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6/21/2010
1
Orange ● House
Partnership
DAY 3
SESSION 8
Presentation 1
1
Orange ● House
Partnership
Session 8: Physical hazards
Part 1: explosive, flammable, self
reactive, organic peroxides
Steve Vaughan
2
Orange ● House
Partnership
Physical hazards: Classification
Roadmap • Part 1 covers bold-faced categories
Hazard class Hazard Category
Explosive Unstable explosive
Division 1.1
Division 1.2
Division 1.3
Division 1.4
Division 1.5
Division 1.6
Flammable gas 1 2
Flammable aerosol 1 2
Oxidising gas 1
Gases under pressure Compressed gas Liquefied gas Refrigerated liquefied gas Dissolved gas
1
Flammable liquid 1 2 3 4
Flammable solid 1 2
Self reactive substances Type A Type B Type C Type D Type E Type F Type G
Self heating 1 2
Emit flammable gas on contact with water
1 2
Oxidising liquids 1 2 3
Oxidising Solids 1 2 3
Organic peroxides Type A Type B Type C Type D Type E Type F Type G
Corrosive to metals 1
3
Orange ● House
Partnership
Session objectives
• Describe hazard classes for explosive,
flammable, self reactive, & organic peroxides
• Provide an overview of hazard classification
methods (detailed methods require complex
testing)
• Introduce relevant hazard symbols
• Provide pointers for practical classification
4
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Explosive hazard
• Explosive – solid or liquid substance or mixture
which reacts to detonate (produce gas at speed to damage
surroundings)
• Includes
– Pyrotechnic substances or mixtures (heat, light, gas, smoke
effects) non-detonative
– Articles (with some exceptions)
• Indicators
– Explosion is a ‘fast fire’ – chemically most explosives contain
combustible plus oxidiser
– Require initiation energy
• Classification is the transport classification (see UNRTDG)
• Explosive class includes substances and articles designed for
explosive (including pyrotechnic) effect
Hazard class Hazard Category
Explosive Unstable explosive
Division 1.1
Division 1.2
Division 1.3
Division 1.4
Division 1.5
Division 1.6
Flammable gas 1 2
Flammable aerosol 1 2
Oxidising gas 1
Gases under pressure Compressed gas Liquefied gas Refrigerated liquefied gas Dissolved gas
1
Flammable liquid 1 2 3 4
Flammable solid 1 2
Self reactive substances Type A Type B Type C Type D Type E Type F Type G
Self heating 1 2
Emit flammable gas on contact with water
1 2
Oxidising liquids 1 2 3
Oxidising Solids 1 2 3
Organic peroxides Type A Type B Type C Type D Type E Type F Type G
Corrosive to metals 1
2.1.1
5
Orange ● House
Partnership
Explosive: hazard
classes
• Division1.1: Mass explosion hazard
• Division 1.2: Projection hazard
• Division 1.3: Fire hazard plus minor blast or projection
hazard (or both)
• Division 1.4: No significant hazard outside package in
which contained
• Division 1.5: Mass explosion hazard – very insensitive
• Division 1.6: Extremely insensitive
Unstable explosives: those which test show are so sensitive
they may be initiated by transport
Hazard class Hazard Category
Explosive Unstable explosive
Division 1.1
Division 1.2
Division 1.3
Division 1.4
Division 1.5
Division 1.6
Flammable gas 1 2
Flammable aerosol 1 2
Oxidising gas 1
Gases under pressure Compressed gas Liquefied gas Refrigerated liquefied gas Dissolved gas
1
Flammable liquid 1 2 3 4
Flammable solid 1 2
Self reactive substances Type A Type B Type C Type D Type E Type F Type G
Self heating 1 2
Emit flammable gas on contact with water
1 2
Oxidising liquids 1 2 3
Oxidising Solids 1 2 3
Organic peroxides Type A Type B Type C Type D Type E Type F Type G
Corrosive to metals 1
2.1.2
6
6/21/2010
2
Orange ● House
Partnership
Explosive: classification
• Complex 3 step procedure
– Requires UNRTDG Tests and Criteria
• Steps
a) Determine if the substance or mixture has explosive effects
(Test series 1)
b) Carry out procedure for acceptance within classification
(Test series 2- 4)
c) Assignment to hazard division (Test series 5-7)
Notes:
• procedure is outside GHS
• Classification involves compatibility grouping designated by
letters (A, B, C, D, E, F, G, H, J, K, L, H, S)
• Special case of ammonium nitrate emulsion
Hazard class Hazard Category
Explosive Unstable explosive
Division 1.1
Division 1.2
Division 1.3
Division 1.4
Division 1.5
Division 1.6
Flammable gas 1 2
Flammable aerosol 1 2
Oxidising gas 1
Gases under pressure Compressed gas Liquefied gas Refrigerated liquefied gas Dissolved gas
1
Flammable liquid 1 2 3 4
Flammable solid 1 2
Self reactive substances Type A Type B Type C Type D Type E Type F Type G
Self heating 1 2
Emit flammable gas on contact with water
1 2
Oxidising liquids 1 2 3
Oxidising Solids 1 2 3
Organic peroxides Type A Type B Type C Type D Type E Type F Type G
Corrosive to metals 1
2.1.4
7
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Explosive: practical
classification
• Obtain proper shipping name & UN
number
• Determine classification from listing
(Chapter 3 UNRTDG)
• If testing is required employ a certified
specialist international laboratory
Hazard class Hazard Category
Explosive Unstable explosive
Division 1.1
Division 1.2
Division 1.3
Division 1.4
Division 1.5
Division 1.6
Flammable gas 1 2
Flammable aerosol 1 2
Oxidising gas 1
Gases under pressure Compressed gas Liquefied gas Refrigerated liquefied gas Dissolved gas
1
Flammable liquid 1 2 3 4
Flammable solid 1 2
Self reactive substances Type A Type B Type C Type D Type E Type F Type G
Self heating 1 2
Emit flammable gas on contact with water
1 2
Oxidising liquids 1 2 3
Oxidising Solids 1 2 3
Organic peroxides Type A Type B Type C Type D Type E Type F Type G
Corrosive to metals 1
8
Orange ● House
Partnership
Explosive: example
classifications
Name UNNumber
Classification
Lead azide wetted with not less than 20% water
0129 1.1A
Sounding devices (explosive) 0204 1.2F
Signals distress ship 0195 1.3G
Black powder (Gunpowder) granular 0027 1.1D
Rockets with inert head 0183 1.3C
Trinitrotoluene (TNT) dry or wetted with less than 30% water
0209 1.1D
Hazard class Hazard Category
Explosive Unstable explosive
Division 1.1
Division 1.2
Division 1.3
Division 1.4
Division 1.5
Division 1.6
Flammable gas 1 2
Flammable aerosol 1 2
Oxidising gas 1
Gases under pressure Compressed gas Liquefied gas Refrigerated liquefied gas Dissolved gas
1
Flammable liquid 1 2 3 4
Flammable solid 1 2
Self reactive substances Type A Type B Type C Type D Type E Type F Type G
Self heating 1 2
Emit flammable gas on contact with water
1 2
Oxidising liquids 1 2 3
Oxidising Solids 1 2 3
Organic peroxides Type A Type B Type C Type D Type E Type F Type G
Corrosive to metals 1
9
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Flammable gas
• Gas (including mixture) which has a flammable
range in air at 200C and 101.3kPa
Flammable range in air?
