Classification of Hazardous Chemicals

CONTENTS
Major Groups of Hazardous Chemicals
Dangerous Goods
Class 1

Explosives

Class 2

Gases - compressed, liquefied or dissolved under pressure.

Class 3

Flammable Liquids

Class 4

Flammable Solids, Substances liable to spontaneous combustion and

Substances which in contact with water emit flammable gases

Class 5

Oxidizing Agents and Organic Peroxides

Class 6

Toxic and Infectious Substances

Class 7

Radioactive Substances

Class 8

Corrosive Substances

Class 9

Miscellaneous Dangerous Goods

Scheduled Drugs and Poisons

Hazardous Substances
Chemicals of Security Concern
MAJOR GROUPS OF HAZARDOUS CHEMICALS
Currently there are three major groups of hazardous chemicals in Australia - dangerous
goods, scheduled drugs & poisons, hazardous substances and chemicals of security
concern.
DANGEROUS GOODS These are materials listed in the Australian Dangerous Goods Code1 or
in state or territory dangerous goods legislation. 2 The term dangerous goods generally
applies to chemicals and materials used in industry that have the potential to be a safety
hazard. To some extent the classification of a dangerous good depends on its quantity, since
the major concern with dangerous goods is the risk associated with their bulk transport and
storage.
There are 9 classes of dangerous goods, each with a characteristic class number and
symbol. Some of these classes are divided into divisions. The classes of dangerous goods
can be considered to be listed in the order from most hazardous to least hazardous. A
chemical may belong to more than one of these classes, for example glacial acetic acid is
classed as both a flammable liquid and a corrosive substance.
Class 1
Class 2
Class 3
Class 4
Class 5
Class 6
Class 7
Class 8
Class 9

Explosives
Gases - compressed, liquefied or dissolved under pressure.
Flammable Liquids
Flammable Solids, Substances liable to spontaneous combustion and
Substances which in contact with water emit flammable gases
Oxidizing Agents and Organic Peroxides
Toxic and Infectious Substances
Radioactive Substances
Corrosive Substances
Miscellaneous Dangerous Goods

Work Environment Group

HR Division

1
Version 1: June 2011

Classes of dangerous goods

Class 1 - Explosives

Explosives pose a major hazard because of the destruction to people and property caused by
their detonation. An explosive, on detonation, undergoes a rapid chemical change with the
production of a large gas volume relative to the volume of explosive. It is this rapidly
expanding pressure wave that produces the devastating destruction characteristic of
explosives. Explosives include: explosive substances, pyrotechnic substances and explosive
articles.
The explosive class of dangerous goods is divided into 6 divisions. These sub-classes do not
include those explosives that are too hazardous to transport, or substances that are not
intrinsically explosive but can form an explosive atmosphere of gas, vapour, or dust.
Division 1.1
Division 1.2
Division 1.3

Division 1.4

Division 1.5

Division 1.6

Substances that have a mass explosion hazard.

Substances and articles that have a projection hazard, but not a mass
explosion hazard.
Substances or articles that have a fire hazard and either a minor blast
hazard or minor projection hazard, or both, but not a mass explosion
hazard.
Substances and articles that present no significant hazard. The effect
would be confined to the package and no projection of fragments of
size or range is expected.
Very insensitive substances that have a mass explosion hazard. These
substances have a low probability of initiation or of transition from
burning to detonation under normal conditions of transport.
Extremely insensitive articles that do not have a mass explosion
hazard.
Divisions of dangerous goods Class 1 - Explosives

There are a number of potentially explosive chemicals that may be found in the laboratory
which are either:
chemicals that are intrinsically explosive; or
may become explosive on deterioration.
Lists of intrinsically and potentially explosive chemicals are located in the Explosive
Chemicals List Document.
Intrinsically explosive chemicals should NOT be used by staff or students at the ANU
(i.e. ordered, stored, handled or disposed of) unless expert advice is received and
appropriate practices are in place.

