Class 5 tdg do you mean

Class 5 TDG do you mean
This
or that in safety?
P bar Y Safety Consultants Alberta Canada

As GHS roles into the workplace
• As GHS roles into the workplace we now
require under law for workers to be not just
GHS ( WHMIS2015) but because those
changes Dangerous Goods/Hazmat trained
due to the cross of over in worker knowledge.

27 into 9 goes
Learning Dangerous Goods is easy all you have
to remember is all 9 Classes and 27 Hazard
Classes to Competent in TDG/Hazmat, now add
all the GHS knowledge!

GHS vs TDG/Hazmat
Oxidizing liquids category 1, 2, 3 Class 5 Division 5.1: Oxidizing substances, Packing group I, II, III
Oxidizing solids category 1, 2, 3 Class 5 Division 5.1: Oxidizing substances, Packing group I, II, III
Organic peroxides type A See explosives. May not be allowed for transport.
Organic peroxides type B, C, D, E, F Class 5 Division 5.2: Organic peroxides
Organic peroxides type G Not dangerous goods

Class 5 TDG/Hazmat

Class 5 is divided into two divisions as
follows:
• Division 5.1 Oxidizing substances
Substances which, while in themselves not necessarily combustible, may,
generally by yielding oxygen, cause, or contribute to, the combustion of
other material. Such substances may be contained in an article;
• Division 5.2 Organic peroxides
Organic substances which contain the bivalent -0-0- structure and may be
considered derivatives of hydrogen peroxide, where one or both of the
hydrogen atoms have been replaced by organic radicals. Organic peroxides
are thermally unstable substances, which may undergo exothermic self-
accelerating decomposition. In addition, they may have one or more of
the following properties:
(i) be liable to explosive decomposition;
(ii) burn rapidly;
(iii) be sensitive to impact or friction;
(iv) react dangerously with other substances;
(v) cause damage to the eyes.

Fire or Boom
Additionally, organic
peroxides may be liable to
explosive decomposition,
burn rapidly, be sensitive to
impact or friction, react
dangerously with other
substances or cause damage
to eyes.

Common but not all of them
Commonly Transported Oxidizers; Organic Peroxides
• Chemical oxygen generators
• Ammonium nitrate fertilizers
• Chlorates
• Nitrates
• Nitrites
• Perchlorates
• Permanganates
• Persulphates
• Aluminium nitrate
• Ammonium dichromate
• Ammonium nitrate
• Ammonium persulphate
• Calcium hypochlorite
• Calcium nitrate
• Calcium peroxide
• Hydrogen peroxide
• Magnesium peroxide
• Lead nitrate
• Lithium hypochlorite
• Potassium chlorate
• Potassium nitrate
• Potassium chlorate
• Potassium perchlorate
• Potassium permanganate
• Sodium nitrate
• Sodium persulphate

Two Separate Guides pending risk
In the Emergency
response guide
book

Common but not always
Commonly transported class 5 dangerous goods
include hydrogen peroxide, potassium
permanganate, sodium nitrite, ammonium
nitrate fertilizers and oxygen generators.

Class 5 has two divisions:
• (a) Class 5.1, Oxidizing Substances, which consists of substances that
yield oxygen thereby causing or contributing to the combustion of other
material, as determined in accordance with section 2.5.2 of Chapter 2.5 of
the UN Recommendations; and
• (b) Class 5.2, Organic Peroxides, which consists of substances that
– (i) are thermally unstable organic compounds that contain oxygen in the
bivalent "-O-O-" structure, as determined in accordance with section 2.5.3 of
Chapter 2.5 of the UN Recommendations,
– (ii) are liable to undergo exothermic self-accelerating decomposition,
– (iii) have one or more of the following characteristics:
• (A) they are liable to explosive decomposition,
• (B) they burn rapidly,
• (C) they are sensitive to impact or friction,
• (D) they react dangerously with other substances, or
• (E) they cause damage to the eyes, or
– (iv) are in the list of currently assigned organic peroxides in section 2.5.3.2.4
of Chapter 2.5 of the UN Recommentations.

