Globally Harmonized System of

Classification and Labelling of Chemicals

(GHS)

Adi Sunariadi
Federasi Industri Kimia Indonesia (FIKI)
E-mail : Adi_Sunariadi@yahoo.com
Jakarta, 14 January 2013
 Contents
 Overview of GHS
 Physical Hazards
 Health Hazards
 Environmental Hazards
 Hazard Communication (SDS and Label)
 GHS Implementation in Indonesia
 GHS Implementation – Actions need to be taken by
Business Operators
Overview of GHS

Fourth Revised Edition 2011

 What is GHS ?
Globally Harmonized System of Classification and
Labelling of Chemicals  GHS
 Scope : Chemical substances and mixtures (products).
 Objective : Communication of hazard information by
Labelling and SDS.
 Specifies classification categories and criteria for hazards.
 Shows methods for labelling and SDS descriptions based
on the classification.
 Common worldwide systems (promotion of mutual
understanding and distribution of products).
 Covers all parties who handling chemicals, such as
business operators, workers, consumers, transportation
personnel, emergency responders etc.
 Basic Principles of Harmonization
 Not degrading health and environmental protection.
 Easy to understand.
 Applicable to ALL chemicals, basically focusing on
the hazards of chemical substances.

 Covering all chemical substances and mixtures.

- Pharmaceutical products, food additives, cosmetics and residual
pesticide in food are excluded because these are considered as
intentional consumption.

 Classifying substances using available data.

 Start from where the system can be introduced.
 Building block approach.
 GHS Classification
Basic concepts of GHS Classification and Labelling systems :
 Classification based on the hazard.
 Mixtures (products) are classified as mixtures.
 Does not require testing of toxicity
- Utilizing existing data and existing classification
(classification based on estimation).
 Not a system of registration / assessment / approval for
uniform classification results
- Communication tool for (self) management.
 Consideration is given to applicability to various fields and
promotion of international agreement.
 Containing multiple options and vague expressions.
 The same labelling elements are used.
 Labelling contents are not standardized.
Hazard and Risks

Hazard X Exposure = Risk

GHS Pictogram
 Transport Pictograms

4 4
5.1
 GHS vs Transport of Dangerous Goods
GHS Implementation

Transport Industrial
workplace

Agriculture

Consumer
products

UNRTDG or orange book GHS or purple book

Physical Hazards
 Physical Hazard Criteria
• Physical hazards are related to the physical and chemical
properties of the substance or mixture involved.
• The physical hazard criteria are based on the criteria of
the UN Recommendations for the Transport of
Dangerous Goods (UNRTDG “Orange Book”).
• They refer to the results of tests performed in
accordance with the UN Recommendations on the Transport
of Dangerous Goods, Manual of Tests and Criteria.
 Physical Hazard Criteria, cont.
• Since all substances or mixtures that are transported have
been classified under the UN Recommendations for
physical hazards, many suppliers will already have
considered the criteria definitions in the GHS as well.
• There are some differences - GHS sectors may cover
additional hazard categories (e.g., Category 4 of
Flammable Liquids).
• As a practical approach to classification, reviewing and
updating the existing transport classifications may help to
minimize the task of completing GHS classifications for
these hazard classes.
 Definition of materials state on GHS
（Gases, Liquid, solids)

1. Gas (i) A substance which is at 50 ℃ has a vapour pressure greater

than 300 kPa (absolute)
(ii) A substance which is completely gaseous at 20 ℃ at a
standard pressure of 101.3 kPa

2. Liquid A substance which does not meet the definition of gas,

and which has a melting point or initial melting point of 20 ℃ or
less at a standard pressure of 101.3 kPa.
A viscous substance or mixture for which a specific melting point
cannot be determined shall be subjected to the ASTM D 4359-90
test; or to the test for determining fluidity (penetrometer test)
prescribed in section 2.3.4 of Annex A of the European Agreement
concerning the International Carriage of Dangerous Goods by
Road (ADR)

3. Solid a substance or mixture which does not meet the definitions of

liquid or gas
 Physical Hazards
1. Explosives
2. Flammable gases
(including chemically
unstable gasses)
3. Aerosols (flammable and
non-flammable aerosols)
4. Oxidizing gases
5. Gases under pressure
6. Flammable liquids
7. Flammable solids
8. Self-reactive substances
and mixtures
9. Pyrophoric liquids
10. Pyrophoric solids
11. Self-heating substances and mixtures
12. Substances and mixtures which in contact
with water, emit flammable gases.
13. Oxidizing liquids
14. Oxidizing solids
15. Organic peroxides
16. Corrosive to metals
 Physical Hazards
Hazard Class Hazard Category
Unstable Div Div Div Div Div
Explosives Explosives Div 1.1
1.2 1.3 1.4 1.5 1.6
Flammable Gases (including
1 1A 1B 2 2A 2B
chemically unstable gases)
Aerosols 1 2 3
Oxidising Gases 1
Gases Under Pressure 1
Compressed Gases
Liquefied Gases
Refrigerated Liquefied
Gases
Dissolved Gases
Flammable Liquids 1 2 3 4
Flammable Solids 1 2
Type Type Type Type Type Type
Self-reactive Substances Type A
B C D E F G
Pyrophoric Liquids 1
Pyrophoric Solids 1
Self-heating Substances and
1 2
Mixtures
Substances and mixtures
which, in contact with water, 1 2 3
emit flammable gases
Oxidising Liquids 1 2 3
Oxidising Solids 1 2 3
Type Type Type Type Type Type
Organic Peroxides Type A
B C D E F G
Corrosive to Metals 1
 1. Explosives
Definition :
A solid or liquid substance (or mixture of substances) which is
in itself capable by chemical reaction of producing gas at
such a temperature and pressure and at such a speed as to
cause damage to the surroundings.

