Classification and Labelling
Ph i l Hazards
Physical
H
d
Eugen Anwander,
Institute for Environment & Food Safety
State of Vorarlberg / Austria
TAIEX Zagreb 29-30.10.2009
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
CLP 16 physical
h i l hazard
h
d classes
l
 CLPs 6 supplemental physical hazard statements
 translation of physical hazards between DSD and CLP
TAIEX Zagreb 29-30.10.2009
Page 2
Current Classification / Labelling Scheme
Five physico-chemical hazards according to DSD 67/548/EEC
 Explosive
 Oxidising
 Exremely flammable
 Highly flammable
 Flammable
TAIEX Zagreb 29-30.10.2009
Page 3
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
TAIEX Zagreb 29-30.10.2009
Page 4
Current Classification / Labelling Scheme
For the oxidising hazard:
 R 7 May cause fire
 R 8 Contact with combustible material may cause fire
 R 9 Explosive when mixed with combustible material
For the extremely flammable hazard:
 R 12 Extremely flammable
TAIEX Zagreb 29-30.10.2009
Page 5
Current Classification / Labelling Scheme
For the highly flammable hazard:
 R 11 Highly flammable
 R 15 Contact with water liberates extremely flammable gases
 R 17 Spontaneously flammable in air
For the flammable hazard:
 R 10 Flammable
TAIEX Zagreb 29-30.10.2009
Page 6
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
TAIEX Zagreb 29-30.10.2009
Page 7
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
TAIEX Zagreb 29-30.10.2009
Page 8
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
mixtures,
1999/45/EC and amending Regulation (EC) No 1907/2006
http://ec.europa.eu/enterprise/reach/ghs/index_en.htm
TAIEX Zagreb 29-30.10.2009
Page 9
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 http://www.unece.org
 testing of substances and mixtures (and explosive articles)
 testing in containers/packages
 testing dependent on amount in package
 testing in different physical states (gas
(gas, liquid)
TAIEX Zagreb 29-30.10.2009
Page 10
Physical Hazards in CLP - Overview
 Annex I / Part 2 defines the classification criteria and the tests
physical
y
hazard classes in CLP
 16 p
 division of hazard classes in categories, types and devisions
 Annex I / Part 2 defines the labelling elements for each
classification
TAIEX Zagreb 29-30.10.2009
Page 11
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
2.5)
5)
 Flammable liquids (Section 2.6)
 Flammable solids (Section 2.7)
 Self-reactive substances and mixtures (Section 2.8)
TAIEX Zagreb 29-30.10.2009
Page 12
Physical Hazard Classes in CLP - Overview
 Pyrophoric liquids (Section 2.9)
 Pyrophoric solids (Section 2.10)
 Self-heating
g 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
2.14)
14)
 Organic peroxides (Section 2.15)
 Corrosive
C
to metals (Section
(S
2.16))
TAIEX Zagreb 29-30.10.2009
Page 13
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
TAIEX Zagreb 29-30.10.2009
Page 14
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
TAIEX Zagreb 29-30.10.2009
Page 15
Labelling Elements for Physical Hazards
Hazard pictograms for physical hazards:
 exploding bomb (GHS01)
 flame (GHS02)
 flame over circle (GHS03)
 gas cylinder (GHS04)
 corrosion (GHS05)
TAIEX Zagreb 29-30.10.2009
Page 16
Physical Hazards Classes in CLP
1 Explosives
E l i
- substances,
b
mixtures,
i
articles
i l (S
(Section
i 2
2.1)
1)
- explosive substances, pyrotechnic articles, unstable explosive
substances
b t
- 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
U
bl
explosive
Devision
D
i i
1.1
Devision
D
i i
1.2
Devision
D
i i
1.3
Devision
D
i i
1.4
Devision
D
i i
1.5
Devision
D
i i
1.6
none
none
Danger
Danger
Danger
Danger
Warning
Danger
none
H200
H201
H202
H203
H204
H205
none
TAIEX Zagreb 29-30.10.2009
Page 17
Physical Hazard Classes in CLP
2 Flammable
Fl
bl gases (Section
(S ti 2
2.2)
2)
- gas showing a flammable range with air at 20 °C and 101,3 kPa
- testing according to ISO 10156 or EN 1839 standards
- two categories: Flam. Gas 1, Flam. Gas 2
Category 1
Category 2
None
TAIEX Zagreb 29-30.10.2009
Danger
Warning
H220
H221
Page 18
Physical Hazard Classes in CLP
3 Flammable
Fl
bl aerosols
l (Section
(S ti 2.3)
2 3)
- aerosol (definition according to legislation on aerosol
dispensers) non
dispensers):
non-reusable
re sable container containing gas and fitted
with a release device
- testing of heat of combustion,
combustion foam aerosol tests
tests, ignition
distance test dependent on constituents of aerosol
Flam. Aerosol 1,
1 Flam
Flam. Aerosol 2
- two categories: Flam
TAIEX Zagreb 29-30.10.2009
Category 1
Category 2
Danger
Warning
H222
H223
Page 19
Physical Hazard Classes in CLP
4 Oxidising
O idi i gases (S
(Section
ti 2
2.4)
4)
- gas / gas mixture contributing to combustion of other material
more than
th air
i
- testing according to ISO 10156
- only one category: Ox. Gas 1
Category 1
Danger