Work Environment Group

HR Division

2
Version 1: June 2011

Class 2 - Gases
Gases pose a hazard because of their ability to diffuse over a large volume to exert a
flammable, asphyxiating, toxic or oxidising effect.
A gas is defined as a dangerous good if:
at 50 C has a vapour pressure greater than 300 kPa, or
it is completely gaseous at 20 C at standard pressure (101.3 kPa).
Gases can be stored compressed, liquefied or dissolved under pressure.
Dangerous goods class 2 is divided into four sub-classes Division 2.1 - Flammable gases

Examples of flammable gases are hydrogen, methane, acetylene

Division 2.2 - Non-flammable, non-toxic gases

Examples of Division 2.2 gases are nitrogen, compressed air, helium, argon.

Division 2.3 - Toxic gases .

Toxic gases include carbon monoxide, chlorine, phosgene.

Work Environment Group

HR Division

3
Version 1: June 2011

Division 2.2 - Subsidiary Risk 5.1 (Oxidising Gases)

Two oxidising gases are oxygen and nitrous oxide

Class 3 - Flammable Liquids

Flammable liquids are liquids which are capable of being ignited and burned. They may also
be mixtures of liquids, containing solids in solution or suspension (eg. paints).
Ignition of the flammable liquid and production of fire is the major hazard here. The flammable
liquids (Class 3) are considered a higher risk than flammable solids (Class 4) because of the:
generally higher vapour pressure exhibited by liquid compounds,
ability of the liquid to flow under gravity and collect in low points or flow into drains
and waterways.
Flammable liquids are further divided into three Packing Groups (PG) according to the degree
of danger they present.
Packing
Group

Degree of
Danger

Flash Point (closed

cup)*

Initial Boiling
Point

High

35 C

II

Medium

< 23 C

> 35 C

III

Low

23 C - 60.5 C

> 35 C

Packing group allocation of flammable liquids

* Liquids that will ignite and burn with a flash point above 60.5 C are classified as
combustible liquids
Class 4 - Flammable Solids
Class 4 dangerous goods are flammable solids, and their major hazard is their flammable
nature.
Class 4 is divided into three divisions, and the substances within each divisions are assigned
to packing group I (highest danger), II (moderate danger), or III (minor danger).
Division 4.1 - Flammable solids
Work Environment Group
HR Division

4
Version 1: June 2011

There are three further sub-divisions of class 4.1, which are flammable solids, self-reactive
and related substances and desensitized explosives.
Flammable solids are solids that, under conditions encountered in transport, are readily
combustible or may cause or contribute to fire through friction. They can also be a powder or
paste. An added danger can be from toxic combustion products. eg. metal powders,
naphthalene.
Self-reactive and related substances are substances that are liable to undergo a strong
exothermic reaction. e.g. aliphatic azo- compounds, organic azides.
Desensitized explosives are substances that may explode if not diluted sufficiently. e.g.
ammonium picrate, wetted; dinitrophenol, wetted; barium azide, wetted; nitrocellulose with
alcohol.
Division 4.2 - Substances liable to spontaneous combustion

This division is comprised of substances that are liable to spontaneous heating under normal
conditions encountered in transport; or heating up in contact with air, and being able to catch
fire due to such heating. e.g. white phosphorus.
Division 4.3- Substances that in contact with water emit flammable gases

These are substances that, by interaction with water, are liable to become spontaneously
flammable or to give off flammable gases in dangerous quantities. e.g. sodium metal.
Class 5 - Oxidising Substances and Organic Peroxides
Oxidising substances and organic peroxide pose a hazard because of their ability to
chemically oxidise matter, including living tissue. Strong oxidisers can greatly enhance the
flammability of material with the production of heat, fire, and dangerous reaction products.