Explosives are classified in one of the seven

types based on Test Series 2 to 8 in Part I of
the UN Recommendations on the Transport
of Dangerous Goods, Manual of Tests and
Criteria.
Example : Nitroglycerine and TNT
 Explosives Classification Criteria
2.1.2.1 Substances, Mixtures, Articles which are not classified as an
unstable explosive :
• Division 1.1 : Mass explosion hazard

• Division 1.2 : Projection hazard - but not a mass explosion 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 are those which are thermally unstable and/or too sensitive
for normal handling, transport, and use. Special precautions are necessary.
 Classification Criteria for Explosives
• Classification in one of the six divisions is based on Test Series 2 through 8 in
Part 1 of the UNRTDG, Manual of Tests and Criteria :
Table 2.1.1: Criteria for explosives

Category Criteria
Unstablea explosives For explosives of Divisions 1.1 to 1.6, the following are the core set of tests that
or explosives of need to be performed:
Division 1.1 to 1.6 Explosibility: according to UN Test Series 2 (Section 12 of the
UN Recommendations on the Transport of Dangerous Goods,
Manual of Tests and Criteria). Intentional explosivesb are not
subject to UN Test Series 2.
Sensitiveness: according to UN Test Series 3 (Section 13 of the
UN Recommendations on the Transport of Dangerous Goods,
Manual of Tests and Criteria).
Thermal according to UN Test 3(c) (Sub-section 13.6.1 of the
stability: UN Recommendations on the Transport of Dangerous Goods,
Manual of Tests and Criteria).
Further tests are necessary to allocate the correct Division.
 Explosive Example Classifications

Name UN Classification*
Number

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 0209 1.1D
30% water

* Compatibility letter (A-G) not part of the GHS

20
 Hazard Communication for Explosives - Annex 1
EXPLOSIVES
Explosives Divisi 1.1 Divisi 1.2 Divisi 1.3 Divisi 1.4 Divisi 1.5 Divisi 1.6
Tidak Stabil

Tanpa Tanpa
pictogram pictogram

1.5 on 1.6 on
orange orange
background background

Bahaya Bahaya Bahaya Bahaya Awas Bahaya Tanpa kata

signal

Explosive Explosive; Explosive; Explosive; Bahaya May mass Tanpa

tidak stabil mass bahaya fire, blast or kebakaran explode pernyataan
explosion lontaran projection atau in fire bahaya
hazard hebat hazard bahaya
lontaran
No pictogram
assigned in
the UN Model
Regulations
(Transport
not allowed)
Suatu bahan atau campuran tidak diklasifikasi sebagai eksplosif,
jika :
(a) Tidak ada gugus kimia spesifik dalam struktur molekul yang
terkait dengan sifat eksplosif
(b) Oxygen Balance kurang dari -200
(c) Energi Dekomposisi Eksotermik kurang dari 500 J/g
(d) Konsentrasi Senyawa Anorganik Pengoksidasi :
 kurang dari 15 % massa, jika bahan pengoksidasi
diklasifikasi dalam Divisi 1.1 atau Divisi 1.2
 kurang dari 30 % massa, jika bahan pengoksidasi
diklasifikasi dalam Divisi 1.3
Contoh gugus fungsi spesifik terkait sifat eksplosif :

1. C-C tak jenuh Acetylene CH≡CH

2. C-Logam, N-Logam Butyl lithium C4H9Li
3. adjacent nitrogen atoms C6H5-S(O2)-NH-NH2
4. adjacent oxygen atoms -O-O-C(CH3)3)2
5. N-O C9H11N3O, -N-N=O
6. N-halogen (CH3)3-C-NF2
7. O-halogen (ClO3)2Mg , -Cl=O
Gugus fungsi dalam struktur Examples

① C-C unsaturation Acetylene (74-86-2)

② C-Metal, N-Metal Butyl lithium (109-72-8)
③ Contiguous nitrogen atoms Benzenesulfonyl Hydrazide (80-17-1)
④ Contiguous oxygen atoms t-Butlyperoxide (110-05-4)
⑤ N-O N’-nitrosornicotine (16543-55-8)
⑥ N-halogen t-Butyldifluoroamine (646-55-9)
⑦ O-halogen Magnesium perchlorate (10034-81-8)
Oxygen Balance

Kesetimbangan oksigen dihitung untuk reaksi kimia berikut :

CxHyOz + [x + (y/4) - (z/2) ] × O2 → x CO2 + (y/2) × H2O

Menggunakan rumus :

Oxygen Balance = -1600× [2x+(y/2)-z) ] / Molecular Weight

Oxygen-balance value Hazard Rating

x > +180  Low

+180 > x > +80  Medium
+ 80 > x > -120  High
-120 > x > -240  Medium
-240 > x  Low
Contoh Oxygen Balance berbagai zat kimia < -200
① Acetylene (74-86-2) - 3,080 ya
② Butyl lithium (109-72-8) -313 ya
③ Benzenesulfonyl Hydrazide (80-17-1) -130 tidak
④ t-Butlyperoxide (110-05-4) -252 ya
⑤ N’-nitrosornicotine (16543-55-8) -185 tidak
⑥ t-Butyldifluoroamine (646-55-9) -183 tidak
⑦ Magnesium perchlorate (10034-81-8) +57 tidak
 Contoh Oxygen Balance beberapa Zat Kimia
Chemicals CAS No. Struktur OB
Sodium nitrate 7631-99-4 NaNO3 47
Potassium perchlorate 7778-74-7 KClO4 46.2
Potassium nitrate 7757-79-1 KNO3 39.6
Barium nitrate 10022-31-8 Ba(NO3)2 30.6
Ammonium nitrate 6484-52-2 NH4NO3 20
Nitroglycerine 55-63-0 C3H5(ONO2)3 3.5
Nitroglycole 628-96-6 C2H4N2O6 0
Penthrit 78-11-5 C5H8O12N4 -10.1
Ammonium sulfate 7783-20-2 (NH4)2SO4 -36.4
Nitrocellulose 9004-70-0 -38.7
Tetryl 479-45-8 C7H5O8N5 -47.4
TNT 118-96-7 C7H5O6N3 -74
Alminum 7429-90-5 Al -89
Sulfur 7704-34-9 S -100
Starch 9005-25-8 -118.5
Paraffin 8002-74-2 CnH2n+2 -346
 2. Flammable Gases
(including chemically unstable gases)
Definition :
- A flammable gas is a gas having a flammable range with air
at 20 °C and a standard pressure of 101.3 kPa.

