College of Maritime Affairs

Marine Engineering Department

ICHEM: Industrial Chemistry and Tribology
First Semester of A.Y. 2020-2021
WEEK 2 - MODULE 2: ENGINE COOLING WATER

Introduction:

This module is intended to explain engine cooling water and its uses.

It also tackles topics on types of boilers, the feed water it uses and its properties as well as
treatment and sample procedures.
As future seafarer this module will ready students in having the actual exposure of handling
boilers especially for marine engineering students and cadets on their cadetship/apprentice ship
program.

Intended Learning Outcome

 Discuss engine cooling water properties, treatment and sampling procedure

Discussion

Cooling water

Cooling water is used in industrial processes to dissipate (break up and scatter) large amounts of
heat. Boiler feed water, on the other hand, is used in the water/steam circuit for electricity
generation in power stations. The water has to meet specific requirements for both applications,
which is why it is analyzed on a regular basis.
Critical parameters are monitored through regular laboratory tests and continuous online. This is
the only way of ensuring flawless and cost-effective operation.

Key parameters of cooling water (depending on the type of facility) include:

•Hardness

The simple definition of water hardness is the amount of dissolved calcium and magnesium in the
water. Hard water is high in dissolved minerals, largely calcium and magnesium. You may have felt
the effects of hard water, literally, the last time you washed your hands. Depending on the
hardness of your water, after using soap to wash you may have felt like there was a film of residue
left on your hands. In hard water, soap reacts with the calcium (which is relatively high in hard
water) to form "soap scum". When using hard water, more soap or detergent is needed to get
things clean, be it your hands, hair, or your laundry.
The specific total hardness for raw water in the cooling system should be 178 mg/L (as CaCO3)

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•Conductivity

Conductivity is a measure of water’s capability to pass electrical flow. This ability is directly related
to the concentration of ions in the water. These conductive ions come from dissolved salts and
inorganic materials such as alkalis, chlorides, sulfides and carbonate compounds. Compounds that
dissolve into ions are also known as electrolytes. The more ions that are present, the higher the
conductivity of water. Likewise, the fewer ions that are in the water, the less conductive it is.
Distilled or deionized water can act as an insulator due to its very low (if not negligible)
conductivity value. Sea water, on the other hand, has a very high conductivity.

•Turbidity

Turbidity is an optical determination of water clarity. Turbid water will appear cloudy, murky, or
otherwise colored, affecting the physical look of the water. Suspended solids and dissolved
colored material reduce water clarity by creating an opaque, hazy or muddy appearance.

•Phosphates

•Disinfection with chlorine, chlorine dioxide or ozone

•Ammonium

•Chlorides – The maximum chloride content should be 80 mg/L

•pH – should be at minimum 6.5

Cooling water systems and closed water systems require careful monitoring to ensure that the
correct water conditions are maintained within an approved treatment program.

Although there is an abundance of free sea water available, marine diesel engines do not use it
directly to keep the hottest parts of the engine cool. This is because of the corrosion which would
be caused in the cooling water spaces, and the salts which would be deposited on the cooling
surfaces interfering with the heat flow. Instead, the water circulated around the engine is fresh
water (or better still, distilled water) which is then itself cooled using sea water. This fresh water is
treated with chemicals to keep it slightly alkaline (to prevent corrosion) and to prevent scale
formation. Of course, if distilled water, which some ships can make from sea water using
evaporators, is used then there is a reduced risk of scale formation.

OBJECTIVES OF COOLING WATER TREATMENT

The primary objectives of cooling water treatment are:

1. To maintain the operating efficiency of the cooling water system.
2. To protect the equipment that contacts the cooling water.

These objectives are accomplished by controlling or minimizing deposition, corrosion, and

microbiological growth on the cooling water equipment. Treatment programs must also address
requirements for environmental compliance, safety, water conservation, and limitation of
chemical costs.

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DEPOSIT FORMATION AND CONTROL

Deposits that occur in cooling water systems are usually divided into two categories: scale and
fouling. The presence of either type of deposit in the heat exchangers or in the film fill can
interfere with heat transfer, thereby reducing the efficiency of operation. Deposits can also
promote under-deposit corrosion.

