Classification and Labelling
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1 Classification and Labelling Physical Hazards Eugen Anwander, Institute for Environment & Food Safety State of Vorarlberg / Austria
2 Tour through the Topic physico-chemical hazards today (DSD 67/548/EEC) physical hazards tomorrow (CLP Regulation No. 1272/2008) classification with hazard classes of CLP labelling elements of CLP CLPs 16 physical hazard classes CLPs 6 supplemental physical hazard statements translation of physical hazards between DSD and CLP Page 2
3 Current Classification / Labelling Scheme Five physico-chemical hazards according to DSD 67/548/EEC Explosive Oxidising Exremely flammable Highly flammable Flammable Page 3
4 Current Classification / Labelling Scheme Ten R-phrases exist for physico-chemical hazards For the explosive hazard: R 2 Risk of explosion by shock, friction, fire or other sources of ignition R 3 Extreme risk of explosion by shock, friction, fire or other sources of ignition Page 4
5 Current Classification / Labelling Scheme For the oxidising hazard: R 7 May cause fire R 8 Contact with combustible material may cause fire R9Explosive when mixed with combustible material For the extremely flammable hazard: R 12 Extremely flammable Page 5
6 Current Classification / Labelling Scheme For the highly flammable hazard: R 11 Highly flammable R 15 Contact with water liberates extremely flammable gases R17Spontaneously flammable in air For the flammable hazard: R 10 Flammable Page 6
7 Current Classification / Labelling Scheme Other physico-chemical properties describing 11 hazards in addition to the classification (R-phrase): R 1 Explosive when dry R 4 Forms very sensitive explosive metallic compounds R 5 Heating may cause an explosion R 6 Explosive with or without contact with air R 7 May cause fire Page 7
8 Current Classification / Labelling Scheme R 14 Reacts violently with water R 16 Explosive when mixed with oxidising substances R 18 In use, may form flammable/explosive vapour-air mixture R 19 May form explosive peroxides R 30 Can become highly flammable in use R 44 Risk of explosion if heated under confinement Page 8
9 Future Classification / Labelling Scheme CLP Legal Basis in EU: REGULATION (EC) No 1272/2008 of 16 December 2008 on classification, labelling and packaging of substances and mixtures, amending and repealing Directives 67/548/EEC and 1999/45/EC and amending Regulation (EC) No 1907/ Page 9
10 Future Classification / Labelling Scheme CLP criteria for physical hazards from UN transport of dangerous goods (UN TDG Model Regulation) are applied in CLP testing methods from Orange Book (UN TDF Manual of Tests and Criteria), see testing of substances and mixtures (and explosive articles) testing in containers/packages testing dependent on amount in package testing in different physical states (gas, liquid) Page 10
11 Physical Hazards in CLP - Overview Annex I / Part 2 defines the classification criteria and the tests 16 physical hazard classes in CLP division of hazard classes in categories, types and devisions Annex I / Part 2 defines the labelling elements for each classification Page 11
12 Physical Hazard Classes in CLP - Overview Explosives - substances, mixtures, articles (Section 2.1) Flammable gases (Section 2.2) Flammable aerosols (Section 2.3) Oxidising gases (Section 2.4) Gases under pressure (Section 2.5) Flammable liquids (Section 2.6) Flammable solids (Section 2.7) Self-reactive substances and mixtures (Section 2.8) Page 12
13 Physical Hazard Classes in CLP - Overview Pyrophoric liquids (Section 2.9) Pyrophoric solids (Section 2.10) Self-heating substances and mixtures (Section 2.11) Substances / mixtures which in contact with water emit flammable gases (Section 2.12) Oxidising liquids (Section 2.13) Oxidising solids (Section 2.14) Organic peroxides (Section 2.15) Corrosive to metals (Section 2.16) Page 13
14 Design of each of the 16 Hazard Entries in Annex I / Part 2 definition of substances subject to the hazard class (properties) classification criteria (test methods) hazard communication - labelling elements additional classification considerations (e.g. exemptions) decision flow charts in case of more complex criteria Page 14
15 Labelling Elements for Physical Hazards Detailed definition of labelling elements for each physical hazard in Annex I / Part 2: pictogram (Annex I and V) signal word: DANGER or WARNING (Annex I) hazard statement (Annex I and III) precautionary statements (Annex I and IV) covering prevention / response / storage / disposal Page 15
16 Labelling Elements for Physical Hazards Hazard pictograms for physical hazards: exploding bomb (GHS01) flame (GHS02) flame over circle (GHS03) gas cylinder (GHS04) corrosion (GHS05) Page 16
17 Physical Hazards Classes in CLP 1 Explosives - substances, mixtures, articles (Section 2.1) - explosive substances, pyrotechnic articles, unstable explosive substances bt - complex classification criteria (decision trees) - seven devisions 1.1 to 1.6 and unstable explosive, abbreviated Unst. Expl., Expl. 1.1, Expl. 1.2,, Expl. 1.6 Unstable Devision i Devision i Devision i Devision i Devision i Devision i explosive none none Danger Danger Danger Danger Warning Danger none H200 H201 H202 H203 H204 H205 none Page 17
18 Physical Hazard Classes in CLP 2 Flammable gases (Section 2.2) 2) - gas showing a flammable range with air at 20 C and 101,3 kpa - testing according to ISO or EN 1839 standards - two categories: Flam. Gas 1, Flam. Gas 2 Category 1 Category 2 None Danger H220 Warning H221 Page 18