5.1
• The packing group of a Division 5.1 material which is a solid shall be assigned using the
following criteria:
– Packing Group I, for any material which, in either concentration tested, exhibits a mean burning time
less than the mean burning time of a 3:2 potassium bromate/cellulose mixture.
– Packing Group II, for any material which, in either concentration tested, exhibits a mean burning time
less than or equal to the mean burning time of a 2:3 potassium bromate/cellulose mixture and the
criteria for Packing Group I are not met.
– Packing Group III for any material which, in either concentration tested, exhibits a mean burning time
less than or equal to the mean burning time of a 3:7 potassium bromate/cellulose mixture and the
criteria for Packing Group I and II are not met.
• The packing group of a Division 5.1 material which is a liquid shall be assigned using the
following criteria:
– Packing Group I for:
• Any material which spontaneously ignites when mixed with cellulose in a 1:1 ratio; or
• Any material which exhibits a mean pressure rise time less than the pressure rise time of a 1:1 perchloric acid (50
percent)/cellulose mixture.
– Packing Group II, any material which exhibits a mean pressure rise time less than or equal to the
pressure rise time of a 1:1 aqueous sodium chlorate solution(40 percent)/cellulose mixture and the
criteria for Packing Group I are not met.
– Packing Group III, any material which exhibits a mean pressure rise time less than or equal to the
pressure rise time of a 1:1 nitric acid (65 percent)/cellulose mixture and the criteria for Packing Group I
and II are not met.

Type 5.2 has
Type, B to F, of organic
peroxides, Organic
peroxides - organic
compounds with the
bivalent
R-O-O-R
structure where at least
one R is a carbon chain,
except for
materials that meet class
1 (Explosive)

A through G on 5.2
• Type A. Organic peroxide type A is an organic peroxide which can detonate or deflagrate rapidly as
packaged for transport. Transportation of type A organic peroxides is forbidden.
• Type B. Organic peroxide type B is an organic peroxide which, as packaged for transport, neither
detonates nor deflagrates rapidly, but can undergo a thermal explosion.
• Type C. Organic peroxide type C is an organic peroxide which, as packaged for transport, neither
detonates nor deflagrates rapidly and cannot undergo a thermal explosion.
• Type D. Organic peroxide type D is an organic peroxide which-
– Detonates only partially, but does not deflagrate rapidly and is not affected by heat when confined;
– Does not detonate, deflagrates slowly, and shows no violent effect if heated when confined; or
– Does not detonate or deflagrate, and shows a medium effect when heated under confinement.
• Type E. Organic peroxide type E is an organic peroxide which neither detonates nor deflagrates
and shows low, or no, effect when heated under confinement.
• Type F. Organic peroxide type F is an organic peroxide which will not detonate in a cavitated state, does
not deflagrate, shows only a low, or no, effect if heated when confined, and has low, or no, explosive
power.
• Type G. Organic peroxide type G is an organic peroxide which will not detonate in a cavitated state, will
not deflagrate at all, shows no effect when heated under confinement, and shows no explosive power. A
type G organic peroxide is not subject to the requirements of this subchapter for organic peroxides of
Division 5.2 provided that it is thermally stable (self-accelerating decomposition temperature is 50 °C
(122 °F) or higher for a 50 kg (110 pounds) package). An organic peroxide meeting all characteristics of
type G except thermal stability and requiring temperature control is classed as a type F, temperature
control organic peroxide. P bar Y Safety Consultants Alberta Canada

It has a quantifying feature
• The material meets one of the following conditions:
For materials containing no more than 1.0 percent
hydrogen peroxide, the available oxygen, as calculated
using the equation, is not more than 1.0 percent, or
• For materials containing more than 1.0 percent but not
more than 7.0 percent hydrogen peroxide, the
available oxygen, content (Oa) is not more than 0.5
percent, when determined using the equation: where,
for a material containing k species of organic peroxides:

Packing Groups
• Packing Groups
• (1) The determination of packing groups for Class 5.1, Oxidizing Substances, must be made
– (a) for solids, using a test sample of a 4:1 or 1:1 mixture of substance and cellulose by mass, prepared and
tested in accordance with section 2.5.2.2 of Chapter 2.5 of the UN Recommendations; or
– (b) for liquids, using a test sample of a 1:1 mixture of substance and cellulose by mass, prepared and tested
in accordance with section 2.5.2.3 of Chapter 2.5 of the UN Recommendations.
• (2) Substances included in Class 5.1, Oxidizing Substances, are included in one of the following
packing groups:
– (a) for solids,
• (i) Packing Group I, if the test sample exhibits an average burning time less than the mean burning time of a 3:2 mixture
by mass of potassium bromate and cellulose,
• (ii) Packing Group II, if the test sample exhibits an average burning time less than or equal to the mean burning time of a
2:3 mixture by mass of potassium bromate and cellulose and the criteria for inclusion in Packing Group I are not met, or
• (iii) Packing Group III, if the test sample exhibits an average burning time less than or equal to the mean burning time of
a 3:7 mixture by mass of potassium bromate and cellulose and the criteria for inclusion in Packing Group I or II are not
met; or
– (b) for liquids,
• (i) Packing Group I, if the substance in a 1:1 mixture by mass of substance and cellulose spontaneously ignites or the
mean pressure rise time is less than or equal to that of a 1:1 mixture by mass of 50 percent perchloric acid and cellulose,
• (ii) Packing Group II, if the mean pressure rise time is less than or equal to the mean pressure rise time of a 1:1 mixture
by mass of 40 per cent aqueous sodium chlorate solution and cellulose and the criteria for inclusion in Packing Group I are
not met, or
• (iii) Packing Group III, if the mean pressure rise time is less than or equal to the mean pressure rise time of a 1:1 mixture
by mass of 65 per cent aqueous nitric acid solution and cellulose and the criteria for inclusion in Packing Group I or II are
not met.
• (3) Class 5.2, Organic Peroxides, are included in Packing Group II.
• (4) The type, B to F, of organic peroxides must be determined in accordance with section 2.5.3.3 of
Chapter 2.5 of the UN Recommendations.