Gas or gas mixture
Ignite at 13% or less volume in air OR
Flammable range of at least 12%
Classify category 1
Classify category 2
Not classified
No
Yes
Yes
No
Hazard class Hazard Category
Explosive Unstable explosive
Division 1.1
Division 1.2
Division 1.3
Division 1.4
Division 1.5
Division 1.6
Flammable gas 1 2
Flammable aerosol 1 2
Oxidising gas 1
Gases under pressure Compressed gas Liquefied gas Refrigerated liquefied gas Dissolved gas
1
Flammable liquid 1 2 3 4
Flammable solid 1 2
Self reactive substances Type A Type B Type C Type D Type E Type F Type G
Self heating 1 2
Emit flammable gas on contact with water
1 2
Oxidising liquids 1 2 3
Oxidising Solids 1 2 3
Organic peroxides Type A Type B Type C Type D Type E Type F Type G
Corrosive to metals 1
2.2.22.2.4
10
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Flammable gas:
mixture
• Calculation: ISO 10156:1996
NB: use of equivalency factors between other inert gases and nitrogen
𝑽𝒊%
𝑻𝒄𝒊
𝒏
𝒊
≥ 𝟏
Vi% Equivalent flammable gas content
Tci Maximum concentration of the flammable gas in nitrogen at which the mixture is not flammable in air
i First component in mixture
n nth component in mixture
Hazard class Hazard Category
Explosive Unstable explosive
Division 1.1
Division 1.2
Division 1.3
Division 1.4
Division 1.5
Division 1.6
Flammable gas 1 2
Flammable aerosol 1 2
Oxidising gas 1
Gases under pressure Compressed gas Liquefied gas Refrigerated liquefied gas Dissolved gas
1
Flammable liquid 1 2 3 4
Flammable solid 1 2
Self reactive substances Type A Type B Type C Type D Type E Type F Type G
Self heating 1 2
Emit flammable gas on contact with water
1 2
Oxidising liquids 1 2 3
Oxidising Solids 1 2 3
Organic peroxides Type A Type B Type C Type D Type E Type F Type G
Corrosive to metals 1
2.2.5
11
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Flammable aerosol
• Coverage: Aerosol dispensers
– Non- refillable
– Compressed gas & liquid, paste, or powder
– Release device to eject gas, foam, paste or
powder
• Basis for classification: contains components which
are
– Flammable liquid
– Flammable gas
– Flammable solid
Flammable gas, liquid or solid classifications do not
apply
Hazard class Hazard Category
Explosive Unstable explosive
Division 1.1
Division 1.2
Division 1.3
Division 1.4
Division 1.5
Division 1.6
Flammable gas 1 2
Flammable aerosol 1 2
Oxidising gas 1
Gases under pressure Compressed gas Liquefied gas Refrigerated liquefied gas Dissolved gas
1
Flammable liquid 1 2 3 4
Flammable solid 1 2
Self reactive substances Type A Type B Type C Type D Type E Type F Type G
Self heating 1 2
Emit flammable gas on contact with water
1 2
Oxidising liquids 1 2 3
Oxidising Solids 1 2 3
Organic peroxides Type A Type B Type C Type D Type E Type F Type G
Corrosive to metals 1
2.3.1 & 2
12
6/21/2010
3
Orange ● House
Partnership
Flammable aerosol
• Classification basis
– Heat of combustion of contents
– Ignition distance test (spray type) - UNRTDG Tests & Criteria Section
31.4
– Foam test (foam type) – UNRTDG Tests & Criteria Section 31.6
• Summary classification logic
a) Check ≤ 1% flammable components and heat of combustion ≤ 20kJ/g if
so Do not classify
b) Check ≥ 85% flammable and heat of combustion ≥ 30kJ/g if so classify
category 1
c) If not, classify (category 1 or2) using
• ignition distance test results
(spray aerosol)
• foam test results(foam aerosols)
𝚫𝑯𝒄 𝒑𝒓𝒐𝒅𝒖𝒄𝒕 = [𝑾𝒊% × ∆𝑯𝒄 𝒊 ]
𝒏
𝒊
Hazard class Hazard Category
Explosive Unstable explosive
Division 1.1
Division 1.2
Division 1.3
Division 1.4
Division 1.5
Division 1.6
Flammable gas 1 2
Flammable aerosol 1 2
Oxidising gas 1
Gases under pressure Compressed gas Liquefied gas Refrigerated liquefied gas Dissolved gas
1
Flammable liquid 1 2 3 4
Flammable solid 1 2
Self reactive substances Type A Type B Type C Type D Type E Type F Type G
Self heating 1 2
Emit flammable gas on contact with water
1 2
Oxidising liquids 1 2 3
Oxidising Solids 1 2 3
Organic peroxides Type A Type B Type C Type D Type E Type F Type G
Corrosive to metals 1
2.3.4
13
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Flammable liquid
• Combustion always in the vapour above
the liquid
• Classifications based on flash point –
mixtures included
• Depends on the definition of liquid used for all of the
GHS
– Vapour pressure of ≤ 300 kPa at 500C and
– Not a gas at 200C and 101.3 kPa and
– Melting point of ≤ 200C and 101.3 kPa
– Includes viscous substances where fluidity criteria
of ADR are met
NB: GHS includes some flammable liquids excluded
from transport classification
Hazard class Hazard Category
Explosive Unstable explosive
Division 1.1
Division 1.2
Division 1.3
Division 1.4
Division 1.5
Division 1.6
Flammable gas 1 2
Flammable aerosol 1 2
Oxidising gas 1
Gases under pressure Compressed gas Liquefied gas Refrigerated liquefied gas Dissolved gas
1
Flammable liquid 1 2 3 4
Flammable solid 1 2
Self reactive substances Type A Type B Type C Type D Type E Type F Type G
Self heating 1 2
Emit flammable gas on contact with water
1 2
Oxidising liquids 1 2 3
Oxidising Solids 1 2 3
Organic peroxides Type A Type B Type C Type D Type E Type F Type G
Corrosive to metals 1
14
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Flammable liquid -
classification
Category Criteria
1 Flash point ≤ 230C and initial boiling point ≤ 350C
2 Flashpoint < 230C and initial boiling point > 350C
3 Flashpoint ≥ 230C and ≤ 600C
4 Flashpoint > 600C and ≤ 930C
See GHS section 2.6.4.2 for acceptable flash point tests- closed cup methods unless exceptional circumstances
Hazard class Hazard Category
Explosive Unstable explosive
Division 1.1
Division 1.2
Division 1.3
Division 1.4
Division 1.5
Division 1.6
Flammable gas 1 2
Flammable aerosol 1 2
Oxidising gas 1
Gases under pressure Compressed gas Liquefied gas Refrigerated liquefied gas Dissolved gas
1
Flammable liquid 1 2 3 4
Flammable solid 1 2
Self reactive substances Type A Type B Type C Type D Type E Type F Type G
Self heating 1 2
Emit flammable gas on contact with water
1 2
Oxidising liquids 1 2 3
Oxidising Solids 1 2 3
Organic peroxides Type A Type B Type C Type D Type E Type F Type G
Corrosive to metals 1
2.6.2 2.6.4
15
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Flammable liquid –
classification examples