19 Physical Hazard Classes in CLP 3 Flammable aerosols (Section 2.3) - aerosol (definition according to legislation on aerosol dispensers): non-reusable container containing gas and fitted with a release device - testing of heat of combustion, foam aerosol tests, ignition distance test dependent on constituents of aerosol - two categories: Flam. Aerosol 1, Flam. Aerosol 2 Category 1 Category 2 Danger H222 Warning H223 Page 19
20 Physical Hazard Classes in CLP 4 Oxidising i gases (Section 2.4) - gas / gas mixture contributing to combustion of other material more than air - testing according to ISO only one category: Ox. Gas 1 Category 1 Danger H270 Page 20
21 Physical Hazard Classes in CLP 5 Gases under pressure (Section 2.5) - gas in receptacle under pressure (>200kPa), liquefied or liquefied-refrigerated dgas, dissolved d gas (.e.g. acetylene) - knowledge of physical state in package is required: vapour pressure, critical point (temperature, pressure), see UN TDG - four groups: compressed liquefied Press. Gas gas gas liquefied refrigerated gas Dissolved gas Warning Warning Warning Warning H280 H280 H281 H280 Page 21
22 Physical Hazard Classes in CLP 6 Flammable liquids id (Section 2.6) - liquids with flash point less equal 60 C - determination (testing, calculation) of flash point and boiling point - flash point test data closed cup according to European standards e.g. EN ISO three categories: Flam. Liq. 1, Flam. Liq. 2, Flam. Liq. 3 Category 1 Category 2 Category 3 Danger Danger Warning H224 H225 H226 Page 22
23 Physical Hazard Classes in CLP 7 Flammable solids (Section 2.7) - solids and metals (powdered, granular, pasty) being readily combustible - testing according to UN TDG: burn rate test (10 cm in 45 ) - two categories: Flam. Sol. 1, Flam. Sol. 2 Category 1 Category 2 Danger H228 Warning H228 Page 23
24 Physical Hazard Classes in CLP 8 Self-reactive substances and mixtures (Section 2.8) - thermally unstable solids/liquids showing strong exothermic decomposition (requiring temperature control) - complex classification excluding explosives and oxidising chemicals accordingtountdg - five categories: Self-react. A, Self-react. B, Self-react. CD, Self-react. EF, Self react. G Type A Type B Type C & D Type E & F Type G none Danger Danger Danger Warning none H240 H241 H242 H242 none Page 24
25 Physical Hazard Classes in CLP 9/10 Pyrophoric liquids id /solids (Sections and d210) 2.10) - chemical liable to ignite even in small quantities after 5 of contact t with air - testing according to UN TDG - one category each: Pyr Sol. 1, Pyr. Liq. 1 Category 1 Danger H250 Page 25
26 Physical Hazard Classes in CLP 11 Self-heating substances and mixtures (Section 2.11) - solid/liquid liable to self-heat in contact with air but not reaching the auto-ignition iti temperature t (showing no ignition) iti - volume dependent property, testing of different sized model cubes according to UN TDG - two categories: Self-heat. 1, Self-heat. 2 Category 1 Category 2 Danger H251 Warning H252 Page 26
27 Physical Hazard Classes in CLP 12 Substances / mixtures which h in contact t with water emit flammable gases (Section 2.12) - reaction of chemical with water emitting flammable gases and a potential to become spontaneously flammable (gas quantity, reaction temperature) - three categories: Water-react. 3, Water-react. 2, Water-react. 3 Category 1 Category 2 Category 3 Danger Danger Warning H260 H261 H261 Page 27
28 Physical Hazard Classes in CLP 13/14 Oxidising i liquids id /solids (Sections and d214) 2.14) - chemical (typically yielding oxygen) causing/contributing to combustion of other material - testing by comparison to standard oxidiser compounds according to UN TDG - Ox. Liq 1, 2 or 3 and Ox. Sol. 1, 2 or 3 Category 1 Category 2 Category 3 Danger Danger Warning H271 H272 H272 Page 28
29 Physical Hazard Classes in CLP 15 Organic peroxides (Section 2.15) - liquid/solid organic compound showing the O-O- structure or mixtures containing such compounds thus being thermally instable - classification dependent on the concentration of the O-Ostructure (and on a hydrogen peroxide content) - 5categories: Org. Perox. A, B, CD, EF and Org. Perox. G Type A Type B Type C & D Type E & F Type G none Danger Danger Danger Warning none H240 H241 H242 H242 none Page 29
30 Physical Hazard Classes in CLP 16 Corrosive to metals (Section 2.16) - materially damage to metals by chemical reaction - test with steel and aluminium alloy and a rate of >6,25 mm per year according to UN TDG - one category: Met. Corr. 1 Category 1 Warning H290 Page 30
31 Supplemental physical hazard statements Additional hazard statements for 6 physical hazards (Annex II): EUH001 Explosive when dry EUH006 Explosive with or without t contact t with air EUH014 Reacts violently with water EUH018 In use, may form flammable/explosive vapour-air mixture EUH019 May form explosive peroxides EUH044 Risk of explosion if heated under confinement (cf original 11 other physico-chemical chemical properties under DSD) Page 31
32 Translation of existing classifications into CLP Translating existing classifications under DSD 67/548/EEC into CLP hazard class / category and hazard statements (Annex VII) Examples: DSD physical CLP hazard class / CLP hazard state category statement E; R2 solid / liquid no direct tranlation possible O, R9 liquid Ox. Liq. 1 H271 F +, R12 liquid Flam. Liq. 1 H224 F; R17 solid Pyr. Sol. 1 H250 Page 32
33 Thank You for Your Attention Some basic concepts of presentation according to Schindler/Umweltbundesamt
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