Substances not accepted for carriage

The chemically unstable substances of Class 4.1 shall not be accepted for carriage unless the
necessary steps have been taken to prevent their dangerous decomposition or polymerization during
carriage. To this end, it shall in particular be ensured that receptacles and tanks do not contain any
substance liable to promote these reactions.

Flammable solids, oxidizing, assigned to UN No. 3097 shall not be accepted for carriage unless they
meet the requirements for Class 1 (see also 2.1.3.7).

The following substances shall not be accepted for carriage:
- Self-reactive substances of type A (see Manual of Tests and Criteria, Part II, paragraph
20.4.2 (a));
- Phosphorus sulphides which are not free from yellow and white phosphorus;
- Solid densitized explosives other than those listed in Table A of Chapter 3.2;
- Inorganic flammable substances in the molten form other than UN No. 2448 SULPHUR,
MOLTEN.

List of collective entries

a Metals and metal alloys in powdered or other flammable form, liable to spontaneous combustion, are substances
of Class 4.2.
b Metals and metal alloys in powdered or other flammable form, which in contact with water, emit flammable
gases, are substances of Class 4.3.
c Metals hydrides which, in contact with water, emit flammable gases, are substances of Class 4.3. Aluminium
borohydride or aluminium borohydride in devices are substances of Class 4.2, UN No. 2870.

List of currently assigned self-reactive substances in packagings

In the column "Packing Method" codes "OP1" to "OP8" refer to packing methods in 4.1.4.1, packing
instruction P520 (see also 4.1.7.1). Self-reactive substances to be carried shall fulfil the classification
and the control and emergency temperatures (derived from the SADT) as listed. For substances
permitted in IBCs, see 4.1.4.2, packing instruction IBC520 and, for those permitted in tanks
according to Chapter 4.2, see 4.2.5.2, portable tank instruction T23.
NOTE: The classification given in this table is based on the technically pure substance (except
where a concentration of less than 100% is specified). For other concentrations, the substance may
be classified differently following the procedures given in Part II of the Manual of Tests and Criteria
and in 2.2.41.1.17.

SELF-REACTIVE SUBSTANCE

Concen- tration (%)

Packing method

Control tempera- ture

(°C)

Emergency tempera- ture

(°C)

UN

generic entry

Remarks

ACETONE-PYROGALLOL COPOLYMER 2-DIAZO-1-NAPHTHOL-5-SULPHONATE

100

OP8

   

3228

 

AZODICARBONAMIDE FORMULATION TYPE B, TEMPERATURE CONTROLLED

< 100

OP5

   

3232

(1) (2)

AZODICARBONAMIDE FORMULATION TYPE C

< 100

OP6

   

3224

(3)

AZODICARBONAMIDE FORMULATION TYPE C, TEMPERATURE CONTROLLED

< 100

OP6

   

3234

(4)

AZODICARBONAMIDE FORMULATION TYPE D

< 100

OP7

   

3226

(5)

AZODICARBONAMIDE FORMULATION TYPE D, TEMPERATURE CONTROLLED

< 100

OP7

   

3236

(6)

2,2' -AZODI(2,4-DIMETHYL- 4-METHOXY- VALERONITRILE)

100

OP7

-5

+5

3236

 

2,2' -AZODI(2,4-DIMETHYL- VALERONITRILE)

100

OP7

+10

+15

3236

 

2,2' -AZODI(ETHYL- 2-METHYL-PROPIONATE)

100

OP7

+20

+25

3235

 

1,1-AZODI(HEXAHYDROBENZONITRILE)

100

OP7

   

3226

 

2,2' -AZODI(ISOBUTYRONITRILE)

100

OP6

+40

+45

3234

 

2,2' -AZODI(ISOBUTYRONITRILE) as a water based paste

 50%

OP6

   

3224

 

2,2' -AZODI(2-METHYLBUTYRONITRILE)

100

OP7

+35

+40

3236

 

BENZENE-1,3-DISULPHONYL HYDRAZIDE, as a

paste

52

OP7

   

3226

 

BENZENE SULPHONYL HYDRAZIDE

100

OP7

   

3226

 