Substance Flash point Initial boiling point
Classification
Diethyl ether -450C 34.60C Class 1
Methanol 120C 64.70C Class 3
Ethanol 12.80C 78.40C Class 3
Gasoline -400C 23.60C - 1900C Class 3
Diesel fuel 520C - 960C 1750C - 3450C Class 4 (most)
Jet A fuel 380C - 660C 1600C - 3000C Class 4
Hazard class Hazard Category
Explosive Unstable explosive
Division 1.1
Division 1.2
Division 1.3
Division 1.4
Division 1.5
Division 1.6
Flammable gas 1 2
Flammable aerosol 1 2
Oxidising gas 1
Gases under pressure Compressed gas Liquefied gas Refrigerated liquefied gas Dissolved gas
1
Flammable liquid 1 2 3 4
Flammable solid 1 2
Self reactive substances Type A Type B Type C Type D Type E Type F Type G
Self heating 1 2
Emit flammable gas on contact with water
1 2
Oxidising liquids 1 2 3
Oxidising Solids 1 2 3
Organic peroxides Type A Type B Type C Type D Type E Type F Type G
Corrosive to metals 1
16
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Flammable solid
• Solids (substance or mixture) which
– Are readily combustible OR
– May cause or contribute to fire through friction
Solid = not a liquid or a gas
Readily combustible: easily ignited by brief contact with an ignition
source followed by the flame spreading rapidly.
Cause or contribute to fire through friction – classification by
analogy (e.g. with matches)
NB: physical form is important
Hazard class Hazard Category
Explosive Unstable explosive
Division 1.1
Division 1.2
Division 1.3
Division 1.4
Division 1.5
Division 1.6
Flammable gas 1 2
Flammable aerosol 1 2
Oxidising gas 1
Gases under pressure Compressed gas Liquefied gas Refrigerated liquefied gas Dissolved gas
1
Flammable liquid 1 2 3 4
Flammable solid 1 2
Self reactive substances Type A Type B Type C Type D Type E Type F Type G
Self heating 1 2
Emit flammable gas on contact with water
1 2
Oxidising liquids 1 2 3
Oxidising Solids 1 2 3
Organic peroxides Type A Type B Type C Type D Type E Type F Type G
Corrosive to metals 1
2.7.1
17
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Flammable solid -
classification
• Methods are those of UNRTDG –
see section 33.2 Tests and Criteria for detail
Screening test also used (see Tests & Criteria section 33.2)
Hazard class Hazard Category
Explosive Unstable explosive
Division 1.1
Division 1.2
Division 1.3
Division 1.4
Division 1.5
Division 1.6
Flammable gas 1 2
Flammable aerosol 1 2
Oxidising gas 1
Gases under pressure Compressed gas Liquefied gas Refrigerated liquefied gas Dissolved gas
1
Flammable liquid 1 2 3 4
Flammable solid 1 2
Self reactive substances Type A Type B Type C Type D Type E Type F Type G
Self heating 1 2
Emit flammable gas on contact with water
1 2
Oxidising liquids 1 2 3
Oxidising Solids 1 2 3
Organic peroxides Type A Type B Type C Type D Type E Type F Type G
Corrosive to metals 1
Category Criteria
1 Burning rate for•Other than metal powders
•Burning time < 45s or burning rate > 2.2m/s AND•Wetted zone does not stop fire
•Metal powders: burn time ≤ 5min
2 Burning rate for•Other than metal powders
•Burning time < 45s or burning rate > 2.2m/s AND•Wetted zone stops fire for at least 4min
•Metal powders: burn time ≤ 10min
2.7.22.7.4
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Flammable solid –
examples
Substance Classification
Aluminium powder Class 1
Silicon powder Class 2
Sulphur Class 2
Matches (safety) Class 2
Hazard class Hazard Category
Explosive Unstable explosive
Division 1.1
Division 1.2
Division 1.3
Division 1.4
Division 1.5
Division 1.6
Flammable gas 1 2
Flammable aerosol 1 2
Oxidising gas 1
Gases under pressure Compressed gas Liquefied gas Refrigerated liquefied gas Dissolved gas
1
Flammable liquid 1 2 3 4
Flammable solid 1 2
Self reactive substances Type A Type B Type C Type D Type E Type F Type G
Self heating 1 2
Emit flammable gas on contact with water
1 2
Oxidising liquids 1 2 3
Oxidising Solids 1 2 3
Organic peroxides Type A Type B Type C Type D Type E Type F Type G
Corrosive to metals 1
19
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Organic peroxides
• Characteristics
– based on chemical structure {-O-O-}
– thermally unstable
– class includes substances and mixtures
• Hazardous effects (depending on type)
– explosive
– rapidly combustible (may be difficult to
extinguish)
– reactive with other substances => fire or
explosion
Hazard class Hazard Category
Explosive Unstable explosive
Division 1.1
Division 1.2
Division 1.3
Division 1.4
Division 1.5
Division 1.6
Flammable gas 1 2
Flammable aerosol 1 2
Oxidising gas 1
Gases under pressure Compressed gas Liquefied gas Refrigerated liquefied gas Dissolved gas
1
Flammable liquid 1 2 3 4
Flammable solid 1 2
Self reactive substances Type A Type B Type C Type D Type E Type F Type G
Self heating 1 2
Emit flammable gas on contact with water
1 2
Oxidising liquids 1 2 3
Oxidising Solids 1 2 3
Organic peroxides Type A Type B Type C Type D Type E Type F Type G
Corrosive to metals 1
2.15.1
20
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Organic peroxides –
classification (1)
{-O-O-} chemical structure means
substance or mixture is included
in the class unless:
• ≤ 1% available oxygen from
organic peroxides when
containing ≤ 1% hydrogen
peroxide OR
• ≤ 0.5% available oxygen
from organic peroxides when
containing between 1% and
7% hydrogen peroxide
𝑨𝒗𝒂𝒊𝒍𝒂𝒃𝒍𝒆 𝒐𝒙𝒚𝒈𝒆𝒏 𝒄𝒐𝒏𝒕𝒆𝒏𝒕 = 𝟏𝟔 × 𝒏𝒊×𝒄𝒊
𝒎𝒊 𝒏
𝒊
ni = number of peroxide groups per molecule of organic peroxide
ci = mass concentration (mass %) of organic peroxide
mi = molecular mass of organic peroxide i
Hazard class Hazard Category
Explosive Unstable explosive
Division 1.1
Division 1.2
Division 1.3
Division 1.4
Division 1.5
Division 1.6
Flammable gas 1 2
Flammable aerosol 1 2
Oxidising gas 1
Gases under pressure Compressed gas Liquefied gas Refrigerated liquefied gas Dissolved gas
1
Flammable liquid 1 2 3 4
Flammable solid 1 2
Self reactive substances Type A Type B Type C Type D Type E Type F Type G
Self heating 1 2
Emit flammable gas on contact with water
1 2
Oxidising liquids 1 2 3
Oxidising Solids 1 2 3
Organic peroxides Type A Type B Type C Type D Type E Type F Type G
Corrosive to metals 1
2.15.2
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Organic peroxides-
classification (2)
• Summary classification - seven categories
Category Description