Flammability should be determined by test or by calculation in accordance

with methods adopted by ISO ( see ISO 10156 : 2010 “Gases and gas
mixtures – Determination of fire potential and oxidizing ability for the
selection of cylinder valve outlets” ).

Example : Propane
 Classification Criteria for Flammable Gases

Table 2.2.1: Criteria for flammable gases

Category Criteria
1 Gases, which at 20 °C and a standard pressure of 101.3 kPa:
(a) are ignitable when in a mixture of 13% or less by volume in air; or
(b) have a flammable range with air of at least 12 percentage points regardless of the
lower flammable limit.
2 Gases, other than those of Category 1, which, at 20 °C and a standard pressure
of 101.3 kPa, have a flammable range while mixed in air.

NOTE 1: Ammonia and methyl bromide may be regarded as special cases for some regulatory
purposes.

NOTE 2: Aerosols should not be classified as flammable gases. See Chapter 2.3.
 Flammable Gases
Kriteria Gas Mudah Menyala Ketegori 1 :

Gas yang pada temperatur 20°C dan tekanan standar 101,3 kPa, dapat
menyala jika bercampur dengan 13% atau lebih volume udara atau
mempunyai rentang nyala dengan udara, tidak kurang dari 12% point
berdasarkan batas bawah nyala (lower flammable limit).

Kriteria Gas Mudah Menyala Ketegori 2 :

Gas, selain yang masuk dalam kategori 1, yang pada temperatur 20°C
dan tekanan standar 101,3 kPa, mempunyai rentang nyala jika
bercampur dengan udara.

32
 2. Flammable Gases
(including chemically unstable gases)
Definition :
- A chemically unstable gas is a flammable gas that is able to
react explosively even in the absence of air or oxygen.

A flammable gas that is also chemically unstable is additionally classified

in one of two categories for chemically unstable gases using the
methods described in Part III of the UNRTDG, “Manual Tests and
Criteria”.

Example : Acetylene
 Criteria for Chemically Unstable Gases
 A flammable gas that is also chemically unstable will be additionally
classified in one of the following categories:

Table 2.2.2: Criteria for chemically unstable gases

Category Criteria
A Flammable gases which are chemically unstable at 20°C and a standard pressure of
101.3 kPa
B Flammable gases which are chemically unstable at a temperature greater than 20°C
and/or a pressure greater than 101.3 kPa
 Hazard Communication for Flammable Gases - Annex 1
FLAMMABLE GASES ( INCLUDING CHEMICALLY UNSTABLE GASES )
Flammable gases Chemically unstable gases
Note
Kategori 1 Kategori 2 Kategori A Kategori B
Under the UN
Recommendations
No additional No additional on the Transport of
Tanpa pictogram Dangerous Goods,
pictogram pictogram
Model Regulations,
the symbol,
number and border
Bahaya Awas No additional signal No additional signal line may be shown
word word in black instead of
white. The
Gas amat mudah Gas mudah May react May react explosively background colour
menyala menyala explosively even in even in the absence stays red in both
the absence of air of air at elevated cases.
pressure and/or
temperature

Not required under the UN Model Regulations

 Gas (Zat / campuran)
Decision Logic 2.2 (a) for
Ya
Flammable Gases

Pada 20 oC & tekanan 101,3 kPa

mempunyai rentang nyala jika Tidak Not classified
bercampur dengan udara ?

Ya

Pada 20 °C & tekanan 101,3 kPa Category 1

(a) dapat menyala jika konsentrasi
di udara 13% Volume atau
kurang ? Atau
(b) Mempunyai flamable range Ya
tidak kurang dari 12 % jika Danger
bercampur dengan udara
berdasarkan batas bawah
nyala ?
Category 2
No
Pictogram
Tidak
Warning
 Flammable Gas : Mixture
 Calculation : ISO 10156 : 2010
𝒏
𝑽𝒊%
≥𝟏
𝑻𝒄𝒊
𝒊

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

NB : Use of equivalency factors between other inert gases and nitrogen

 Classification of Flammable Gas Mixtures (1)
1) only few measured data on mixtures are available (ISO-10156:2010).
2) To calculate/determine as ingredients are known,
only judge the Category 1 or 2 but not distinguish 1or 2
n
V%

i

Formula: i Tci

Where:
Vi%: equivalent content of flammable gas i
Tci: maximum concentration of a flammable gas i in nitrogen at which
the mixture is still not flammable in air

If the mixed gas contains an inert gas other than nitrogen, the formula is
H +N
2 2
adjusted using the equivalency
n
factor Ki. H
2 +CO
2
Ｘ

V%

i Range

Criterion: i Tci
≧1
 Classification of Flammable Gas Mixtures (2)

Classification by means of calculations concerning flammable gas mixtures

Procedure:

(1) Ascertain the equivalency factors (Ki) for the inert gases in the
mixture versus nitrogen
(2) Calculate the equivalent volume of the mixture, converting the
non-nitrogen inert gases into nitrogen
(3) Adjust the sum of the contents to 100%
(4) Ascertain the Tc coefficients for the flammable gases
(Obtain the Tc coefficients from ISO 10156: 2010, Table 2
Maximum concentration at which a mixture of a flammable gas
and nitrogen does not ignite in air (Tci))
(5) Use the criterion to calculate whether the gas should be classed
as a flammable gas
 Classification of Flammable Gas Mixtures (3)

Example: 2% (H2) + 6% (CH4) + 27% (Ar) + 65% (He)