SCALE

Scale is formed from minerals, formerly dissolved in water, which were deposited from the water
onto heat transfer surfaces or in-flow water lines. As water is evaporated in a cooling tower, the
concentration of dissolved solids becomes greater until the solubility of a particular scale-causing
mineral salt is exceeded. When this situation occurs in an untreated cooling water system, the
scale will form on any surface in contact with the water, especially on heat transfer surfaces. The
most common scaling minerals are:
calcium carbonate calcium phosphate
calcium sulfate silica

Formation of magnesium silicate scale is also possible under certain conditions.

Most other salts, including silica, are more soluble in hot water than in cold water; however, most
calcium and magnesium salts, including calcium phosphate and calcium carbonate, are more
soluble in cold water than in hot water. This is called “reverse solubility.” The water temperature
will increase as recirculating water passes through the cooling system. As a result, calcium and
magnesium scales may form anywhere in the system, but most likely on heated surfaces such as
heat exchangers or surface condensers. Silica will form in areas having the lowest water
temperature, such as in the cooling tower fill.

CORROSION IN COOLING SYSTEMS

The term “corrosion” (in a cooling water system) is defined as the electrochemical deterioration of
a metal that is in contact with cooling water. Corrosion occurs when an electric current flow from
one part of the metal (anode) through the water (electrolyte) to another part of the metal
(cathode). Corrosion takes place at the anode only. The cathode is the driving force of the
corrosion action.

Galvanic Corrosion
This term refers to corrosion that occurs when two different metals are coupled together. The
metal with the least resistance becomes the anode and will corrode due to the electrochemical
reaction produced. One of the most common instances of galvanic corrosion occurring in cooling
water systems results when mild steel and copper alloy metals are brought into contact with one
another.

Ex.
1. Copper tubing attached to a mild steel tube sheet or brass valves connected to mild steel or
galvanized piping. As a result of the electrochemical reaction, the copper is dissolved in the water
and corrosion of copper alloy results. The copper can also plate out (stick) on mild steel surfaces,
setting up additional galvanic cells.

2. The electrochemical reaction that occurs when mild steel and zinc (galvanizing) are coupled

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together at temperatures normally found in cooling tower systems. The zinc becomes the anode
and is corroded.
The table below shows the galvanic series. Any coupling of a metal that is higher in the galvanic
series with a metal or alloy that is lower in the galvanic series results in an electrochemical
reaction in which the “higher” metal functions as the anode or active metal.

Galvanic Series of Materials in Seawater

________________________________________
Titanium Noble end of table
Graphite
Monel metal
Stainless steel (with one oxide film)
Inconel
Nickel
170/30 Cupro-nickel
Gunmetal
Aluminum bronze
Copper
Admiralty brass
Manganese steel (without oxide film)
Cast iron
Mild steel
Zinc
Aluminum
Magnesium Base end of table
________________________________________

Any material in the table is anodic to those above it. The more noble metals are the metals to be
protected. The less noble will experience galvanic corrosion.
Ex.
Steel is anodic to bronze in seawater, therefore it will corrode.
We say that the steel has given cathodic protection to the bronze.
Cathodic protection is a technique to control corrosion of metal surface by making it the cathode
of an electrochemical cell. It is a simple protection that connects protected metal to a more easily
corroded metal to act as the anode, a sacrificial anode. The sacrificial anodes are used to give
cathodic protection to more expensive materials.
Sacrificial anode – an anode attached to a metal object to electrolysis, and it is decomposed
instead of the object.
Ex. * Fe anode gives cathodic protection to brass tubes & plates in condensers
* Zn sacrificial anode protects an iron or steel ship’s hull; the Zn sacrificial anode will dissolve unto
the seawater and prevent the hull from being corroded

General Corrosion

The term “general corrosion” refers to uniform corrosion of metal surfaces. A single piece of
metal will have cathodic and anodic areas due to differences in impurities and stresses. These
areas will change periodically, causing the metal to corrode over the entire surface at a more or
less uniform rate.

