CHM 230 – Process Plant Safety

Chemical Reactivity Hazards

 Introduction

Chemicals have the ability to react when exposed to other chemicals

or certain physical conditions.

The reactive properties of chemicals vary widely and they play a vital
role in the production of many chemical, material, pharmaceutical,
and food products we use daily.

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Introduction

When chemical reactions are not properly managed, they can have
harmful, or even catastrophic consequences, such as toxic fumes, fires,
and explosions.

These reactions may result in death and injury to people, damage to

physical property, and severe effects on the environment.

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Introduction

The worst process industry disasters worldwide have involved

unintended or uncontrolled chemical reactions. Some examples:

 The Union Carbide incident that occurred in Bhopal, India in

1984;

 The AZF fertilizer factory incident that occurred in Toulouse,

France in 2001;

 The T2 Laboratories incident that occurred in Jacksonville,

Florida in 2007.

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 What is a Chemical Reactivity Hazard?

A chemical reactivity hazard is a situation with the potential

for an uncontrolled chemical reaction that can result directly
or indirectly in serious harm to people, property or the
environment. The uncontrolled chemical reaction might be
accompanied by a temperature increase, pressure increase,
gas evolution or other form of energy release.

Runaway reactions are a major source cause of chemical

reactivity hazards particularly in process industries

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Runaway Reaction

A runaway reaction is a thermally unstable reaction system

which exhibits an uncontrolled accelerating rate of reaction
leading to rapid increases in temperature and pressure.

A runaway reaction occurs when the energy and products

released by the reaction are not able to be safely absorbed
by the reaction environment (such as the vessel in which it is
otherwise contained).

The incident that occurred at the T2 Laboratories plant in

Jacksonville, Florida was a result of a runaway reaction due in
part to a lack of cooling of the reactor.

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 Types of Chemical Reactivity Hazards
There are two basic types of chemical reactivity hazards:

1. Those that are a result of self-reactive materials, which

include materials that are:
o Polymerizing;
o Decomposing;
o Rearranging

2. Those that are the result of reactive interactions from

materials that are:
• Reactive with atmospheric oxygen;
• Reactive with water;
• Reactive with ordinary combustible materials;
• Chemically incompatible.
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 Polymerizing material

Polymerizing materials are those in which two or more small

molecules combine to form larger molecules during the chemical
reaction. A hazardous polymerization reaction is a reaction which
takes place at a rate which releases a large amount of energy.

Styrene is one of the most widely used monomers and has a variety
of applications in the chemical industry to produce polystyrene,
acrylonitrile–butadiene–styrene rubber, and many other polymers.
However, the storage and polymerization processes are prone to
runaways as monomers are thermally unstable. A reactive chemical
incidents report published by the Chemical Safety Board (CSB)
reported that almost 15% of incidents involving uncontrolled
chemical reactions in 1980–2001 in the US are polymerization
thermal runaways.

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 Decomposing materials

Decomposition is the breakdown of a material or substance

(initiated by some form of energy input) into simpler compounds
that are the decomposition products.

The importance of decomposition in the study of chemical

reactivity hazards is that the decomposition reaction can release a
large amount of energy very rapidly. In addition, decomposition
products often present different hazards than the original
material. Decomposing materials can be shock-sensitive and/or
thermally-sensitive. The rate at which decomposition reactions
occur varies greatly, from slow to nearly instantaneous.

The incident at Toulouse, France involved the decomposition of

ammonium nitrate.
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 Rearranging materials
Rearranging materials may result in disproportionation, isomerization or
tautomerization.

Disproportionation is a chemical reaction in which a single compound serves

as both oxidizing and reducing agent and is thereby converted into a more
oxidized and a more reduced derivative. For example, with appropriate
heating, a hypochlorite yields a chlorate and a chloride.

Isomerization is the conversion of a chemical with a given molecular formula

to another compound with the same molecular formula but a different
molecular structure. Examples include the isomerization of ethylene oxide
to acetaldehyde (both C2H4O) and butane to isobutane (both C4H10).

Tautomerization refers to the conversion of one isomer into another organic

compound that differ from one another in the position of a hydrogen atom
and a double bond.

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Materials that are Reactive with Oxygen
There are several types of materials that are reactive with oxygen,
which of course is readily available in the atmosphere. These
include materials that are:

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Materials that are Reactive with Oxygen

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Materials that are Reactive with Oxygen

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Materials that are Reactive with Oxygen

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Materials that are Reactive with Oxygen

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 Materials that are Reactive with Water

A water-reactive material is one that will react upon contact with

water under normal ambient conditions, including materials that
react violently with water and other materials that react slower
but can generate heat or gases that can result in elevated
pressure if contained.

Recall from the Bhopal disaster that the prevailing conclusion is

that water was introduced to a MIC storage vessel through an
instrument connection, causing a dramatic chain of events.

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Oxidizers
An oxidizer is a material that readily yields oxygen or other
oxidizing gas, or that readily reacts to promote or initiate
combustion of combustible materials.

Examples of oxidizing gases include:

Bromine
Chlorine
Fluorine.

Other examples of oxidizers include:

Hypochlorites,
Nitrites
Organic peroxides.

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 Chemical Incompatibility

Two (or more) materials are incompatible if they produce

an undesired chemical reaction when combined together
under a defined scenario.

There are software that can be used to determine the

compatibility of chemicals. Example of these software
include

• CHEMICAL REACTIVITY WORKSHEET

• CAMEO CHEMICALS WEBSITE

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