Classification of Hazardous Chemicals

CONTENTS Major Groups of Hazardous Chemicals Dangerous Goods 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

Scheduled Drugs and Poisons Hazardous Substances Chemicals of Security Concern

M AJOR 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.
1

DANGEROUS GOODS These are materials listed in the Australian Dangerous Goods Code or 2 in state or territory dangerous goods legislation. 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
1 Version 1: June 2011

Work Environment Group HR Division

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 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

Division 1.4

Division 1.5

Division 1.6

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 I II III

Degree of Danger High Medium Low

Flash Point (closed cup)* < 23 C 23 C - 60.5 C

Initial Boiling Point 35 C > 35 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- (O2 ) 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.

2-

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 Category II Category III the maximum radiation level at the surface of the package does not exceed 5 Sv/hr. the radiation level at the surface of the package is more than 5 Sv/hr but the maximum does not exceed 500 Sv/hr. the radiation level at the surface of the package is more than 500 Sv/hr but the maximum does not exceed 2000 Sv/hr.
6

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 3 or in state or territory drugs and poisons Uniform Scheduling of Drugs and Poisons 4 legislation. 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 1 2 Regulated Substance title Pharmacy Medicine Property of Poison (Not currently in use) Drugs (medicinal poisons for therapeutic use) Drugs of higher potency Prescription drugs Availability

Pharmacy retail

3 4

Pharmacist Only Medicine Prescription only Medicine

5 6 7 8

Low Harm Poison Moderate Harm Poison Dangerous Poison Controlled Medicine

Domestic poisons Industrial and Agricultural poisons Special poisons Drugs of Addiction

Restricted pharmacy retail Medical/dental/vete rinary 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

Work Environment Group HR Division

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 5 territory Hazardous Substances legislation. 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 Highly Flammable (F)

Corrosive

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 - Chronic hazards Health hazard - Environmental hazard Environment Health

Skull and crossbones - Certain health Hazards(e.g. sensitisers) Exclamation mark

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 Explosives Self-reactives Organic peroxides Flammables Self-reactives Pyrophorics Self-heating Emits flammable gas on contact with water Dangerous Goods class labels (pictograms) Dangerous goods classes Explosive

FLAMMABLE LIQUID

FLAMMABLE SOLID

SPONTANEOUSLY COMBUSTIBLE

DANGEROUS WHEN WET

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

NON-FLAMMABLE NON-TOXIC GAS

Oxidiser Organic Peroxide Oxidising gas Non-toxic nonflammable 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

Eye corrosion Skin corrosion Corrosive to metal Aquatic toxicity

Corrosive Metals
CORROSIVE

to

Environmental hazard

No equivalent hazard pictogram Not covered within the scope of workplace hazardous chemicals requirements Not covered within the scope of workplace hazardous chemicals requirements

MISCELLANEOUS DANGEROUS GOODS

Misc. Dangerous Goods

Infectious
INFECTIOUS SUBSTANCE

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. 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.
Work Environment Group HR Division
13 Version 1: June 2011

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 Edition, National Road Transport Commission,2007.
th

[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