Type A May detonate or deflagrate rapidly as packaged
Type B Explosive properties: as packaged does not detonate or deflagrate but may undergo thermal explosion
Type C Explosive properties: when packaged cannot detonate or deflagrate or undergo thermal explosion
Type D •Detonates partially, does not deflagrate & shows no violent effect when heated under confinement OR•Does not detonate, deflagrates slowly & shows no violent effect when heated OR• does not detonate or deflagrate and shows medium effect when heated under confinement
Hazard class Hazard Category
Explosive Unstable explosive
Division 1.1
Division 1.2
Division 1.3
Division 1.4
Division 1.5
Division 1.6
Flammable gas 1 2
Flammable aerosol 1 2
Oxidising gas 1
Gases under pressure Compressed gas Liquefied gas Refrigerated liquefied gas Dissolved gas
1
Flammable liquid 1 2 3 4
Flammable solid 1 2
Self reactive substances Type A Type B Type C Type D Type E Type F Type G
Self heating 1 2
Emit flammable gas on contact with water
1 2
Oxidising liquids 1 2 3
Oxidising Solids 1 2 3
Organic peroxides Type A Type B Type C Type D Type E Type F Type G
Corrosive to metals 1
2.15.22.15.4
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Organic peroxides-
classification (3)
• Summary classification continued
NB failure to meet any part of the type G criteria requires reassignment to
type F
Category Description
Type E In laboratory testing neither detonates nor deflagrates and shows low or no effectwhen heated under confinement
Type F In laboratory testing neither detonates in the cavitated state, shows no or low effect when heated under confinement and low or no explosive power
Type G In laboratory testing neither detonates nor deflagrates and shows no effect when heated under confinement nor any explosive power and is • thermally stable (self accelerating decomposition temperature (SADT) is ≥ 600C for 50kg package) and • for liquid mixtures a diluent with a boiling point of ≥ 1500C is used for desensitisation
Hazard class Hazard Category
Explosive Unstable explosive
Division 1.1
Division 1.2
Division 1.3
Division 1.4
Division 1.5
Division 1.6
Flammable gas 1 2
Flammable aerosol 1 2
Oxidising gas 1
Gases under pressure Compressed gas Liquefied gas Refrigerated liquefied gas Dissolved gas
1
Flammable liquid 1 2 3 4
Flammable solid 1 2
Self reactive substances Type A Type B Type C Type D Type E Type F Type G
Self heating 1 2
Emit flammable gas on contact with water
1 2
Oxidising liquids 1 2 3
Oxidising Solids 1 2 3
Organic peroxides Type A Type B Type C Type D Type E Type F Type G
Corrosive to metals 1
2.15.22.15.4
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Organic peroxides –
classification
method • Classification method is outside the GHS
• Complex test sequences as set out in
UNRTDG Tests and Criteria part II
• Requires specifically set up laboratory (e.g. Some tests require
testing of in excess of 50kg in intended package)
• Overall logic
– test if substance or mixture propagates detonation
– test if substance or mixture propagates deflagration
– determine behaviour as packaged & under confinement
NB: temperature sensitive organic peroxides (as measured by
SADT) require continuous temperature control
Hazard class Hazard Category
Explosive Unstable explosive
Division 1.1
Division 1.2
Division 1.3
Division 1.4
Division 1.5
Division 1.6
Flammable gas 1 2
Flammable aerosol 1 2
Oxidising gas 1
Gases under pressure Compressed gas Liquefied gas Refrigerated liquefied gas Dissolved gas
1
Flammable liquid 1 2 3 4
Flammable solid 1 2
Self reactive substances Type A Type B Type C Type D Type E Type F Type G
Self heating 1 2
Emit flammable gas on contact with water
1 2
Oxidising liquids 1 2 3
Oxidising Solids 1 2 3
Organic peroxides Type A Type B Type C Type D Type E Type F Type G
Corrosive to metals 1
2.15.4
24
6/21/2010
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Organic peroxides –
practical classification
• Obtain chemical name of organic peroxide and
information on diluents used (if any)
• Obtain generic UN number from section 2.5.3.2.4
UNRTDG
• Use generic number to determine classification
• If testing is required, employ a certified specialist
international laboratory
NB: list includes only substances
permitted for transport
Hazard class Hazard Category
Explosive Unstable explosive
Division 1.1
Division 1.2
Division 1.3
Division 1.4
Division 1.5
Division 1.6
Flammable gas 1 2
Flammable aerosol 1 2
Oxidising gas 1
Gases under pressure Compressed gas Liquefied gas Refrigerated liquefied gas Dissolved gas
1
Flammable liquid 1 2 3 4
Flammable solid 1 2
Self reactive substances Type A Type B Type C Type D Type E Type F Type G
Self heating 1 2
Emit flammable gas on contact with water
1 2
Oxidising liquids 1 2 3
Oxidising Solids 1 2 3
Organic peroxides Type A Type B Type C Type D Type E Type F Type G
Corrosive to metals 1
25
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Self reactive
substances
• Characteristics
– Substances or mixtures which are thermally unstable
– Undergo strong exothermic decomposition (oxygen (air)) not
required
• Does not include
– Substances classified as explosive
– Oxidising liquids or solids (unless a mixture containing ≥ 5% of a
combustible organic substance)
– Organic peroxides
• Chemically often organic azides or compounds derived from them
but other compounds and mixtures also possible
Hazard class Hazard Category
Explosive Unstable explosive
Division 1.1
Division 1.2
Division 1.3
Division 1.4
Division 1.5
Division 1.6
Flammable gas 1 2
Flammable aerosol 1 2
Oxidising gas 1
Gases under pressure Compressed gas Liquefied gas Refrigerated liquefied gas Dissolved gas
1
Flammable liquid 1 2 3 4
Flammable solid 1 2
Self reactive substances
Type A Type B Type C Type D Type E Type F Type G
Self heating 1 2
Emit flammable gas on contact with water
1 2
Oxidising liquids 1 2 3
Oxidising Solids 1 2 3
Organic peroxides Type A Type B Type C Type D Type E Type F Type G
Corrosive to metals 1
2.8.12.8.2
26
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Self reactive substances
– classification (1)
• Sensitivity & effect threshold
– Heat of decomposition < 300 J/g OR
– SADT > 750C (50kg package)
• Summary classification ...