4-(BENZYL(ETHYL)AMINO)-3-ETHOXY- BENZENEDIAZONIUM ZINC CHLORIDE

100

OP7

   

3226

 

4-(BENZYL(METHYL)AMINO)-3-ETHOXY- BENZENEDIAZONIUM ZINC CHLORIDE

100

OP7

+40

+45

3236

 

3-CHLORO-4-DIETHYLAMINOBENZENE- DIAZONIUM ZINC CHLORIDE

100

OP7

   

3226

 

2-DIAZO-1-NAPHTHOL-4-SULPHONYL CHLORIDE

100

OP5

   

3222

(2)

2-DIAZO-1-NAPHTHOL-5-SULPHONYL CHLORIDE

100

OP5

   

3222

(2)

SELF-REACTIVE SUBSTANCE

Concen- tration (%)

Packing method

Control tempera- ture

(°C)

Emergency tempera- ture

(°C)

UN

generic entry

Remarks

2-DIAZO-1-NAPHTHOL SULPHONIC ACID ESTER MIXTURE, TYPE D

< 100

OP7

   

3226

(9)

2,5-DIBUTOXY-4-(4-MORPHOLINYL)- BENZENEDIAZONIUM, TETRACHLOROZINCATE (2:1)

100

OP8

   

3228

 

2,5-DIETHOXY-4-MORPHOLINO- BENZENEDIAZONIUM ZINC CHLORIDE

67-100

OP7

+35

+40

3236

 

2,5-DIETHOXY-4-MORPHOLINO- BENZENEDIAZONIUM ZINC CHLORIDE

66

OP7

+40

+45

3236

 

2,5-DIETHOXY-4-MORPHOLINO- BENZENEDIAZONIUM TETRAFLUOROBORATE

100

OP7

+30

+35

3236

 

2,5-DIETHOXY-4-(4-MORPHOLINYL)- BENZENEDIAZONIUM SULPHATE

100

OP7

   

3226

 

2,5-DIETHOXY-4-(PHENYLSULPHONYL)- BENZENEDIAZONIUM ZINC CHLORIDE

67

OP7

+40

+45

3236

 

DIETHYLENEGLYCOL BIS (ALLYL CARBONATE)

+ DI- ISOPROPYL-PEROXYDICARBONATE

 88+ 12

OP8

-10

0

3237

 

2,5-DIMETHOXY-4-(4-METHYL- PHENYLSULPHONYL)BENZENE- DIAZONIUM ZINC CHLORIDE

79

OP7

+40

+45

3236

 

4-(DIMETHYLAMINO)-BENZENE-DIAZONIUM TRICHLOROZINCATE (-1)

100

OP8

   

3228

 

4-DIMETHYLAMINO-6-(2-DIMETHYL- AMINOETHOXY) TOLUENE- 2-DIAZONIUM ZINC CHLORIDE

100

OP7

+40

+45

3236

 

N,N'-DINITROSO-N,N'- DIMETHYL

TEREPHTHALAMIDE, as a paste

72

OP6

   

3224

 

N,N'-DINITROSOPENTAMETHYLENE- TETRAMINE

82

OP6

   

3224

(7)

DIPHENYLOXIDE-4,4'-DISULPHONYL HYDRAZIDE

100

OP7

   

3226

 

4-DIPROPYLAMINOBENZENE- DIAZONIUM ZINC CHLORIDE

100

OP7

   

3226

 

2-(N,N-ETHOXYCARBONYL- PHENYLAMINO)-3-METHOXY-4-

(N-METHYL-N-CYCLOHEXYLAMINO) BENZENEDIAZONIUM ZINC CHLORIDE

63-92

OP7

+ 40

+ 45

3236

 

2-(N,N-ETHOXYCARBONYL- PHENYLAMINO)-3-METHOXY-4-

(N-METHYL-N-CYCLOHEXYLAMINO) BENZENEDIAZONIUM ZINC CHLORIDE

62

OP7

+ 35

+ 40

3236

 

N-FORMYL-2-(NITROMETHYLENE)

-1,3-PERHYDROTHIAZINE

100

OP7

+45

+50

3236

 

