2.2.41.2.3

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.

2.2.41.3

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, UNNo.2870.

2.2.41.4

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 4.2.5.2.6, portable tank instruction T23. The formulations listed in packing instruction IBC520 of 4.1.4.2 and in portable tank instruction T23 of 4.2.5.2.6 may also be carried packed in accordance with packing method OP8 of packing instruction P520 of 4.1.4.1, with the same control and emergency temperatures, if applicable.

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

SELF-REACTIVE SUBSTANCE	Concen- tration (%)	Packing method	Control tempera- ture (°C)	Emergency tempera- ture (°C)	UN generic entry	Remarks
2-DIAZO-1-NAPHTHOL-4-SULPHONYL CHLORIDE	100	OP5			3222	(2)
2-DIAZO-1-NAPHTHOL-5-SULPHONYL CHLORIDE	100	OP5			3222	(2)
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

SELF-REACTIVE SUBSTANCE	Concen- tration (%)	Packing method	Control tempera- ture (°C)	Emergency tempera- ture (°C)	UN generic entry	Remarks
3-METHYL-4-(PYRROLIDIN-1-YL) BENZENEDIAZONIUM TETRAFLUOROBORATE	95	OP6	+45	+50	3234
4-NITROSOPHENOL	100	OP7	+35	+40	3236
PHOSPHOROTHIOIC ACID, O-[(CYANOPHENYL METHYLENE) AZANYL] O,O-DIETHYL ESTER	82-91 (Z isomer)	OP8			3227	(10)
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 7.1.7.3.1 to 7.1.7.3.6.
(2) "EXPLOSIVE" subsidiary hazard 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 7.1.7.3.1 to 7.1.7.3.6.
(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 7.1.7.3.1 to 7.1.7.3.6.
(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.
(10) This entry applies to the technical mixture in n-butanol within the specified concentration limits of the (Z) isomer.

2.2.42

Class 4.2 Substances liable to spontaneous combustion

2.2.42.1

Criteria

2.2.42.1.1

The heading of Class 4.2 covers:

-Pyrophoric substanceswhich are substances, including mixtures and solutions (liquid or solid),which even in small quantities ignite on contact with air within five minutes. These are theClass4.2 substances the most liable to spontaneous combustion; and

-Self-heating substances and articleswhich are substances and articles, including mixtures andsolutions, which, on contact with air, without energy supply, are liable to self-heating. Thesesubstances will ignite only in large amounts (kilograms) and after long periods of time (hoursor days).

2.2.42.1.2

The substances and articles of Class 4.2 are subdivided as follows:

S Substances liable to spontaneous combustion, without subsidiary hazard:

S1 Organic, liquid;

S2 Organic, solid;

S3 Inorganic, liquid;

S4 Inorganic, solid;

S5 Organometallic;

S6 Articles

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.

2.2.42.1.3

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.

2.2.42.1.4

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, PartIII, Section 33.3. Assignment to general N.O.S. entries of Class 4.2 shall be based on the results of thetest 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.

2.2.42.1.5

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 hazards, depending on their properties, a specific classification flow chart for these substances is given in 2.3.5.

2.2.42.1.6

If substances of Class 4.2, as a result of admixtures, come into different categories of hazard 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.

2.2.42.1.7

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.

2.2.42.1.8

Assignment of packing groups

Substances and articles classified under the various entries in Table A of Chapter 3.2 shall be assigned to packing groups I, II or III on the basis of test procedures of the Manual of Tests and Criteria, Part III, section 33.3, in accordance with the following criteria:

(a) Substances liable to spontaneous combustion (pyrophoric) shall be assigned to packing group I;

(b) Self-heating substances and articles in which, in a 2.5 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 packing group II; Substances with a temperature of spontaneous combustion higher than 50 °C for a volume of 450 litres are not to be assigned to packing group II;

(c) Slightly self-heating substances in which, in a 2.5 cm sample cube, the phenomena referred tounder (b) are not observed, in the given conditions, but in which in a 10 cm sample cubeat140°C test temperature spontaneous combustion or a rise in temperature to over 200°C isobserved within 24hours, shall be assigned to packing group III.

2.2.42.2

Substances not accepted for carriage

The following substances shall not be accepted for carriage:

-UN No. 3255 tert-BUTYL HYPOCHLORITE; and

-Self-heating solids, oxidizing, assigned to UN No. 3127 unless they meet the requirements forClass1 (see 2.1.3.7).

2.2.42.3

List of collective entries

_____________________
a Dust and powder of metals, non toxic in a non-spontaneous combustible form which nevertheless, in contact with water, emit flammable gases, are substances of Class 4.3.

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