Hazard class Hazard Category
Explosive Unstable explosive
Division 1.1
Division 1.2
Division 1.3
Division 1.4
Division 1.5
Division 1.6
Flammable gas 1 2
Flammable aerosol 1 2
Oxidising gas 1
Gases under pressure Compressed gas Liquefied gas Refrigerated liquefied gas Dissolved gas
1
Flammable liquid 1 2 3 4
Flammable solid 1 2
Self reactive substances
Type A Type B Type C Type D Type E Type F Type G
Self heating 1 2
Emit flammable gas on contact with water
1 2
Oxidising liquids 1 2 3
Oxidising Solids 1 2 3
Organic peroxides Type A Type B Type C Type D Type E Type F Type G
Corrosive to metals 1
Category Description
Type A May detonate or deflagrate rapidly as packaged
Type B Explosive properties: as packaged does not detonate or deflagrate but may undergo thermal explosion
Type C Explosive properties: when packaged cannot detonate or deflagrate or undergo thermal explosion
2.8.22.8.4
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Self reactive substances –
classification (2)
• Summary classification continued
Hazard class Hazard Category
Explosive Unstable explosive
Division 1.1
Division 1.2
Division 1.3
Division 1.4
Division 1.5
Division 1.6
Flammable gas 1 2
Flammable aerosol 1 2
Oxidising gas 1
Gases under pressure Compressed gas Liquefied gas Refrigerated liquefied gas Dissolved gas
1
Flammable liquid 1 2 3 4
Flammable solid 1 2
Self reactive substances
Type A Type B Type C Type D Type E Type F Type G
Self heating 1 2
Emit flammable gas on contact with water
1 2
Oxidising liquids 1 2 3
Oxidising Solids 1 2 3
Organic peroxides Type A Type B Type C Type D Type E Type F Type G
Corrosive to metals 1
Category Description
Type D •Detonates partially, does not deflagrate & shows no violent effect when heated under confinement OR•Does not detonate, deflagrates slowly & shows no violent effect when heated OR• does not detonate or deflagrate and shows medium effect when heated under confinement
Type E In laboratory testing neither detonates nor deflagrates and shows low or no effect when heated under confinement
Type F In Laboratory testing neither detonates in the cavitated state, shows no or low effect when heated under confinement and low or no explosive power
Type G In laboratory testing neither detonates nor deflagrates and shows no effect when heated under confinement nor any explosive power and is • thermally stable (self accelerating decomposition temperature (SADT) is ≥ 600C for 50kg package) and • for liquid mixtures a diluent with a boiling point of ≥ 1500C is used for desensitisation
2.8.22.8.4
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Self reactive substances
– classification method
• Classification method is outside the GHS
• Complex test sequences as set out in
UNRTDG Tests and Criteria part II
• Requires specifically set up laboratory (e.g. Some tests require
testing of in excess of 50kg in intended package)
• Overall logic
– test if substance or mixture propagates detonation
– test if substance or mixture propagates deflagration
– determine behaviour as packaged & under confinement
NB: temperature sensitive self reactive substances (as measured
by SADT) require continuous temperature control
Hazard class Hazard Category
Explosive Unstable explosive
Division 1.1
Division 1.2
Division 1.3
Division 1.4
Division 1.5
Division 1.6
Flammable gas 1 2
Flammable aerosol 1 2
Oxidising gas 1
Gases under pressure Compressed gas Liquefied gas Refrigerated liquefied gas Dissolved gas
1
Flammable liquid 1 2 3 4
Flammable solid 1 2
Self reactive substances
Type A Type B Type C Type D Type E Type F Type G
Self heating 1 2
Emit flammable gas on contact with water
1 2
Oxidising liquids 1 2 3
Oxidising Solids 1 2 3
Organic peroxides Type A Type B Type C Type D Type E Type F Type G
Corrosive to metals 1
2.8.4
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Self reactive substances
– practical classification
• Obtain chemical name of substance or
components of mixture and information on
diluents used (if any)
• Obtain generic UN number from section 2.4.3.2.3
UNRTDG
• Use generic number to determine classification
• If testing is required, employ a certified specialist
international laboratory
NB: list includes only substances
permitted for transport
Hazard class Hazard Category
Explosive Unstable explosive
Division 1.1
Division 1.2
Division 1.3
Division 1.4
Division 1.5
Division 1.6
Flammable gas 1 2
Flammable aerosol 1 2
Oxidising gas 1
Gases under pressure Compressed gas Liquefied gas Refrigerated liquefied gas Dissolved gas
1
Flammable liquid 1 2 3 4
Flammable solid 1 2
Self reactive substances
Type A Type B Type C Type D Type E Type F Type G
Self heating 1 2
Emit flammable gas on contact with water
1 2
Oxidising liquids 1 2 3
Oxidising Solids 1 2 3
Organic peroxides Type A Type B Type C Type D Type E Type F Type G
Corrosive to metals 1
30
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DAY 3
SESSION 8
Presentation 2
1
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Physical Hazards Part 2
Dr. Helmut Fleig, Germany
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Contents
2. 9 Pyrophoric liquids
2.10 Pyrophoric solids
2.11 Self-heating substances and mixtures
2.12 S&M which, in contact with water, emit
flammable gases
2. 4 Oxidising gases
2.13 Oxidising liquids
2.14 Oxidising solids
2.16 Corrosive to metals
2. 5 Gases under pressure
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2.9 Pyrophoric Liquids
Definition:
A liquid which, even in small quantities, is liable
to ignite within five minutes after coming into
contact with air.
Criteria:
Category Criteria
1 The liquid ignites within 5 min when added to an
inert carrier and exposed to air, or it ignites or chars
a filter paper on contact with air within 5 min.
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Label Elements
Category 1 UN TDG
Pictogram Flame
Signal word Danger
Hazard
statement
H 250: Catches fire spontaneously if exposed to air
Precaution-
ary statement
P222=Do not allow contact with air (Prevention)
P370+P378=In case of fire: Use… *for extinction (Response)
P422=Store contents under…* (Storage)
* To be specified by Manufacturer or Competent Authority
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Examples
Category Chemical
1 Pentaborane (CAS 19624-22-7: UN 1380)
1 Aluminiumalkyls (UN 3394; Organometallic substance,
liquid)
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2.10 Pyrophoric Solids
Definition:
A solid which, even in small quantities, is liable to ignite within five
minutes after coming into contact with air.