H270
TAIEX Zagreb 29-30.10.2009
Page 20
Physical Hazard Classes in CLP
5 Gases
G
under
d pressure (Section
(S i 2
2.5))
- gas in receptacle under pressure (>200kPa), liquefied or
li
liquefied-refrigerated
fi d f i
t d gas, dissolved
di
l d gas ((.e.g. acetylene)
t l
)
- knowledge of physical state in package is required: vapour
pressure critical point (temperature,
pressure,
(temperature pressure)
pressure), see UN TDG
- four groups:
”Press
Press. Gas”
Gas
TAIEX Zagreb 29-30.10.2009
compressed
gas
liquefied
gas
refrigerated
liq efied
liquefied
gas
Dissolved
gas
Warning
Warning
Warning
Warning
H280
H280
H281
H280
Page 21
Physical Hazard Classes in CLP
6 Flammable
Fl
bl liliquids
id (Section
(S ti 2
2.6)
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 1516
- three categories: Flam. Liq. 1, Flam. Liq. 2, Flam. Liq. 3
TAIEX Zagreb 29-30.10.2009
Category 1
Category 2
Category 3
Danger
Danger
Warning
H224
H225
H226
Page 22
Physical Hazard Classes in CLP
7 Flammable
Fl
bl solids
lid (S
(Section
ti 2
2.7)
7)
- solids and metals (powdered, granular, pasty) being readily
combustible
b tibl
- testing according to UN TDG: “burn rate test” (10 cm in 45”)
- two categories: Flam. Sol. 1, Flam. Sol. 2
TAIEX Zagreb 29-30.10.2009
Category 1
Category 2
Danger
Warning
H228
H228
Page 23
Physical Hazard Classes in CLP
8 Self-reactive
S lf
ti substances
b t
and
d mixtures
i t
(S
(Section
ti 2
2.8)
8)
- thermally unstable solids/liquids showing strong exothermic
decomposition (requiring temperature control)
- complex classification excluding explosives and oxidising
chemicals according to UN TDG
- five categories: Self-react. A, Self-react. B, Self-react. CD,
Self-react.
Self
react. EF, Self–react.
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
TAIEX Zagreb 29-30.10.2009
Page 24
Physical Hazard Classes in CLP
9/10 Pyrophoric
P
h i liliquids
id /solids
/ lid (Sections
(S ti
2 9 and
2.9
d2
2.10)
10)
- chemical liable to ignite even in small quantities after 5’ of
contact
t t with
ith air
i
- testing according to UN TDG
- one category each: Pyr Sol. 1, Pyr. Liq. 1
Category 1
Danger
H250
TAIEX Zagreb 29-30.10.2009
Page 25
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
th auto-ignition
the
t i iti ttemperature
t
(showing
( h i no iignition)
iti )
- volume dependent property, testing of different sized model
cubes according to UN TDG
- two categories: Self-heat. 1, Self-heat. 2
TAIEX Zagreb 29-30.10.2009
Category 1
Category 2
Danger
Warning
H251
H252
Page 26
Physical Hazard Classes in CLP
12 Substances
S b t
/ mixtures
i t
which
hi h iin contact
t t with
ith water
t emitit
flammable gases (Section 2.12)
- reaction of chemical with water emitting flammable gases and a
potential to become spontaneously flammable (gas quantity,
reaction temperature)
p
)
- three categories: Water-react. 3, Water-react. 2, Water-react. 3
TAIEX Zagreb 29-30.10.2009
Category 1
Category 2
Category 3
Danger
Danger
Warning
H260
H261
H261
Page 27
Physical Hazard Classes in CLP
13/14 Oxidising
O idi i liliquids
id //solids
lid (S
(Sections
ti
2
2.13
13 and
d2
2.14)
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
TAIEX Zagreb 29-30.10.2009
Category 1
Category 2
Category 3
Danger
Danger
Warning
H271
H272
H272
Page 28
Physical Hazard Classes in CLP
15 Organic
O
i peroxides
id (S
(Section
ti 2
2.15)
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)
- 5 categories: 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
TAIEX Zagreb 29-30.10.2009
Page 29
Physical Hazard Classes in CLP
16 Corrosive
C
i tto metals
t l (S
(Section
ti 2
2.16)
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
TAIEX Zagreb 29-30.10.2009
Page 30
Supplemental physical hazard statements
Additional hazard statements for 6 physical hazards (Annex II):
 EUH001 Explosive when dry
 EUH006 Explosive
E l i with
ith or without
ith t contact
t t with
ith air
i
 EUH014 Reacts violently with water
 EUH018 In use, may form flammable/explosive vapour-air mixture
y form explosive
p
p
peroxides
 EUH019 May
 EUH044 Risk of explosion if heated under confinement
(cf original 11 “other
other physico
physico-chemical
chemical properties
properties” under DSD)
TAIEX Zagreb 29-30.10.2009
Page 31
Translation of existing classifications into CLP
Translating existing classifications under DSD 67/548/EEC into
CLP hazard class / category and hazard statements (Annex VII)
p
Examples:
DSD
physical
state
E; R2
solid / liquid
O R9
O,
liquid
Ox Liq.
Ox.
Liq 1
H271
F+, R12
liquid
Flam. Liq. 1
H224
F; R17
solid
Pyr Sol.
Pyr.
Sol 1
H250
TAIEX Zagreb 29-30.10.2009
CLP hazard class /
category
CLP hazard
statement
no direct tranlation possible
Page 32
Thank You for Your Attention
Some basic concepts of presentation according to Schindler/Umweltbundesamt
TAIEX Zagreb 29-30.10.2009