Work Environment Group

HR Division

5
Version 1: June 2011

Class 5 dangerous goods are divided into two divisions, with substances within each subclass being assigned to packing group I (great danger), II (moderate danger), or III (minor
danger).
Division 5.1 - Oxidizing Substances

Although these substances are not necessarily combustible, they may:

readily liberate oxygen; or
be the cause of, or contribute to the combustion of, other materials.
Examples of oxidising agents are hydrogen peroxide, copper chlorate and fluorine.
Division 5.2 - Organic Peroxides

Organic peroxides all contain the bivalent -O-O- (O 22-) structure. They are thermally
unstable substances, that may undergo exothermic, self-accelerating decomposition and
most substances of this class are combustible. In addition, they may have one or more of the
following properties - be liable to:
explosive decomposition;
burn rapidly;
be sensitive to impact or friction;
react dangerously with other materials; or
cause damage to the eyes.
Examples of organic peroxides are dibenzoyl peroxide, peracetic acid and perbenzoic acid.
Class 6 Toxic and Infectious Substances
Class 6 dangerous goods are hazardous because of their chemical toxicity or biological
infectivity to people, animals or the environment. The words "toxic" and "poisonous" are
synonyms.
Class 6 is divided into two divisions, with the substances in each division being assigned to
packing group I (great danger), II (moderate danger), or III (minor danger).
Division 6.1 - Toxic Substances

Work Environment Group

HR Division

6
Version 1: June 2011

These are substances that if swallowed, inhaled, come into contact with skin are liable to
cause death, serious injury, or to harm human health.
Division 6.2 - Infectious Substances

Infectious substances are materials known, or reasonably expected, to contain pathogens.

Pathogens are defined as microorganisms including bacteria, viruses, rickettsia, parasites,
fungi, or are genetically modified microorganisms that are known, or reasonably believed, to
cause disease in humans or animals. Genetically Modified Microorganisms which do not meet
the criteria of an infectious substance should be considered for classification in Class 9.
Class 7 - Radioactive Substances

Class 7 dangerous goods spontaneously emit ionizing radiation. For packaging and transport
requirements, this class is divided into three categories Category I

the maximum radiation level at the surface of the package does not
exceed 5 Sv/hr.

Category II

the radiation level at the surface of the package is more than 5 Sv/hr
but the maximum does not exceed 500 Sv/hr.

Category III

the radiation level at the surface of the package is more than 500
Sv/hr but the maximum does not exceed 2000 Sv/hr.

The ARPANSA Code of Practise for the Safe Transport of Radioactive Substances
also be considered.

should

Class 8 Corrosives

Work Environment Group

HR Division

7
Version 1: June 2011

Class 8 dangerous goods are corrosive substances that, by chemical action, will cause
severe damage when in contact with living tissue, or in the case of leakage, will damage or
destroy other materials.
Corrosive substances are assigned to packing group I (great danger), II (moderate danger),
or III (minor danger).
Class 9 - Miscellaneous Dangerous Goods

Class 9 dangerous goods are substances and articles that during transport present a danger
not covered in other classes. This class includes substances that are transported or offered
for transport at temperatures 100 C in a liquid state, or at temperatures 240 C in a solid
state. Examples of Class 9 dangerous goods dry ice, strong magnets.
Class 9 dangerous goods are assigned to packing group I (great danger), II (moderate
danger), or III (minor danger).
SCHEDULED DRUGS and POISONS These are materials included in the Standard for the
Uniform Scheduling of Drugs and Poisons 3 or in state or territory drugs and poisons
legislation. 4 The term applies to pharmaceuticals, poisons and domestic and agricultural
chemicals, many of which are available in small quantities to the general public, either directly
from retail outlets or by medical prescription from a pharmacy. For more information see the
scheduled medicines and poisons document.
There are 9 schedules of medicines (drugs) and poisons, indicated below:
Schedule

Regulated Substance title

Property of
Poison
(Not currently in use)
Drugs (medicinal
poisons for
therapeutic use)
Drugs of higher
potency
Prescription drugs