Criteria:
Note: For classification tests on solid substances or mixtures, the tests should be
performed on the substance or mixture as presented. If for example, for the purposes
of supply or transport, the same chemical is to be presented in a physical form
different from that which was tested and which is considered likely to materially alter
its performance in a classification test, the substance or mixture must also be tested
in the new form.
Category Criteria
1 The solid ignites within 5 min of coming into contact with air.
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Guidance
Screening: Use of experience from manufacturing/handling
about non-ignition at air/stability at room temperature for
prolonged periods of time (days).
Tests to be performed with chemical as marketed
Importance of particle size:
The finer greater area exposed influence on ability for
spontaneous ignition
Labelling: The labelling rules are the same
as for Pyrophoric liquids
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ExamplesCategory Substance
1 Phosphorous, white or yellow, dry or underwater or in sdolution
( CAS 7723-14-0; UN 1381)
1 Iron powder (UN 1383; Pyrophoric metal, N.O.S.=Not otherwise stated)
1 Magnesium powder (pyrophoric)
(EU Index-No 012-001-00-3; 7439-95-4CAS ; UN-)
Remark: Mg or Mg alloys > 50% Mg in pellets, turnings or ribbonsFlammable
solid Cat 1 (UN 1869)
1 Sodium sulphide, anhydrous or with<30% water of crystallisation
(CAS 1313-82-2; UN 1185)
1 Wool waste, wet (UN 1387)
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2.11 Self-heating Substances and Mixtures
Definition
Liquid or solid chemical which by reaction with air and without
energy supply, is liable to self-heat
- No inclusion of pyrophoric chemicals
- Ignition only when in large amounts (kilograms) and after long
periods of time (hours or days).
Criteria: Self ignition or temperature increase of > 60°C in 24 h
No classification
At all
Temperature of
spontaneous combustion
>50°C
Volume 27 m3
No classification in Cat 1 Temperature of
spontaneous combustion
>50°C
Volume 450 litres
Exemptions
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2.11 Self-heating Substances and Mixtures
Remarks:
- Reaction of the substance or mixture with oxygen (in the
air) and the heat developed not being conducted away
rapidly enough
- Rate of heat production exceeds the rate of heat loss
and the auto-ignition temperature is reached
- Liquids normally not self-heating due to unsufficient
surface for reaction with air
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Apparatus for Testing selfheating
Substances
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Criteria
Cate-
gory
Criteria
1 A positive result is obtained in a test using a 25 mm sample cube at 140 °C
2 (a) A positive result is obtained in a test using a 100 mm sample cube at 140 °C and
a negative result is obtained in a test using a 25 mm cube sample at 140 °C and
the substance or mixture is to be packed in packages with a volume of more than
3 m3; or
(b) A positive result is obtained in a test using a 100 mm sample cube at 140 °C and
a negative result is obtained in a test using a 25 mm cube sample at 140 °C, a
positive result is obtained in a test using a 100 mm cube sample at 120 °C and
the substance or mixture is to be packed in packages with a volume of more than
450 litres; or
(c) A positive result is obtained in a test using a 100 mm sample cube at 140 °C and
a negative result is obtained in a test using a 25 mm cube sample at 140 °C and a
positive result is obtained in a test using a 100 mm cube sample at 100 °C.
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Label Elements
Category 1 Category 2
Pictogram Flame Flame
Signal word Danger Warning
Hazard
statement
H 251: Self-heating; may catch fire H 252: Self-heating in
large quantities;
may catch fire
Precautionary
statement
(excerpt)
P235+P410=Keep cool. Protect from
sunlight (Prevention)
P407=Maintain gap between
stacks/pallets (Storage)
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ExamplesCategory Chemical UN TDG
1 Metal powder, self-heating N.O.S. (UN
3189)
Class 4.2
Packing Group II
1 Sodium hydrosulphide with < 25 % of water
of crystallisation (UN 2318)
Class 4.2
Packing Group II
2 Alkaline Earth Metal, alkoholates, N.O.S.
(UN 3205)
Class 4.2
Packing group III
2 Titaniumdisulphide (CAS 12039-13-3; UN
3174)
Class 4.2
Packing group III
2 Charcoal(UN1361) Class 4.2
Packing group III
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2.12 SUBSTANCES AND MIXTURES WHICH, IN CONTACT WITH WATER,
EMIT FLAMMABLE GASES
Definition
Chemicals
- Emitting in contact with water flammable gases
- Becoming spontaneously flammable by
interaction with water or
- Giving off flammable gases in dangerous
quantities
Remark: Reaction also with water vapour and air
humidity under normal ambient conditions
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CriteriaCategory Criteria
1 Any substance or mixture which reacts vigorously with water at
ambient temperatures and demonstrates generally a tendency for the
gas produced to ignite spontaneously, or which reacts readily with
water at ambient temperatures such that the rate of evolution of
flammable gas is equal to or greater than 10 litres per kilogram of
substance over any one minute.
2 Any substance or mixture which reacts readily with water at ambient
temperatures such that the maximum rate of evolution of flammable
gas is equal to or greater than 20 litres per kilogram of substance
per hour, and which does not meet the criteria for Category 1.
3 Any substance or mixture which reacts slowly with water at ambient
temperatures such that the maximum rate of evolution of flammable
gas is equal to or greater than 1 litre per kilogram of substance per
hour, and which does not meet the criteria for Categories 1 and 2.
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Issues
Tests to be performed in physical form as
marketed/transported
- UN N.5 test with demineralised water.
(Remark: Revision in progress)
Relevant parameters/Influencing factors:
- Chemical structure
- Physical state/form (e.g. particle size)
- Water solubility
- Friability
Other hazardous properties: e.g. pyrophoric , toxicity
Practical experience for screening
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Label ElementsElement Category 1 Category 2 Category 3
Pictogram Flame Flame Flame
Signal
word
Danger Danger Warning
Hazard
statement
H 260: In contact with
water releases flammable
gases which may ignite
spontaneously
H 261: In contact with
water releases
flammable gases
H 261: In contact
with water
releases
flammable gases
Precaution-
ary
statement
P231+P232=Handle
under inert gas.Protect
from moisture
(Prevention)
P370+P334=In case of
fire: Use…*for
distinction.
*If water increases risk,
to be specified
(Response)
P
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Examples
Categ
ory
Substance Gas emitted Remark
1 Potassium (CAS ; UN 2257) H2
1 Lithiumaluminiumhydride (CAS
16853;UN 1410)
H2
2 Aluminiumcarbide (CAS1299-86-
1; UN 1394)
Acetylene
3 Calciumcyanamide (CAS ; UN
1403)
Cyanamide
3 Aluminiumsilicon (CAS; UN SiH4
? Aluminiumphoshide (CAS ; UN
1397)
PH3 Entry in Orange Book:
Class 4.3 (= GHS 2.12)
and Class 6.1
(=GHS 3.1; Acute
Toxicity)
Packing Group: 1
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2.4 Oxidising Gases
Category Criteria
1
Any gas which may, generally by providing oxygen,
cause or contribute to the combustion of other
material more than air does
Definition:Any gas which may, generally by providing oxygen, cause or contribute to
the combustion of other material more than air does. (GHS 2.4.1)
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Classification Screening:
Organic substance having no oxygen, chlorine and fluorine, or if it
has these elements, but they are chemically NOT bound only to C or
H.