Did you Segregate it properly
Check the tables !

Where the worker gets confused

GHS Oxidizer
• In chemistry, an oxidizing agent (oxidant, oxidizer) is a
substance that has the ability to oxidize other
substances (cause them to lose electrons). Common
oxidizing agents are oxygen, hydrogen peroxide and the
halogens.
• In one sense, an oxidizing agent is a chemical
reaction that removes an electron from another atom.
It is one component in an oxidation–reduction (redox)
reaction. In the second sense, an oxidizing agent is a
chemical species that transfers electronegative atoms,
usually oxygen, to a substrate. Combustion, many
explosives, and organic redox reactions involve atom-
transfer reactions.

Free Radicals

APPLIED
As heat is applied to a combustible material, the
molecules that compose the material start to vibrate
rapidly. If the vibrations become strong enough, the
molecules break into fragments known as free radicals.
The process of breaking into free radicals is known as
pyrolysis and is endothermic (requiring heat from an
outside source). The free radicals encounter oxygen in the
air. Oxygen has a great attraction for electrons
(electronegativity) and reacts with the free radicals. The
reaction that occurs is known as oxidation and is simply
the forming of a chemical bond between a free radical
and oxygen. The bond-forming process is exothermic
(heat producing) and is, in essence, combustion

Gases
For oxidizing compressed gases in cylinders, a unique hazard is that fire
can result from the gas passing through a gauge or piping system that
is not free of hydrocarbons, even in trace amounts. Spontaneous
ignition of the hydrocarbon will occur. This ignition can result in an
explosion accompanied by fragmentation of the equipment and
possible fire.
A second hazard unique to oxidizing gases is the potential to
concentrate in a room or other unvented or poorly vented space. In
oxidizer-enriched environments, the flammable range of flammable
gases and liquids is widened at both the upper and lower flammable
limits. They will burn when normally they would be either too rich or
lean. Flash points and ignition temperatures are also lowered. In some
cases, flash points and ignition temperatures are lowered to the point
that the substance can ignite at room temperature.

Solids
Oxidizing solids also have a few unique properties. Oxidizing solids include:
• Oxysalts such as potassium permanganate, sodium nitrate, sodium
persulfate, and other nitrates, nitrites and chlorates.
• Inorganic peroxides include alkali metal (Na, K, Rb, Li, Cs, Fr) peroxides and
transition metal (e.g., Cu, Zn, Co, Fe, Cr, Se, Ag, Pb, etc.) peroxides. When
wetted, alkali metal peroxides can produce sufficient heat to ignite nearby
combustibles (or explosively rupture their containers). Transition metal
peroxides are less reactive than those of alkali metals. Solid oxidizers in
solution may be too dilute to react with combustible materials to produce a
fire. However, if a combustible material (e.g., a paper towel or a lab coat) is
contaminated with a solution containing an oxidizer, as the solution dries, the
oxidizer is concentrated. This can cause the combustible material to
spontaneously ignite and burn intensely. Solid oxidizers saturated with
combustible materials can be explosive. An example is the explosive behavior
of ammonium nitrate combined with fuel oil.