2-(2-HYDROXYETHOXY)-1-

(PYRROLIDIN-1-YL)BENZENE-4- DIAZONIUM ZINC CHLORIDE

100

OP7

+ 45

+ 50

3236

 

3-(2-HYDROXYETHOXY)-4- (PYRROLIDIN-1-YL) BENZENE DIAZONIUM ZINC CHLORIDE

100

OP7

+40

+45

3236

 

2-(N,N-METHYLAMINOETHYLCARBONYL)-

4-(3,4-DIMETHYLPHENYLSULPHONYL) BENZENEDIAZONIUM HYDROGEN SULPHATE

96

OP7

+45

+50

3236

 

4-METHYLBENZENESULPHONYLHYDRAZIDE

100

OP7

   

3226

 

3-METHYL-4-(PYRROLIDIN-1-YL) BENZENEDIAZONIUM TETRAFLUOROBORATE

95

OP6

+45

+50

3234

 

4-NITROSOPHENOL

100

OP7

+35

+40

3236

 

SELF-REACTIVE SUBSTANCE

Concen- tration (%)

Packing method

Control tempera- ture

(°C)

Emergency tempera- ture

(°C)

UN

generic entry

Remarks

SELF-REACTIVE LIQUID, SAMPLE

 

OP2

   

3223

(8)

SELF-REACTIVE LIQUID, SAMPLE, TEMPERATURE CONTROLLED

 

OP2

   

3233

(8)

SELF-REACTIVE SOLID, SAMPLE

 

OP2

   

3224

(8)

SELF-REACTIVE SOLID, SAMPLE, TEMPERATURE CONTROLLED

 

OP2

   

3234

(8)

SODIUM 2-DIAZO-1-NAPHTHOL- 4-SULPHONATE

100

OP7

   

3226

 

SODIUM 2-DIAZO-1-NAPHTHOL- 5-SULPHONATE

100

OP7

   

3226

 

TETRAMINE PALLADIUM (II) NITRATE

100

OP6

+30

+35

3234

 
Remarks
(1) Azodicarbonamide formulations which fulfil the criteria of paragraph 20.4.2 (b) of the Manual
of Tests and Criteria. The control and emergency temperatures shall be determined by the
procedure given in 2.2.41.1.17.
(2) "EXPLOSIVE" subsidiary risk label required (Model No. 1, see 5.2.2.2.2).
(3) Azodicarbonamide formulations which fulfil the criteria of paragraph 20.4.2 (c) of the Manual
of Tests and Criteria.
(4) Azodicarbonamide formulations which fulfil the criteria of paragraph 20.4.2 (c) of the Manual
of Tests and Criteria. The control and emergency temperatures shall be determined by the
procedure given in 2.2.41.1.17.
(5) Azodicarbonamide formulations which fulfil the criteria of paragraph 20.4.2 (d) of the Manual
of Tests and Criteria.
(6) Azodicarbonamide formulations which fulfil the criteria of paragraph 20.4.2 (d) of the Manual
of Tests and Criteria. The control and emergency temperatures shall be determined by the
procedure given in 2.2.41.1.17.
(7) With a compatible diluent having a boiling point of not less than 150 °C.
(8) See 2.2.41.1.15.
(9) This entry applies to mixtures of esters of 2-diazo-1-naphthol-4-sulphonic acid and 2-diazo-1-
naphthol-5-sulphonic acid which fulfil the criteria of paragraph 20.4.2 (d) of the Manual of
Test and Criteria.

Class 4.2 Substances liable to spontaneous combustion

Criteria

The heading of Class 4.2 covers:
- Pyrophoric substances which are substances, including mixtures and solutions (liquid or solid),
which even in small quantities ignite on contact with air within five minutes. These are the
Class 4.2 substances the most liable to spontaneous combustion; and
- Self-heating substances and articles which are substances and articles, including mixtures and
solutions, which, on contact with air, without energy supply, are liable to self-heating. These
substances will ignite only in large amounts (kilograms) and after long periods of time (hours
or days).