1
2

Pharmacy Medicine

Pharmacist Only Medicine

Prescription only Medicine

5
6

Low Harm Poison

Moderate Harm Poison

Dangerous Poison

Domestic poisons
Industrial and
Agricultural poisons
Special poisons

Controlled Medicine

Drugs of Addiction

Work Environment Group

HR Division

Availability
Pharmacy retail
Restricted
pharmacy retail
Medical/dental/veter
inary prescription
At ANU this should
be under the control
of a veterinarian or
medical officer.
General retail
Restricted retail
Restricted
wholesale
Restricted
medical/dental/vet
prescription
At ANU, also
contact the OHS
8
Version 1: June 2011

Branch for advice

9

Prohibited Substance

Prohibited
substances or
Appendix C
substances

Restricted
wholesale
At ANU, also
contact the OHS
Branch for advice

The Schedule number for a chemical can be found in its Material Safety Data Sheet, or on the
label (eg. S4). Some general exemption for certain materials exist and these can be found in
Appendix A, B and G of the Poison Standard 2008.
HAZARDOUS SUBSTANCES These are substances included in the Australian Safety and
Compensation Councils Hazardous Substance Information System or in federal, state or
territory Hazardous Substances legislation. 5 The term applies to a material that has the
potential, through being used at work, to harm the health or safety of persons in the
workplace.
The criteria for identifying a hazardous substance have been defined, in the Approved Criteria
For Classifying Hazardous Substances. A substance may be classified as hazardous, and
assigned one of the following hazard terms and symbols, because they have the indicated
effect on health:

Very Toxic (T+)

Toxic (T)
Harmful (Xn)
Corrosive (C)
Irritant (Xi)
Sensitisation
Other toxicological effects, including:
o Interact with other substances to release toxic gas
o May cause harm to breastfed babies
Carcinogenic
Mutagenic
Toxic to reproduction
Systemic toxicity

The symbols commonly used to represent these hazards are Symbols under the Global
harmonisation system and are shown below:

Work Environment Group

HR Division

9
Version 1: June 2011

European Union Hazard Symbols

Explosive Hazard

Harmful (Xn)

Extremely Flammable (F+) or

Corrosive

Highly Flammable (F)

Oxidising

Irritant (Xi)

Very Toxic (T+) or Toxic (T)

Radioactive

Work Environment Group

HR Division

10
Version 1: June 2011

The nine hazard pictograms from the Classification Criteria (Globally Harmonized System of
Classification and Labelling of Chemicals) that are representative of the physical, health
and/or environmental hazards are shown below:

Pictogram

Hazard

Pictogram

Hazard

- Explosive

- Gases under pressure

Exploding bomb

Gas cylinder
- Flammability

- Corrosive

Flame

Corrosion
- Oxidising

- Acute toxicity

Flame over circle

Skull and crossbones

- Chronic
hazards

- Certain health
Hazards(e.g.
sensitisers)

Health

Health hazard

Exclamation mark
- Environmental
hazard

Environment

Work Environment Group

HR Division

11
Version 1: June 2011

Comparison of Hazard Pictograms from the Classification Criteria and

ADG Code Class Labels
Hazard
Pictograms

GHS Hazard

Dangerous Goods class labels (pictograms)

Explosives
Self-reactives
Organic
peroxides
Flammables
Self-reactives
Pyrophorics
Self-heating
Emits
flammable gas
on
contact
with water

FLAMMABLE
LIQUID

FLAMMABLE
SOLID

SPONTANEOUSLY
COMBUSTIBLE

DANGEROUS
WHEN WET

Dangerous
goods classes
Explosive

Flammability
(Liquid, Solid
or Gas)
Pyrophoric,
Emits
Flammable Gas

FLAMMABLE
GAS

Oxidisers
Organic
peroxides

OXIDIZING
AGENT

ORGANIC
PEROXIDE

OXIDIZING
GAS

5.1

5.2

Gases under
pressure

Oxidiser
Organic
Peroxide
Oxidising
gas
Non-toxic nonflammable gas

NON-FLAMMABLE
NON-TOXIC
GAS

Acute toxicity
TOXIC

TOXIC
GAS

Acute
toxicity
Acute Toxic
gas

Acute toxicity No equivalent

Skin irritation
Eye irritation
Skin
sensitisers
Carcinogens
No equivalent
Respiratory
sensitisers
Reproductive
toxicity
Target organ
toxicity
Germ
cell
mutagens
Work Environment Group
HR Division