Hazards of the oxidizing materials that
you use in the workplace
• An example is ammonium perchlorate. This material is a white or
colourless, odourless crystals. It is used in explosives and fireworks;
as an oxidizing agent in solid rocket and missile propellants; as an
adhesive; as an engraving agent; laboratory (analytical) reagent;
chemical intermediate for alkali and alkaline metal perchlorates;
animal feed supplement; and in oxygen-generating devices for life-
support systems in submarines, spacecraft, bomb shelters and
breathing apparatus.
• Ammonium perchlorate can decompose at high temperatures
forming toxic gases, such as chlorine, hydrogen chloride and
nitrogen oxides. Closed containers or tanks may rupture and
explode if heated. It does not burn but is a powerful oxidizer and
explosive when mixed with combustible materials. It is highly
reactive and impact or high temperatures can cause violent
decomposition or explosion. It can form shock-sensitive mixtures
with finely powdered metals, metal oxides, strong reducing agents,
sulfur and phosphorus. It may cause eye irritation.

Any
Oxidizing materials can:
• speed up the development of a fire and make it more
intense.
• cause substances that do not normally burn readily in air to
burn rapidly.
• cause combustible materials to burn spontaneously
without the presence of obvious. ignition sources such as a
spark or flame.
• What happens when an oxidizing material comes in contact
with a combustible substance largely depends on the
chemical stability of the oxidizing material. The less stable
an oxidizing material is, the greater the chance that it will
react in a dangerous way.

Oxidizer Storage
• Store oxidizing materials according to the occupational health and safety regulations and the fire
and building codes that apply to your workplace. These laws may specify the kinds of storage areas
such as storage rooms or buildings allowed for different oxidizers. They may also specify how to
construct these storage areas, and the amounts of oxidizing materials that can be stored in each
area.
• Before storing, inspect all incoming containers to ensure that they are undamaged and properly
labelled. Do not accept delivery of defective containers.
• Store oxidizing materials in containers that the chemical supplier recommends. Normally these are
the same containers in which the material was shipped. Repackaging can be very dangerous
especially when using contaminated or incompatible containers. Protect containers against banging
or other physical damage when storing, transferring or using them. Do not use wooden pallets or
other combustible pallets for storing containers of oxidizing materials.
• Make sure containers are suitably labelled. For oxidizing materials requiring temperature control,
the recommended storage temperature range should be plainly marked on the container. It is also a
good practice to mark the date that the container was received and the date it was first opened.
• Normally keep containers tightly closed when storing unless the supplier's instructions state
otherwise. This helps to avoid contamination of the material or evaporation of solvents used to
dilute oxidizers, such as organic peroxides, to safer concentrations.
• Some oxidizing agents, such as solutions of 8% or higher hydrogen peroxide in water, must be
stored with specially vented caps. Hydrogen peroxide gradually decomposes at room temperature
to produce oxygen gas and water. The properly working vent will prevent the build-up of pressure
inside containers. The normal build-up of pressure could rupture an unvented container. Check vent
caps regularly to ensure that they are working properly. Keep vented containers in the upright
position. NEVER stack vented containers on top of each other.

Temperature
• For these oxidizers, ensure that the storage
temperature is kept at least 14°C (25°F) below
their decomposition temperature. Avoid
storing any oxidizer at temperatures above
49°C (120°F).
• Storage areas may need alarms that provide a
warning when storage temperatures are
higher or lower than required.

Risks everyone should know
• The main hazard related to organic peroxides are their fire and explosion hazards. Organic peroxides may
also be toxic or corrosive. Depending on the material, route of exposure (inhalation, eye or skin contact, or
swallowing) and dose or amount of exposure, they could harm the body. Corrosive organic peroxides can
also attack and destroy metals.
• It is the double oxygen of the "peroxy" group that makes organic peroxides both useful and hazardous.
The peroxy group is chemically unstable. It can easily decompose, giving off heat at a rate that increases
as the temperature rises. Many organic peroxides give off flammable vapours when they decompose.
These vapours can easily catch fire.
• Most undiluted organic peroxides can catch fire easily and burn very rapidly and intensely. This is because
they combine both fuel (carbon) and oxygen in the same compound. Some organic peroxides are
dangerously reactive. They can decompose very rapidly or explosively if they are exposed to only slight
heat, friction, mechanical shock or contamination with incompatible materials.
• Organic peroxides can also be strong oxidizing agents. Combustible materials contaminated with most
organic peroxides can catch fire very easily and burn very intensely (i.e., deflagrate). This means that the
burn rate is very fast: it can vary from 1 m/sec to hundreds of metres per second. Also the combustion rate
increases as the pressure increases and the combustion (or reaction) zone can travel through air or a
gaseous medium faster than the speed of sound. However, the speed of combustion in a solid medium
does not exceed the speed of sound.
• This is one characteristic that distinguishes deflagration from detonation. We mention these two terms
because they are used in classifying organic peroxide formulations (see next question). Deflagrations and
detonations are similar chemical reactions except that in detonations the burn rate in a solid medium is
faster than the speed of sound. This supersonic speed results in a shock wave being produced. They can
transmit the shock wave at speeds of about 2,000 to 9,000 m/sec and is not dependent on the surrounding
pressure. This is another difference between detonation and deflagration: deflagration rates increase as the
pressure becomes greater.

