment.
Cycles of Concentration:
This is a numerical expression of the degree to which the soluble
mineral salts have been concentrated in a water. It is a direct ratio of
the minerals in a system subjected to evaporation and the minerals in
the make-up water to that system.
D
Delignification: Action on wood resulting from chemical or biological activity that
destroys tannins and lignins from wood leaving the structure in a
fibrous, weakened state.
Deposit: Material formed or deposited on a surface in contact with a solution.

In cooling, this will be material of surfaces of vessels, piping or related
equipment in contact with the cooling.
Deposition: This can indicate the act of depositing. Sometimes used synonymously
with deposits.
E
EDTA: Ethylenediaminetetraacetic acid - a chelating agent widely used as a
reagent in hardness determination.
Eductor: The mechanical arrangement for the removing of a gas or a liquid from
a system by means of a high velocity flow of another gas or water
stream through an orifice, etc.
Electro-Chemical: A chemical reaction that requires the transfer of electrons between

anodes and cathodes in an electrolytic solution.
Electrolyte: A solution of positive and negative ions which will conduct electric
currents.
Electrons: Negatively charged sub-atomic particles.
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EPS: This stands for extracellular polysaccharide or extracellular
polymeric substance, in both cases it is formed by micro-organisms
and acts as a binder in slime and other deposits.
Extractives: Generally refers to those natural substances in wood that are soluble in
water and therefore can be dissolved out of it over time.
F
Ferric Iron: A form of iron oxidized to its trivalent, most stable state. Ferric salts
are generally insoluble in water.
Ferrous Iron: A form of iron oxidized to a divalent state.
Filtration: The removal of suspended matter from water by passage through a

porous material.
Film: A very thin coating or layer of material.
Flow Rate: The movement of water expressed in volume per unit time, eg. M3/hr
gallons per minute, etc.
Flushing: The act of cleaning out a system, using a flow of water generally at
high rates.
Foulants: Any obstructive material in a cooling system other than scale-forming

precipitates.
Fouling: Act of obstructing the flow of water, evaporation, or heat transfer by

materials contaminating the system by any other mechanism other than
scale formation.
Free Chlorine: The residual in circulating water consisting of hypochlorite ion or

hypochlorous acid (or combination), which is established by chlorine
treatment.
Fungi: A lower form of plant life, filamentous and without chlorophyll.

Responsible for slime and destruction of cooling tower wood.
G
Galvanic: An electrochemical action due to a couple made up of dissimilar
metals.
General Corrosion: A form of corrosion that is distributed widely and more or less
uniformly over a metal surface.
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Hardness: A condition of water due to its content of calcium and magnesium

salts.
Hydrogen: In ionic form in water it represents the degree of acidity of a solution.
Hydrogen Sulfide: A toxic gas which smells like rotten eggs. It forms a weak acid in
water.
Hydroxide: The counter part to hydrogen ions in water solutions. It represents the
degree of basicity of a solution.
I
Inhibitor: Refers to material or materials in water solutions that prevent or
minimize corrosion or scale.
Internal Decay: Decay of wood beneath its surface.
Intermittent Feed: Feed of chemicals at separate, generally set intervals, i.e. not
continuous.
Iron: The major component of steel - widely used in cooling water systems.
Iron Oxides: A reaction product of oxygen with iron. It may refer to ferrous oxide,
ferric oxide, or a combination that produces magnetite.
Iron
Phosphate: A reaction product of iron with ortho phosphate. A frequent foulant in
phosphate-treated systems which have experiences excessive
corrosion.
Iron Rot: Deterioration of wood in contact with iron, a problem associated with
iron fastenings, or other iron-wood assemblies.
L
Langelier Index: An empirical correlation for calcium carbonate solubility that is useful
in predicting scaling behavior in cooling waters.
Leaching: The act of extracting a soluble constituent from a material by the

dissolving action of water.
Lignin: Substance forming an essential part of wood it is the binder of