(1) Ascertain the equivalency factor (Ki) of the inert gas to nitrogen
Ki (Ar) = 0.5，Ki (He) = 0.5

(2) Use the Ki value of the inert gas to convert it to nitrogen and calculate the equivalent
volume of the mixture
2% (H2) + 6% (CH4) + [27%x0.5 + 65%x0.5] (N2)
= 2% (H2) + 6% (CH4) + 46% (N2) = 54%
(3) Adjust the sum of the contents to 100%
100/54 x [2% (H2) + 6% (CH4) + 46% (N2) ]
= 3.7% (H2) + 11.1% (CH4) + 85.2% (N2)

(4) Ascertain the Tci coefficient for the flammable gas

Tci H2 = 5.7% Tci CH4 = 14.3%

(5) Calculate
n
the flammability of the equivalent mixture using the formula:
 3.7/5.7  11.1/14.3  1.42
Vi %
i Tci

1.42>1, so this mixture is flammable.

 3. Aerosols
Definition :
Any non-refillable receptacles made of metal, glass or
plastics and containing a gas compressed, liquefied or
dissolved under pressure, with or without a liquid, paste or
powder, and fitted with a release device allowing the
contents to be ejected as solid or liquid particles in
suspension in a gas, as a foam, paste or powder or in a
liquid state or in a gaseous state.

The test method is described in the Section 31, Part III of the UNRTDG,
“Manual Tests and Criteria”.

Example : Insecticides
 Classification Criteria for Aerosols
• Aerosols should be considered for classification as
flammable if they contains any component which is
classified as flammable according the GHS criteria,
i.e. :

– Flammable liquids (see chapter 2.6)

– Flammable gases (see chapter 2.2)
– Flammable solids (see chapter 2.7)
 Aerosols Classification Criteria
• 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 ≤ 20 kJ/g if so
Do not classify
b) Check ≥ 85% flammable and heat of combustion ≥ 30 kJ/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)

• Non-flammable aerosol. If the aerosol does not meet requirements for

Category 1 or 2, it should be classified as Category 3 (non-flammable aerosol).
Hazard Communication for Aerosols - Annex 1
AEROSOLS
Kategori 1 Kategori 2 Kategori 3 Note
Under the UN
Recommendations on the
Transport of Dangerous
Tanpa Pictogram Goods, Model
Regulations, the symbol,
number and border line
may be shown in black
Bahaya Awas instead of white. The
Awas
background colour stays
red in the first two cases
Extremely flammable Flammable aerosol and green in the third
aerosol case.
Pressurized container:
Pressurized container: Pressurized container:
may burst if heated
may burst if heated may burst if heated
 2. 3 Decission Logic Flammable Aerosols
Flammable aerosol
Aerosol Decision logic 2.3 (a)

Apakah aerosol mengandung ≤ 1% komponen

Tidak diklasifikasi
mudah menyala dan juga mempunyai panas
Ya
pembakaran < 20 kJ/g?

Tidak

Kategori 1
Apakah aerosol mengandung ≥ 85% komponen
mudah menyala dan apakah juga mempunyai Ya
panas pembakaran ≥ 30 kJ/g?

Tidak
Bahaya
 2. 3 Decission Logic Flammable Aerosols
Spray aerosol
Aerosol semprot Decision logic 2.3 (b)

Kategori 1
Dalam pengujian jarak
pembakaran, apakah pembakaran
terjadi pada jarak ≥ 75 cm ? Ya

Tidak Bahaya

Apakah aerosol mempunyai panas Kategori 2

pembakaran < 20 kJ/g? Tidak

Ya
Awas

Dalam uji jarak kebakaran, apakah

kebakaran terjadi pada jarak ≥ 15 cm? Kategori 2
Ya
Tidak

Awas
Dalam uji terbakar ruang tertutup, apakah
(waktu ekuivalen ≤ 300 s/m3; atau Kategori 2
(deflagrasi densitas ≤ 300 g/m3? Ya
Tidak

Awas
Tidak
diklasifikasikan
 2. 3 Decission Logic Flammable Aerosols
Foam aerosol
Aerosol busa Decision logic 2.3 (c)

Kategori 1

Dalam pengujian busa, apakah

Ya
(tinggi nyala ≥ 20 cm dan durasi nyala ≥ 2 detik;
atau Bahaya
(tinggi nyala ≥ 4 cm dan durasi nyala ≥ 7 detik?
Tida
k Kategori 2

Dalam pengujian busa, apakah tinggi nyala Ya

≥ 4 cm dan durasi nyala ≥ 2 detik?

Awas
Tidak

Tidak
diklasifikasikan
 Examples of Aerosol
 Examples of products
Use Physical state of spray
hair spray foam, liquid
deodorants powder, liquid, gas
shaving foams foam
perfumes liquid
coatings liquid, paste
insect sprays liquid
Pharmaceutical liquid, powder, foam, paste
 Examples of propellants
Liquefied gas Flammable aerosol
Hydrocarbons Propane, butane, isobutene
Halocarbons <environmental destruction>
Dissolved gas Compressed gas Aerosol
CO2, N2 food
 4. Oxidizing Gases
Definition :
Any gas which may, generally by providing oxygen, cause
or contribute to the combustion of other material more than
air does.

To classify an oxidizing gas, test or calculation methods as described in

ISO 10156 : 2010 “Gases and gas mixtures – Determination of fire
potential and oxidizing ability for the selection of cylinder valve outlet”
should be performed.

Examples : Oxygen and Chlorine

NOTE: “Gases which cause or contribute to the combustion of other material more
than air does” means pure gases or gas mixtures with an oxidizing power greater
than 23.5% as determined by a method specified in ISO 10156 : 2010.
 Guidance from ISO 10156 : 2010
The classification method described in ISO 10156 uses the criterion that a gas mixture should be considered
as more oxidising than air if the oxidising power of the gas mixture is higher than 0.235 (23.5%).