Inorganic substances do not need to be considered if they do
not contain any oxygen or halogen atoms.
Test and Calculation Method:
ISO Standard 10156-2:2005 “Gas cylinders – Gases and gas mixtures –
Part 2: Determination of oxidizing ability of toxic and corrosive gases and
gas mixtures” (Revised)
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Calculation Method for Oxidising
Power (Option Purple Book Rev.3)
n
i
i CiV %
Where:
Vi% = the volume percentage of a gas
Ci = the coefficient of oxygen equivalency
i = the first gas in the mixture
n = the nth gas in the mixture
NOTE: Balance gas is not taken into consideration.
Criterion:
n
i
ii CV % > 21
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Example
Composition: 9%(O2) + 16%(N2O) + 75%(N2)
Calculation
1. Ascertain the coefficient of oxygen equivalency (Ci) for the oxidizing
gases in the mixture
Ci (N2O)=0.6 (nitrous oxide)
Ci (O)=1 (oxygen)
2. Calculation:
9%(O2) + 16%(N2O) + 75%(N2) = (9 × 1) + (16 × 0.6)
18.6 < 21
Therefore the mixture is considered less oxidizing than air.
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Calculation Method Option 2
( ISO Standard 10156-2:2005 Rev)
Ci is specific to each oxidising gas.
By definition the Ci of oxygen is 1.0.
xi is the molar fraction in mol% of the i:th oxidising gas in the mixture
Ci is the coefficient of oxygen equivalency of the i:th oxidising gas in the mixture
Kk is the coefficient of equivalency of the inert gas k compared to nitrogen
Bk is the molar fraction in mole % of the k:th inert gas in the mixture
n is the total number of oxidising gases in the mixture
p is the total number of inert gases in the mixture
n
i
p
k
kki
n
i
ii
BKx
Cx
OP
1 1
1
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Calculation Method for Oxidising Power
(Option 2)
A gas mixture considered to be more oxidising than air if the following
condition is fulfilled:
Oxidising power = OP ≥ 0.235 (23.5 mol%)
NOTE: Dry air contains under normal conditions approximately 21
mol% of oxygen.
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Coefficients of Oxygen Equivalency
(Ci) of Toxic and Corrosive GasesGas Ci
Bromine trifluoride 40
Chlorine 0.7
Chlorine pentafluoride 40
Fluorine 40
Iodine pentafluoride 40
Nitric oxide (NO) 0.3
Gas Ci
Nitrous oxide (N2O) 0.6
Nitrogen dioxide 1
Nitrogen trifluoride 1.6
Nitrogen trioxide 40
Oxygen difluoride 40
Ozone 40
Remark: For non-tested oxidising gases, the Ci values
are fixed conservatively to be 40. (M.Molarne)
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Example using the calculation method of ISO
10156 (Option 2)
Example Mixture: 9 % (O2) + 16 % (N2O) + 75 % (N2) (ECHA )
Step 1: Ascertain the coefficient of oxygen equivalency (Ci) for the
oxidising gases in the mixture and the nitrogen equivalency factors
(Kk) for the non-flammable, non-oxidising gases.
Ci (N2O) = 0.6 (nitrous oxide)
Ci (O) = 1 (oxygen)
Kk (N2) = 1 (nitrogen)
Step 2: Calculate if the Oxidising Power (OP) of the gas mixture
OP=0.09x1 + 0.16x0.6/ 0.09 + 0.16 + 0.75x1=0.186
Classification: Not classified, since 18.6 %< 23.5%
Important note: Use always most recent version of ISO
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Label Elements
Table :
Classification Category 1
GHS Pictogram Flame over circle
Signal word Danger
Hazard statement H270: May cause or intensify fire; oxidiser
Precautionary Statement PreventionP220=Keep /Store away from combustible materials
P244=Keep reduction valves free from grease and oils
Precautionary Statement Response P370 + P376=In case of fire: Stop leak if safe to do so
Precautionary Statement Storage P403:Store in well ventilated place
Precautionary Statement Disposal None proposed
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2.13 Oxidising Liquids
Definition:
A liquid which, while in itself not necessarily com-
bustible, may, generally by yielding oxygen, cause,
or contribute to, the combustion of other material.
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Criteria
Category Criteria
1 Any substance or mixture which, in the 1:1 mixture, by mass, of substance (or
mixture) and cellulose tested, spontaneously ignites; or the mean pressure rise time
of a 1:1 mixture, by mass, of substance and cellulose is less than that of a 1:1 mixture,
by mass, of 50% perchloric acid and cellulose;
2 Any substance or mixture which, in the 1:1 mixture, by mass, of substance (or
mixture) and cellulose tested, exhibits a mean pressure rise time less than or equal to
the mean pressure rise time of a 1:1 mixture, by mass, of 40% aqueous sodium
chlorate solution and cellulose; and the criteria for Category 1 are not met;
3 Any substance or mixture which, in the 1:1 mixture, by mass, of substance (or
mixture) and cellulose tested, exhibits a mean pressure rise time less than or equal to
the mean pressure rise time of a 1:1 mixture, by mass, of 65% aqueous nitric acid and
cellulose; and the criteria for Categories 1 and 2 are not met.
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Distinction between potentially oxidising
and non-oxidising Chemicals
Inorganic substances or mixtures if:
- No content of oxygen or halogen
Organic substances or mixtures if:
- No content of oxygen, fluorine or chlorine or
- Oxygen, fluorine or chlorine only bound to C or H
Inert materials
- Cannot contribute to the oxidising capability
- Addition cannot result in a more severe category
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Label Elements
Category 1 Category 2 Category 3
Pictogram Flame over circle Flame over circle Flame over circle
Signal word Danger Danger Warning
Hazard statement H 271: May cause fire
or explosion; strong
oxidizer
H 272: May intensify
fire; oxidizer
H 272: May intensify
fire; oxidizer
Precautionary
statement
(excerpt)
P210=Keep away from
heat
P501=Dispose of
contents/container to..