woods structure.
M
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Magnesium Hardness:
Water hardness due to soluble magnesium.
Make-Up: Refers to fresh or raw water added to a system to replace that lost by
evaporation, bleed-off, leaks, wind drift, etc.
Methyl Orange: An indicator dye used to determine total alkalinity. Color change at
end point (pH 4.3) from yellow to salmon pink. Also used as part of a
test that is specific for free halogen.
Methyl Purple: An indicator due used to determine total alkalinity. End point color
change is from green to purple (Acid) at pH 4.3 4.5.
Microbiological: Referring to biological organisms of microscopic size.
Mill Scale: Accumulated oil, grease, and debris which is associated with the
manufacturing process of (and is found adherent to) pipes and
equipment used in water systems.
Minerals: Generally refers to any soluble or insoluble metal salt, eg. CaCO3,
Fe2O3, MgSO4, etc.
Monomolecular: A descriptive term used with thim films to indicate dimensional

thickness that does not exceed one molecule in thickness.
N
Nitrites: Common term for sodium nitrite which is used for corrosion inhibition
in water solutions.
Nonferrous: Metals other than iron or steel, or alloys containing as their principle
constituent, metals other than iron or steel.
O
Open Recirculating: Any system in which water is recirculated and cooled primarily by
evaporation.
Organic: Generally referred to cooling water treatments not containing metal or

inorganic phosphate components.
Ortho phosphate: A stable oxide of phosphorous which forms a trivalent anion.

Combines with calcium to form insoluble calcium phosphate which is
useful in cooling water corrosion inhibition when properly applied.
Oxide: Reaction product of oxygen with a metal.
Oxide film: A thin film formed by the reaction product of oxygen with a metal.
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Oxygen: A gaseous material that is very reactive with most common metals
when it is dissolved in water contacting these metals. In cooling
waters, air is the source of the dissolved oxygen.
P
Parts Per Million: A measure of concentration (parts of solution per million parts of
solvent), i.e. ppm. It is also equivalent to mg/L.
Passivation: A reduction of the activity of an electrode involved in electrochemical

action such as corrosion.
Penetration: Corrosive relative to the thickness of a metal. Attack in depth.
Perforation: Corrosive action that is completely through the thickness dimension or

wall of a metal surface.
pH: A measure of the hydrogen ion concentration (activity) of a solution.
pH of Saturation: The pH above which a solution of otherwise soluble ions will begin to
precipitate. Useful in predicting scaling potential of a water.
Phenolphthalein: A titrimetric indicator used in the determination of carbonate and

hydroxide forms of alkalinity. Color change occurs at pH 8.3, going
from colourless to pink (>8.3).
Photometric: Refers to a method for determining concentration of certain materials

in water by measuring the degree of light absorption of a beam passing
through a prepared sample.
Pits: Corrosion of a metal surface confined to a point or a very small area.

Attack progresses in depth rather than generally over the metal surface.
Pitting: Corrosive action that produces pits.
Polarization: A change in the electrical potential of a corrosion cell brought about by

the accumulation of species as a consequence of the corrosion process.
Polyphosphate: Molecularly dehydrated forms of phosphate.
Potential: The electromotive force developed between a metal in an electrolytic

solution and a reference electrode.
Potential Difference:Difference in electromotive force between electrodes of an

electrochemical cell.
Precipitation: The act of formation of insoluble salts from a solution.
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Proportional Feed: The addition of chemical to a water system in an amount proportionate
to the make-up.
R
Recirculating Cooling Water:
Any cooling water system where the water is repeatedly used to cool a
system, rather than being used once and then discharged.
Reversion: Degradation of organic or polyphosphate to ortho phosphate.
Rot: Wood destruction by biological organisms that use the wood for food.
Rust: Common designation for the stable ferric oxide product of corrosion of
iron or steel.
Ryznar Stability Index:

An index that is used to indicate scaling tendency of a water, it serves
the same function as LSI.
S
Sample: A small portion of a solution taken from a system for purpose of tests
to determine chemical and physical conditions therein.
Saturation Index: See Langelier Index.
Scale: Any dense, cohesive, crystalline material that forms a tightly adhering
mass on a surface. In cooling water systems, this may include
precipitated mineral salts, corrosion products, and/or suspended matter.
Scale Control: Any measure that will prevent or minimize scale deposits.
Sequestration: Formation of a weak water soluble complex.
Silica: Common designation for silicon dioxide (SiO2).
Silt: Insoluble suspended matter in a water. The source may be air-borne

dust or dirt entrained in the make-up.
Slime: Susbtances of viscous organic nature usually derived from

microbiological growth. Often refers to the total accumulated mass
of slime and various trapped insoluble organic and inorganic
materials.
Softening: The act of removing all or part of the hardness constituents from a
water solution.
Solubility: The maximum concentration of a substance that can be dissolved in a