The oxidizing power (OP) is calculated as follows:

n

x C
i 1
i i
OP  n p

x  K
i 1
i
k 1
k Bk

Where:
xi = molar fraction of the i:th oxidising gas in the mixture;
Ci = coefficient of oxygen equivalency of the i:th oxidising gas in the mixture;
Kk = coefficient of equivalency of the inert gas k compared to nitrogen;
Bk = molar fraction of the k:th inert gas in the mixture;
n = total number of oxidising gases in the mixture;
p = total number of inert gases in the mixture;

Example mixture: 9% (O2) + 16% (N2O) + 75% (He)

 Guidance from ISO , cont.
Calculation steps
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 (O2) = 1 (oxygen)
Kk (He) = 0.9 (helium)
Step 2:
Calculate the oxidising power of the gas mixture
n

x C
i 1
i i
0.09  1  0.16  0.6
OP    0.201 20.1 < 23.5
n p
0.09  0.16  0.75  0.9
x  K
i 1
i
k 1
k Bk

Therefore the mixture is not considered as an oxidising gas.

Hazard Communication for Oxidizing Gases - Annex 1

OXIDIZING GASES
Category 1 - - - Note

Danger

May cause or
intensify fire;
oxidizer
Pictogram colours:

Symbol (flame over

circle): black;
5.1 Background:
yellow; Figure
“5.1” in bottom
corner: black.
 5. Gases under Pressure
Definition :
Gas which are contained in a receptacle at 20 oC under
pressure of 200 kPa (gauge) or more, or which are liquefied,
or refrigerated liquefied.

Gases under pressure include compressed gases, liquefied gases,

refrigerated liquefied gases and dissolved gases.

Examples :
Compressed Gas : Helium
Liquefied Gas : Ammonia
Refrigerated Liquefied Gas : Liquid Nitrogen
Dissolved Gas : Acetylene
 Gases under Pressure Classification Criteria
Table 2.5.1: Criteria for gases under pressure

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 A gas which when packaged is made partially liquid because of its low temperature.
liquefied gas
Dissolved gas A gas which when packaged under pressure is dissolved in a liquid phase solvent.

The critical temperature is the temperature above which a pure gas cannot be liquefied, regardless of the
degree of compression.

NOTE: Aerosols should not be classified as gases under pressure. See Chapter 2.3.
 Guidance
• In order to classify substances or mixtures as gases under
pressure, the following information will be needed:

– The vapor pressure at 50 °C

– The physical state at 20 °C at standard ambient pressure
– The critical temperature

• Data can be found in literature, calculated, or determined

by testing. Most pure gases have already been classified
under the UNRTDG.
2. 5 Decission Logic for Gases under Pressure
Bahan/campuran berupa gas

Apakah
(a) tekanan uap pada 500C lebih besar dari 3 bar?; atau
Tidak
Tidak
(b) Bahan atau campuran menjadi gas sempurna pada diklasifikasikan
200C dan 101,3 kPa?
Gas terlarut
Ya

Apakah gas terlarut dalam pelarut cair Ya

bertekanan?
Awas
Tidak
Gas cair

Apakah titik kritis di atas +650C? Ya

Awas
Tidak

Bersambung …..
56
 Gas Cair
Apakah titik kritis antara -500C dan +650C?
Ya

Tidak
Awas

Apakah gas menjadi cair sebagian pada

suhu rendah? Ya Gas cair
terdinginkan

Tidak
Awas

Apakah seluruh gas dalam keadaan gas pada - Gas terkompresi

500C? Ya

Awas

57
 Examples - Gases Under Pressure
Classification Gas Critical temperature

Compressed gas Argon, compressed [UN -122.3 °C

1006]

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 9.5°C

[UN 1038]

Dissolved gas Acetylene, dissolved [UN 35.1°C

1001] (e.g. in acetone)
 Hazard Communication for Gases Under Pressure -
Annex 1
GASES UNDER PRESSURE
Refrigerated
Compressed gas Liquefied gas Dissolved gas Note
liquefied gas
Under the UN
Recommendations
on the Transport of
Dangerous Goods,
Model Regulations,
pictogram
Warning Warning Warning Warning elements:
(1) Not required
Contains Contains Contains Contains for toxic or
gas under pressure; gas under pressure; refrigerated gas; gas under pressure; flammable
may explode if may explode if may cause may explode if gases.
heated heated cryogenic burns heated
or injury (2) The symbol,
number and
border line
may be shown
in white
instead of
black. The
background
stays green in
both cases.
 6. Flammable Liquids
Definition :
A liquid having a flash point of not more than 93 °C.

The flash points of flammable liquids should be determined using test

methods specified in ISO, ASTM and etc.
ISO, ASTM and other specified test methods should be used for
determining the initial boiling point of flammable liquids.

Examples : Toluene, Acetone

 Classification Criteria for flammable liquids

Table 2.6.1: Criteria for flammable liquids

Category Criteria
1 Flash point < 23 °C and initial boiling point  35 °C
2 Flash point < 23 °C and initial boiling point > 35 °C
3 Flash point  23 °C and  60 °C
4 Flash point > 60 °C and  93 °C
Decision Logic for Flammable Liquids
 Examples : Flammable Liquids

Substance Flash point Initial boiling Classification

point
Diethyl ether -450C 34.60C Category 1
Methanol 120C 64.70C Category 2
Ethanol 12.80C 78.40C Category 2
Gasoline -400C 23.60C - 1900C Category 2 (most)
Diesel fuel 520C - 960C 1750C - 3450C Category 4 (most)
Jet A fuel 380C - 660C 1600C - 3000C Category 3 (most)
 Examples : Flammable Liquids
Category 1
 Acrylonitrile (107-13-1)
 Carbondisulphide (75-15-0)
 Ethyl isocyanate (109-90-0)
Category 2
 Acetone (67-64-1)
 Diethylamine (109-89-7)
 Acetyl chloride (75-36-5)
 Methanol (67-56-1)
Category 3
 Diisobutylketone (108-83-8)
 Triisopropylamine (3424-21-3)Isobutyric acid (79-31-2)
Category 4
 Divinylbenzene (1321-74-0)Nitrobenzene (98-95-3)
 N-ethyl aniline (103-69-5)Ethylene cyanhydrin (109-78-4)
64
Hazard Communication for Flammable Liquids - Annex 1