Fire
Extinguishing Agents for Oxidizer Fires Extinguishing
fires involving an oxidizer is difficult. A carbon
dioxide extinguisher is not an effective choice for an
oxidizer-fed fire because it works on the principle of
excluding atmospheric oxygen, and atmospheric
oxygen is not required for an oxidizer-fed fire. Dry
chemical extinguishing agents will also be
ineffective for the most part. They act to interrupt
the chemical chain reaction, but will be overcome
by the oxidizer in all but the smallest fires.

NFPA and GHS
Class 1 Oxidizers:
• slightly increase the burning rate of combustible materials.
• do not cause spontaneous ignition when they come in contact with them.
Class 2 Oxidizers:
• increase the burning rate of combustible materials moderately with which they
come in contact.
• may cause spontaneous ignition when in contact with a combustible material.
Class 3 Oxidizers:
• severely increase the burning rate of combustible materials with which they come
in contact.
• will cause sustained and vigorous decomposition if contaminated with a
combustible material or if exposed to sufficient heat.
Class 4 Oxidizers:
• can explode when in contact with certain contaminants.
• can explode if exposed to slight heat, shock, or friction.
• will increase the burning rate of combustibles.
• can cause combustibles to ignite spontaneously.

Organic Peroxides can form
• Yes, some chemicals can form explosive peroxides when they are stored (e.g.,
isopropyl ether, vinylidene chloride). Exposure to light and heat can increase the
rate of peroxide formation. Others form peroxides that become hazardous when
concentrated (e.g., by distillation). Some examples include ethyl ether,
tetrahydrofuran (THF), p-dioxane, some secondary alcohols like 2-propanol and 2-
butanol, and some unsaturated hydrocarbons like propyne (an acetylene
compound), cyclohexene, and tetra-and deca-hydronaphthalenes.
• Another kind of peroxide-forming compound are unsaturated monomers that, in
the presence of a peroxide, can polymerize exothermically (i.e., produces heat
when it reacts). For example, uninhibited styrene can form a peroxide that can
cause the styrene to polymerize. It can occur explosively under certain conditions.
Other examples of some unsaturated monomeric compounds are acrylic acid,
acrylonitrile, butadiene, methyl methacrylate, and vinyl chloride.
• To generalize, the kinds of chemicals that can form peroxides include aldehydes,
ethers, and numerous unsaturated hydrocarbon compounds (i.e. hydrocarbon
compounds having double or triple bonds). Examples in this group include allyl
compounds, haloalkenes, dienes, monomeric vinyl compounds, vinylacetylenes,
unsaturated cyclic hydrocarbons like tetrahydronaphthalene or dicyclopentadiene.

NFPA 432 "Code for the Storage of
Organic Peroxide Formulations"
In general:
• Class I formulations are capable of deflagration but not
detonation.
• Class II formulations burn very rapidly and are a severe
reactivity hazard.
• Class III formulations burn rapidly and have a moderate
reactivity hazard.
• Class IV formulations burn in the same manner as ordinary
combustibles and have a minimal reactivity hazard.
• Class V formulations burn with less intensity than ordinary
combustibles or they do not support combustion and
present no reactivity hazard.

Waste• Oxidizing wastes are hazardous. Always handle them safely. Consider
oxidizing materials accidently mixed with an unknown or foreign material
as contaminated and do not use. Dispose of contaminated material
immediately.
• "Empty" drums, bottles, bags, sacks and other "oxidizing agent" containers
usually have hazardous oxidizing residues inside them. NEVER use these
containers for anything else, no matter how clean they seem. Treat them
as oxidizing wastes. The chemical supplier can give advice about how to
safely handle or decontaminate "empty" containers or other packaging
material.
• Store oxidizing wastes, including contaminated empty combustible
containers, in the same way as unused oxidizing materials. Only use
compatible containers for oxidizing wastes. Identify their contents with
suitable labels.
• NEVER dispose of oxidizers in ordinary garbage or down sinks or drains
that connect to sanitary or storm sewers. Dispose of them according to
the supplier's directions, or through hazardous waste collection and
disposal companies. In all cases, dispose of oxidizing wastes according to
the environmental laws that apply to your jurisdiction. Contact the
appropriate environmental officials for details.

Class 5 tdg do you mean

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