solution under given conditions.
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Solution: Any liquid containing dissolved matter.
Stability Index: See Ryznar Stability and Langelier Index.
Sulfur Dioxide: A gaseous oxide of sulfur, which gives rise to sulfurous acid in water.
Sulfur Trioxide: A gaseous oxide of sulfur. Forms sulfuric acid in water.
Sump: A reservoir into which water collects and from which it can be
pumped, used synonymously with cooling tower basin.
Supersaturated: Refers to a solution or water system that contains one or more

dissolved compounds in excess of their normal solubility limit.
Surface Rot: Biological wood attack that is active at the surface.
Synergistic: A system in which the total effect is greater than the sum of the two
effect taken independently.
T
Tannins: Dark colored extractives present in cell cavities of wood.
Titrimetric: A method of quantitative determination of the concentration of a select

constituent of a solution by adding a measured amount of another
solution that produces an easily recognized reaction.
Titration: The act of carrying out a titrimetric determination.
Total Hardness: The combined calcium and magnesium concentration in a water

solution.
Treated Lumber: Wood treated with a chemical preservative prior to its use in
fabrication of a cooling tower. CCA (chromate, copper, arsenic) is the
most commonly used treatment.
Tubercle: Mounds of corrosion products covering the anodic spots where pits are
developing.
W
Wood Deterioration:Degradation of cooling tower wood through chemical or biological
action.
Z
Zinc Ion: Cathodic inhibitor commonly used in conjunction with ortho
phosphate, phosphonates, organics or combinations of these.
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Cooling Water Treatment

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Cooling Water Treatment

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COOLING WATER TREATMENT MANUAL

WATER TECHNOLOGIES DIVISION

1. Physical Layout of Cooling Systems

2. Types of Cooling Systems

5. Cooling Water Treatment

6. Cooling Water Microbiology

1. PHYSICAL LAYOUT OF COOLING SYSTEMS

A. Types of Cooling Systems

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A. Cooling Water Systems

Cooling water systems can be categorized into three types :

(or OTHER PLANT USE)

COOLING WATER SUPPLY

Figure 1.1 Once Through heat transfer

HOT WATER OUT

COLD COLD WATER

Figure 1.2 Closed Recirculating cooling water system

Figure 1.3 Open Recirculating cooling water system

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Figure 1.4 Spray Pond

Air in Air out

Figure 1.5 Once Through shell and tube

systems into one overall system design.

Figure 1.6 Evaporative Condensers

combination. This particular system design is called an evaporative cooler or evaporative

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Figure 1.7 Induced Draft Tower

Figure 1.8 Forced Draft Tower

Figure 1.9 Counter-flow Figure 1.10 Cross-flow

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WET BULB TEMPERATURE Wet-bulb temperature is an extremely important parameter

iii) COOLING PROCESSES

(1,000,000 lbs water) x (0.005 evaporated) x (1,000 BTU/lb.evap.)= 5,000,000 BTUs

dry bulb T = wet bulb T

wet bulb T > dry bulb T

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Figure 1.11 Shell & Tube Exchanger

Figure 1.12 Shell-side Cooler

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Saturation and/or Stability Index and pH

ii) SCALING AND DEPOSITION

High Heat Exchanger Skin Temperatures

iii) SUSPENDED SOLIDS

Interference with the Normal Function of the Corrosion Inhibitor(s)

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Saturation (Stability) Index and pH

Cooling water can be maintained in this alkaline pH range by:

Allowing makeup water to concentrate

Scale is prevented from forming under alkaline conditions by:

1) limiting the calcium concentration

ferrous and non-ferrous metals from corrosion attack.

Figure 2.1 Solubility of Oxygen at Different Temperatures

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High heat exchange skin temperatures

Saturation level for calcium sulphate or calcium phosphate

iii) SUSPENDED SOLIDS

Interfere with corrosion inhibitor film formation.

Suspended solids may originate from any of the following sources:

Interferes with the normal function of the corrosion inhibitor(s)

Growth of anaerobic bacteria

Flow and Heat Transfer Restriction

Hardness T.H. in makeup water Same as makeup water

Suspended Solids (S.S.) Present in makeup water Present in makeup water

Breakdown of corrosion inhibitor(s)