FLAMMABLE LIQUIDS
Category 1 Category 2 Category 3 Category 4 Note
Under the UN
Recommendations
No pictogram on the Transport of
Dangerous Goods,
Model Regulations,
the symbol,
number and
Danger Danger Warning Warning border line may be
shown in black
Extremely Highly Flammable liquid Combustible liquid instead of white.
flammable liquid flammable liquid and vapour The background
and vapour and vapour colour stays red in
Not required under both cases.
the UN
Recommendations
3 3 3 on the Transport of
Dangerous Goods
Model Regulations
 7. Flammable Solids
Definition :
A flammable solid is a solid which is readily combustible, or
may cause or contribute to fire through friction.

Readily combustible solids are powdered, granular, or pasty substances

which are dangerous if they can be easily ignited by brief contact with an
ignition source, such as a burning match, and if the flame spreads
rapidly.
Powdered, granular or pasty substances that are Readily Combustible
should be classified based on the results of the Test Method N.1
performed as described in the UN Recommendations on the Transport
of Dangerous Goods (UNRTDG).

Note : Aerosols should not be classified as flammable solids.

Example : Metal powder
 Classification Criteria for Flammable Solids
Table 2.7.1: Criteria for flammable solids

Category Criteria
1 Burning rate test:
Substances or mixtures other than metal powders:
(a) wetted zone does not stop fire; and
(b) burning time < 45 s or burning rate > 2.2 mm/s
Metal powders: burning time  5 min
2 Burning rate test:
Substances or mixtures other than metal powders:
(a) wetted zone stops the fire for at least 4 min; and
(b) burning time < 45 s or burning rate > 2.2 mm/s
Metal powders: burning time > 5 min and  10 min

NOTE 1: 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 must also be tested in the new form.

NOTE 2: Aerosols should not be classified as flammable solids. See Chapter 2.3.
 Classification Criteria for Flammable Solids, cont.

 Classification is based on tests in the UNRTDG Manual of

Tests and Criteria, Part III, sub-section 33.2.1.
 Solids which may cause fire through friction will be classified
by analogy with existing entries (e.g., matches) until
definitive criteria are established.
Flammable solids; Decision logic
The substance/mixture is a solid?

Ye
s

Screening Test Negative Not classified

Positive

Burning rate test

For substances or mixtures other than
metal powders: Burning No Not classified
time < 45 s or rate > 2.2 mm/s?
Metal powders: Burning time 10 min?
Ye
s

For substances or mixtures other than metal Category 1

powders: Does the wetted zone stop
propagation of the flame? No
Metal powders: Burning time > 5 min? Danger
Yes

Category 2

Warning
 Flammable solid – examples
Substance Classification

Aluminium powder Category 1

Silicon powder Category 2

Sulphur Category 2

Matches (safety) Category 2

70
Example of Aluminum Powder Packaging
Hazard Communication for Flammable Solids - Annex 1

FLAMMABLE SOLIDS
Category 1 Category 2 - - Note
Colours for
pictogram
under the UN
Recommendations
on the Transport of
Dangerous Goods,
Danger Warning Model Regulations:
Symbol (flame):
Flammable solid Flammable solid black; Background:
white with seven
vertical red stripes;
Figure “4” in the
4 4 bottom corner:
black.
8. Self-reactive Substances and Mixtures
Definition :
Self-reactive substances or mixtures are thermally unstable liquid or solid
substances or mixtures liable to undergo a strongly exothermic
decomposition even without participation of oxygen (air).
This definition excludes substances and mixtures classified under the GHS
as explosives, organic peroxides or as oxidizing.

• A self-reactive substance or mixture is regarded as possessing

explosive properties when in laboratory testing the formulation is liable
to detonate, to deflagrate rapidly or to show a violent effect when heated
under confinement.
Self-reactive substances and mixtures should be tested using the methods
given in the Part II of the UNRTDG, “Manual of Tests and Criteria.”

Example : m-Dinitrobenzene
 Classification Criteria (1)
• Sensitivity and effect threshold
– Heat of decomposition < 300 J/g OR
– Self-Accelerating Decomposition Temperature (SADT) >
750C (50 kg package)
• Summary classification ...
 Classification Criteria (2)
 Summary classification, cont.
Hazard Communication for Self-Reactive Substances and Mixtures, Annex 1

SELF-REACTIVE SUBSTANCES AND MIXTURES

Type A Type B Types C and D Types E and F Type G

There are no label

elements allocated to
this hazard category

Danger Danger Danger Warning

Heating may cause Heating may cause Heating may Heating may
an explosion a fire or explosion cause a fire cause a fire
Same as for Not
explosives (follow required
same symbol under the UN
selection process) 4 4 4
Recommendations on
the Transport of
Dangerous Goods,
Model Regulations
 9. Pyrophoric Liquids
Definition :
A pyrophoric liquid is a liquid which, even in small quantities,
is liable to ignite within five minutes after coming into contact
with air.

A pyrophoric liquid is classified based on the results of the Test N.3 as

described in Part III, sub-section 33.3.1.5 of the UN Recommendations on
the Transport of Dangerous Goods, “Manual of Tests and Criteria”.

Examples : Pentaborane, Organoaluminium.

 Classification Criteria for Pyrophoric Liquids
• Classification is based on testing in Part III of the UNRTDG
Tests and Criteria Manual:

Table 2.9.1: Criteria for pyrophoric liquids

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.
Example Chemicals Classified as Pyrophoric Liquids
 Hazard Communication for Pyrophoric Liquids,
Annex 1

PYROPHORIC LIQUIDS
Category 1 - - - Note
Colours of UN
Recommendations
on the Transport of
Dangerous Goods,
Model Regulations,
pictogram:
Danger Symbol (flame):
black; Background:
Catches fire upper half white,
spontaneously if lower half red;
exposed to air figure “4” in bottom
corner: black.