The substances and articles of Class 4.2 are subdivided as follows:
S Substances liable to spontaneous combustion, without subsidiary risk:
S1 Organic, liquid;
S2 Organic, solid;
S3 Inorganic, liquid;
S4 Inorganic, solid;
S5 Organometallic;
SW Substances liable to spontaneous combustion, which, in contact with water, emit flammable
gases;
SO Substances liable to spontaneous combustion, oxidizing;
ST Substances liable to spontaneous combustion, toxic:
ST1 Organic, toxic, liquid;
ST2 Organic, toxic, solid;
ST3 Inorganic, toxic, liquid;
ST4 Inorganic, toxic, solid;
SC Substances liable to spontaneous combustion, corrosive:
SC1 Organic, corrosive, liquid;
SC2 Organic, corrosive, solid;
SC3 Inorganic, corrosive, liquid;
SC4 Inorganic, corrosive, solid.

Properties

Self-heating of a substance is a process where the gradual reaction of that substance with oxygen (in
air) generates heat. If the rate of heat production exceeds the rate of heat loss, then the temperature of
the substance will rise which, after an induction time, may lead to self-ignition and combustion.

Classification

Substances and articles classified in Class 4.2 are listed in Table A of Chapter 3.2. The assignment of
substances and articles not mentioned by name in Table A of Chapter 3.2 to the relevant specific
N.O.S. entry of 2.2.42.3 in accordance with the provisions of Chapter 2.1 can be based on experience
or the results of the test procedures in accordance with the Manual of Tests and Criteria, Part III,
Section 33.3. Assignment to general N.O.S. entries of Class 4.2 shall be based on the results of the test
procedures in accordance with the Manual of Tests and Criteria, Part III, section 33.3; experience shall
also be taken into account when it leads to a more stringent assignment.

When substances or articles not mentioned by name are assigned to one of the entries listed in
2.2.42.3 on the basis of the test procedures in accordance with the Manual of Tests and Criteria, Part
III, section 33.3, the following criteria shall apply:
(a) Solids liable to spontaneous combustion (pyrophoric) shall be assigned to Class 4.2 when they
ignite on falling from a height of 1 m or within five minutes;
(b) Liquids liable to spontaneous combustion (pyrophoric) shall be assigned to Class 4.2 when:
(i) on being poured on an inert carrier, they ignite within five minutes, or
(ii) in the event of a negative result of the test according to (i), when poured on a dry,
indented filter paper (Whatman No. 3 filter), they ignite or carbonize it within five
minutes;
(c) Substances in which, in a 10 cm sample cube, at 140 °C test temperature, spontaneous
combustion or a rise in temperature to over 200 °C is observed within 24 hours shall be
assigned to Class 4.2. This criterion is based on the temperature of the spontaneous combustion
of charcoal, which is at 50 °C for a sample cube of 27 m3. Substances with a temperature of
spontaneous combustion higher than 50 °C for a volume of 27 m3 are not to be assigned to
Class 4.2.
NOTE 1: Substances carried in packages with a volume of not more than 3 m3 are exempted from
Class 4.2 if, tested with a 10 cm sample cube at 120 °C, no spontaneous combustion nor a rise in
temperature to over 180 °C is observed within 24 hours.
NOTE 2: Substances carried in packages with a volume of not more than 450 litres are exempted
from Class 4.2 if, tested with a 10 cm sample cube at 100 °C, no spontaneous combustion nor a rise in
temperature to over 160 °C is observed within 24 hours.
NOTE 3: Since organometallic substances can be classified in Class 4.2 or 4.3 with additional
subsidiary risks, depending on their properties, a specific classification flow chart for these
substances is given in 2.3.5.

 

If substances of Class 4.2, as a result of admixtures, come into different categories of risk from those
to which the substances mentioned by name in Table A of Chapter 3.2 belong, these mixtures shall be
assigned to the entries to which they belong on the basis of their actual degree of danger.
NOTE: For the classification of solutions and mixtures (such as preparations and wastes), see
also 2.1.3.

On the basis of the test procedure in the Manual of Tests and Criteria, Part III, section 33.3 and the
criteria set out in 2.2.42.1.5, it may also be determined whether the nature of a substance mentioned
by name is such that the substance is not subject to the provisions for this Class.
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