Flammable aerosol 1 2 Flammable gas 1 2 explosive 1.1 1.2 ... · PDF fileOxidising Solids 1 2...

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DAY 3

SESSION 8

Presentation 1

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Session 8: Physical hazards

Part 1: explosive, flammable, self

reactive, organic peroxides

Steve Vaughan

[email protected]

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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

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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

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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



Division 1.1

Division 1.2

Division 1.3

Division 1.4

Division 1.5

Division 1.6

Flammable gas 1 2


Oxidising gas 1


1


Flammable solid 1 2


Self heating 1 2


1 2





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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



Division 1.1

Division 1.2

Division 1.3

Division 1.4

Division 1.5

Division 1.6

Flammable gas 1 2


Oxidising gas 1


1


Flammable solid 1 2


Self heating 1 2


1 2





2.1.2

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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



Division 1.1

Division 1.2

Division 1.3

Division 1.4

Division 1.5

Division 1.6

Flammable gas 1 2


Oxidising gas 1


1


Flammable solid 1 2


Self heating 1 2


1 2





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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



Division 1.1

Division 1.2

Division 1.3

Division 1.4

Division 1.5

Division 1.6

Flammable gas 1 2


Oxidising gas 1


1


Flammable solid 1 2


Self heating 1 2


1 2





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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



Division 1.1

Division 1.2

Division 1.3

Division 1.4

Division 1.5

Division 1.6

Flammable gas 1 2


Oxidising gas 1


1


Flammable solid 1 2


Self heating 1 2


1 2





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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



Division 1.1

Division 1.2

Division 1.3

Division 1.4

Division 1.5

Division 1.6

Flammable gas 1 2


Oxidising gas 1


1


Flammable solid 1 2


Self heating 1 2


1 2





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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



Division 1.1

Division 1.2

Division 1.3

Division 1.4

Division 1.5

Division 1.6

Flammable gas 1 2


Oxidising gas 1


1


Flammable solid 1 2


Self heating 1 2


1 2





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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



Division 1.1

Division 1.2

Division 1.3

Division 1.4

Division 1.5

Division 1.6

Flammable gas 1 2


Oxidising gas 1


1


Flammable solid 1 2


Self heating 1 2


1 2





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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



Division 1.1

Division 1.2

Division 1.3

Division 1.4

Division 1.5

Division 1.6

Flammable gas 1 2


Oxidising gas 1


1


Flammable solid 1 2


Self heating 1 2


1 2





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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



Division 1.1

Division 1.2

Division 1.3

Division 1.4

Division 1.5

Division 1.6

Flammable gas 1 2


Oxidising gas 1


1


Flammable solid 1 2


Self heating 1 2


1 2





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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



Division 1.1

Division 1.2

Division 1.3

Division 1.4

Division 1.5

Division 1.6

Flammable gas 1 2


Oxidising gas 1


1


Flammable solid 1 2


Self heating 1 2


1 2





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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



Division 1.1

Division 1.2

Division 1.3

Division 1.4

Division 1.5

Division 1.6

Flammable gas 1 2


Oxidising gas 1


1


Flammable solid 1 2


Self heating 1 2


1 2





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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



Division 1.1

Division 1.2

Division 1.3

Division 1.4

Division 1.5

Division 1.6

Flammable gas 1 2


Oxidising gas 1


1


Flammable solid 1 2


Self heating 1 2


1 2





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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)



Division 1.1

Division 1.2

Division 1.3

Division 1.4

Division 1.5

Division 1.6

Flammable gas 1 2


Oxidising gas 1


1


Flammable solid 1 2


Self heating 1 2


1 2





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

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Flammable solid –

examples

Substance Classification

Aluminium powder Class 1

Silicon powder Class 2

Sulphur Class 2

Matches (safety) Class 2



Division 1.1

Division 1.2

Division 1.3

Division 1.4

Division 1.5

Division 1.6

Flammable gas 1 2


Oxidising gas 1


1


Flammable solid 1 2


Self heating 1 2


1 2





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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



Division 1.1

Division 1.2

Division 1.3

Division 1.4

Division 1.5

Division 1.6

Flammable gas 1 2


Oxidising gas 1


1


Flammable solid 1 2


Self heating 1 2


1 2





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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



Division 1.1

Division 1.2

Division 1.3

Division 1.4

Division 1.5

Division 1.6

Flammable gas 1 2


Oxidising gas 1


1


Flammable solid 1 2


Self heating 1 2


1 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



Division 1.1

Division 1.2

Division 1.3

Division 1.4

Division 1.5

Division 1.6

Flammable gas 1 2


Oxidising gas 1


1


Flammable solid 1 2


Self heating 1 2


1 2





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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


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



Division 1.1

Division 1.2

Division 1.3

Division 1.4

Division 1.5

Division 1.6

Flammable gas 1 2


Oxidising gas 1


1


Flammable solid 1 2


Self heating 1 2


1 2





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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



Division 1.1

Division 1.2

Division 1.3

Division 1.4

Division 1.5

Division 1.6

Flammable gas 1 2


Oxidising gas 1


1


Flammable solid 1 2


Self heating 1 2


1 2





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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



Division 1.1

Division 1.2

Division 1.3

Division 1.4

Division 1.5

Division 1.6

Flammable gas 1 2


Oxidising gas 1


1


Flammable solid 1 2


Self heating 1 2


1 2





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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



Division 1.1

Division 1.2

Division 1.3

Division 1.4

Division 1.5

Division 1.6

Flammable gas 1 2


Oxidising gas 1


1


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


1 2





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– classification (1)

• Sensitivity & effect threshold

– Heat of decomposition < 300 J/g OR

– SADT > 750C (50kg package)

• Summary classification ...



Division 1.1

Division 1.2

Division 1.3

Division 1.4

Division 1.5

Division 1.6

Flammable gas 1 2


Oxidising gas 1


1


Flammable solid 1 2



Self heating 1 2


1 2






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

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Self reactive substances –

classification (2)

• Summary classification continued



Division 1.1

Division 1.2

Division 1.3

Division 1.4

Division 1.5

Division 1.6

Flammable gas 1 2


Oxidising gas 1


1


Flammable solid 1 2



Self heating 1 2


1 2






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

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– 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



Division 1.1

Division 1.2

Division 1.3

Division 1.4

Division 1.5

Division 1.6

Flammable gas 1 2


Oxidising gas 1


1


Flammable solid 1 2



Self heating 1 2


1 2





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– 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



Division 1.1

Division 1.2

Division 1.3

Division 1.4

Division 1.5

Division 1.6

Flammable gas 1 2


Oxidising gas 1


1


Flammable solid 1 2



Self heating 1 2


1 2





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DAY 3

SESSION 8

Presentation 2

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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)

http://upload.wikimedia.org/wikipedia/commons/6/6d/GHS-pictogram-flamme.svg

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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.

http://upload.wikimedia.org/wikipedia/commons/e/e5/GHS-pictogram-rondflam.svg

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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;


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;


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.


(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.


(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)

http://upload.wikimedia.org/wikipedia/commons/a/a1/GHS-pictogram-acid.svg

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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

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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

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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

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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);

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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)

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