4
 10. Pyrophoric Solids
Definition :
A pyrophoric solid is a solid which, even in small quantities,
is liable to ignite within five minutes after coming into contact
with air.

A pyrophoric solid is classified based on the results of the Test N.3

performed as described in Part III, sub-section 33.3.1.5 of the UN
Recommendations on the Transport of Dangerous Goods, “Manual of
Tests and Criteria”.

Example : Sodium metal

 Classification Criteria for Pyrophoric Solids

• Classification is based on testing in Part III of the UNRTDG Tests

and Criteria Manual:
Table 2.10.1: Criteria for pyrophoric solids

Category Criteria
1 The solid ignites within 5 min of coming into contact with air.

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.
 Examples of Chemicals Classified as Pyrophoric Solids

Category Substance

1 Phosphorous, white or yellow, dry or underwater or in solution

1 Iron powder

1 Magnesium powder (pyrophoric)

Remark: Mg or Mg alloys > 50% Mg in pellets, turnings or

ribbonsFlammable solid Cat 1
1 Sodium sulphide, anhydrous or with<30% water of crystallisation

1 Wool waste, wet

Hazard Communication for Pyrophoric Solids,
Annex 1

PYROPHORIC SOLIDS
Category 1 - - - Note
Colours of UN
Recommendations
on the Transport of
Dangerous Goods,
Model Regulations,
pictogram:
Danger Symbol (flame):
black;
Catches fire Background: upper
spontaneously if half white, lower
exposed to air half red; figure “4”
in bottom corner:
black.

4
 11. Self-heating Substances and Mixtures
Definition :
A self-heating substance or mixture is a solid or liquid
substance or mixture, other than a pyrophoric liquid or
solid, which, by reaction with air and without energy
supply, is liable to self-heat;

This self-heating substance or mixture differs from a pyrophoric liquid or

solid in that it will ignite only when in large amounts (kilograms) and
after long periods of time (hours or days).

A self-heating substance or mixture should be classified based on

the results of the Test N.4 performed as described in Part III, sub-
section 33.3.1.6 of the UN Recommendations on the Transport of
Dangerous Goods, “Manual of Tests and Criteria”.

Examples : Charcoal, Magnesium ethoxide

 Classification Criteria for self-heating
substances and mixtures
Table 2.11.1: Criteria for self-heating substances and mixtures

Category 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.

NOTE 1: 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.

NOTE 2: The criteria are based on the self-ignition temperature of charcoal, which is 50 °C for a
sample cube of 27 m3. Substances and mixtures with a temperature of spontaneous combustion higher than
50 °C for a volume of 27 m3 should not be assigned to this hazard class. Substances and mixtures with a self-
ignition temperature higher than 50 °C for a volume of 450 litres should not be assigned to hazard
Category 1 of this hazard class.
Examples of Chemicals Classified as Self-Heating
Substances and Mixtures

Category Chemical UN TDG

1 Metal powder, self-heating N.O.S. (UN Class 4.2
3189) Packing Group II
1 Sodium hydrosulfide with < 25 % of water Class 4.2
of crystallization (UN 2318) Packing Group II

2 Alkaline Earth Metal, alcoholates, N.O.S. Class 4.2

(UN 3205) Packing Group III

2 Titanium disulfide (CAS 12039-13-3; UN Class 4.2

3174) Packing Group III

2 Charcoal (UN1361) Class 4.2

Packing Group III
 Hazard Communication for Self-Heating
Substances and Mixtures, Annex 1

SELF-HEATING SUBSTANCES AND MIXTURES

Category 1 Category 2 - - Note
Colours of UN
Recommendations
on the Transport of
Dangerous Goods,
Model Regulations,
pictogram:
Danger Warning
Symbol (flame):
Self-heating; may Self-heating in black;
catch fire large quantities; Background:
may catch fire upper half white,
lower half red;
figure “4” in
bottom corner:
black.
4 4
12. Substances and Mixtures which, in Contact with
Water, Emit Flammable Gases
Definition :
Substances or mixtures which, in contact with water, emit flammable gases
are solid or liquid substances or mixtures which, by interaction with
water, are liable to become spontaneously flammable or to give off
flammable gases in dangerous quantities.

A substance or mixture which, in contact with water, emit

flammable gases should be classified based on the results of the
Test N.5 performed as described in Part III, sub-section 33.4.1.4 of
the UN Recommendations on the Transport of Dangerous Goods,
“Manual of Tests and Criteria”.

Examples : Potassium, Phosphorus pentasulfide

 Classification Criteria for Substances and Mixtures
which, in Contact with Water, Emit Flammable Gases
Table 2.12.1: Criteria for substances and mixtures which, in contact with water,
emit flammable gases

Category 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.
Examples of Chemicals Classified as Emit
Flammable Gases in Contact with Water
Hazard Communication for Chemicals that Emit
Flammable Gases in Contact with Water, Annex 1
SUBSTANCES AND MIXTURES, WHICH IN CONTACT WITH WATER,
EMIT FLAMMABLE GASES
Category 1 Category 2 Category 3 - Note
Under the UN
Recommendations
on the Transport of
Dangerous Goods,
Model Regulations,
the symbol,
Danger Danger Warning number and border
line may be shown
In contact with In contact with In contact with in black instead of
water releases water releases water releases white. The
flammable gases flammable gases flammable gases background stays
which may ignite blue in both cases.
spontaneously

4 4 4
 13. Oxidizing Liquids
Definition :
An oxidizing liquid is a liquid which, while in itself not
necessarily combustible, may, generally by yielding oxygen,
cause, or contribute to, the combustion of other material.

An oxidizing liquid should be classified based on the results of the

Test O.2 performed as described in Part III, sub-section 34.4.2 of the
UN Recommendations on the Transport of Dangerous Goods,
“Manual of Tests and Criteria”.