…in accordance
with…regulations
P370+378=In case of
fire: use …for
extinction
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Examples
Category Chemical
1 Iodinepentafluoride (CAS 7783-66-6; UN 2495 )
1 Perchloric acid, > 50%and <=72% (CAS 7601-90-3; UN 1873)
2 H2O2, aqu. solution with not < 20% but <60%
(stabilised as necessary; CAS 7722-84-1; UN2014)
3 H2O2, aqu. solution with not < 8% but <20%
(stabilised as necessary; CAS 7722-84-1; UN 2984 )
Not classified Silver nitrate, satur. Aqueous solution
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2.14 Oxidising Solids
Definition
Asolid which, while in itself is not necessarily
combustible, may, generally by yielding oxygen,
cause, or contribute to, the combustion of
material.
Also called ”Fire or combustion enhancing ”
Labelling: Identical to 2.13
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CriteriaCategory Criteria
1 Any substance or mixture which, in the 4:1 or 1:1 sample-to-cellulose ratio
(by mass) tested, exhibits a mean burning time less than the mean burning
time of a 3:2 mixture, by mass, of potassium bromate and cellulose.
2 Any substance or mixture which, in the 4:1 or 1:1 sample-to-cellulose ratio
(by mass) tested, exhibits a mean burning time equal to or less than the mean
burning time of a 2:3 mixture (by mass) of potassium bromate and cellulose
and the criteria for Category 1 are not met.
3 Any substance or mixture which, in the 4:1 or 1:1 sample-to-cellulose ratio
(by mass) tested, exhibits a mean burning time equal to or less than the mean
burning time of a 3:7 mixture (by mass) of potassium bromate and cellulose
and the criteria for Categories 1 and 2 are not met.
NOTE 1: Some oxidizing solids may also present explosion hazards under certain conditions (e.g. when stored in large quantities). For example, some types of ammonium nitrate may give rise to an explosion hazard under extreme conditions…. Appropriate comments should be made in the Safety Data Sheet.
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Important Issues
Physical form
Particle size: the smaller the higher the capacity
Other hazards besides combustion hazard
Dilution: no linear decrease
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Examples
Category Substance
1 Ko2 =Potassium superoxide (CAS 12030-88-5; UN 2466)
2 AgNo3=Silver nitrate (CAS 7761-88-8; UN1493)
3 MnNO3=Manganese nitrate ( CAS 10377-66-9; UN 2724)
Not classified Calcium nitrate, tetrahydrate
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2.16 Corrosive to Metals
Category Criteria
1 Corrosion rate on either steel or aluminium surfaces exceeding 6.25
mm per year
at a test temperature of 55 °C when tested on both materials.
• Definition
A substance or a mixture which by chemical action
will materially damage, or even destroy, metals.
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Minimum Mass loss.
Equivalency to Criterion 6.25 mm/year
Exposure Time
[d]
Mass Loss
[%]
7 13.5
14 26.5
21 39.2
28 51.5
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Labelling Elements
Category 1
Pictogram Corrosion
Signal word Warning
Hazard statement H 290: May be corrosive to metals
Precautionary
statement
P234=Keep only in oiginal container (Prevention)
P390=Absorb spillage to prevent material damage
(Response)
P406= Store in corrosive resistant/…*container with resistant
inner liner
*To be specified (Storage)
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Examples
Category substance
1 Iodine (CAS No; UN 3495)
1 Hydrochloric acid (CAS 7647-01-0; UN 1789)
1 NaOH solid (CAS 1310-73-2; UN 1823)
1 NaOH, solution (CAS 1310-73-2; UN 1824)
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Examples of Metal Specimen
Plate located
in the liquid
Plate located
in the
interface
Plate located in the
vapour phase ECHA
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2.5 Gases under Pressure
Definitions:
Gas means a substance which:
(i) at 50 oC has a vapour pressure greater than 300 kPa (absolute); or
(ii) is completely gaseous at 20 oC at a standard pressure of 101,3
kPa;
Gases under pressure are gases which are contained in a
receptacle at a pressure of 200 kPa (gauge) or more, or which are
liquefied or liquefied and refrigerated.
The critical temperature is the temperature above which a pure gas
cannot be liquefied, regardless of the degree of compression (GHS
.
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Criteria
Group Criteria
Compressed gas A gas which when packaged under pressure is
entirely gaseous at -50 °C; including all gases
with a critical temperature -50 °C.
Liquefied gas A gas which when packaged under pressure, is
partially liquid at temperatures above -50 °C. A
distinction is made between:
(a) High pressure liquefied gas: a gas
with a critical temperature between -50°C
and +65°C; and
(b) Low pressure liquefied gas: a gas
with a critical temperature above +65°C.
Refrigerated liquefied gas A gas which when packaged is made partially
liquid because of its low temperature.
Dissolved gas A gas which when packaged under pressure is
dissolved in a liquid phase solvent.
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Label Elements
Compressed gas Liquefied gasRefrigerated
liquefied gasDissolved gas
Pictogram Gas cylinder Gas cylinder Gas cylinder Gas cylinder
Signal word Warning Warning Warning Warning
Hazard
statement
Contains gas under
pressure; may
explode if heated
Contains gas
under pressure;
may explode if
heated
Contains
refrigerated gas;
may cause
cryogenic burns or
injury
Contains gas
under pressure;
may explode if
heated
Precautionary
statement
P410+P403=Pro-
tect from
sunlight.Store in a
well-ventilated
place
P410+P403 P282=Wear cold
insulating
gloves/face
shield/eye
protection
P410+P403
Orange ● House
Partnership
ExamplesClassification Gas Critical temperature
Compressed gas Argon, compressed [UN
1006]
-122.3 °C
High pressure liquefied gas Xenon [UN 2036] 16.5°C
Low pressure liquefied gas Propane [UN 1978] 96.6°C
Refrigerated gas Ethylene, refrigerated liquid
[UN 1038]
9.5°C
Dissolved gas Acetylene, dissolved [UN
1001]
35.1°C
Orange ● House
Partnership
Application of PC-Properties
Health
- Extreme pH corrosivity
- Viscosity aspiration hazard
- SVC(=Saturated Vapour Pressure)
- - Risk Management Measures
- - Packing Group in Transport
Environment
- log Pow: bioaccumulation
6/21/2010
9
Orange ● House
Partnership
SourcesPurple Book (UN): GHS Third revised Edition 2009:
CLP Regulation (EC) No 1272/2008 on the Classification,
Labelling and Packaging of Substances and Mixtures; Criteria
(Annex I) and Harmonised List of classified Substances (Annex
VI)
Orange Book (UN): 16th rev. Edition 2009
Recommendations on the Transport of Dangerous Goods
(RTDG); Model Regulations; Criteria and Dangerous Goods
List (UN)
RTDG Manual of Tests and Criteria (UN): Test Methods and
Criteria 5th Edition (2009)
ECHA Guidance on the Application of the CLP Criteria (2009);
Module 3 on Labelling in preparation (2010);
http://echa.europa.euOrange ● House
Partnership
Open Issues. UN Working Groups
Revision of the format in chapter 9 of the
Safety Data Sheet
Chemically unstable gases
Water activated toxicity: (EU left-over:
EUH29=Contact with water liberates toxic
gas)
More Guidance