Inhibitor: A substance used to prevent or retard cargo deterioration or a potentiallyhazardous chemical self-

reaction, e.g. Polymerisation.

Polymerisation : the phenomenon whereby the molecules of a particular compound link togetherinto a larger unit
containing anything from two to many thousands of molecules,the new unit being called a polymer. A compound
may thereby change from afree flowing liquid into a viscous one or even a solid. A great deal of heat may
beevolved when this occurs. Polymerisation may occur spontaneously with nooutside influence, or it may occur if
the compound is heated, or if a catalyst orimpurity is added. Polymerisation may, under some circumstances,
bedangerous but may be delayed or controlled by the addition of inhibitors.

Self-reaction: the most common form of self-reaction is polymerisation. Polymerisation generally results in the
conversion of gases or liquids into viscous liquids or solids. It may be a slow, natural process which only degrades
the product without posing any safety hazards to the ship or the crew, or it may be a rapid, exothermic reaction
evolving large amounts of heat and gases. Heat produced by the process can accelerate it. Such a reaction is called
a run-off polymerization that poses a serious danger to both the ship and its personnel. Products that are susceptible
to polymerisation are normally transported with added inhibitors to prevent the onset of the reaction. See Appendix
C for details. An inhibited cargo certificate should be provided to the ship before a cargo is carried. An example is
shown in Appendix N. The action to be taken in case of a polymerisation situation occurring while the cargo is on
board should be covered by the ship's emergency contingency plan.

Reaction with water

Certain cargoes react with water in a way that could pose a danger to both the ship and its personnel. Toxic gases
may be evolved. The most noticeable examples are the isocyanates; such cargoes are carried under dry and inert
condition. Other cargoes react with water in a slow way that poses no safety hazard, but the reaction may produce
small amounts of chemicals that can damage equipment or tank materials, or can cause oxygen depletion.
Reaction with air
Certain chemical cargoes, mostly ethers and aldehydes, may react with oxygen in air or in the chemical to form
unstable oxygen compounds (peroxides) which, if allowed to build up, could cause an explosion. Such cargoes can
be either inhibited by an anti-oxidant or carried under inert conditions.
Reaction with other cargoes
Some cargoes react dangerously with one another. Such cargoes should be stowed away from each other (not in
adjacent tanks) and prevented from mixing by using separate loading, discharging and venting systems. When
planning the cargo stowage, the master must use a recognised compatibility guide to ensure that cargoes stowed
adjacent to each other are compatible.
Reaction with other materials
The materials used in construction of the cargo systems must be compatible with the cargo to be carried, and care
must be taken to ensure that no incompatible materials are used or introduced during maintenance (e.g. by the
material used for replacing gaskets). Some materials may trigger a self-reaction within the product. In other cases,
reaction with certain alloys will be non-hazardous to ship or crew, but can impair the commercial quality of the
cargo or render it unusable.

If nitrogen is used to clear the cargo hose after loading a cargo treated with an inhibitor that depends on oxygen,
care should be taken to minimise the volume of nitrogen entering the cargo tank. Not only may bubbling the
nitrogen through the liquid in the tank deplete the dissolved oxygen and affect the inhibitor by requiring it to take
oxygen from the atmosphere in the ullage space, but it is also possible that excessive nitrogen will linger in the
ullage space.

Cargoes that may self-react should be monitored daily in order to detect any abnormal behaviour at an early stage.
Unexpected changes of temperature are an important early indicator of a possible self-reaction, and attention
should be given to ensuring that any required heating does not cause part of the cargo to become overheated.
Crystallisation of inhibited liquid cargoes can lead to depletion of inhibitor in parts of the tank's contents (because
the inhibitor does not crystallise as well), and subsequent remelting of the crystals can thus yield pockets of
uninhibited liquid, with the risk of starting dangerous self-polymerisation.
With inhibited cargoes, the precautions and limitations described in the inhibitor certificate
should be carefully observed. If control of the tank atmosphere is being used, ullage spaces
should be monitored regularly to ensure that the correct atmosphere and overpressure are
being maintained. Most inhibitors are not themselves volatile, so they do not vaporise with the
cargo and are unlikely to be present in cargo vapours. Therefore, polymerisation may occur
where cargo vapours condense. Such places as inside vent valves and flame arresters should
be regularly inspected, and any blockage by solid polymers promptly cleared.

S
Inhibited cargoes often need the presence of some oxygen in the tank atmosphere in order to permit the inhibitor to
work properly. The minimum level of oxygen is usually stated on the inhibitor certificate but, as a general rule, a
cargo containing an inhibitor that needs oxygen should not be carried in an inerted tank.
If nitrogen is bubbled through an inhibited cargo (such as when compressed nitrogen is used to clear the cargo hose
after loading) the nitrogen will deplete the oxygen dissolved in the liquid, thereby requiring the inhibitor to take
oxygen from the atmosphere. It is possible that excessive nitrogen used for blowing through might linger in the
ullage space.

The Inhibitor Certificate must contain:

• what additive has been or should be introduced into the product, and how much;
• when the additive was or should be introduced, and for how long it is expected to be effective;
• the temperature conditions to be met in order to preserve the effectiveness and lifetime of the additive;
• whether oxygen must be present in the liquid for an inhibitor to be effective;
• what action should be taken if the voyage lasts longer than the effect of the additive.

A tank should not be inerted if it is to carry a product protected by an additive that needs
oxygen to be effective.
Most inhibitors are not themselves volatile, so they do not vaporise with the cargo and are
unlikely to be present in cargo vapours. Therefore, where cargo vapours condense, for
instance inside vent valves and flame arresters, polymerisation may occur.
Local solidification of polymerising cargoes, sometimes referred to as crystallisation, within a
cargo system should be prevented, as it may affect the uniform distribution of the additive
within the mass of the cargo and therefore allow self-polymerisation to start in part of the
cargo system.

There are occasions when inerting is not appropriate for safety reasons, because exclusion of
oxygen could create hazardous situations with a number of chemicals when shipped in monomer form. Such
chemicals (e.g. acrylic acid, styrene and vinyl acetate) have added inhibitors to prevent polymerisation during
transportation. In order to be effective, the inhibitors require the presence of oxygen dissolved in the monomer, and
that oxygen is obtained from the air in the ullage space. Inhibited monomers must therefore be carried in tanks
where the atmosphere has an oxygen level sufficient for the inhibitor to fulfil its purpose.