Examples : Nitric Acid (HNO3), Hydrogen Peroxide (H2O2)

 Classification Criteria for Oxidizing Liquids

Table 2.13.1: Criteria for oxidizing liquids

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.
Examples of Chemicals Classified as Oxidizing
Liquids
 Hazard Communication for Oxidizing Liquids,
Annex 1

OXIDIZING LIQUIDS
Category 1 Category 2 Category 3 - Note
Under the UN
Recommendations
on the Transport of
Dangerous Goods,
Model Regulations,
pictogram colours:
Danger Danger Warning
Symbol (flame
May cause fire or May intensify May intensify over circle): black;
explosion; strong fire; oxidizer fire; oxidizer Background:
oxidizer yellow; Figure
“5.1” in bottom
corner: black.

5.1 5.1 5.1

 14. Oxidizing Solids
Definition :
An oxidizing solid is a solid which, while in itself is not
necessarily combustible, may, generally by yielding oxygen,
cause, or contribute to, the combustion of other material.

An oxidizing solid should be classified based on the results of the Test

O.1 performed as described in Part III, sub-section 34.4.1 of the UN
Recommendations on the Transport of Dangerous Goods, “Manual of
Tests and Criteria”.

Examples : Potassium Chlorate, Silver Nitrate

 Classification Criteria for Oxidizing Solids

Table 2.14.1: Criteria for oxidizing solids

Category 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.
Examples of Chemicals Classified as Oxidizing
Solids
 Hazard Communication for Oxidizing Solids,
Annex 1

OXIDIZING SOLIDS
Category 1 Category 2 Category 3 - Note
Under the UN
Recommendations
on the Transport of
Dangerous Goods,
Model Regulations,
pictogram colours:
Danger Danger Warning Symbol (flame
over circle): black;
May cause fire May intensify fire; May intensify fire; Background:
or explosion; strong oxidizer oxidizer yellow; Figure
oxidizer “5.1” in bottom
corner: black.

5.1 5.1 5.1

 15. Organic Peroxide
Definition :
Organic peroxides are liquid or solid organic substances which contain
the bivalent -O-O- structure and may be considered derivatives of
hydrogen peroxide, where one or both of the hydrogen atoms have been
replaced by organic radicals.
.
An organic peroxide should be classified based on the results of the Test
O.1 performed as described in Part II, Section 28 of the UN
Recommendations on the Transport of Dangerous Goods, “Manual of
Tests and Criteria”.

Example : Methyl ethyl ketone peroxide

 Organic Peroxides
• In addition, they may have one or more of the following
properties:
(a) be liable to explosive decomposition;
(b) burn rapidly;
(c) be sensitive to impact or friction;
(d) react dangerously with other substances.

• An organic peroxide is regarded as possessing

explosive properties when in laboratory testing the
formulation is liable to detonate, to deflagrate rapidly
or to show a violent effect when heated under
confinement.
 Classification Criteria for Organic Peroxide

 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
 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 𝒏 𝒏𝒊 ×𝒄𝒊
𝑨𝒗𝒂𝒊𝒍𝒂𝒃𝒍𝒆 𝒐𝒙𝒚𝒈𝒆𝒏 𝒄𝒐𝒏𝒕𝒆𝒏𝒕 = 𝟏𝟔 × 𝒊 𝒎
𝒊
peroxide OR
ni = number of peroxide groups per molecule of organic peroxide

• ≤ 0.5% available oxygen from ci = mass concentration (mass %) of organic peroxide

organic peroxides when mi = molecular mass of organic peroxide i
containing between 1% and
7% hydrogen peroxide
 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
 Organic Peroxides Classification (3)
 Summary Classification continued

 Note: Failure to meet any part of the Type G criteria requires

reassignment to Type F.
 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 behavior as packaged and under confinement

Note:Temperature-sensitive organic peroxides (as measured by SADT)

require continuous temperature control.
 Practical Classification Method
• 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.

Note: List includes only substances permitted for

transport.
 Hazard Communication for Organic Peroxides,
Annex 1
ORGANIC PEROXIDES
Type A Type B Types C and D Types E and F Type G

There are no label

elements allocated to
this hazard category

Danger Danger Danger Warning

Heating may cause Heating may cause Heating may Heating may
an explosion a fire or explosion cause a fire cause a fire
Same as for Not required under
explosives (follow the UN
same symbol Recommendations on
selection process) 5.2 5.2 5.2 the Transport of
Dangerous Goods,
Model Regulations.
 16. Corrosive to Metals
Definition :
A substance or a mixture which is corrosive to metals is a
substance or a mixture which by chemical action will
materially damage, or even destroy, metals.
.
A substance or a mixture which is corrosive to metal is classified based
on the results of the test performed as described in Part III, sub-section
37.4 of the UN Recommendations on the Transport of Dangerous
Goods, “Manual of Tests and Criteria”.

Examples : Ammonia water, Sulphuric Acid, HCl, NaOH

 Classification Criteria for substances and
mixtures corrosive to metal

Table 2.16.1: Criteria for substances and mixtures corrosive to metal

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.

NOTE: Where an initial test on either steel or aluminium indicates the substance or mixture being
tested is corrosive the follow-up test on the other metal is not required.
Minimum Mass Loss Equivalency to Criterion
6.5 mm/year

Exposure Time Mass Loss

[d] [%]

7 13.5
14 26.5
21 39.2
28 51.5
Examples of Chemicals Classified as Corrosive to
Metals
 Hazard Communication for Corrosive to Metals,
Annex 1
CORROSIVE TO METALS
Category 1 - - - Note
Under the UN
Recommendations
on the Transport of
Dangerous Goods,
Model Regulations,
pictogram colours:
Warning
Symbol
May be corrosive (corrosion): black;
to metals background: upper
half: white; lower
half: black with
white border;
Figure “8” in the
bottom corner:
white.