12
Version 1: June 2011

Hazard
Pictograms

GHS Hazard
Eye corrosion
Skin corrosion
Corrosive to
metal

Dangerous Goods class labels (pictograms)

CORROSIVE

Aquatic
toxicity

No
equivalent
hazard
pictogram

Dangerous
goods classes
Corrosive
to
Metals

Environmental
hazard

Misc.
Dangerous
Goods

MISCELLANEOUS
DANGEROUS
GOODS

Not covered within the scope

of workplace hazardous
chemicals requirements

Infectious
INFECTIOUS
SUBSTANCE

Not covered within the scope

of workplace hazardous
chemicals requirements

Radioactive
RADIOACTIVE I
CONTENTS . . . . . . . . . . . . . . . . . . . .
ACTIVITY . . . . . . . . . . . . . . . . . . . . .

CHEMICALS OF SECURITY CONCERN These chemicals can be attributed as Weapons of Mass Destruction and High
Consequence Dangerous Goods (HCDG).

Chemicals associated with Weapons of Mass Destruction have been scheduled

by an international treaty called the Chemical Weapons Convention (CWC). The
CWC schedules, which list the chemicals in question, are available from the
Commonwealth Department of Foreign Affairs' related publication.

The term High Consequence Dangerous Goods refers to dangerous goods that are
of security concern due to their potential to cause mass casualties and/or destruction.
The following chemicals have been declared to be HCDG:
ammonium nitrate in concentrations > 45%; and
calcium ammonium nitrate in concentrations > 45%.
See: Chemicals of Security Concern.

Definitions
Gas in solution - a compressed gas which when packaged is dissolved in a solvent. e.g.
acetylene which is dissolved in acetone.

Work Environment Group

HR Division

13
Version 1: June 2011

Auto-Ignition Temperature - the minimum temperature at which combustion will occur in the
absence of a spark or flame.
Compressed gas - a gas (other than in solution) which when packaged under pressure is
entirely gaseous at 20 C. e.g. nitrogen.
Flammable (Explosive) Limits the range of concentrations in air at which the material will
burn or explode. For a mixture of gas or vapour in air to be flammable, it must also have both
sufficient fuel (defining the lower explosive limit) and sufficient oxygen (defining the upper
explosive limit).
Flash Point - the lowest temperature at which a flammable liquid will release sufficient vapour
for it to burn. e.g. the flash point of diethyl ether is - 45 C.
Liquefied gas - a gas which when packaged is partially liquid at 20 C. e.g. LPG.
Refrigerated liquefied gas - a gas which when packaged is partially liquid because of its low
temperature.
References
[1] Australian Dangerous Goods Code. Volume 1 - Requirements and Recommendations, 7 th
Edition, National Road Transport Commission,2007.
[2] Occupational Health And Safety (Safety Standards) Regulations. Part 8 Storage and
Handling of Dangerous Goods, Commonwealth of Australia, 1994.
[3] Standard for the Uniform Scheduling of Drugs and Poisons. Number 21, Therapeutic
Goods Administration, 2006.
[4] Poisons and Drugs Regulation, ACT Government, 1993.
[5] Occupational Health And Safety (Safety Standards) Regulations. Part 6 Hazardous
Substances, Commonwealth of Australia, 1994.
[6] Code of Practise: Safe Transport of Radioactive Material. Series No 2. Australian
Radiation Protection and Nuclear Safety Agency, 2008.

Work Environment Group

HR Division

14
Version 1: June 2011