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Concentration Cell Corrosion

When two pieces of the same metal are in a solution capable of acting as an electrolyte, and the
electrolyte contains different substances or the same substance in different amounts, such as a
salt or a mixture of salts, or oxygen, an electrical potential difference will develop between them.

Crevice Corrosion
The term “crevice corrosion” refers to corrosion that occurs in a slight separation between two
pieces of metal, such as at the contact point of two mild or stainless-steel plates that have been
bolted together. Water flow is restricted in a crevice and, as a result, oxygen is consumed faster
than it can be replenished. The metal in the crevice functions as an anode and corrodes. This is a
form of concentration cell corrosion, also called “differential oxygen cell” corrosion. Stainless steel
is particularly susceptible to this type of corrosion, which results in localized or pitting attack.
Pitting Corrosion-is a form of extremely localized corrosion that leads to the creation of small
holes or pits in the metal.

Microbiologically Influenced Corrosion (MIC).

This term refers to metal corrosion associated with microbiological organisms whose presence
contribute to the creation of, or maintenance of, a corrosive environment. MIC can be either
eliminated or prevented to a large degree by the proper use of biocides.

CORROSION CONTROL METHODS

In cooling water systems, two basic techniques are used to provide corrosion protection to the
metals that the water contacts:
1. Use of chemical corrosion inhibitors and
2. Raising the pH of the cooling water.

Many cooling water systems contain components fabricated primarily of copper alloy and mild
steel. Galvanized steel is present in galvanized cooling towers and stainless steel may be present
in piping. As the cooling water pH is increased (ideally to within the range of 8.0 to 9.5), copper
and mild steel corrosion rates will decrease, although very high pH levels are corrosive to copper.
The increase in pH alone cannot always protect metals adequately, especially since cooling water
is highly aerated (oxygen saturated). Chemical corrosion inhibitors are used to provide protection
from corrosion of the metal components of cooling water systems. The principal strategy for a
cooling system corrosion protection program is to ensure protection of the metal in the heat
exchanger (that is the thinnest metal in the system). The secondary goal is to provide protection
from corrosion of the mild steel piping. When galvanized steel cooling towers are part of the
cooling system, specialized corrosion inhibitors are the best control method. Galvanized steel is
corroded at pH levels above 9.0 and below 6.0.

EFFECTIVE CORROSION CONTROL

Effective corrosion control requires maintaining appropriate pH levels, and adding maintenance
dosages of chemical corrosion inhibitors. Chemical corrosion inhibitors form a protective film or
barrier on the cooling system metal surfaces that have been cleaned prior to adding an initial high
dosage of inhibitor. The initial high dosage of inhibitor passivates (protects) the metal. The

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appropriate dosage of corrosion inhibitor must be maintained continuously in the cooling water to
ensure continuing protection. Corrosion inhibitors are divided into three classes: cathodic, anodic,
and general filters. Corrosion inhibitors form a protective film on either the anode, the cathode, or
over the entire metal surface.
Chemical films

The use of metals which from passive oxide film. Passivation is a process through which a thin film
of corrosion products builds on a surface to serve as a barrier against oxidation. The formation of
a passivation layer is affected by environment pH, temperature chemical conditions. The Statue of
Liberty, for example, is coated with a blue-green patina caused by several chemical reactions
which serves to protect the copper metal underneath. Some films on metal surface can provide
protection so long as they remain intact.

OPERATIONAL FEATURES AND PARAMETERS

Operational features and parameters of the cooling water system must be known to select the
proper scale and deposit inhibitors. This requirement refers to operational parameters such as
maximum temperature, minimum velocities, usage patterns, and whether or not layup periods
occur. The best chemical treatment programs cannot overcome the stresses of poorly operated
systems. A good example of system stress (SS) is intermittent chiller operation that allows for SS
accumulation (deposits) in chiller tube surfaces due to low flow or lack of flow. This situation
creates a strong potential for under-deposit corrosion and for MIC that the chemical treatment
may not be able to overcome completely. Stagnant water can also cause deposits and corrosion.
High water temperatures can cause scale. The maximum water temperature should be known so
that the proper scale-control method can be used.

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